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		<title>Über Hydrodynamisierung, Information und Leben</title>
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				<category><![CDATA[Articles about Water]]></category>
		<category><![CDATA[Biology of Water]]></category>
		<category><![CDATA[Chemistry of Water]]></category>
		<category><![CDATA[Physics of Water]]></category>
		<category><![CDATA[Hydrodynamisierung]]></category>
		<category><![CDATA[Information und Leben]]></category>
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		<description><![CDATA[Über Hydrodynamisierung, Information und Leben Herbert J. Klima *, * Akademie für Holistische Kultur Wien, ** Alexander Steinke  EL-Technologie GmbH   „Was heute noch als wahr genannt, wird morgen vielleicht als falsch erkannt“   1. Einführung Die „Dynamisierung von Wasser“ oder „Hydrodynamisierung“ ist eine physikalische Art der Wasseraufbereitung, die in einer «Dynamisierungsmaschine» durchgeführt wird. Dabei<a href="http://korotkov.org/water/2011/10/uber-hydrodynamisierung-information-und-leben/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p>Über Hydrodynamisierung, Information und Leben</p>
<p align="center">Herbert J. Klima *, * Akademie für Holistische Kultur Wien, **</p>
<p align="center">Alexander Steinke  EL-Technologie GmbH</p>
<p align="center"><strong><em> </em></strong></p>
<p align="center"><em>„Was heute noch als wahr genannt,</em></p>
<p align="center"><em>wird morgen vielleicht als falsch erkannt“</em></p>
<p align="center"> <span id="more-282"></span></p>
<p align="center"><strong><em>1. Einführung</em></strong></p>
<p>Die „Dynamisierung von Wasser“ oder „Hydrodynamisierung“ ist eine physikalische Art der Wasseraufbereitung, die in einer «Dynamisierungsmaschine» durchgeführt wird<strong>.</strong> Dabei wird die flüssig-kristalline und damit geometrisch beschreibbare Clusterstruktur des Wassers durch mechanisch erzeugte Wirbelströmungen und schwache Magnetfelder physikalisch beeinflusst. Das Wasser erhält definierte Informationen: es wird dynamisiert.</p>
<p>&nbsp;</p>
<p>Diese auf dem erste Blick komplizierte Darstellung der „Dynamisierung von Wasser“ wird aber verständlich, wenn wir – wie in der weiteren Folge gezeigt wird &#8211; die Bedeutung der verwendeten Begriffe klären. Jede Sprache verwendet Fachwörter mit entsprechender Bedeutung; wir gebrauchen täglich einige davon, machen uns aber selten Gedanken über deren Bedeutung und deren Zusammenhänge in Sätzen.</p>
<p>&nbsp;</p>
<p><strong>Um es aber vorerst auf einfache Weise zu sagen: „Dynamisiertes</strong><strong> </strong>Wasser“ hat Eigenschaften, die denen des natürlichen Quellwassers gleichen. Welche aber sind diese Eigenschaften des natürlichen Quellwassers? Diese Eigenschaften wollen wir nun mit dem Begriff der Ordnung verbinden: man kann sie dann nicht nur verstehen, sondern sogar mathematisch unterlegen.</p>
<p>&nbsp;</p>
<p align="center"><strong><em>2. Was bedeutet Mathematik?</em></strong></p>
<p>&nbsp;</p>
<p>Was bedeutet der Begriff Mathematik? Im Griechischen bedeutet mathema bzw. maqemam die Wissenschaft, die Lehre, das Lernen. Mathematik kann daher als die Kunst des Lernens gedeutet werden. In maqema steckt auch thema bzw. qema das Gesetz, damit auch das Geistige und letztlich das Göttliche. In allen Kulturen, daher auch in den Hochkulturen der Babylonier, Ägypter und Griechen spielte das Göttliche, aus dem das Geistige und damit das Gesetz hervorging, eine zentrale Rolle. In dieser Hinsicht kann die Mathematik, die ursprünglich eine Schöpfung der Babylonier war, nicht von der Gottesgelehrsamkeit getrennt werden. Sie wurde danach vor allem von griechischen Philosophen (Thales, Pythagoras, Platon) übernommen und von den großen antiken Mathematikern (Euklid, Heron, Archimedes) in Alexandrien weiter entwickelt und kultiviert.</p>
<p>&nbsp;</p>
<p>Das polare Gegenstück, das Komplement, zum maqema bzw. dem Geist, ist die Materie, die vor allem von den griechischen Materialisten (Leukipp, Demokrit, Aristoteles) als grundlegend favorisiert wurde. Berühmt geworden ist das so genannte Platonische Dreieck, das an der Basis die Begriffe „Geist“ und „Materie“ trägt – und an der Spitze das „Göttliche“ als „Platonische Ideen“. Wie sagte doch der kluge Scholastiker Petrus Abelard auf wunderbare Weise: „Die Platonischen Ideen findet man vor den Dingen (der Materie) als Gottes schöpferische Gedanken, in den Dingen als Ähnlichkeiten ihrer Eigenschaften und nach den Dingen als abstrakte Begriffe“.</p>
<p>&nbsp;</p>
<p>Daher  kann es der Sinn und Zweck eines erfüllten Lebens sein, diese Polaritäten aus „Geist“ und „Materie“ zu überwinden und zur Einheit bzw. zum Ganzen, zur Spitze des Platonischen Dreiecks zurückzukehren: zum Göttlichen und seiner kosmischen Vernunft, wie sie auch als denknotwendige Wahrheit in der Mathematik und damit auch in der Geometrie vorherrscht.</p>
<p>Ein wichtiger Teilbereich der Mathematik ist nämlich die Geometrie. Was aber bedeutet der Begriff Geometrie? Im Griechischen heißt „geos“ die Erde und „metros&#8221; das Maß. Es liegt also ein göttliches Erdmaß im Wesen der Geometrie. Was  sich geometrisch verhält, hat daher viel mit Regelmäßigkeit und Ordnung zu tun, wie es auf ideale Weise in den fünf Platonischen Körpern als regelmäßige Polyeder (Tetraeder, Hexaeder, Oktaeder, Dodekaeder, Ikosaeder) verwirklicht ist.</p>
<p>&nbsp;</p>
<p align="center"><strong><em>3. Über die Energie und die Umwandlung ihrer Formen</em></strong></p>
<p>&nbsp;</p>
<p>Das Bindeglied zwischen dem „Geist“, der die ewigen kosmischen Gesetze repräsentiert, und der „Materie“, deren Wesen in der Veränderung liegt, ist die Energie. Einerseits hat die Energie Anteil an der Ewigkeit, da für sie der wichtigste Erhaltungssatz der Physik gilt, und andererseits hat sie Anteil am Wandel, da sie sich von einer Form in eine andere wandeln kann (Kernenergie, Sonnenenergie, elektromagnetische Energie, Bioenergie, mechanische Energie, Wärmeenergie etc.). Dabei gilt für die Richtung der Umwandlung der Energie ein wichtiges kosmisches Prinzip: das Prinzip der maximalen Entropie, das man auch Prinzip des Todes nennt. Nach diesem Prinzip erfolgt die Umwandlung der unterschiedlichen Energieformen in geschlossenen Systemen immer in Richtung zunehmender Unordnung, an deren Ende die Wärmeenergie und aus biologischer Sicht der Tod stehen.</p>
<p>Wird einem Stoff bzw. einer kristallisierten Materie – beispielsweise einem Wasserkristall – Wärmeenergie zugeführt, so verflüssigt sich der Kristall bei einer bestimmten Schmelztemperatur: die Regelmäßigkeit des Kristalls geht verloren, die Unordnung des Stoffes wächst. Wenn sich umgekehrt flüssige Materie – wie beispielsweise flüssiges Wasser – durch Abkühlung verfestigt und kristallisiert, so erfolgt eine Umwandlung in umgekehrter Richtung, nämlich in Richtung zunehmender Ordnung, wie man am nachfolgenden Bild eines wunderschönen Wasserkristalls sehen kann.</p>
<p>&nbsp;</p>
<p align="center"> <a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima1.jpg"><img class="alignnone size-full wp-image-283" title="Klima" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima1.jpg" alt="" width="206" height="150" /></a></p>
<p>&nbsp;</p>
<p>Bild1: Wasserkristall nach Masaro Emoto</p>
<p>Foto von Rasmus Gaupp-Berghausen Leiter des Labors von Masaro Emoto in Europa Hado Life Europe.</p>
<p>&nbsp;</p>
<p>Die gleiche wunderbare Ordnung wie beim Wasserkristall gilt auch für einen Bergkristall, der aus Quarz bzw. kristallisiertem Siliziumoxid besteht. Er hat ein trigonales Kristallsystem, das eng mit dem hexagonalen System des Platonischen Körpers verwandt ist.</p>
<p>&nbsp;</p>
<p align="center"> <a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima2.jpg"><img class="alignnone size-full wp-image-285" title="Klima2" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima2.jpg" alt="" width="206" height="180" /></a></p>
<p>&nbsp;</p>
<p align="center">Bild 2 eines Bergkristalls</p>
<p>&nbsp;</p>
<p>Wir wissen zwar aus Erfahrung, dass es niemals zwei gleiche materialisierte Bergkristalle gibt, dennoch legt uns die Geometrie nahe, dass jeder Bergkristall immer dieselbe geometrische Kristallklasse aufweist und mit dem Hexaeder der Platonischen Körpern verwandt ist.</p>
<p>&nbsp;</p>
<p align="center"><strong><em>4. Über die Ordnung der Kristalle und Salbung des Christos</em></strong></p>
<p>&nbsp;</p>
<p>Ein Kristall ist demnach ein materialer Ausdruck hoher geometrischer Ordnung und Regelmäßigkeit. Beamte und Priester als Hüter hoher gesellschaftlicher Ordnung (Pharaonentum, Königtum) wurden unter den Ägyptern und Babyloniern vom Herrscher (Pharao, König) zur Einweihung mit einem Salböl gesalbt, einer Mischung aus Olivenöl Myrre, Zimt, Kalmus und Cassia. Diese Salbung hatte die Aufgabe, die Ordnung der Herrschaft nicht nur zu bewahren, sondern sie zu optimieren. Einen derartig Gesalbten nannte die Hebräer später „Messias“, der von Jahwe gesalbt wurde, um das Reich Gottes auf Erden zu errichten und zu bewahren. Die antiken Griechen nannten einen Gesalbten „Christos“.</p>
<p>&nbsp;</p>
<p>Jesus von Nazareth ist nach Auffassung der Christen der von Gott Gesalbte, den man im Griechischen „Christos“ und im Lateinischen „Christus“ nennt. Nach Auffassung der jüdischen Theologen ist Jesus jedoch nicht der Gesalbte bzw. Christos, weil auf Erden immer noch Unordnung, Krieg und Uneinigkeit herrschen.</p>
<p>&nbsp;</p>
<p>Vor Tausenden von Jahren, als es noch gar keine Christen gab, nannte man schon im antiken Griechenland den Hüter der Ordnung „Christos“ &#8211; und dabei ging es den antiken Griechen nicht nur um die äußere Ordnung des Reiches, die es zu bewahren galt, sondern auch um die innere Ordnung des menschlichen Geistes, die man Bewusstsein nennt. Das eigentliche Ziel in einem Menschenleben war es, den inneren „Christos“ zu finden, zu heben und zu vervollkommnen. Der wahre Zweck des Lebens ist daher, dieses Christos-Bewusstsein so weit zu entwickeln, dass wir ein All-Bewusstsein bekommen, einen Christ-all.</p>
<p>&nbsp;</p>
<p>Was ist nun ein Christ-all  bzw. Krist-all wirklich?  Welche Macht und welche Gesetze stecken dahinter, dass beispielsweise Bergkristalle einen so perfekten und immer gleichen geometrischen Aufbau haben. Und um diese Geometrie der Kristalle geht es uns hier, um die Form der Kristalle und um die Einflüsse, welche es ermöglichen, dass Kristalle in diese wunderbare Form gebracht werden: es geht um Information!</p>
<p>&nbsp;</p>
<p align="center"><strong><em>5. Über Information und Leben</em></strong></p>
<p>&nbsp;</p>
<p>Was ist Information überhaupt?  Dieses Wort drückt schon aus, was es bedeutet könnte: nämlich einen bestimmten Stoff in seine Form zu bringen bzw. wieder zurückbringen oder in einem Lebewesen Bewusstsein zu schaffen bzw. dessen Geist zu perzipieren..</p>
<p>&nbsp;</p>
<p>Mit Information und Materie befasst sich nicht nur die Physik im allgemeinen, sondern auch die Biophysik im speziellen. Der Begriff Biophysik setzt sich zusammen aus den griechischen Begriffen<em> </em><em>βίος</em> &#8211; <em>bios</em>, was „Leben“ bedeutet, und <em>φυσική</em> – <em>physike</em>, was „Natur“ heißt. Konventionelle Physiker verstehen unter Physik üblicherweise die „Lehre von der unbelebten Materie“ und traditionelle Biologen unter Biologie die „Lehre von der belebten Materie“. Es scheint daher, dass der Begriff „Biophysik“ zunächst einen Widerspruch in sich darstellt.</p>
<p>&nbsp;</p>
<p>Allerdings muss beachtet werden, dass die Zellen aller Lebewesen – ob Einzeller oder Mehrzeller &#8211; aus unbelebter Materie (Atomen, Molekülen und makromolekularen Verbänden) aufgebaut sind. Die Grundprozesse der Biologie müssen also auch den Gesetzen der Physik gehorchen. Dazu zählt man nicht nur die Gesetze der Thermodynamik des Gleichgewichtes, die das schon angeführte Prinzip der maximalen Entropie bzw. der Unordnung als Prinzip toter Systeme enthält, sondern auch die Gesetze der Thermodynamik offener, dissipativer  Systeme fern vom thermodynamischen Gleichgewicht, die auch lebende Prozesse erklären können und für deren Entdeckung im Jahre 1977 der Nobelpreis für Chemie an den belgische Physikochemiker Ilya Prigogine vergeben wurde.</p>
<p>&nbsp;</p>
<p>Begreift man außerdem die Physik im modernen Sinne als Wissenschaft von den Eigen-schaften und dem Verhalten der Materie und der Felder (somit generell von Stoffen, egal ob klassisch oder quantisiert) in Raum und Zeit, so wird klar, dass auch alle biologischen Prozesse den Gesetzen einer systemisch orientierten klassischen Physik und Quantenphysik genügen müssen.</p>
<p>&nbsp;</p>
<p>Die Biophysik befasst sich daher mit den Zuständen und Zustandsänderungen des lebendigen Organismus, sei es bei Pflanzen, bei Tieren oder auch beim Menschen. Wenn wir bloß die Materie und ihre Felder betrachten, so müssen wir anerkennen, dass jede Materie und jedes zugehörige Feld – ob anorganisch oder organisch &#8211; aus so genannten Elementarteilchen wie Elektronen, Quarks und Photonen aufgebaut  ist. Diese Teilchen bilden schließlich Atome und Moleküle, zwischen denen elektromagnetische Feldquanten bzw. Photonen wechselwirken und die man für biologische Systeme auch „Biophotonen“ nennt.</p>
<p>&nbsp;</p>
<p>Da Materie bzw. Masse m und Energie E untrennbar verbunden sind, wie man Einsteins berühmter Formel E = mc<sup>2</sup> (c ist die Lichtgeschwindigkeit) entnimmt, geht es in der Biophysik weniger um Energie, die ja eine Erhaltungsgröße ist, sondern um die Bereitstellung von Information für Organellen, die aus vielen Atomen und Molekülen sowie Makro-molekülen bestehen. Man kann diese Behauptung, wonach es in der Biologie mehr um Information als um Energie bzw. Masse geht, sehr dramatisch darstellen: wird ein Säugling geboren, so wiegt er beispielsweise 2 Kilogramm; stirbt er unmittelbar darauf, weil sein Herz versagt, so hat er noch immer die gleiche Masse, wie man durch Abwägen feststellen kann. Was also hat sich durch den Übergang von Leben in den Tod verändert? Es ist die Ordnung, die geordnet Form, die Information, die ein Lebewesen von einem Toten unterscheidet!</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>Da lebende Systeme überwiegend elektromagnetische Systeme sind, benutzt man zum Verständnis der Zustände und Zustandsänderungen biologischer Systeme in der Biophysik neben den physikalischen Gesetzen der Mechanik und Hydrodynamik vor allem die physikalischen Gesetze der Elektrodynamik bzw. der Quantenelektrodynamik. Gerne stellt man diesen physikalischen Disziplinen in der Biophysik noch ein „Bio“ vor und bezeichnet sie dann mit „Biomechanik“ oder „Bioelektrodynamik“, ähnlich wie man statt Photonen dann „Biophotonen“ sagt.</p>
<p>&nbsp;</p>
<p>Das biologische Verhalten ist aber vor allem und überwiegend ein systemischer Prozess, der innig mit dem Informationsbegriff und Prigogines Gesetzen der Thermodynamik offener dissipativer Systeme zusammenhängt. Lebende Systeme müssen sich nämlich – wie es schon der geniale Physiker Erwin Schrödinger erkannte &#8211; fern vom Zustand der maximalen Entropie bzw. Unordnung aufhalten, um zu überleben. Sie müssen all die Entropie bzw. Unordnung, die ein lebendes System ständig zur Aufrechterhaltung der Gleichgewichtsferne bzw. des Lebens bei der Umwandlung der Sonnenenergie und der Nährstoffe in hoch geordnete biologische Strukturen (Eiweiß, Kohlehydrate, Nukleinsäuren, etc.) produziert, ständig los werden, indem sie diese Entropie in Form der Stoffwechselprodukte und der Wärme an die Umgebung ab- bzw. zurückgeben (als Kot, Harn, CO<sub>2</sub>, Wärme, infrarote Wärmestrahlung).</p>
<p>&nbsp;</p>
<p>Es geht demnach in der Biophysik nicht um die Energie, sondern um die Umwandlung der hohen Ordnung einer Energieform in eine andere, um ein biologisches System in die erforderliche hoch geordnete Form zu bringen und zu erhalten: um es zu informieren. Man nennt diesen Bedarf an hoher Ordnung in der Thermodynamik auch „Negentropie“ und in der Systemtheorie „Information“.  Den Pflanzen geht es dabei um die Umwandlung der elektromagnetischen Feldenergie der Sonnenstrahlen durch Photosynthese in die Negentropie bzw. Information der biochemisch gespeicherten Energie und um deren Bereitstellung für ihre Lebensprozesse (Aufnahme von Nährstoffen, Aufbau von Zellen und Pflanzenteilen,  Fortpflanzung etc.). Den Tieren und Menschen geht es um den Erwerb der Negentropie bzw. Information in der biochemisch gespeicherter Energie aus Pflanzen und Tieren der Nahrungskette und um deren Bereitstellung für ihre Lebensprozesse (Bewegung, Verdauung, Aufbau und Erhaltung von Zellen und Organen, Fortpflanzung etc.).</p>
<p>&nbsp;</p>
<p>Negentropie bzw. Information sind damit fundamentale immaterielle Begriffe, die deutlich von dem materiellen Energiebegriff unterschieden werden sollten. Um Nachrichten bzw. Informationen wie Sprache oder Musik zu übertragen, benötigt man einen materiellen energetischen Träger, z.B. Schallwellen oder elektromagnetische Wellen wie Radiowellen spezieller Wellenlängen bzw. Frequenzen bei Hörfunk- und Fernsehübertragungen; um Informationen wie den genetischen Code als eine definierte lineare Folge von Triplets entsprechender Basenpaare von einer DNA auf eine RNA weiterzugeben, benötigt man materielle Nukleotide, die sich zur polymerisierten DNA verbinden.</p>
<p>&nbsp;</p>
<p>Damit aber ein Empfänger eine Information aufnehmen kann, die ihm ein Sender übermittelt, müssen beide, nämlich Sender und Empfänger, in Resonanz stehen, d.h. die gleiche Trägerfrequenz verwenden. Der Fernsehsender 3sat, der vor allem für Zuseher aus Deutschland, Österreich und Schweiz sendet, benutzt eine Trägerfrequenz von 11, 95350 GHz = 11953500000 Hz bzw. Schwingungen pro Sekunde. Um aber die Ton- und Bildinformationen  von 3sat zu empfangen, muss man daher den Schwingkreis des Empfängers seines Fernsehgerät auf genau diese Trägerfrequenz einstellen, damit es zur Resonanz zwischen Sender- und Empfängerfrequenz kommt. Dann kann man auch durch einen passenden Knopfdruck auf den Kanal seiner Fernbedienung die gesendeten Informationen (Nachrichten, Musik, Dokumentationen, etc.) empfangen.</p>
<p>&nbsp;</p>
<p>Bei jeder Informationsübertragung geht es darum, gleiche Wellenlängen bzw. Frequenzen unterschiedlicher Technik (Rundfunk, TV, automatisches Garagentoröffner etc.) zu benutzen, um in Resonanz zu geraten und die Informationen zu verarbeiten. Um beispielsweise ein Garagentor automatisch durch eine Fernsteuerung zu öffnen, müssen nicht nur die Trägerfrequenzen von Fernbedienung und Empfänger übereinstimmen, sondern der Empfänger muss die Information des Senders auch verarbeiten können – etwa durch einen Stromimpuls, der einen Schaltkreis schließt und einen Motor einschaltet, der das Tor öffnet.</p>
<p>&nbsp;</p>
<p>Was aber hat dies alles mit der „Dynamisierung von Wasser“ zu tun? Lebewesen und damit auch Menschen bestehen zu einem großen Teil, bis zu 75 % , aus Wasser. Der Rest ist organische Materie (Proteine, Kohlenwasserstoffe, Nukleinsäuren, Lipide etc.) und anorganische Materie (Salze, Spurenelemente etc.). Der Grund für den hohen Anteil an Wasser liegt darin, dass Lebewesen als einzellige Prokaryoten im Meer entstanden sind. Proteine und Nukleinsäuren sind Polymere, die sich – wie uns der Nobelpreisträger Manfred Eigen hinterließ – in so genannten Hyperzyklen gemeinsam im Meerwasser besser reproduzieren konnten als jedes einzelne Polymer für sich. Eine Zellmembran aus Lipoproteinen umschloss dieses sich selbst reproduzierende System aus Meerwasser, Proteinen und Nukleinsäuren, das jedoch als offenes System auf die Negentropie bzw. Information des Sonnenlichtes und auf den Stoffwechsel angewiesen war, um den ständigen Bedarf an Materie (gelöste Stoffe) aus dem umgebenden Meerwasser für den Aufbau seiner organischer Bestandteile zu decken. Es ist in diesem Zusammenhang wichtig, wieder darauf hinzuweisen, dass die Sonnenenergie als Erhaltungsgröße schon bei den einfachen Einzellern nicht verbraucht, sondern nur die benötigte Negentropie bzw. Information bei der Umwandlung der Sonnenenergie in biochemische Energie gewonnen und verbraucht wurde!</p>
<p>&nbsp;</p>
<p align="center"><strong><em>6. Über dissipative Systeme</em></strong></p>
<p>&nbsp;</p>
<p>Um das Verhalten von Wasser in Lebewesen als offene Systeme zu verstehen, ist es empfehlenswert, die thermodynamischen Gesetze zu betrachten, die in offenen Systemen wirken, und sie von den thermodynamischen Gesetzen zu unterscheiden, die in geschlossenen und damit auch in toten Systemen vorherrschen. Flüssigkeiten als offene Systeme organisieren sich zu so genannten dissipativen Systemen, die durch eine hohe Ordnung ausgezeichnet sind und deren thermodynamisch-physikalisches Verhalten der bereits genannte Nobelpreisträger Ilya Prigogine untersucht hatte. Als bevorzugte dissipative Strukturen findet man so genannte bienenwabenartige Benard-Zellen sowie spiralige Muster, die mit Hilfe der Mathematik nichtlinearer Differentialgleichungen im Rahmen der Wissenschaft der „Nichtlinearen Dynamik“ nicht nur beschrieben, sondern aus den vielfältigen Lösungen dieser Gleichungen (z.B. periodisches, mehrfach periodisches oder chaotisches Verhalten) auch verstanden werden können.</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p align="center"> <a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima3.jpg"><img class="alignnone size-medium wp-image-286" title="Klima3" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima3-288x100.jpg" alt="" width="288" height="100" /></a></p>
<p align="center">Abb.3: Dissipative Flüssigkeitsstruktur (Benard-Zellen) einer erwärmten Flüssigkeit als offenes System,</p>
<p align="center">sichtbar gemacht mit Aluminumpulver (links); dissipative spiralige Strukturen vom AMP, das von einzelligen Schleimpilzen bei Nahrungsmangel ausgesendet wird (rechts), um den mehrzelligen Verband zu bilden (rechts).</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p align="center"><strong><em>7. Über das Wasser </em></strong></p>
<p align="center"><strong><em> </em></strong></p>
<p align="center"><em>Die Dipolnatur von Wasser</em></p>
<p>&nbsp;</p>
<p>Die physikalischen und chemischen Eigenschaften des Wassers<a title="" href="#_ftn1">[1]</a>,<a title="" href="#_ftn2">[2]</a> können im Wesentlichen aus der polaren Natur des Wassermoleküls erklärt werden, das durch eine kovalente Bindung von zwei Wasserstoffatomen und einem Sauerstoffatom entsteht.</p>
<p>&nbsp;</p>
<p>Die Verbindung von zwei Wasserstoffatomen mit einem Sauerstoffatom zu einem Wassermolekül kommt folgendermaßen zustande: Im atomaren Sauerstoff ist das 1s Orbital vollständig mit zwei Elektronen besetzt, das 2s Orbital ebenfalls, auch eines der drei 2p Orbitale ist mit zwei Elektronen gefüllt, die beiden anderen 2p Orbitale haben je ein Elektron. Die zwei fehlenden Elektronen können mit je einem 1s Wasserstoffelektron besetzt werden, womit ein sp-Hybridorbital entsteht. Der Sauerstoff ist elektronegativer als der Wasserstoff (H&lt;C&lt;N&lt;O&lt;F), wodurch sich  die Elektronenwolke aus den sechs Elektronen im sp-Hybridorbital polarisiert: die Ladungswolke wird stärker zum Sauerstoffkern gezogen, durch diese Symmetriebrechung wird ein elektrischer Dipol mit einer Ladungsverteilung Q<sup>+</sup> und Q<sup>- </sup>ausgebildet. Der positive Teil der Ladungsverteilung Q<sup>+</sup> liegt in dem ursprünglich mit zwei Elektronen voll besetzten p Orbital, der negative Teil Q<sup>-</sup> teilt sich auf die beiden anderen p Orbitale auf, die nun miteinander einen Winkel j von etwa 104 Grad einschließen<a title="" href="#_ftn3">[3]</a></p>
<p>&nbsp;</p>
<p>Unter einem Dipol versteht man eine Ladungsstruktur, die zwei entgegengesetzte Ladungen Q<sup>+</sup> und  Q<sup>-</sup> gleicher Größe auf einem definierten Abstand <strong>r</strong> besitzt, die aber als Ganzes elektrisch neutral ist. Man charakterisiert einen Dipol durch das Dipolmoment <strong>m</strong><sub>e</sub> = Q. <strong>r</strong>, dessen Einheit [Coulomb.Meter] = [C.m] beträgt. Die Einheit von 1 Cm ist für molekulare Dipole viel zu groß, weshalb man das molekulares Dipolmoment in Debye [1 D = 3,3 10<sup>-30</sup> Cm] angibt. Der Dipolmomentbetrag des Wassermoleküls beträgt  <strong>m</strong><sub>e</sub> = 1,85 D, die Richtung liegt in der Winkelsymmetralen des Winkels, der von den beiden Wasserstoffkernen und dem Sauerstoffkern gebildet wird.</p>
<p>&nbsp;</p>
<p>Die meisten Organismen bestehen zum Großteil (70 &#8211; 80%) aus Wasser, das jedoch kein träger Füllstoff, sondern eine sehr reaktive Substanz im intra- sowie interzellulären Bereich ist und den Aufbau biologischer Strukturen, aber auch den Ablauf biologischer Prozesse entscheidend mitgestaltet.</p>
<p>&nbsp;</p>
<p>Diese Reaktivität liegt an den ungewöhnlichen physikalischen und chemischen Eigenschaften des Wassers, die sich alle mehr oder weniger leicht aus der Dipolstruktur des Wassermoleküls herleiten lassen.</p>
<p><strong> </strong></p>
<p align="center"><em>Intermolekulare Wechselwirkungen</em></p>
<p>&nbsp;</p>
<p>Zwischen den einzelnen Molekülen können anziehende Kräfte auftreten, die intermolekular wirken und zu Bindungen von Molekülkomplexen führen. Diese Kräfte, die im wesentlichen elektrodynamischer Natur sind, fasst man unter dem Terminus »Van-der-Waals-Kräfte« zusammen, ihre Bindungsenergien sind jedoch geringer als die Energien bei der Molekülbildung. So beträgt beispielsweise die Stärke der Dipol-Dipol-Wechselwirkung von Wassermolekülen nur etwa 0,2 eV (d. s. 4,5 kcal/mol bzw. 18,8 kJ/mol) im Vergleich zur          0-H-Bindungsenergie von 4,8 eV (463 kJ/mol) bei. Die Reichweite von Dipol-Dipol-Wechselwirkung ist proportional zu 1/r<sup>5</sup>, sie ist sehr kurzreichend. Dennoch führt diese intermolekulare Wechselwirkung  zweier Wasserdipole zur Bildung von beachtlichen Molekülkomplexen bzw. Cluster. Beispielweise liegt der Abstand des H-Atoms eines Wassermoleküls vom O-Atom eines anderen Wassermoleküls im Angströmbereich (10<sup>-10</sup> m). Diese Bindung ist jedoch nicht zeitlich konstant, sondern zerfällt nach etwa 10<sup>-11</sup> sec<a title="" href="#_ftn4">[4]</a>.</p>
<p>&nbsp;</p>
<p>Eine spezielle Art einer Dipol-Dipol-Wechselwirkung ist die Wasserstoffbrückenbindung. Tritt ein H-Atom mit einem elektronegativen Partner, etwa mit Sauerstoff in Verbindung, so entsteht ein polares Molekül, wobei das H-Atom den positiven Pol desselben bildet. Dieser Dipol kann ein weiteres polares Molekül anziehen, das dem gebundenen H-Atom seinen negativen Pol zuwendet. Die Annäherung beider Dipole kann auf sehr kleine Entfernung erfolgen (2,6 &#8211; 3,1 .10<sup>-10</sup> m), wobei sogar die Van-der-Waals-Radien unterschritten werden. Das weist darauf hin, dass bei der Bildung dieser Bindung außer der elektrostatischen Wechselwirkung auch kovalente Beiträge eine Rolle spielen. Bei genügender Annäherung beider Moleküle lässt sich letzten Endes das H-Atom nicht mehr eindeutig einem der beiden Moleküle zuordnen. Es gehört quasi beiden Molekülen gleichzeitig an und bildet eine Wasserstoffbrücke.</p>
<p>&nbsp;</p>
<p>Die Bindungsenergie der Wasserstoffbrücke beträgt etwa 13 bis 25 kJ/mol und ist eine Funktion des Bindungsabstandes. Die H-Brücke kann aber schon durch thermische Stöße zerstört werden, die im biologischen Temperaturbereich auftreten. Die Bindungsenergie der H-Brücken ist nicht allein elektrostatisch zu erklären, sondern es müssen, ähnlich wie bei der kovalenten Bindung, quantentheoretische Aspekte miteinbezogen werden.</p>
<p><span style="text-decoration: underline;"> </span></p>
<p align="center"><em>Die thermischen Strukturen des Wassers</em></p>
<p>&nbsp;</p>
<p>Die Bildung von Eiskristallen, aber auch von wässrigen Flüssigkeitskristallen im Zustand des thermodynamischen Gleichgewichtes wird überwiegend durch die Dipolnatur der Wassermoleküle bestimmt. Nimmt die thermische Bewegung der Wassermoleküle ab, so ordnen sich die Wasserdipole zu einem fiktiven Tetraeder. Die Bindung der Wasserstoffbrücke H&#8212;O ist mit 0,177 nm geringer als die kovalente Bindung H <strong>__ </strong>O mit 0,099 nm. Die Fortsetzung der Tetraederstruktur führt zu einem Gitter, das beim Schmelzen des Eises nicht völlig abgebaut wird und sogenannte Cluster bildet.</p>
<p>&nbsp;</p>
<p align="center"> <a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima4.jpg"><img class="alignnone size-full wp-image-287" title="Klima4" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima4.jpg" alt="" width="284" height="190" /></a></p>
<p align="center">Abb.4: Modell der Tetraederstruktur aus Wasserdipolen</p>
<p>&nbsp;</p>
<p>Man nimmt an, dass die Zahl der Wasserdipole in der Nähe des Schmelzpunktes zwischen 100 bis 600 und beim in der Nähe des Siedepunkt zwischen 25 &#8211; 75 liegt. Die Wasserstoffbrücken oszillieren als Dipole mit einer Frequenz von 0,5. 1013 Hz. Die Clusterstrukturen sind aber nicht starr, sondern haben vermutlich nur eine Existenzdauer von 10<sup>-10</sup> bis 10<sup>-11</sup> s, so dass eine Wasserstoffbrücke im Mittel 100 &#8211; 1000 mal oszilliert, bis</p>
<p>diese Wasserstoffbrückenbindung aufbricht<a title="" href="#_ftn5">[5]</a>.</p>
<p>Im Unterschied zur Dynamik, deren Systeme meist eine überschaubare Anzahl N von Teilchen enthalten, handelt die Thermodynamik von einer riesigen Anzahl von Teilchen N. Beispielsweise befinden sich in 1 mol = 18 g flüssigem Wasser H<sub>2</sub>O  (2 x 1 g Wasserstoff plus 1 x 16 g Sauerstoff) N<sub>L</sub> = 6,022.10<sup>23</sup> Wassermoleküle.</p>
<p>Das in der Abb. dargestellte Beispiel von 1 mol = 18 g Wasser enthält N<sub>L</sub> = 6,022.10<sup>23</sup> =  602 200 000 000 000 000 000 000 Wassermoleküle, deren mittlere Geschwindigkeit &lt;v&gt;  = 467 m/s bei T = 20 <sup>o</sup>C und &lt;v&gt;  = 495 m/s bei T = 37 <sup>o</sup>C beträgt.</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima5.jpg"><img class="alignnone size-full wp-image-288" title="Klima5" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima5.jpg" alt="" width="198" height="156" /></a></p>
<p>Abb.5: 1 mol = 18 g Wasser</p>
<p>Wie jeder Stoff kommt auch Wasser in drei Aggregatzuständen vor</p>
<ul>
<li>als Feststoff, Eis genannt                  =&gt; Kristallstruktur</li>
<li>als Flüssigkeit, Wasser genannt         =&gt; Clusterbildung über Wasserstoffbrücken</li>
<li>als Gas, Wasserdampf genannt         =&gt; Einzelmoleküle</li>
</ul>
<p align="center"><em>Cluster-Strukturen von flüssigem Wasser</em></p>
<p>In der Folge sieht man drei Modelle von Wassermolekülen, die die Clusterstruktur des flüssigen Wassers illustrieren. Ständig werden Wasserstoffbrücken zwischen den verschiedenen Wassermolekülen gebildet und auch wieder gebrochen. Im Durchschnitt bleibt der Prozentsatz der an den Wasserstoffbrückenbindungen beteiligten H-Atome konstant, doch die einzelnen Bindungen ändern sich ständig. Nur im gasförmigen Zustand existieren tatsächlich einzelne diskrete Wassermoleküle<strong>. </strong>Somit sollte die Summenformel des flüssigen Wassers anstelle von &#8220;H<sub>2</sub>O&#8221; wegen der Cluster-Bildung eigentlich lauten: (H<sub>2</sub>O)<sub>n</sub></p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima6.jpg"><img class="alignnone size-medium wp-image-289" title="Klima6" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima6-288x75.jpg" alt="" width="288" height="75" /></a></p>
<p align="center">Abb.6: Modelle von dynamischen Cluster-Strukturen des flüssigen Wassers<a title="" href="#_ftn6">[6]</a></p>
<p align="center"><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima7.jpg"><img class="alignnone size-medium wp-image-290" title="Klima7" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima7-288x166.jpg" alt="" width="288" height="166" /></a></p>
<p align="center">Abb.7: Modellcluster von Wassermolekülen und deren Schwingungs-Wellenzahlen bzw- -Frequenzen</p>
<p align="center"><em> </em></p>
<p align="center"><strong><em>Dichteanomalie des Wassers </em></strong></p>
<p>Wasser zeigt bei der Temperatur von T = 4°C seine größte Dichte. Dies  ist eine Folge seiner Assoziationsfähigkeit mit Nachbarmolekülen, die bei T = 4°C die kompaktesten Cluster bilden. Bei Temperaturen größer als 4°C verhält sich Wasser normal, bei Temperaturen kleiner als 4°C verhält sich Wasser anormal: seine Dichte müsste zunehmen, tatsächlich nimmt sie ab.</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima8.jpg"><img class="alignnone size-full wp-image-291" title="Klima8" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima8.jpg" alt="" width="283" height="169" /></a></p>
<p align="center">Abb. 8 : Volumen und Dichte des Wassers als Funktion der Temperatur</p>
<p align="center"><em>Siedetemperatur des Wassers im Vergleich zu den Verbindungen der 6. Hauptgruppe des Periodensystems</em></p>
<p>&nbsp;</p>
<p>Wasser als Wasserstoffverbindung des Sauerstoffs lässt sich gut mit anderen Wasserstoffverbindungen der Elemente der 6. Hauptgruppe des PSE vergleichen: während sich die Verbindungen H<sub>2</sub>S (Schwefelwasserstoff), H<sub>2</sub>Se (Selenwasserstoff) und H2Te (Tellurwasserstoff) gemäß der in dieser Reihe zunehmenden Molekülmasse durch steigende Siedetemperaturen erwartungsgemäß verhalten, macht die Verbindung Wasser eine Ausnahme. Als leichtestes Molekül, das den Stoff &#8220;Wasser&#8221; aufbaut, sollte Wasser eigentlich bei etwa T = -75°C sieden !!! Tatsächlich liegt die Siedetemperatur des Wassers bekanntlich bei T = 100 °C. Dies ist nur mit dem hohen Energieaufwand zu erklären, der zum Aufbrechen des Cluster-Netzwerks aus Wasserstoffbrücken notwendig ist. Gäbe es diese Erscheinung nicht, müsste Wasser trendgemäß bei der oben angegebenen sehr niedrigen Temperatur sieden. Leben auf dieser Wasserbasis wäre auf der Erde damit nicht möglich.</p>
<p>&nbsp;</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima10.jpg"><img class="alignnone size-full wp-image-293" title="Klima10" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima10.jpg" alt="" width="148" height="245" /></a></p>
<p>Abb. 9 :  Siedetemperaturen von Wasser (Sauerstoffwasserstoff) im Vergleich zu H<sub>2</sub>S (Schwefelwasserstoff), H<sub>2</sub>Se (Selenwasserstoff) und H<sub>2</sub>Te (Tellurwasserstoff)<a title="" href="#_ftn7">[7]</a></p>
<p align="center"><em>Literaturhinweise zu dem Phänomen der Clusterbildung von Wassermolekülen</em><em></em></p>
<p><em>E. R. Batista,<sup>(a)</sup> H. Jónsson,<sup>(a)</sup> and S. S. Xantheas</em><em> ,</em> Multipole Moments of Water Molecules in Clusters and Ice</p>
<p><em><a href="http://www.emsl.pnl.gov/" target="_top">William R. Wiley Environmental Molecular Sciences Laboratory</a></em><em>, </em><em>April 10, 2000</em></p>
<p>Supported by the Division of Chemical Sciences, Office of Basic Energy Sciences and the Division of Environmental Sciences, Office of Biological and Environmental Research (Atmospheric Chemistry) in DOE, and by a grant of computer time at the NERSC by the Office of Scientific Computing, DOE.                                                                                               (a) Department of Chemistry, University of Washington.</p>
<p>The study of small clusters of water provides useful information regarding the transition from the gas to bulk phase environments. Of particular importance is the magnitude of the nonadditive many-body interaction in the clusters and in bulk environments such as water and ice. These nonadditive effects are usually accounted for by polarizable water models via an induction scheme in which the dipole moment on each molecule is computed self-consistently. Although the individual dipole moment of a system of more than two water molecules is not an observable, a rough estimate of its variation between different environments such as clusters, interfaces and/or water/ice serves as an indication of the importance of non-additive effects and how well these are reproduced by the various polarizable water models.</p>
<p>A previous induction-model study (Coulson and Eisenberg 1966) suggested a value of 2.6 D for the molecular dipole moment of water in ice Ih. This value has been used extensively in recent years as a reference point in the development of various polarizable interaction potentials for water as well as for assessment of the convergence of water cluster properties to those of bulk. We have used an induction model including dipole, dipole-quadrupole, quadrupole-quadrupole polarizability and first hyperpolarizability as well as fixed octopole and hexadecapole moments to study the electric field in ice. The self-consistent induction calculations gave an average total dipole moment of 3.09 D, a 67% increase over the dipole moment of an isolated water molecule and a value significantly (~0.5 Debye) larger than the one previously proposed by Coulson and Eisenberg (see Figure 6.16). The reason for this difference is not due to approximations made in the computational scheme of Coulson and Eisenberg but rather due to the use of less accurate values for the molecular quadrupole moment in these earlier calculations. Our induction scheme produces a value of 2.75 Debye for the average molecular dipole in the water hexamer, a value that is smaller than the one for ice Ih as expected from the different nearest and distant environments in these two systems.</p>
<p>&nbsp;</p>
<p>The convergence of the calculated molecular dipole moment as a function of the cutoff distance used in summing up the electric potential due to the neighbors indicates that it is sufficient to include only neighbors that are closer to 7 Å when evaluating the electric field at a given molecule. &#8220;Effective convergence&#8221; to the ice value has therefore been reached for a sphere of this radius around a water molecule that includes about 80 molecules in the ice Ih lattice.</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima11.jpg"><img class="alignnone size-full wp-image-294" title="Klima11" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima11.jpg" alt="" width="216" height="208" /></a></p>
<p>Chaplin, M. F. A proposal for the structuring of water</p>
<p><em>Biophys. Chem</em><em>.</em>, 83 (3), (2000), 211-221.</p>
<p>In spite of much work, many of the properties of water remain puzzling. A fluctuating network of water molecules, with localised icosahedral symmetry, is proposed to exist derived from clusters containing, if complete, 280 fully hydrogen-bonded molecules. These are formed by the regular arrangement of identical units of 14 water molecules that can tessellate locally, by changing centres, in three-dimensions and interconvert between lower and higher density forms. The structure allows explanation of many of the anomalous properties of water including its temperature-density and pressure-viscosity behaviour, the radial distribution pattern, the presence of both pentamers and hexamers, the change in properties and `two-state&#8217; model on supercooling and the solvation properties of ions, hydrophobic molecules, carbohydrates and macromolecules. The model described here offers a structure on to which large molecules can be mapped in order to offer insights into their interactions.</p>
<p>&nbsp;</p>
<p>Marcus Svanberg, Liu Ming, Nikola Markovic, and Jan B. C. Pettersson<br />
Collision dynamics of large water clusters</p>
<p><em>Journal of Chemical Physics 108(14), (1998) 5888-5897. </em><br />
Classicaltrajectory calculations of (H<sub>2</sub>O)<em><sub>n</sub></em> + (H<sub>2</sub>O)<em><sub>n</sub></em> collisions are carried out for <em>n</em> = 125and <em>n</em> = 1000. We investigate energy redistribution and fragmentation behavior forrelative collision velocities up to 3000 ms<sup> – 1</sup>, impact parameters up to4 nm, and initial cluster temperatures of 160 and 300K. Three main scattering channels are identified; coalescence, stretching separation,and shattering collisions. For small impact parameters, low collision velocitiesproduce coalesced clusters while high velocities yield shattering behavior. Largeimpact parameters combined with high velocities result in stretching separationcollisions. A decreased internal temperature influences the dynamics by increasingthe stability of the collision complex. The results for (H<sub>2</sub>O)<sub>125</sub>and (H<sub>2</sub>O)<sub>1000</sub> are comparable, although the smaller size allows individualmolecules to have a larger influence on the overall behavior.We find good agreement between the cluster simulations and experimentaldata for water drops in the micrometer range concerning thetransition between coalescence and stretching separation, which shows that theclusters in some respects resemble &#8220;macroscopic&#8221; objects. ©<em>1998 American Instituteof Physics.</em></p>
<p>Shinji Saito and Iwao Ohmine</p>
<p>Dynamics and relaxation of an intermediate size water cluster (H<sub>2</sub>O)<sub>108</sub><strong><br />
</strong><em>Journal of Chemical Physics Vol 101(7) (1994) 6063-6075</em><strong><em></em></strong></p>
<p>Thepotential surface, melting, surface structure, and hydrogen bond network ofan intermediate size water cluster (H<sub>2</sub>O)<sub>108</sub> are investigated. The orientationrelaxations of single molecule and of collective molecules are analyzedand compared with those of liquid water. The collective orientationrelaxation (COR) (i.e., dielectric relaxation) of the water cluster isfound to be much faster than that of liquid waterdue to different boundary conditions. In both liquid and cluster,the cross correlation between individual molecular dipoles plays an importantrole in static and dynamic quantities. COR of the clusteryields a so-called 1/<em>f</em> fluctuation in contrast to the well-knownDebye relaxation in liquid water. In order to understand thesedifferences of COR between the water cluster and liquid water,the wave vector dependence of the transverse and longitudinal componentsof COR is examined. A surface effect on hydrogen bondnetwork and the correlation between structural change and coordination numberare analyzed.</p>
<p>J. Brudermann<sup>1</sup>, P. Lohbrandt<sup>1</sup>, V. Buch<sup>2</sup> und U. Buck<sup>1</sup> ; <sup>1</sup>MPI für Strömungsforschung, Bunsenstr. 10, 37073 Göttingen; <sup>2</sup>The Fritz Haber Institute for Molecular Dynamics, Jerusalem 91904, Israel</p>
<p>Untersuchung von Oberflächenschwingungen großer Wassercluster durch ineleastische Helium-Streuung <em>Deutsche Physikalische Gesellschaft e.V (DPG) Frühjahrstagung 1998, Sitzung MO7 – Poster: Cluster</em></p>
<p>In einem gekreuzten Molekularstrahlexperiment wurde ein He-Atomstrahl bei thermischen Energien (ca. 65 meV) inelastisch an einem (H<sub>2</sub>O)<sub>n</sub> (n £ 100) Clusterstrahl gestreut. Der Cluster wird dadurch schwingungsangeregt. Die Analyse der übertragenen Energien bei verschiedenen Ablenkwinkeln mithilfe der Flugzeitmethode ergibt Energieüberträge im Bereich von 5-40 meV.  Um den Anregungsprozeß und die angeregten Schwingungen zu verstehen wurden zunächst Clusterstrukturen und Schwingungsspektren des Clusters mit klassischen Verfahren bestimmt. Weiterhin wurden Querschnitte für die Stoßanregung verschiedener Moden (Energien) mit Hilfe von Normalmodenanalyse und zeitabhängiger Störungsrechnung berechnet. Diese Berechnungen ergaben, dass sich die gemessenen Verteilungen durch die Anregung von Winkelschwingungen d. O-Atome in 3-fach koordinierten Wassermolekülen an der Oberfläche erklären lassen.</p>
<p align="center"><strong><em>8. Über die Dynamisierung von Wasser</em></strong></p>
<p>Generell lässt sich über die hydrodynamische Aufbereitung bzw. „Hydrodynamisierung“ von Wasser nur sagen, dass – abgesehen von chemischer Veränderung durch gelöste Stoffe wie Chlor, Mineralien etc. – im Grunde nur die Dynamik der Wassercluster beeinflussbar ist. Dies kann auf thermische Weise geschehen, indem man die Temperatur erhöht, womit nicht nur die Cluster, sondern auch die Anzahl der Dipole in den Clustern reduziert wird; dies kann auch auf mechanische Weise geschehen, indem man die dynamischen Wassercluster „aufbricht“ und damit mehr freie Wasserdipole erzeugt; dies kann aber auch auf elektrodynamische Weise erfolgen, indem man über elektrische und magnetische Gleich- oder Wechselfelder auf die dynamische Organisation der Dipole, z.B. auf die „dissipativen Strukturen“ bzw. Cluster im Wasser als offenes System Einfluss ausübt. Alle diese hydrodynamischen Aktivierungen des Wassers, ob thermisch, mechanisch oder elektrodynamisch, haben vermutlich nicht unterschätzbare Einflüsse auf die Prozesse in biologischen Systemen, ob auf die Keimung von Pflanzen oder auf die Pulsdynamik von Menschen nach dem Trinken derartig aufbereiteter Wässer, wie auch unsere Untersuchungen zeigten.</p>
<p>Man kann Wasser hydrodynamisch aufbereiten, wenn man sich einer der genannten Methoden (thermisch, mechanisch, elektrodynamisch) bedient. Lässt man Sonnenlicht auf Wasser einfallen, so wird es sowohl thermisch als auch elektrodynamisch beeinflusst. Anstelle von sichtbarem Sonnenlicht mit geringen Anteilen an Ultraviolett und Infrarot kann man aber auch andere Lichtquellen verwenden, die ein anderes Spektrum an elektro-magnetischen Wellen aufweisen. Mit geeigneten mechanischen Geräten kann man Wasser stark verquirreln und damit „dynamsieren“ kann. Da jeder Schall einen mechanischen Einfluss darstellt, eignen sich auch Schallquellen unterschiedlicher Art, die nur die Fähigkeit besitzen müssen, genügende Kräfte auf die Wasserstoffbrücken zwischen den Wasserdipolen auszuüben. Da die Wassercluster nicht statisch sind, sondern dynamisch fluktuieren, kann man die Dynamik der Cluster auch durch entsprechende intensive Musik beeinflussen, deren Rhythmen und Harmonien sich dann teilweise in den dynamisch „tanzenden“ Wasserclustern wiederfinden können.</p>
<p>&nbsp;</p>
<p>Derartige rhythmisch-harmonische Beeinflussungen von Wasser kann man mit elastischer Lichtstreuung, die den Laser-Doppler-Effekt verwendet, untersuchen. Eine entsprechende Untersuchungsmethode wurde ausgearbeitet und bietet sich interessierten Institutionen bzw. Unternehmen an, die besondere Methoden und Geräte der Wasseraktivierung betreiben.</p>
<p>&nbsp;</p>
<p>Hydrodynamisch aufbereitetes Wasser kann man überall dort mit Vorteil verwenden, wo Wasserbedarf ist: in der Landwirtschaft, in der Ernährungswirtschaft, in der Medizin, in der industriellen und privaten Wasserversorgung, in der Bauindustrie, etc. Es gibt daher kaum einen Kulturbereich der Menschheit, wo nicht Wasserbedarf vorhanden ist. Überall dort kann man hydrodynamisch aufbereitetes Wasser verwenden – vorausgesetzt, dass es vorher wissenschaftlich untersucht wurde!</p>
<p>&nbsp;</p>
<p><em>Selbstorganisation von Wasser</em></p>
<p align="center"><em> </em></p>
<p>Man muss zwei Arten der Selbstorganisation von Wasser unterscheiden. Die eine Art ist thermisch bedingt und kommt für geschlossene Systeme durch das Spiel gegensätzlicher Kräfte zustande, nämlich von Dipol-Dipol-Wechselwirkung der Wassermoleküle einerseits und thermischer Bewegung mit Boltzmann-Verteilung der Wasserdipole bei bestimmten Temperaturen andererseits. Das Ergebnis bzw. Ziel dieser thermischen Selbstorganisation sind chaotisch und statistisch fluktuierende Wassercluster.</p>
<p>&nbsp;</p>
<p>Die andere Art der Selbstorganisation ist das Ergebnis eines Nichtgleichgewichts-Prozesses von Wasser als offenes System. Dazu werden die Wasserdipole einem Gradienten (Temperatur, elektrische oder magnetische Felder, Gravitation) unterworfen und beginnen, sich als offenes System selbst zu organisieren. Diese Selbstorganisation mündet nach den Erkenntnissen der Nichtgleichgewichts-Thermodynamik (berühmte Vertreter dazu sind Hermann Haken und Ilya Prigogine) in einer kohärenten Bewegung der Wasserdipole und deren Cluster. Das Ziel dieser nichtthermischen Selbstorganisation ist Kohärenz bzw. Ausbildung hoch geordneter Strukturen, die man auch „dissipative Strukturen“ nennt. Diese Art der Selbstorganisation spielt bei der hydrodynamischen Wasseraufbereitung wie auch in lebenden Zellen als offene Systeme eine wesentliche Rolle.</p>
<p>&nbsp;</p>
<p>Da Wasser neben Luft und den Gesteinen zu den grundlegenden Sphären auf dem Planeten Erde gehört, sind alle Organismen, daher auch die Menschen am Wesen des Wassers interessiert. Hydro-, Atmo-, Litho- und Biospäre der Erde sind untrennbar miteinander verbunden und bilden einen großen Organismus, den man seit James Lovelock „Gaia“ nennt. Diese vier Sphären und damit „Gaia“ stehen als offenes, dissipatives System seit Jahrmilliarden unter dem Einfluss des Sonnenlichtes und bilden eine evolvierende Ganzheit weit weg vom thermodynamischen Gleichgewicht. Dabei wird die hochgeordnete Energie des Sonnenlichtes in niedrig geordnete Wärmeenergie umgewandelt bzw. dissipiert und vor allem als infrarote Wärmestrahlung in den Kosmos abgestrahlt.</p>
<p>&nbsp;</p>
<p>Dissipative Systeme – und dazu gehört nicht nur die Erde als Ganzheit, sondern auch die Hydrosphäre – sind weit weg vom thermodynamischen Gleichgewicht und haben gleichsam ein so genanntens „Gedächtnis“, was man stochastisch mit Nicht-Markov-Prozessen beschreibt, – im Gegensatz zum thermodynamischen Gleichgewicht, dessen Systeme Markov-Prozessen genügen und kein „Gedächtnis“ besitzen. Dabei versteht man im allgemeinen unter „Gedächtnis“, dass die Ursache für ein eingetretenes Ereignis nicht unmittelbar aus dem vorhergehenden Ereignis hervorgeht, sondern aus Ereignissen, die je Speicherfähigkeit des Systems, weiter in der Vergangenheit zurückliegen.</p>
<p>&nbsp;</p>
<p>Die radioaktive Strahlung genügt beispielsweise einem Markov-Prozess (dN/dt = lN  =&gt; N = N<sub>o</sub>e<sup>-</sup><sup>l</sup><sup>t</sup>), bei dem die Zerfallsrate dN/dt nur von der Anzahl N momentan vorhandener Atomkerne abhängt, wobei anfänglich zur Zeit t = 0 eine Anzahl N = N<sub>o</sub> vorhanden war, und der daher nach einer Exponentialfunktion abfällt. Die Photolumineszenz lebender Systeme genügt hingegen einem kohärenten Nicht-Markov-Prozess, der nach einer hyperbolischen Funktion abfällt. Mit Hilfe der Kinetik der Photolumineszenz von Wasser kann man daher auch das sogenannte „Gedächtnis“ von Wasser untersuchen: ist der zeitliche Abfall exponentiell, dann hat es kein „Gedächtnis“, ist er beispielsweise hyperbolisch, dann kann man dem Wasser so etwas wie „Gedachtnis“ zuordnen – jedoch nur in einem analogen Sinn.</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p align="center"><strong><em>9. Biophysikalische Methoden der Wasseruntersuchung</em></strong></p>
<p><em> </em></p>
<p><em>Spektralphotometrische Methode:</em></p>
<p>&nbsp;</p>
<p>Einer der Entwickler EL Technologie ist Alois Gruber. Im Atominstitut der Österreich Universitäten, A-1020 Wien, Stadionallee 2 Projektleiter Prof. Dr. H. Klima, hat im Jahr 2003 Untersuchungen mit Wasserproben durchgeführt, die nach verschiedenen Methoden (Hacheney, Alois Gruber, AROPUR) hydrodynamisch aufbereitet bzw. aktiviert wurden. Als physikalische Nachweismethode für mögliche Einflüsse der oben genannten „Aktivierungen“ verwendeten wir die Spektralphotometrie. In der folgenden Abbildung sieht man die Änderung der Transmissionsspektren einer dynamisch aufbereiteten Wasserprobe gegenüber der nicht aufbereiteten Kontrolle.</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima12.jpg"><img class="alignnone size-medium wp-image-295" title="Klima12" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima12-288x197.jpg" alt="" width="288" height="197" /></a></p>
<p>&nbsp;</p>
<p align="center">Abb.11: Eine einzelne Kurve drückt Änderung des Transmissionsspektrums einer hydrodynamisch aufbereiteten Wasserprobe gegenüber der nicht aufbereiteten Kontrolle im Bereich von 200 nm bis 1300 nm aus.</p>
<ul>
<li>Die relaxierenden Kurven sind Messergebnisse derselben Probe an vier aufeinanderfolgenden Tagen.</li>
</ul>
<p><em>Biophysikalische Methode der Biophotonen </em></p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima13.jpg"><img class="alignnone size-medium wp-image-296" title="Klima13" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima13-288x143.jpg" alt="" width="288" height="143" /></a></p>
<p>Bild 12.: Sojabohnen-Keimlinge am 3. Tag der Aufzucht mit unbehandelten Kontrollen</p>
<p>in der linke Schale und von „Dynamisierung Gerät“- behandelten Proben in der rechten Schale</p>
<p>Zur quantitativen Beurteilung der Keimung von Sojabohnen wurden deren Photonenemission nach Lichtanregung, d.h. deren abklingende Photolumineszenz gemessen, und daraus deren relative Photonenemission berechnet, indem jeder Messwert durch den Anfangswert dividiert wurde. Anstelle des gesamten Abklingverhaltens kann man auch die relative Photonen-emission nach einer bestimmten Abklingszeit betrachten, beispielsweise nach 100 Sekunden. Diese Prozedur lässt sich für einige Tage während der Keimung der Sojabohnen durchführen.</p>
<p align="center"><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima14.jpg"><img class="alignnone size-medium wp-image-297" title="Klima14" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima14-288x180.jpg" alt="" width="288" height="180" /></a></p>
<p align="center">Bild13:Relative Photonenemission von Sojabohnenkeimlingen nach 100 Sekunden Messdauer für unbehandelte Kontrollen (rot) und von „Dynamisierung Gerät“- behandelte Proben (grün), gemessen vom 2. bis 6. Keimtag</p>
<p>In der obigen Abbildung 7 ist die nach einer Abklingzeit von 100 s bestimmte, relative Photonenemission einer Messreihe für den 2. bis zum 6. Keimtag graphisch dargestellt. Die Photonenemission der mit Gruber Gerät -Wasser gekeimten Probe (grüne Balken) unterscheidet sich insbesondere am 3. Keimtag von der unbehandelten Kontrolle (rote Balken).</p>
<p>&nbsp;</p>
<p><em>Physiologische Methode der Pulsplethysmographie</em></p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>Die Pulsplethysmographie (PPG) ist eine nichtinvasive medizinische Methode zur Untersuchung der peripheren Durchblutung (Pulsdynamik). Sie wird biophysikalisch mittels photometrischer Messtechnik durchgeführt.<strong> </strong>Dazu wird auf den Zeigefinger der Probanden ein PPG-Meßsensor (Nellcor DS-100A), bestehend aus Leuchtdiode, Phototransistor und Halterung, geklemmt.</p>
<p>&nbsp;</p>
<p>Das Licht der Leuchtdiode durchleuchtet dabei die winzigen peripheren Blutgefäße.</p>
<p>&nbsp;</p>
<p>Diese ändern ihren Querschnitt je nach Einfluss durch die Wirkung von Hacheney-aktiviertem Wasser und verändern damit die Menge des durchgelassenen Lichtes.</p>
<p>&nbsp;</p>
<p>Dieses Licht fällt auf eine Fotodiode und erzeugt damit das elektrisches PPG-Signal.</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima15.jpg"><img class="alignnone size-medium wp-image-298" title="Klima15" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima15-288x221.jpg" alt="" width="288" height="221" /></a></p>
<p align="center">Abb.14: Typisches Plethysmogramm eines Menschen vor (schwarz) und nach (grün) dem Trinken von Wasser</p>
<p>Zur Quantifizierung der Plethymogramme verwendeten wir nichtlineare Methoden der Zeitreihenanalyse, nämlich</p>
<p>* “Attractor Reconstruction” nach F. Takens, in „Dynamical Systems and Turbulence“, Eds. D.A.Rand, L.S.Young, Lect. Notes in Math. 898, Springer, Berlin 1981, pg. 366</p>
<p>* „Recurrence Plot Analysis“ nach J.P.Eckmann, D. Ruelle, Europhys. Lett. 4 (1987) ).</p>
<p>Damit lassen sich folgende Maßzahlen bestimmen:</p>
<p><em> </em></p>
<p><em> </em></p>
<p><em>% Recurrence</em>             = ähnliche Systemzustände : alle Systemzustände</p>
<p>&nbsp;</p>
<p><em># Lines</em>                        = Anzahl w<sub>i </sub> vorgegeb. Linien [gleiche Systemzustände]</p>
<p>&nbsp;</p>
<p><em>% Determinismus</em>       = Anzahl gleicher Zustände (Linien) :  Anzahl ähnlicher Zustände</p>
<p>&nbsp;</p>
<p><em>Ratio</em>                           = % Determinismus : % Recurrence</p>
<p>&nbsp;</p>
<p><em>Entropie</em>                      = Shannon-Entropie: S = S w<sub>i</sub> ln w<sub>i</sub> (Einheit: bit)</p>
<p>&nbsp;</p>
<p><em>Trend  </em>                        = Gradient der %-Recurrence (d/dr mit r als Abstand von Diagonalen)</p>
<p><em>Standardabweichung</em>  = statistische Schwankung der Datenpunkte in der Zeitreihe</p>
<p>&nbsp;</p>
<p><em>Divergenz       </em>            = Inverse der Länge der längsten Linie (Lyapunov-ähnliches Maß)</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/Klima16.jpg"><img class="alignnone size-medium wp-image-299" title="Klima16" src="http://korotkov.org/water/wp-content/uploads/2011/10/Klima16-288x202.jpg" alt="" width="288" height="202" /></a></p>
<p>&nbsp;</p>
<p align="center">Abb.15: Nichtlineare Analyse der Plethysmogramme von Probanten, die hydrodynamisch aufbereitetes tranken (grün) und unaufbereitetes Wasser (rot)</p>
<p>Die nichtlineare Analyse, insbesondere deren quantitatives Maß „Ratio“, zeigt den Einfluss von hydrodynamisch nach der Methode von Hacheney aufbereitetem Wasser auf die Photoplethysmogramme von Probanden.</p>
<p><em> </em></p>
<p><em>Sensorische Methode der Dreiecksprüfung</em></p>
<p>&nbsp;</p>
<p>Die sensorische Methode der Dreicksprüfung ist eine Standardmethode in den Ernährungswissenschaften. Der Test prüft zwei ähnlich schmeckende Proben P und K</p>
<p>Dazu werden zertifizierten Prüfern jeweils drei Proben in mehreren Serien zum Verkosten vorgelegt. Jede Serie besteht aus einer Anordnung von zwei gleichen und einer verschiedenen Probe. Insgesamt gibt es 6 Anordnungen (PPK, PKP, KPP, KKP, KPK, PKK). Die Aufgabe besteht darin, die unterschiedliche Probe zu erkennen Die Auswertung und Ermittlung der Signifikanz der Testergebnisse erfolgt mit der Binomialverteilung.</p>
<p>&nbsp;</p>
<p>Retzer Trinkwasser wurde 1 Stunde vor Beginn der Untersuchung mittels eines Kunststoffschlauches (Firma Tygon, chemisch inert), durch das beigestellte „Dynamisierung&#8221; Gerät – ¾“  unter normalem Leitungsdruck und bei normaler Leitungswasser-Temperatur geleitet, für 5 Minuten gespült und danach in vier Einliter-Glasflaschen als Probe P aufbewahrt. Das gleiche Retzer Trinkwasser als Kontrolle K wurde ohne „Dynamisierung&#8221;</p>
<p>- Gerät unmittelbar in vier gleichen Einliter-Glasflaschen aufbewahrt. Die Durchführung der Dreiecksprüfung an der Lehranstalt  für Tourismus im Landesweingut Retz wurde unter folgenden Bedingungen durchgeführt:</p>
<ul>
<li>Die 6 Prüfer dürfen keinen Sichtkontakt zueinander haben, sondern nur zum Prüfleiter.</li>
<li>Sensorisch neutrale, gleichartige Gläser (alle mit a, b und c markiert)</li>
<li>Proben P und Kontrolle K müssen exakt die gleiche Temperatur haben (gemessen)</li>
<li>Redeverbot während der Bewertung</li>
<li>Frische Luft  im Prüfraum (keine Fremdgerüche)</li>
<li>Die drei Gläser a, b, c am Tisch vor dem Prüfer haben voneinander einen Abstand von mindestens 50 cm</li>
<li>Während der Bewertung darf nichts (Brot, Wasser, etc.) konsumiert werden</li>
<li>Alle Proben und Kontrollen sind in gleichartigen, neutralen  Flaschen</li>
<li>Tatsächliche Anordnungen der sechs Serienfolgen (PPK, PKP, KPP, KKP, KPK, PKK) wird erst vor dem Einschenken ausgelost</li>
<li>Die Vorbereitung der einzelnen Prüfsätze erfolgt in einem gesonderten Raum, wo die Proben P und Kontrollen K genügend großen Abstand voneinander haben</li>
<li>Die Realisierung der ausgelosten Prüfsätze kann von den Prüfern nicht verfolgt werden</li>
</ul>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p align="center">Abb.16: Die Durchführung der sensorischen Dreiecksprüfung unter standardisierten Bedingungen an der Lehranstalt  für Tourismus im Landesweingut Retz mit sechs zertifizierten Prüfern</p>
<p>&nbsp;</p>
<p>Die statistische Auswertung der sensorischen Dreiecksprüfung ergab, dass die Nullhypothese, wonach die Treffer der Prüfer zwischen „Dynamisierung&#8221; &#8211; aufbereitetem Retzer Trinkwasser (Probe P) und unaufbereitetem Retzer Trinkwasser (Kontrolle K) zufällig sind, verworfen wird:</p>
<p>Zwischen Probe P und Kontrolle K besteht ein hoch signifikanter sensorischer Unterschied<strong> </strong>von 99%. Die Wahrscheinlichkeit für einen Fehler dieser Verwerfung der Nullhypothese beträgt nur 1%.</p>
<p>&nbsp;</p>
<p><em>Gibt es eine Ähnlichkeit der Informationsspeicherung zwischen Wasser und Computern?</em></p>
<p>&nbsp;</p>
<p>Computer sind elektronische Rechenmaschinen, deren Zahlensystem nicht dekadisch mit den 10 Ziffern (0,1, &#8230; 9), sondern dual mit den zwei Ziffern (0,1) ist und deren Logik der Boole’schen Algebra folgt. Der Erfinder des dualen Zahlensystems ist der berühmte Philosoph und Mathematiker Gottfried Wilhelm Leibniz, der schon seinerzeit vorführte, wie man mit Dualzahlen grundlegende Rechenoperationen (Addition, Subtraktion, Multiplikation etc.) durchführen kann. Der englische Mathematiker George Boole ist der Schöpfer der Boole’schen Algebra, eines von ihm entworfenen Systems der Aussagenlogik, das auf logischen, zweiwertigen mathematische Regeln basiert.</p>
<p>&nbsp;</p>
<p>Die Boole’sche Algebra ist eine zweiwertige Logik, d.h. entweder es „ist“ oder es „ist nicht“, eine dritte Möglichkeit gibt es nicht. In der Philosophie nennt man eine derartige Logik „tertium non datur“ bzw. „ein Drittes gibt es nicht“. Die Boole’sche Algebra ist auf den beiden Wahrheitswerten WAHR (w) und FALSCH (f) sowie auf den Funktionen UND (^), ODER (v) und NICHT (┐) aufgebaut. Anstelle von „w &#8211; f“ kann man auch „ist &#8211; ist nicht, „ja &#8211; nein“ oder „1 &#8211; 0“ verwenden. Jede Aussage p, q, &#8230; (beispielsweise p = Kind hat Halsschmerzen, q = Kind hat Fieber, &#8230;) kann nur entweder wahr (w) oder falsch (f) sein, eine dritte Möglichkeit gibt es in der Boole’schen Logik nicht. Grundlegende Verknüpfungen bzw. Funktionen von zwei Aussagen p, q, aus denen sich alle anderen logisch herleiten lassen, sind die folgenden, die man in sogenannten Wahrheitstabellen zusammenfasst:</p>
<p>&nbsp;</p>
<p><span style="text-decoration: underline;">p      q  | (p ^ q)</span>                                   <span style="text-decoration: underline;">p     q   | (p v q)</span>                            <span style="text-decoration: underline;">p     |  (┐p)</span></p>
<p>w     w |    w                                       w    w  |    w                                 w    |    f</p>
<p>w     f  |    f                                         w    w  |    w                                 f     |    w</p>
<p>f      w |    f                                         f     w  |    w</p>
<p>f      f   |    f                                         f     f    |    f</p>
<p>&nbsp;</p>
<p>Haben zwei Verknüpfungen die gleiche Wahrhheitstabelle, so sind sie äquivalent (), d.h. sie sind immer wahr. Alle anderen Verknüpfungen von Aussagen p, q, r, &#8230; lassen sich auf die obigen drei Funktionen (^ , v , ┐) zurückführen, beispielsweise die sogenannte „wenn-dann“-Aussage bzw. Implikation (→); man kann stets zeigen, dass (p → q  ┐v q) immer wahr ist.</p>
<p>&nbsp;</p>
<p>Die praktische Weiterentwicklung der Boole’schen Aussagenlogik ist die Schaltalgebra, auf der die Funktionsweise aller Computer- und Programmiersprachen beruhen. Alle Handlungen, die ein Digitalcomputer vornimmt, basieren daher im Prinzip auf einer einzigen digitalen Grundoperation: auf der Fähigkeit zu erkennen, ob ein Schalter bzw. ein „Gatter” geöffnet oder geschlossen ist. Ein Computer kann also nur zwei Zustände in seinen mikroskopisch kleinen Schaltungen erkennen: an oder aus, hohe oder niedrige Spannung bzw. die Zahlen 0 oder 1.</p>
<p>&nbsp;</p>
<p>Während des 2. Weltkrieges wurden für die elektronischen Schaltungen erstmals Elektronenröhren verwendet (John Atanasoff, Alan Turing), Ende der 1950-iger Jahre kamen dafür Transistoren zum Einsatz und Ende der 1960-iger Jahre Integrierte Schaltungen ICs. Mitte der 1970-iger Jahre waren bereits Very Large Scale Integrated Schaltungen (VLSI) technisch möglich. Bei Mikroprozessoren sind heutzutage viele tausend miteinander verbundene Transistoren – also wesentlich mehr als beim IC – auf ein einzelnes Siliciumsubstrat geätzt. Die Geschwindigkeit, mit der ein Computer heute die einfache Schaltung „an“ oder „aus“ bewältigt, macht ihn zu einem Spitzengerät der modernen Technologie. Computergeschwindigkeiten werden heute in Gigahertz gemessen, also in Milliarden Zustandsänderungen (Takten) pro Sekunde.</p>
<p>&nbsp;</p>
<p>Sowohl die Programme bzw. die Software, nach der ein Computer seine Berechnungen durchführt bzw. abarbeitet, als auch Zwischenergebnisse und Ergebnisse überhaupt werden in elektronischer Schaltern abgespeichert. Computer können Daten intern (im Arbeitsspeicher) oder extern (auf Speichermedien) speichern. Interne Anweisungen oder Daten können temporär in RAM-Siliciumchips (RAM: Random Access Memory, wahlfreier Zugriffsspeicher) direkt auf der Hauptplatine des Computers oder auf eigenen Speichersteckkarten abgelegt werden. Diese RAM-Chips bestehen heute schon aus Milliarden Schaltern, die auf Veränderungen des elektrischen Stromes reagieren. Eine andere Art von internem Speicher besteht aus Siliciumchips, deren Schalter schon alle eingestellt sind. Die Muster in diesen ROM-Chips (Read-Only Memory: Nur-Lese-Speicher) bilden die Befehle, Daten und Programme, die der Computer für eine korrekte Funktionsweise benötigt. RAM-Chips sind im Prinzip wie Papierseiten, die beschrieben, wieder radiert und neu verwendet werden können. ROM-Chips dagegen sind wie Bücher, bei denen bereits alle Wörter auf den Seiten gedruckt stehen. Sowohl RAM- als auch ROM-Chips sind über Schaltungen mit der CPU verbunden.</p>
<p>&nbsp;</p>
<p>Wassercluster speichern Informationen – beispielsweise mechanische, thermische oder elektrodynamische Einflüsse nach hydrodynamischer Aufbereitung – für einige Zeit auf dynamische Weise, indem die beteiligten Wasserdipole ihre stets auf- und abbauenden Wasserstoff-Brückenbindungen &#8211; metaphorisch gesprochen ihren rhythmischen „Tanz“ &#8211; je nach Stärke und Art des hydrodynamischen Einflusses mehr oder weniger stark für gewisse Zeiten widerspiegeln.</p>
<p>&nbsp;</p>
<p>Aus der Perspektive elektronischer Speicherung von permanenten ROM- oder temporären RAM- Schalteinstellungen im Computer einerseits und dem temporären, hydrodynamisch beeinflussbaren Öffnen und Schließen von Wasserstoffbrücken zwischen den Wasserdipolen dynamischer Wassercluster andererseits kam man daher <span style="text-decoration: underline;">nur bedingt</span> und wenn überhaupt, dann nur <span style="text-decoration: underline;">analog</span> von <span style="text-decoration: underline;">Ähnlichkeiten </span>zwischen Computern und dem Wasser sprechen.</p>
<p>&nbsp;</p>
<p><em>Weltweite Untersuchungen über dynamisiertes Wasser</em></p>
<p>&nbsp;</p>
<p>Man kann davon ausgehen, dass fast alle Technischen Universitäten der Erde sich der Erforschung und Wissenschaft der Hydrodynamik des  Wassers widmen. Diese Forschung ist ein Zweig der Mechanik von Flüssigkeiten, der auch im Bereich der Physik angesiedelt ist. Dabei spielt die chemische Aufbereitung des Wassers eine nebensächliche und nur geringe Rolle.</p>
<p>&nbsp;</p>
<p>Was das Studium der nichtlineare Dynamik von Flüssigkeiten anlangt, so wird dies in erster Linie am „Institut für Physikalische Chemie“ an der  Freien Universität Brüssel und am „Center for Statistical Mechanics and Thermodynamics“ an der Universität Austin in Texas gelehrt. Wir schlagen aber vor, ein „Internationales Institut für Wasserforschung IIW“ zu gründen, das die weltweite Wasserforschung nicht nur dokumentiert, sondern das die Untersuchung von hydrodynamischer Aufbereitung von Wasser mit unterschiedlichen Methoden auch anbietet. Dazu sollte man derartige Methoden (Spektralphotometrie, Oberflächenspannung, Elastische Lichtstreuung, Biophotonen, Nichtlineare Analyse physiologischer Zeitreihen, Sensoriktests, etc.) im Rahmen eines Workshops oder Symposiums darstellen und Experten auf diesem Gebiet dazu einladen. Wir sind bereit, an der Etablierung eines derartigen IIW mitzuwirken.</p>
<p>&nbsp;</p>
<p><em>Wasserverschmutzung aus globaler Sicht</em></p>
<p><em> </em></p>
<p>Es gibt zwei Arten von Wasserverschmutzung: eine chemische und eine physikalische. Normalerweise verbindet man damit nur die chemische Verschmutzung von Wasser. Darüber zu reflektieren, würde Bücher füllen. Was die „physikalische Verschmutzung“, insbesondere jene, die auf hydrodynamische Weise erfolgt, so sollte man einen Standard festlegen, unter welchen Bedingungen der Zustand des Wassers ein Optimum darstellt, vor allem hinsichtlich seiner Bedeutung für die Biosphäre generell und insbesondere für uns Menschen speziell. Dabei habe ich vor mir als Vorbild frisches Quellwasser, dessen Eigenschaften man hinsichtlich seiner dynamischen Wassercluster mit den oben beschriebenen Methoden standardisieren könnte. Erst dann ließe sich jene kritische Schwelle angeben, ab der man von physikalischer bzw. hydrodynamisch induzierter Wasserverschmutzung sprechen könnte. Im Bereich der chemischen und biologischen Verschmutzung gibt es ja ohnehin Grenzwerte, die aber weltweit verschieden festgelegt sind.</p>
<p>&nbsp;</p>
<p>Durch den bereits eingetretenen Klimawandel (Abschmelzen der Polkappen und der Gletscher in den Bergen; zunehmende lokale Trockengebiete, aber auch zunehmende lokale Überschwemmungen) kann es regional zum Versiegen von Quellen einerseits, aber auch zur Verschmutzung des Trinkwassers nach Überschwemmungen andererseits kommen. Wie mir vor kurzem Hydrogeologen bestätigten, ist jedoch in tieferen Schichten Gesteinswasser in ausreichender Menge zur Verfügung – die Brunnen müssen regional nur tiefer geschlagen werden.</p>
<p>&nbsp;</p>
<p><em>Ist Wasser lebendig?</em></p>
<p>&nbsp;</p>
<p>Wir gehen davon aus, dass mit dem Terminus “lebendiges Wasser” eher eine Metapher als eine tatsächliche Behauptung für jenes Wasser gemeint ist, das auf eine besondere Weise hydrodynamisch aufbereitet bzw. aktiviert wird. Die Metapher bezieht sich vermutlich auf die Analogie hinsichtlich des sogenannten „Gedächtnisses“ von Wasser, aber auch auf manche wunderschönen Kristalle, mit denen Wasser zu Eis kristallisiert.</p>
<p><strong><em> </em></strong></p>
<p align="center"><strong><em> </em></strong></p>
<p align="center"><strong><em>10. Thesen über die Resonanzwirkung von dynamisiertem Wasser</em></strong></p>
<p><strong><em> </em></strong></p>
<p>Die lebensnotwendige Information von Nahrungsmitteln wird normalerweise durch das Zellwasser als Lebensmittel wie in einem Empfänger resonanzartig an den Körper als hochgeordnetes dissipatives System vermittelt. Wenn aber keine Resonanz eintritt, weil das Wasser als Empfänger nicht wie natürliches Quellwasser dissipativ dynamisiert und eigentlich ein totes Mittel ist, dann erzeugt dieses Nahrungsmittel eine Art Dissonanz im Körper und lässt Schlacken zurück. Es ist ein danach ein enormer energetischer Aufwand unseres Körpers erforderlich, um zu entschlacken. Wir verlieren damit wertvolle Energie, anstatt die erforderliche Information aus der Nahrung zu gewinnen.</p>
<p>&nbsp;</p>
<p>Es geht daher in Lebewesen nicht um Wasser, sondern um die Fähigkeit von Wasser, Information zu übertragen. Durch seine dynamischen Wassercluster ist das Wasser – wie bereits dargestellt &#8211; eigentlich keine Flüssigkeit, sondern ein dynamischer Flüssigkristall. In einem solchen Flüssigkristall, der sich bestenfalls wie die Tänzer in einem Ballett verhält, steckt tatsächlich Energie hoher Ordnung und damit Negentropie bzw. Information. Die elektrischen Wasserdipole verstärken sich dabei als Cluster zu dynamischen Giantdipols, was zur Polarisation des Flüssigkristalls Wasser führt. In der Physik kennt man diese Erscheinung als Piezoelektrizität, die man tatsächlich nachweisen kann, weil es dabei zu einem Stromfluss kommt.</p>
<p>&nbsp;</p>
<p>Was also geschieht in natürlichem Quellwasser bzw. in einem dynamisierten Flüssigkeitskristall wirklich, wenn es die gespeicherte Negentropie bzw. die Information der Umgebung oder Nahrung vermittelt. Die bereitgestellte Information wird nicht an eine statische, sondern an eine dynamische Geometrie schwingender Dipole des Flüssigkristalls angekoppelt. Die hohe Energie des Sonnenlichtes oder der Nahrung materialisiert sich als Schwingung bzw. dynamischer Tanz der Wasserdipole in dem dynamischen Flüssigkristall Wasser.</p>
<p>&nbsp;</p>
<p>Schwingungen lassen sich durch deren Frequenzen bzw. Wellenlängen ausdrücken, denen in der Quantentheorie Energie E = h.n zugeordnet werden. Da der lebende Organismus vor allem der elektromagnetischen Wechselwirkung unterliegt, äußern sich diese Schwingungen des Flüssigkristalls Wasser im wesentlichen als elektromagnetische Wellen bzw. Photonen der Energien E = h.n, z.B. als Licht &#8211; die Elektrizität selbst können wir ja nicht beobachten, sondern nur deren Wirkung. Und diese schwingende elektrischen Wasserdipole sowie die elektromagnetischen Wellen, die man im Fall von Zellwasser auch als Biophotonen bezeichnet, fließen durch unseren Körper.</p>
<p>&nbsp;</p>
<p>Hier beginnt moderne Naturwissenschaft. Wasser hat in seinem optimalen Zustand als Quellwasser bzw. dynamisiertes Wasser nicht nur eine flüssig-kristalline Struktur, sondern vor allem Zustände von geordnet und clusterartig schwingenden, molekularen Dipolen. In solch einem tanzenden Flüssigkristall steckt tatsächlich hohe Ordnung als Information bzw. Negentropie, die als dynamisch-geometrischen Ordnung aufgefasst werden kann.</p>
<p>&nbsp;</p>
<p>Als Symbol für die Wiederholbarkeit steht der Kreis. Als wissenschaftlich gilt, was wiederholbar, was messbar ist. Aber es gibt weder einen idealen Kreis noch eine ideale Wiederholbarkeit in der Natur! Auch gibt es niemals zwei gleiche Wassermoleküle. Und doch stellen wir jedes Wassermolekül durch das gleiche Symbol H<sub>2</sub>O dar! Ähnliches gilt für die Jahreszeiten. Jedes Jahr haben wir wieder Sommer &#8211; und doch wir wissen, dass uns jedes neue Jahr einen anderen Sommer bringt. In der Natur kennen wir nur die Spirale, sie ist ein Symbol der Evolution!</p>
<p>&nbsp;</p>
<p>Die Spiralform findet sich auch im Wasser, wenn es sich um frisches Quellwasser handelt und sich gleichsam wie „lebendiges“ Wasser bewegt. Im Wasser findet man auch elektromagnetische Wellen in Form von Licht, das nicht nur eine von der Temperatur des Wassers abhängige Plancksche Wärmestrahlung darstellt, sondern außerdem auch ein zwar schwaches, aber doch nicht-thermisches Leuchten enthält. Aus der Sicht der Quantentheorie besteht dieses nicht-thermische Leuchten aus Lichtquanten bzw. Photonen, die man für Zellwasser auch als Biophotonen bezeichnen kann.</p>
<p>Je höher nun die flüssig-kristalline und spiralig-dynamische Phase im Wasser ist, umso höher ist auch der Informationsgehalt des Wassers in Form von Schwingungen der geordneten Wasserdipole bzw. Cluster und des damit verbundenen Leuchtens. Es sind also tatsächlich elektromagnetische Schwingungen bzw. nicht-thermische Photonen im Wasser mit empfindlichen Geräten (Photoelektronen-Vervielfacher) messbar.</p>
<p>&nbsp;</p>
<p>Wenn sich Wasser in seiner spiraligen Mäanderform bewegt, dann verwirbeln sich dabei die Wasserdipole, was nach Viktor Schauberger zu einer Implosion und zu einer entsprechenden Photonenemission führt. Bevor Quellwasser dynamisiert ist, bevor es also levitant durch artesische Quellen an die Oberfläche kommt, nimmt es im Inneren der Erde geomagnetische Frequenzmuster als Informationen auf. Wasser hat damit – wie schon oben dargestellt &#8211; gleichsam ein Gedächtnis. Dieses Quasi-Gedächtnis ist an eine dynamische Geometrie gebunden, die in der Lage ist, seine Information für einige Zeit zu bewahren. Schwingungen zu Clustern geordneter Wasserdipole finden sich nach dem Trinken von frischem Quellwasser als Informationen auch in unserem Körper, der ja überwiegend aus Wasser besteht und ein nicht-thermisches, offenes und dissipatives System darstellt.</p>
<p>&nbsp;</p>
<p>Es geht also um die dynamische Ordnung der Wasserdipole zu flüssig-kristallinen Clustern und daher um die dynamische Geometrie des Wassers: letztlich um Information, die im Wasser bewahrt und danach dem Organismus zur Verfügung gestellt wird. Man sollte frisches Quellwasser oder dynamisiertes Wasser aber nicht nur trinken, um gesünder zu sein, sondern auch, weil es kraft der dynamischen Geometrie seiner schwingenden Dipol-Cluster in der Lage ist<strong><em>, </em></strong>unser Bewusstsein zu erweitern.</p>
<p>&nbsp;</p>
<p>In der ursprünglichen, intakten Natur findet das Wasser Bedingungen vor, unter denen es seine lebenspendenden Eigenschaften voll zur Entfaltung bringen kann. Diese natürlichen Bedingungen sind: dynamischer Fluss, Wirbel bildend, Reinheit von Schadstoff-Informationen, natürliche Regeneration im Falle einer sauberen Atmosphäre. Diese Bedingungen werden von bestimmten Merkmalen begleitet, die Voraussetzung dafür sind, dass Wasser seine natürlichen Eigenschaften wie hochgeordnete dynamische Cluster, Dipolschwingungen und nicht-thermische Photonenemission ausbilden kann, die für das Leben von Mensch, Tier und Pflanze von größter Bedeutung sind. Das ist der wahre Grund für die <strong>belebende und reinigende Wirkung</strong><strong> </strong>des frischen Quellwassers, aber auch des in ähnlicher Weise aufbereiteten, dynamisierten Wassers.</p>
<p>&nbsp;</p>
<p>Diese Wassereigenschaften sind eng miteinander verbunden und in ihrem Zusammenspiel an der gesunden Entwicklung und Erhaltung von Leben in  all seinen Arten und Formen beteiligt. <strong>Warum weist Trink- und Gießwasser in vielen Ländern der Erde diese Eigenschaften nur mehr in geringem Maß auf? </strong> Zurückzuführen ist das aus biophysikalischer Sicht auf unnatürliche Behandlung des Wassers, vor allem aber auf die Umweltverschmutzung in allen drei Sphären: in der Hydro-, der Atmo- und der Lithosphäre. Das kann dazu führen, dass Wasser die dynamisch-geometrische Struktur seiner Cluster und deren Ordnungszustand verliert &#8211; der Flüssigkristall Wasser und seine dynamisch-geometrische Struktur fallen dann zusammen, das Wasser verhält sich bloß thermisch. Es fällt in einen dissonanten, chaotischen Zustand, was schädlich auf den Organismus wirkt.</p>
<p>&nbsp;</p>
<p>Wenn Wasser über mehrere hundert Meter durch Rohrleitungen fließt und dabei dem jeweiligen Rohrleitungsdruck unterliegt, wird aus biophysikalischer Sicht die dynamische Geometrie der nicht-thermisch schwingenden Wassercluster durch den Druck in den Leitungen stark vermindert: es bricht die dynamisch-kristalline, dissipative Phase des Wassers auseinander. Ein normales Leitungswasser hat also allein aus diesem Grund schon nicht mehr optimale biophysikalische Eigenschaften &#8211; ganz abgesehen von den chemischen Veränderungen. Es ist daher empfehlenswert, d<strong>ynamisiertes </strong>Wasser zu trinken: es vermittelt uns ein gesünderes Leben. Wenn wir aber bloß thermisches, gleichsam totes Wasser zu uns nehmen, dann schwächt es vielfach unsere Gesundheit.</p>
<p><a href="http://korotkov.org/water/wp-content/uploads/2011/10/1_EINBAU-EL.jpg"><img class="alignnone size-medium wp-image-304" title="1_EINBAU EL" src="http://korotkov.org/water/wp-content/uploads/2011/10/1_EINBAU-EL-288x111.jpg" alt="" width="288" height="111" /></a></p>
<p>Wasser ist ein gutes Lösungsmittel, wenn es <strong>dynamisiert ist</strong>; damit ist es in der Lage, unseren Körper zu entschlacken und uns andererseits durch seine Dynamisierung die lebensnotwendige Information zu vermitteln. Gerade frisches Quellwasser, wie es in der Natur vorkommt, aber auch dynamisiertes Wasser haben diese lebensfördernden Eigenschaften.</p>
<p>&nbsp;</p>
<p align="center"><strong><em> </em></strong></p>
<p align="center"><strong><em> </em></strong></p>
<p align="center"><strong><em> </em></strong></p>
<p align="center"><strong><em> <a href="http://korotkov.org/water/wp-content/uploads/2011/10/1_LE_w.png"><img class="alignnone size-medium wp-image-303" title="1_LE_w" src="http://korotkov.org/water/wp-content/uploads/2011/10/1_LE_w-288x280.png" alt="" width="288" height="280" /></a></em></strong></p>
<p align="center"><strong><em>11.  LuxEL-Geräte und  These ihrer Wirksamkeit</em></strong><strong></strong></p>
<p>&nbsp;</p>
<p>Normales Leitungswasser tritt über die Einlassöffnung in das<em> LuxEL-Geräten</em>, wird über die Schauberger-Spirale geleitet, fließt spiralig zwischen zwei zylindrischen Gefäße, die mit entsprechenden Frequenzmustern aufbereitet wurden, und tritt spiralig-hydrodynamisch aufbereitet aus der Auslassöffnung wieder aus.</p>
<p>Ein Wassermolekül besteht aus einer chemischen Verbindung von zwei Wasserstoffatomen und einem Sauerstoffatom. Das Wassermolekül hat Dipolcharakter, weil der Atomkern des Sauerstoffes die beiden Wasserstoff-Elektronen wegen seiner hohen Elektronegativität stärker an sich bindet, und es damit zu einer Ladungstrennung innerhalb des Wassermoleküls kommt: der Sauerstoff hat dann den elektrisch negativen, die beiden Wasserstoffatome den elektrisch positiven Anteil des elektrisch Dipols. Die elektrischen Dipole vernetzen sich zu dynamischen fluktuierenden Clustern, welche diese flüssig-kristalline, jedoch dynamische Struktur des Wassers bilden.  Die „Dynamisierung von Wasser&#8221; in einer sogenannten „Dynamisierungsmaschine“ ist daher ein physikalischer Vorgang, der einem nachvollziehbaren Prozess in der «Dynamisierungsmaschine» unterliegt. Durch die spiralförmige, biogeometrische und stabilisierende Führung des Wassers nach Viktor Schaubergers Wirbelthesen wird eine laminare Strömung in Wirbelströmungen umgewandelt und wird hydrodynamisch aufbereitet.</p>
<p>Im <em>LuxEL-Geräten </em>erfolgt eine Veränderung der Wasserstruktur durch die „Dynamisierung&#8221; der fluktuierenden Clusterstrukturen auf folgende Weise:</p>
<p>„Normales Leitungswasser wird zuerst über die Schauberger-Spirale verwirbelt. Die dem Quellwasser analogen, den beiden zylindrischen Gefäßen magnetisch eingeprägten Frequenzmuster üben Einflusses auf die dynamisch-geometrische Clusterstruktur aus: sie werden informiert. Die „Informationträger“ der Frequenzmustern sind in den beiden zylindrischen Gefäße des <em>LuxEL-Gerätes </em>gespeichert<em> </em>(siehe in der modellhaften Abbildung) platziert. Diese beiden Gefäße wurden mittels einer nur dem Hersteller bekannten hydrologischen Technologie kontaktlos „informiert“ bzw. „reinformiert“. Damit diese „Information&#8221; auch erhalten bleibt, ist das <em>LuxEL-Gerät </em>mit einem Gehäusemantel umgeben, welcher gleichzeitig einen Resonanzraum erzeugt. Dieser Gehäusemantel ist mit einer Frequenz von ca. 7.83 Hz (Schumann-Resonanzen) magnetisiert und soll damit schwache Störfelder der Umgebung abschirmen.</p>
<p>&nbsp;</p>
<p>&nbsp;</p>
<p><strong>Herr Prof.Dr.Herbert J.Klima.  </strong><strong>Alexander Steinke.</strong></p>
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<p><strong>„F</strong><strong>requenz mustern </strong><strong>Informatio</strong><strong>n</strong><strong>träger“  befindet sich in zwei zylindrischen Gefäßen.</strong><strong></strong></p>
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<p><strong>Spiralförmige biogeometrische Stabilisatoren</strong><strong>.</strong><strong> </strong><strong></strong></p>
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<p><strong>Gehäusemantel ist magnetisiert mit einer Frequenz von ca. 7.83  Hz (Schumann-Resonanzen), das dem natürlichen Magnetismus der Erde entspricht, und soll damit schwache Störfelder der Umgebung abschirmen.</strong></p>
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<p><strong>Kalkschutz + Rostschutz + Wasserdynamisierung.</strong></p>
<p>Durch Magnetisierung des Gehäusemantels mit der Frequenz des natürlichen Erdmagnetfeldes ca. 7.83 Hz (Schumann-Resonanzen)  werden die Kalziumchlorid &#8211; Kristalle verändert. Umwandlung von Calcit in Aragonit. Es ist eine Tatsache, dass ein und dieselbe Substanz (egal ob chemisches Element, oder eine Verbindung) in verschiedenen kristallinen Phasen vorkommen kann und wird als Polymorphie (Vielgestaltigkeit) bezeichnet.</p>
<p>CaCO3  Calcit / Aragonit  Calcit : trigonal Aragonit <img src='http://korotkov.org/water/wp-includes/images/smilies/icon_surprised.gif' alt=':o' class='wp-smiley' /> rthorhombisch Beim Übergang von Calcit zu Aragonit erfolgt eine rekonstruktive Phasenumwandlung, wobei die gesamte Calcitstruktur durch Neukristallisation wird geendert  und kleine Aragonitkristalle entstehen. Diese Kristalle können sich in Wasserrohr- und Boilersystemen nicht mehr stark ablagern, wobei sogar bestehende Kalk- und Rostablagerungen abgebaut werden können. Durch die verbesserten Qualitäten des Wassers ergeben sich natürlich viele Vorteile im täglichen Umgang mit die,, Dynamisierungs &#8221; Wasser. LuxEL  Geräte kombiniert auf natürliche Weise Kalk &#8211; und Rostschutz mit „Wasservitalisierung bzw Dynamisierung&#8221;. Verkalkung wird vermindert. Die Rostbildung wird reduziert und der Kalk bildet deutlich kleinere Kristalle. Schäden durch Rost können zwar nicht mehr rückgängig gemacht werden, aber weitere Korrosionen können Sie mit LuxEL reduzieren. LuxEL  «belebtes Wasser» bewirkt eine Veränderung des Kalkverhaltens. Kalkablagerungen in Rohrleitungen können sukzessive wieder abgebaut werden. Wasserhähne, Perlatoren, Duschköpfe und Armaturen verkalken kaum mehr, Kalkrückstände auf Fliesen, Duschwänden usw. sind leichter entfernbar. Haushaltgeräte können so besser geschont werden und das Wasser fühlt sich spürbar weicher auf der Haut an. In unzähligen Privathaushalten oder in Die Industrie  wurden die positiven Auswirkungen der EL-Technologie Produkte beobachtet und teilweise dokumentiert. Dabei ist wichtig zu erwähnen, dass klarerweise die unterschiedlichsten Wasserqualitäten ( ph- Werte, Härtegrade, etc.) zur Verfügung stehen und trotzdem immer eine signifikante Erhöhung der Wasserqualität festgestellt werden konnte. Langjährige Erfahrungen haben gezeigt, dass auf die Zugabe von Phosphat und Salzen fast vollständig verzichtet werden konnte. Es entstehen keine Folgekosten für Strom oder chemische Zusätze. Im Privatbereich ergeben sich alle oben genannten Vorteile</p>
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<p><a title="" href="#_ftnref1">[1]</a> H. Klima, „Wasserstrukturen in dissipativen Systemen – Weitreichende Korrelationen zwischen Wassermolekülen“, in: <span style="text-decoration: underline;">Wasser</span> (Ed. I. Engler), Sommer-Verlag 1988</p>
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<p><a title="" href="#_ftnref2">[2]</a> H. Klima, „Dissipative Systeme am Beispiel Wasser“, in &#8220;<span style="text-decoration: underline;">Struktur und Funktion des Wassers</span>&#8221; (Ed. O. Bergsmann), Facultas-Verlag, Wien 1994, 88-133</p>
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<p><a title="" href="#_ftnref3">[3]</a> A. Lehninger, <span style="text-decoration: underline;">Biochemie</span>, Verlag Chemie, Weinheim 1977</p>
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<p><a title="" href="#_ftnref4">[4]</a> R. Glaser, Biophysik, UTB, Gustav Fischer Verlag, Stuttgart 1986</p>
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<p><a title="" href="#_ftnref5">[5]</a> R. Glaser, Biophysik, UTB, Gustav Fischer Verlag, Stuttgart 1986</p>
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<p><a title="" href="#_ftnref6">[6]</a> Dickersen/Geis: „Chemie &#8211; Eine lebendige und anschauliche Einführung“, Verlag Chemie. Weinheim 1981</p>
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<p><a title="" href="#_ftnref7">[7]</a> Dickersen/Geis: „Chemie &#8211; Eine lebendige und anschauliche Einführung“, Verlag Chemie, Weinheim 1981</p>
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		<title>IUMAB webinars by Dr. Korotkov</title>
		<link>http://korotkov.org/water/2010/10/iumab-webinars-by-dr-korotkov/</link>
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		<pubDate>Wed, 27 Oct 2010 18:17:09 +0000</pubDate>
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				<category><![CDATA[Articles about Water]]></category>
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		<description><![CDATA[IUMAB webinars by Dr. Korotkov 4 November 2010 Contemporary Physics of Water (part II) Share and Enjoy:]]></description>
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<p><a title="IUMAB webinars by Dr. Korotkov" href="http://new.korotkov.org/index.php?option=com_content&amp;view=article&amp;id=55"><img title="IUMAB" src="http://new.korotkov.org/images/stories/iumab.jpg" alt="IUMAB" width="79" height="79" /> IUMAB webinars by Dr. Korotkov</a></p>
<p><a title="IUMAB webinars by Dr. Korotkov" href="http://www.facebook.com/#%21/event.php?eid=137659912949628" target="_blank">4 November 2010</a></p>
<p><strong><a title="Contemporary Physics of Water (part II)" href="http://www.facebook.com/#%21/event.php?eid=137659912949628" target="_blank">Contemporary Physics of Water (part II)</a></strong></p>
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		<title>Enzymes and Surface Water</title>
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		<pubDate>Thu, 21 Oct 2010 12:33:51 +0000</pubDate>
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				<category><![CDATA[Articles about Water]]></category>
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		<description><![CDATA[Enzymes and Surface Water Wiggins, Philippa M.1 1*Retired from the Department of Medicine,University of Auckland, New Zealand, and from Genesis Research and Development Company, Auckland, New Zealand. Correpondence: p.wiggins@paradise.net.nzThis e-mail address is being protected from spambots. You need JavaScript enabled to view it Key Words: allostery, protein folding, water Received 12 February 2009; revised 17<a href="http://korotkov.org/water/2010/10/enzymes-and-surface-water/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p><strong>Enzymes and Surface Water </strong></p>
<p>Wiggins, Philippa M.<sup>1</sup></p>
<p><em><sup>1</sup></em><em>*Retired from the Department of Medicine,University of Auckland, New Zealand, and from Genesis Research and Development Company, Auckland, New Zealand. </em></p>
<div><img title="man1wigginsfig4.jpg" src="http://www.waterjournal.org/images/figs/vol1/wiggins2/man1wigginsfig4.jpg" alt="man1wigginsfig4.jpg" width="176" height="107" /></div>
<p>Correpondence: <a href="mailto:p.wiggins@paradise.net.nz">p.wiggins@paradise.net.nz</a>This e-mail address is being protected from spambots. You need JavaScript enabled to view it<br />
Key Words: allostery, protein folding, water</p>
<p>Received 12 February 2009; revised 17 March 2009; accepted 9 April 2009. Published 1 July 2009. Available online 1 July 2009.</p>
<p><strong>Summary</strong></p>
<p>The broad OH-stretch band of the infra red spectrum of liquid water is shown to comprise two overlapping bands peaking at 3250 cm<sup>-1</sup> (the value in ice, and, presumably, strongly bonded water) and 3635 cm<sup>-1</sup>(presumably weakly bonded water). The spectra also reveal the coexistence of zones of LDW and HDW in small-pored polymeric matrices. Possible mechanisms of reactions catalysed by these zones of water associated with enzymes are described. There is a crucial functional connection between the force that drives folding of an enzyme andreactions that it catalyses. When water can move to abolish osmotic pressure gradients created by selective uptake of solutes into HDW or LDW, it does so with some decrease in the partition coefficients of the reactants. When water is prevented from moving, partition coefficientsare unchanged, increased or transiently inverted. Examples of allostery and Michaelis-Menten kinetics (Matthews and van Holde, 1990) are given.<strong><span id="more-224"></span><br />
</strong><strong>Introduction</strong><a name="Intro"></a></p>
<p>Amino acids are capable of only weak interactions such as dipole-dipole attractions, H-bonds and some attraction between positive and negative sites. It is hard to see, even with induced fit, what generates the extreme specificity of the assumed binding sites. When they were first proposed, there was no plausible alternative mechanism. This vacuum was not helped in the early 1970s by the polywater debacle, which erased water from the biochemical lexicon (Franks, 1981). Now, however, two kinds of surface water with different solvent properties do supply plausible alternatives of great specificity. They have been shown to exist in solutions and at surfaces in non-biological systems such as porous beads and desalination membranes. Other attributes of these different surface waters are discussed here to see to what extent they are consistent with the extensive experimental data on enzyme reactions.</p>
<p><strong>Generation and Properties of the Zones</strong><a name="Zones"></a><strong> of High Density Water (HDW) and Low Density Water (LDW)</strong> <img title="man1wigginsfig1.jpg" src="http://www.waterjournal.org/images/figs/vol1/wiggins1/man1wigginsfig1.jpg" alt="man1wigginsfig1.jpg" width="650" height="196" /><br />
<em><strong>Figure 1:</strong> a small solute (red) has dissolved in (a) ‘classical water&#8217;,(b) HDW, and (c)  LDW. In each case,water immediately adjacent to the solute has a lower concentration (activity) than the same volume away from the solute. This activity gradient results in a pressure gradient, which is positive immediately adjacent to the solute and negative further away. a, nothing happens because ‘classical&#8217; water is assumed to be impervious to the low pressures encountered in osmotic systems; b, water immediately adjacent to the solute is already HDW and is not further affected; c, water immediately adjacent to the surface is converted to HDW, while water in the zone of negative pressure is already LDW and is not further affected.</em></p>
<p>Figure 1 shows that at a surface, such as that of a protein, there is a gradient of water activity (Wiggins, 2008a), low near the surface and higher further out. Water in the zone of higher activity tends to move in to increase its activity in the zone of low activity. Since it cannot do this, the water activity gradient becomes a pressure gradient, with positive pressure on water at the surface and negative pressure further out. Hitherto, this gradient has been interpreted as just two zones of water: high density water (HDW) immediately close to the surface and low density water (LDW)<em> </em>further out. When it comes to enzyme function, this sharp division lacks subtlety. The gradient of pressure is continuous: the composition of the water changes from highly enriched in HDW at the surface to highly enriched in LDW where the pressure is most negative. The zones of HDW and LDW at the surface, therefore, are not pure and can be manipulated. This modification is necessary in order to explain many experimental results with enzymes and with non-living systems such as small-pored polyamide beads, and solutions of dextran sulphate. These results will be shown as they become relevant.</p>
<h2><strong>A Representative Reaction in HDW</strong><a name="Represent"></a></h2>
<div>Most if not all active sites are in narrow clefts between domains of the folded protein. Presumably, water in those clefts consists of zones of enriched HDW and zones of enriched LDW, similar to those identified in small-pored polyamide beads (Wiggins, 1988) and cellulose acetate films (Wiggins and van Ryan, 1986), both of which have pores (1-2 nm in diameter). It will be assumed that the particular enzyme under consideration is one such, and that it catalyses the reaction</div>
<div>A + B = C + D</div>
<div>Let the enzyme be of such an amino acid composition that it partitions into HDW and induces extra LDW; and let the reaction be one that takes place in highly enriched HDW at the surface. Since this water is under positive pressure, solutes do not induce LDW as they do in Figure 1.Therefore HDW can ionise freely without producing the LDW which inhibits ionisation in LDW/HDW (Wiggins, 2007). Its low viscosity and relatively high concentrations of H+ and OH- ions make it a powerful catalyst. The steps of the reaction are:1.      Uptake of A and B into HDW <a name="_Hlk226011663"></a>from an external concentration of C<sub>A</sub> and C<sub>B</sub></p>
<p>2.      Reaction, A + B = C + D</p>
<p>3.      Release of products.</p>
<p>In order to reach the zone of HDW, A and B must pass through the zone of LDW for which they have low affinity. Since all four participants in the reaction are biomolecules, they consist of both moieties that partition into HDW and moieties that partition into LDW; so although A and B have lower affinity for LDW than for HDW, they are not totally excluded: they can diffuse across.</p>
<p>A general principle of osmotic theory says that if water can move to abolish an osmotic pressure gradient, it must and will. If water moves to abolish the osmotic pressure gradient created by uptake of A and B, it must move into the zone under positive pressure where A and B are in solution. In so doing, some LDW/HDW is converted to HDW. Folding of this protein was driven by the need to reduce the excess LDW induced by its elongated conformation. Production of excess HDW by uptake of A and B, therefore, cancels some of this excess LDW and the protein can relax and open its cleft a little: so, water can move in and therefore does. The partition coefficients are modest and the flux of water not great.</p>
</div>
<div><img title="man1wigginsfig2.png" src="http://www.waterjournal.org/images/figs/vol1/wiggins2/man1wigginsfig2.png" alt="man1wigginsfig2.png" width="244" height="203" /></div>
<div><em><strong>Figure 2:</strong> a, a cleft between two protein domains contains HDW at the surfaces and LDW in the centre; b, A and B partition into HDW; LDW/HDW moves into abolish the osmotic pressure gradient; most of this water converts to HDW because it is in the zone under positive pressure from the surface, but the extra water encroaches on the zone of negative pressure; its average enrichment with HDW decreases. The reaction (A + B = C + D) takes place and C and D diffuse out.</em>Figure 2 shows that uptake of A and B is accompanied by flux of water from the external solution of LDW/HDW into the zone of HDW. Since, however, the pressure gradient imposed by the surface has not changed, some extra water encroaches on the zone of negative pressure. This decreases the effective enrichment of HDW in the solution round A and B and, therefore, the partition coefficients of A and of B between LDW/HDW and the HDW-enriched zone. It is labelled ‘less enriched HDW.&#8217; Water, however, retains enough enrichment of HDW and high enough concentrations of H<sup>+</sup> and OH<sup>-</sup> to catalyse the reaction, producing C + D.</p>
<p>Although C and D have greater affinity for HDW than have A and B (or the reaction would not take place), their concentrations in the larger volume of LDW/HDW are both zero, allowing them to diffuse out spontaneously.<br />
To summarize: each time a solute is taken up into HDW:</p>
</div>
<ul>
<li>folding of the parent protein loosens, as HDW increases, allowing the cleft to open to the influx of water.</li>
<li>LDW/HDW moves into the zone of HDW surrounding the solutes</li>
<li>where it is in the zone of positive pressure, it is converted to HDW</li>
<li>the extra water cannot all fit in the zone of positive pressure: it encroaches on the zone of negative pressure (compare Figures 2a and b)</li>
<li>the average enrichment of  HDW in the zone nearest the surface is lower than it was initially.</li>
<li>concentrations of all solutes in HDW decrease because their partition coefficients are lowered.</li>
</ul>
<div>Following loss of A, B, C and D, the protein reverts to its original folded state.<strong>Apparent Saturation Kinetics</strong><a name="Apparent"></a></p>
<p>As the concentration of A (or B) in the outside solution increases, its partition coefficient decreases (see above). Therefore, the increase in rate with increasing concentration levels off, which gives the appearance of a saturated binding site and Michaelis-Menten kinetics.</p>
<p><strong>Promoters and Inhibitors (Allostery)</strong><a name="Promoters"></a></p>
<p>Any molecule, which partitions into HDW, partially or totally inhibits this reaction by decreasing enrichment of HDW in water surrounding the reactants. Thus a higher external concentration is needed to obtain the same rate of reaction. On the other hand, a molecule which partitions into LDW induces more LDW, compacting the enzyme and preventing swelling, so that there is no decrease in the partition coefficients. In fact partition coefficients increase because the inability of water to move in to abolish the osmotic pressure gradient acts as a pressure and increases the enrichment of HDW surrounding solutes (see under cellulose acetate).</p>
<p><strong>The Same Reaction Catalysed by an Enzyme that Partitions into LDW</strong><a name="Same"></a></p>
<p>This enzyme folds to reduce excess HDW that is induced by its elongated state. When A and B are taken up selectively into HDW, the compensatory flux of water must induce more HDW. Thus the enzyme folds more tightly, somewhat closing the cleft and the flux of water is not permitted. Therefore the osmotic pressure gradient stands, and acts as an additional pressure on all enriched HDW, increasing its enrichment The reaction takes place extremely rapidly in this highly enriched HDW with increased concentrations of H<sup>+</sup> and OH<sup>-</sup>. Products, presumably, can still leave to their zero external concentrations.</p>
<p><strong>A Representative Reaction in LDW</strong><a name="Reaction"></a></p>
<p>Let the enzyme be one that partitions into HDW and induces LDW, and let the reaction be</p>
</div>
<div>ADP + KPi = ATP</div>
<div>1.      ADP and KPi are taken up into LDW.</div>
<div>2.      The reaction takes place with spontaneous production of ATP.ADP<sup>2-</sup> and ATP<sup>3-</sup> and K<sup>+</sup> have extremely large partition coefficients between LDW and LDW/HDW. This is entirely because of their ionic character. Anions in general, and phosphates in particular, have very great affinity for LDW, as has K<sup>+</sup>. They, therefore, create a steep osmotic pressure gradient. If water moves in to abolish this gradient, it will move into the region under negative pressure, thus converting much HDW to LDW. But this enzyme has folded in order to decrease its excess production of LDW. Therefore induction of more LDW and opening up of the cleft is prohibited. The osmotic pressure gradient, therefore, stands.</p>
</div>
<div><img title="man1wigginsfig3.png" src="http://www.waterjournal.org/images/figs/vol1/wiggins2/man1wigginsfig3.png" alt="man1wigginsfig3.png" width="432" height="122" /></div>
<div><em><strong><br />
Figure 3:</strong> a cleft between protein domains contains zones of HDW and ofLDW; b, ADP and KPi partition into LDW which is not permitted to swell; thereaction takes place and c, the pressure due to the uncompensated osmoticpressure gradient converted LDW to HDW so that ATP was released.</em>Figures 3a and b show that uptakes of ADP and KPi do not increase LDW and do not open the cleft. The reaction takes place but the inability of water to move becomes a pressure acting on all the water in the cleft. In Fig.3c it converts LDW to HDW and releases all solutes from LDW, including ATP. Following release of solutes, zones of HDW and LDW reform at the surfaces (Fig 3a). This action of K<sup>+</sup> salts to convert LDW to HDW with release of all solutes was observed in neutral cellulose acetate films with narrow pores. (See below.)</p>
<p><strong>Cellulose Acetate Membranes</strong><a name="Cell"></a></p>
<p>The infra red spectra of water in cellulose acetate membranes confirmed the basic hypothesis on which this treatment of enzymes rests (Wiggins and van Ryn, 1986). The membranes were soaked in water or solution; blotted dry; and their water contents, OH-stretch difference, infrared spectra, and ion contents measured. They did not swell: presumably the cross-linked matrix was too rigid. The three peak wave numbers of interest were: 3250 cm<sup>-1</sup> (the value in ice, and, presumably LDW; 3444 cm<sup>-1</sup> (bulk liquid water) and 3635 cm<sup>-1</sup> (presumably HDW). Membranes soaked in water had a large peak at 3250 cm<sup>-1</sup> and a smaller peak at 3635 cm<sup>-1</sup> but nothing at 3444 cm<sup>-1</sup>.</p>
<p>Membranes soaked in 100 mM LiCl had a greatly increased peak at 3635 cm<sup>-1</sup> which was as large as the peak at 3250 cm<sup>-1</sup></p>
<p>Membranes soaked in 10 mM KCl had a broad band with a single peak at 3444 cm<sup>-1</sup>. These are now interpreted in the following way:</p>
<p>·        the two peaks that revealed themselves inside the membrane pores, inexplicable at the time, are the overlapping bands in liquid water that have since been proposed to account for the single broad band at 3444 cm<sup>-1</sup> (Wiggins, 2009).</p>
<p>·        100 mM LiCl accumulated into HDW, creating an osmotic pressure gradient which could not be eliminated by flux of water. It acted instead as a pressure gradient, greatly increasing the enrichment of HDW. The LiCl concentration in the membrane water was 22 mmol/kg water;i.e., although LiCl was accumulated into HDW, it was strongly excluded from LDW.</p>
<p>·        10 mM KCl accumulated into LDW, creating an osmotic pressure gradient which could not be eliminated by flux of water. It acted as a pressure on the water in the pore converting it to HDW with loss of all KCl. Immediately afterwards zones of HDW and LDW reformed in the pores. Thus, while bulk water was a mixture in space of microdomains of LDW and of HDW, pore water in the presence of 10 mM KCl, oscillated in time between HDW and LDW. They had the same single broad spectral band at 3444 cm<sup>-1</sup>. The observed concentration of KCl in the membranes was 10 mmol/kg water: i.e., it oscillated between 0 mM (in HDW) and some undetermined high concentration (in LDW).</p>
<p>Small-pored polyamide beads also reached a limit in swelling. They selectively took up a molecule like glucose with a modest partition coefficient, but then released it rapidly upon addition of 100 mM KNO<sub>3</sub> which, evidently, created an osmotic pressure gradient requiring a larger flux of water than the matrix would allow. In the enzyme the limiting factor was not rigidity of the matrix but the force folding the protein to its active conformation, which in the present case was elimination of excess LDW. This has been suggested as the mechanism of sodium channel-opening (Wiggins, 2007). If water in the entrance compartment of the channel is predominantly LDW, the channel is closed to Na<sup>+</sup>. If  K<sup>+</sup>, then accumulates into the LDW and water is not permitted to follow it to eliminate the osmotic pressure gradient,  LDW converts to HDW and the channel loses K<sup>+</sup> and is open to Na<sup>+</sup>. After passage of Na<sup>+</sup> water reverts to LDW.</p>
<p><strong>Reaction in LDW with Swelling</strong><a name="Swelling"></a></p>
<p>Let the enzyme be one that has partitioned into LDW and induced HDW. Let the reaction be</p>
</div>
<div>X + Y = Z</div>
<div>Uptake of X and Y into LDW produces more LDW, which loosens the folding of the protein and allows water to move in and abolish the osmotic pressure gradient. Most extra water goes into the zone under negative pressure, but, as with the corresponding reaction in HDW, some extra water encroaches on the region of positive pressure, or it moves out beyond the zone in which the negative pressure operates. In either case it loses some of its initial enrichment in LDW. The reaction takes place and Z diffuses out into the larger volume of LDW/HDW in which its concentration is zero.This reaction also has saturation kinetics and is promoted by molecules which partition into HDW and inhibited by molecules that partition into LDW.</p>
<p><strong>Reaction at a Charged Site</strong><a name="Charged"></a></p>
<p>Each charged group on the surface of an enzyme generates pockets of enriched HDW and LDW because the counterion creates an osmotic pressure gradient which acts as a pressure gradient. Water in the compartment marked out by the counterion, diffusing under the influence of the fixed charge, becomes enriched in HDW, while an adjacent zone under negative pressure becomes enriched in LDW. The degree of enrichment of both zones depends upon the nature of the counterion, and the presence of other solutes. Figure 4 illustrates a typical negatively charged site with Na<sup>+</sup> as counterion. The pressure gradient is shown in red.</p>
</div>
<div><img title="man1wigginsfig4.jpg" src="http://www.waterjournal.org/images/figs/vol1/wiggins2/man1wigginsfig4.jpg" alt="man1wigginsfig4.jpg" width="176" height="107" /></div>
<div><em><strong>Figure 4:</strong> a negatively charged surface has Na<sup>+</sup> ascounterion. The osmotic pressure gradient acts as a pressure gradient, inducingHDW in the pocket defined by the diffusion of Na<sup>+</sup> and .LDW furtherout. The pressure gradient is shown in red. </em>Dextran sulphate, a highly charged polymer, has been used to determine the effects of added solutes upon the viscosity of its solutions.</p>
</div>
<div><img title="man1wigginsfig5.jpg" src="http://www.waterjournal.org/images/figs/vol1/wiggins2/man1wigginsfig5.jpg" alt="man1wigginsfig5.jpg" width="640" height="461" /></div>
<p><em><strong>Figure 5:</strong> The viscosity of dextran sulphate solutions (3 g water to 1 g </em><em>sodium dextran sulphate</em><em>) to which various solutes were added. </em></p>
<p>Figure 5 shows some representative results which were reproduced many times. It was assumed that increase in viscosity was due to increase of LDW and/or decrease of HDW. Urea which partitions into LDW is of particular interest, as it appears to be one of the more eccentric molecules in Figure 5 and it links the discussion of enzymes to the properties of charged surfaces. Low concentrations of urea increased LDW by partitioning into it and drawing other water into the same zone of negative pressure either from the external solution of LDW/HDW or from the neighbouring zone of HDW. It then quite suddenly stopped increasing LDW at about 0.1 M and viscosity steadily decreased with higher concentrations. From these results alone, it is not possible to determine the source of the water that abolishes the osmotic pressure gradient caused by selective uptake of urea. By combining this result with that of other experiments, however, the decision could be made. It became clear that below 0.1 M, urea drew water from the counterion zone and that above 0.1 M it had exhausted that source of water and thereafter the main effect was a decrease in viscosity as urea increased HDW in the rest of the solution. The extreme sharpness of this transition is comparable with that shown by 10 mM KCl in cellulose acetate membranes and, indeed by KCl in Figure 5, suggesting that urea and KCl both exhaust available HDW at about 0.1 M, convert water to HDW, and lose all solutes.</p>
<p>The other experiments which made this conclusion possible consisted of measuring the rate of loss of silicates from the surfaces of small glass beads or of charged groups from cation or anion exchange resins. Urea below 0.1 M greatly accelerated these losses. Cleavage of silicates from the surface only takes place in highly enriched HDW in which concentrations of H<sup>+</sup> and OH<sup>-</sup>are both high. This shows that in the presence of urea or KCl, water was leaving the HDW zone for the LDW zone so that the concentration of the counterion increased and the enrichment of HDW increased. This is just one example of the general principle that measurement of a single property of a system does not give enough information for a uniquesolution. Another example from the same pair of experiments is that NaCl, which decreased the viscosity of dextran sulphate solutions, protected silicates from cleavage by HDW. NaCl partitions into HDW, increasing the dielectric constant of the solution round the fixed charge, and allowing water to move in so that there is an increase in the amount of enriched HDW but not in its degree of enrichment. These apparently simple systems are in fact complex.</p>
<p><strong>Dangers of Charged Sites</strong><a name="Dangers"></a></p>
<p>Enzymes must beware of charged sites because there are many ways in which HDW becomes reactive enough to cleave the bond linking the charged group to the backbone. Loss of an essential amino acid residue or cleavage of a peptide bond would destroy the enzyme.  Mg<sup>2+</sup> as counterion can often induce this level of reactivity. Electrophoresis of DNA with Tris as counterion gave a series of bands showing that many different sized oligonucleotides were present. When Mg<sup>2+</sup> was counterion, the bands all disappeared. Presumably the oligonucleotides that had been identified with Tris had been hydrolysed by highly reactive HDW. Since Mg<sup>2+</sup> is divalent, it was held very closely to the charged group, which was therefore contained in a small volume of highly enriched HDW. The osmotic pressure gradient increased further because, in order to maintain electroneutrality, the divalent counterion was  accompanied by an anion. The extreme effects of Mg<sup>2+</sup> as counterion are obscured by the presence of excess MgCl<sub>2</sub>,which behaves like NaCl in Figure 5. Again two sets of experiments are needed to understand its action. It has been shown that the cation transport ATPases apparently make subtle use of the power of Mg<sup>2+</sup>, at the same time evading the danger.</p>
<p>MgATP can enter most zones of water because it comprises a chelate of Mg<sup>2+</sup>, which partitions strongly into HDW, and ATP, which partitions strongly into LDW. Its own partition coefficient is therefore quite low. In the Na,K-ATPase, for example, it phosphorylates an aspartyl residue in the cleft of the active site, leaving Mg<sup>2+</sup> as the counterion. Since there is only a single Mg<sup>2+</sup>, its effect is not opposed by excess MgCl<sub>2</sub>, and it readily out-competes other cations at higher concentrations because it has the greatest affinity for HDW and is divalent. The result is an extremely enriched pocket of LDW to accomplish the transport step and an extremely enriched pocket of HDW to hydrolyse the phosphoenzyme. (Wiggins, 2007). Na<sup>+</sup> is pushed up to the apex of the cleft by an advancing wave of LDW and out through an open channel, while K<sup>+</sup>, with its high affinity for LDW, moves in. K<sup>+</sup>, more powerfully than urea, accumulates into LDW, extracting water from the region of positive pressure and completing the enrichment of HDW, which then hydrolyses the phosphoenzyme. In this way the enzyme uses the unique properties of water at a charged site with Mg<sup>2+</sup> as counterion, but retains its integrity. Many enzymes are phosphorylated, used, and dephosphorylated in this way.</p>
<p><strong>Oxygenation of Haemoglobin</strong><a name="Oxygenation"></a></p>
<p>Oxygenation of haemoglobin (Matthews and van Holde, 1990) may be a process that can be simply explained in terms of LDW and HDW. Four chains fold to achieve the active state. The reaction takes place in the haeme which has a Fe atom held by bonds donated by nitrogens in the haeme. This Fe is doubly positively charged with two counterions that generate their own localised pockets of highly enriched HDW and highly enriched LDW. It is a powerful system because with two counterions it generates double the usual osmotic pressure gradient.</p>
<p>This results in differences from reactions so far discussed:</p>
<p>·        the volume of the compartment under pressure is determined by the diffusive path marked out by the counterions, which are assumed to be Cl<sup>-</sup> -the most common anion in the extracellular solution.</p>
<p>·        the volume increases only if the local dielectric constant increases with uptake of electrolytes (eg NaCl) which partition into HDW: as the concentration of NaCl increases, the volume of the compartment increases and allows influx of water to abolish the osmotic pressure gradient.</p>
<p>·        The volume decreases with uptake of a solute which decreases the dielectric constant (e.g., a hydrophobic solute).</p>
<p>·        The volume also decreases if  a solute partitions selectively into LDW, drawing water from the counterion compartment, a movement which is permitted because it reinforces (rather than opposes) the electrostatic force</p>
<p>·        All movements of water are internal exchanges so that they depend, not upon the folding of the protein, but on the control of the electrostatic field, which  generates much stronger forces than those of osmotic systems.</p>
<p><strong>Haemoglobin</strong><a name="Haem"></a></p>
<p>There are several observations that have to be addressed: oxygen must be taken up strongly to be transported round the body, but it must also be released in tissues where it is needed.</p>
<p><strong>1. Cooperative Binding of Oxygen</strong></p>
<p>Oxygen binds weakly at low concentrations but the binding strength increases with its concentration. In terms of LDW/HDW, oxygen partitions into enriched HDW in the pocket occupied by counterions. Water does not follow to abolish the osmotic pressure gradient. As the concentration of oxygen increases, the standing osmotic pressure gradient increases, the pressure gradient increases and water is increasngly enriched in HDW. This accounts for ‘weak binding&#8217; at low concentrations and ‘strong binding&#8217; at high concentrations.</p>
<p><strong>2. </strong><strong>Conformational Change When Oxygen Binds</strong></p>
<p>Although folding of the enzyme does not control movement of water at the charged site, production of either HDW or LDW during the reaction must generate a change in folding. Accumulation of oxygen in HDW increases enrichment of HDW in that pocket. This appears to result in a tightening of the folded structure because X-ray crystallography shows that a central hole decreases when oxygen is taken up. Presumably, the extended haemoglobin chains induced more HDW on solution in LDW/HDW (Wiggins, 2009).</p>
<p><strong>CO<sub>2</sub> and Biphosphoglycerate</strong><a name="Biphos"></a></p>
<p>These two compounds modify oxygen uptake. CO<sub>2</sub> at physiological pH is principally HCO<sub>3</sub><sup>-</sup>. Like most anions (including biphosphoglycerate) HCO<sub>3</sub><sup>-</sup> partitions into LDW, taking a cation with it. As it does so it draws water from the zone under positive pressure, decreasing the volume of HDW accessible for uptake of O<sub>2</sub> and slightly increasing the standing osmotic pressure gradient and the degree of enrichment in HDW. The net result appears to be that uptake of oxygen is slightly decreased. This proposal can be tested experimentally in, perhaps, a dextran sulphate solution.</p>
<p><strong>The Bohr Effect</strong><a name="Bohr"></a></p>
<p>At extremely low concentrations of venous O<sub>2</sub> there is a drop in pH. Of univalent cations, H<sup>+</sup> ions have by far the greatest affinity for HDW. Even from low concentrations they are taken up, together with an anion, probably Cl<sup>-</sup>, increasing the dielectric constant in the zone under pressure, allowing entry of water from the associated zone of LDW. This dilutes not only oxygen, but also the two counterions which determine the osmotic pressure gradient, so that both concentration of oxygen and enrichment of HDW are depressed, with further loss of oxygen.</p>
<p>This scheme also allows ‘binding&#8217; of O<sub>2</sub> and HCO<sub>3</sub><sup>-</sup> at the same site.</p>
<p><strong>Role of Aminoacid Sequences</strong><a name="Role"></a></p>
<p>The infra red spectra have confirmed that<strong> </strong>poresin membranes or clefts in proteins contain both LDW and HDW. If, asseems probable, HDW zones are immediately close to the surface, theamino acid sequences in the active site become another factor toconsider. The surface of a protein is, in fact, an array of side chainswith some kinetic energy. The HDW zone will allow hydrophobic sidechains to extend freely from the polypeptide chain, but side-chainswhich have an affinity for LDW tend to lie flat along the surface. Thusthe local composition of the polypeptide chain controls to a degree thevolume available to the reaction.</p>
<p><strong>Conclusion</strong><a name="Conclusion"></a></p>
<p>The long neglected variable, pressure (Franzese et al, 2008), makes this scheme versatile and, perhaps, credible.<br />
<strong><br />
References</strong><a name="Ref"></a></p>
<p>Franks F (1981). Polywater. Cambridge Mass MIT Press.</p>
<p>Franzese G, Stokely K, Chu X-Q, Kimar P, Mazza MG, Chen S-H and Stanley HE (2008). Pressure Effects in Supercooled Water, <em>J. Phys</em>. <em>A Condensed Matter</em> <strong>20</strong>: 494210.</p>
<p>Matthews CK, van Holde KE (1990). <em>Biochemistry</em>. The Benjamin/Cummings Publishing Company, New York, 373.</p>
<p>Wiggins PM and van Ryn RT (1986). The solvent properties of water in desalination membranes. <em>J Macromol Sci-Chem</em> <strong>A23</strong>: 875-903.</p>
<p>Wiggins PM (1988). Water structure in polymer membranes. <em>Progress in Polymer Science</em> <strong>13</strong>: 1-35.</p>
<p>Wiggins PM (2002). Enzymes and two-state water. <em>J. Biol. Phys Chem. </em><strong>2</strong>: 25-37.</p>
<p>Wiggins PM (2007). Life depends upon two types of water. <em>PloS ONE </em><strong>3</strong><strong> </strong>(1): e1406. doi:10.1371/journal.pone.00014068Q Wiggins PM, (2008a). Prions, plaques and polyelectrolytes. <em>J Biol Phys Chem</em>. <strong>8</strong>: 49-54</p>
<p>Wiggins PM (2008b). DNA as a Darwinian self-replicator <em>J Biol Phys Chem</em>.<strong> 8</strong>: 89-93</p>
<p>Wiggins PM (2009). The Source of Some of the Extraordinary Powers and Properties of Enzymes, <em>WATER </em><strong>1</strong>: 35-41.<br />
<strong><br />
Discussion with Reviewers</strong><a name="DWR"></a></p>
<p><strong>Frank Mayer<sup>1</sup>:</strong> What about possible influences of water moieties further away from the enzymes? After all, data from a number of workers (e.g., Ling, Pollack) allow to state that a distribution of LDW and HDW moieties may exist that may be different from that depicted in the figures of the article (&#8220;exclusion zones&#8221; may be of importance). <strong> </strong></p>
<p><strong>Philippa Wiggins:</strong> I intended this article to be about enzyme reactions which must take place within a very few nm of the surface. Exclusion zones and more distant interactions of water molecules (a la Ling) are not excluded but are certainly not included in this limited treatment. They are just irrelevant.  The particular mechanism that I have proposed for induction of HDW and LDW at surfaces is extremely unlikely to extend far into the solution. Experiments with polyamide beads have suggested that a diameter of 3 nm is about maximum. That means 1.5 nm at a planar surface.</p>
<p><strong>Mayer:</strong> Many data are available which indicate that membrane-associated enzymes are not directly attached to the surface of the membrane, but connected to the membrane by &#8220;stalks&#8221; 3 to 7 nm long, or that typical &#8220;soluble&#8221; enzymes are, in fact, also connected to membrane surfaces by stalks of this size. Could that mean that a size range between 3 and 7 nm is the optimum for the positioning of the active site of an enzyme relative to a surface (the membrane surface) that is known to influence water structure?</p>
<p><strong>Wiggins:</strong> I suggest that these stalks are devices to protect the membrane not to pander to enzymes. If an enzyme that partitioned into HDW diffused all the way to the membrane it would meet a barrage of charged headgroups and counterions: phosphates with Ca<sup>2+</sup> and amino groups with Cl<sup>-</sup>. It would then diffuse into a pocket of HDW and unfold. It originally folded only because it had to decrease the excess LDW that it induced in its extended state. In the pocket of HDW, however, it is under positive pressure and cannot induce LDW. Therefore there is no driving force for it to fold. In its elongated state it greatly reduces the dielectric constant at the fixed charge so that the counterion moves in closer to the fixed charge. This increases the osmotic pressure gradient, the pressure gradient and the degree of enrichment with HDW. It cleaves the phosphate or the amino group off the membrane, destroying its barrier properties. I have suggested (Wiggins, 2008a) that prions wreak their havoc by this means. Your distance of 3 to 7 nm is to be expected for a charged site. The 2-3 nm is the thickness at an uncharged surface. The only paper I have read that measured the thickness of the double layer gave a value of 6 nm. It depends upon the counterion. This measurement was made with Zn<sup>2+</sup>.</p>
<p><strong>Mayer: </strong>Could it be envisaged that the structural state of the water at a distance of about 3 to 7 nm from the enzyme cleft sets the basic conditions, and that reactions/alterations of water structure taking place within the cleft are &#8220;embedded&#8221; into (or even regulated by) the basic conditions?</p>
<p><strong>Wiggins: </strong>You would have to come up with a good mechanism. There may well be one. I am particularly inclined toward a 2-3 nm limit because the original division of water into microdomains involves a decrease in entropy which can only increase as the size of the domains increases. According to Gene Stanley, the microdomains separate into two solutions at about -50<sup>o</sup>C. This would involve a very large decrease in entropy.</p>
<p><strong>Ivan Cameron<sup>2</sup>:</strong> My question concerns the hemodynamics on oxygenation of<br />
haemoglobin. It seems likely that erythrocyte shape change and shear<br />
force (stenosis) occurs when erythrocytes pass through the capillary<br />
bed. This perturbation probably disrupts their LDW state and thereby<br />
modifies oxygen as well as CO<sub>2</sub> exchange. What is your comment on this<br />
possibility?</p>
<p><strong>Wiggins:</strong> This pressure acts on the whole red cell. It may well modify the C0<sub>2</sub>/O<sub>2</sub> exchange, but it would be rapidly reversible. But that is a very good point.</p>
<p><strong>Cameron:</strong> How can your water model of enzyme action be tested?</p>
<p><strong>Wiggins:</strong> There is a wealth of experimental data on enzyme reactions, all interpreted in terms of binding sites. If these can also be interpreted in terms of surface water, then that is a good test of the mechanism. I have done that here with Michaelis-Menten kinetics and with allostery. There are many more things one could do, but my personal ignorance of biochemistry gets in the way. As I said earlier, there are plenty experiments showing the properties of water at other surfaces, and no reason why protein surfaces should be different.</p>
<p><sup>1</sup><em> Head, Structural Biology Department, Georg-August-University, Göttingen, Germany. </em></p>
<p><sup>2 </sup><em>University of Texas Health Science Center at San Antonio, Graduate School of Biomedical Sciences, Cellular and Structural Biology.</em></p>
<p>http://www.waterjournal.org/archives/volume-1/50-wiggins2-full-text</p>



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		<title>Theory Versus Experiment</title>
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		<description><![CDATA[Theory Versus Experiment. What is the Charge at the Surface of Water? Chaplin, MF1 1*Department of Applied Science, London South Bank University, 103 Borough Road, London SE10AA, UK Correspondence: martin.chaplin@lsbu.ac.ukThis e-mail address is being protected from spambots. You need JavaScript enabled to view it Key Words: interfacial water, surface charge, water-gas interface, surface tension, surface<a href="http://korotkov.org/water/2010/10/212/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<h4><strong>Theory Versus Experiment. What is </strong><strong>the Charge at the Surface of Water? </strong></h4>
<h1>Chaplin, MF<sup>1</sup></h1>
<p><img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig2.jpg" alt="vol1_chaplin_fig2" width="349" height="213" /></p>
<div>
<p> <em><sup>1</sup></em><em>*Department of Applied Science, London South Bank University, 103 Borough Road, London SE10AA, UK</em><strong><em><br />
</em></strong><br />
Correspondence: <a href="mailto:martin.chaplin@lsbu.ac.uk">martin.chaplin@lsbu.ac.uk</a>This e-mail address is being protected from spambots. You need JavaScript enabled to view it</p>
<p>Key Words: interfacial water, surface charge, water-gas interface, surface tension, surface spectroscopy</p>
<p>Received 11 November 2008; revised 14 December 2008; accepted 6 February 2009. Published 1 July 2009. Available online 1 July 2009.</p>
<p><strong>Summary</strong></p>
<p>There is considerable disagreement over whether the gas/liquid surface of water is positive due to the presence of surface-active hydrogen ions or negative due to the presence of surface-active hydroxyl ions. Much has been written and many experimental and simulation studies have been undertaken. We critically analyze these studies to establish what is known unambiguously and what assumptions underlie these opposite views. The conclusion reached after this examination is that there is much misunderstanding over the strength of the evidence for hydrogen ions being surface active and less support for the positive surface than generally regarded. The surface of neutral water is negatively charged.<span id="more-212"></span></p>
<p><strong>Introduction</strong></p>
<p>One of the great debates that currently concerns water science is that of the surface of water with the atmosphere. What, if any, structure does it have? Is it positive or negative? Is it acidic or basic? Modeling studies and some molecular-scale experimental work indicate that it is positive due to the preferential presence of oxonium ions (H <sub>3</sub>O<sup>+</sup>, H<sub>5</sub>O<sub>2</sub><sup>+</sup>, etc.) on the surface but with no excess surface hydroxide ions. In contrast, many macroscopic experimental studies show the aqueous surface to be negatively charged. Even when similar data is derived using similar experimental methods, this data may often be interpreted diffierently to agree with one or the other view. Interested scientists belong to one or other of these two factions with both sides sure of their ground and suggesting that the other view is supported by incomplete or faulty models on the one side or contaminated surfaces on the other. Which view is correct? Or are they both, to some extent? The Faraday Discussion 141 (2009) and the themed issue of PCCP (10 (32) 2008) were envisaged as unifying the views on the structure of water at interfaces (McCoustra, 2008), but only served to stir the controversy deeper.</p>
<p>It is clear that the air-water surface, contrary to expectations of some, is a very complex system. It is a complex interfacial system and certainly not as simple as often assumed. We remain undecided over the best description for the bulk structuring of water or water&#8217;s interactions with ions and other solutes. Most importantly, our models are poor at predicting water&#8217;s properties. The surface of water is even more complex and behaves differently to other liquid surfaces just as bulk water behaves differently to other bulk liquids. Water&#8217;s surface appears even more complex than bulk water with its structure changing with temperature, gas molecules binding, ions binding or being excluded, electrical gradients being set up and with its dielectric and chemistry changing with apparent unpredictability.</p>
<p>How far does the surface extend? Certainly, the volume of water considered ‘surface&#8217; should be electrically neutral and this probably best defines the surface thickness for water. The interface must include the outer monolayer, the boundary that gives rise to any zeta potential, any double layer of ions, plus deeper layers where there is surface-influenced anisotropy in either charge or structure. The depth of this surface remains undetermined but it is likely to be somewhat greater than given by most techniques that look only at a restricted range of selected properties. Clearly, such a definition of surface depth cannot encompass a charged surface. Therefore, the charge on the surface may depend upon the surface layer thickness under consideration. It may well vary between methodologies with different probe depths.  Also confusing the issue is that the surface is rough rather than planar and is in constant flux. Vrij (1968) discusses how surface capillary waves on water scatter light with low intensity due to its high surface tension and low refractive index. Energetic considerations indicate, however, that these surface capillary waves are unlikely to be more than about a water diameter high due to water&#8217;s high surface tension. In addition to this, several million monolayers exchange with the gas phase every second (Shultz et al. 2000) and cause evaporation-dependent temperature gradients, so giving rise to long-lasting surface discontinuities and non-equilibrium (Khizhnyak and Khizhnyak, 2007).</p>
<p>The density, dielectric permittivity (Teschke and de Souza, 2005) and dipole moment of interfacial water change from their bulk water values to those of the gas over a distance generally regarded as less than about a nanometer. Thus, water&#8217;s solvation and ionization properties change at the interface, with ions and hydrophilic solutes generally being less evident at the interface but non-polar gasses being more soluble there (Vácha et al. 2004). Ions, including hydrogen and hydroxide ions, and other solutes behave differently at the surface to their behavior in the bulk. An important property of the surface concerns how it affects the local ion distribution. Some ions prefer the surface whereas others avoid it, as shown by their effects on the surface tension (Petersen et al. 2004b) and bubble coalescence (Craig, 2004).</p>
<p>Many papers discuss the results of a combination of simulations and experiments. It is often difficult to determine whether their conclusions are primarily those of the simulations, or those of the experimental work as interpreted using the simulations, or derived solely from the experimental work alone. The resultant discussions may be biased as a number of supporting factors of dubious significance for a point of view will never add up to much more than the best bit of support taken by itself.</p>
<p>In this paper, we attempt to show the conclusions that can be drawn from the different techniques and only then put the totality of the conclusions together, so trying to avoid the trap fallen in by others of selectively picking the results that support their viewpoint.<br />
<strong>Discussion</strong></p>
<p>The properties of liquid water are very different from most other liquids, with many anomalies being identified (Web ref. 1). These properties are due partially to water being a very small and highly polar molecule, but mainly due to water&#8217;s capacity to form ordered tetrahedrally-placed cooperative intermolecular hydrogen bonding. In liquid water, clusters of water molecules are continually forming and dissociating. Water clusters, when held together primarily by many hydrogen bonds, have lower molecular density and are favored at lower temperatures and pressures, whereas volumes containing poorly hydrogen-bonded water molecules collapse somewhat due to competition from multiple non-directional van der Waals attractions. Hydrogen bonds and van der Waals interactions are both distance sensitive and individually very fleeting. A typical hydrogen bond between two water molecules lasts just a picosecond or so, followed by a period much shorter than this when the two water molecules are not hydrogen-bonded to each other. Hydrogen bonding shows strong cooperativity as a water molecule that accepts a hydrogen bond is more able to donate one to another water molecule. Thus, the strength and directionality of the bonding increases in a cooperative manner with the extent of the formed cluster. However, hydrogen bonding and van der Waals interactions destructively interfere with each other, with stronger hydrogen bonding reducing the prevalence of van der Waals interactions and van der Waals interactions being more in evidence when the hydrogen bonding is weak or absent. These conflicting associations cause heterogeneities within the liquid water, such that volumes of higher and lower densities exist, if only fleetingly. These heterogeneities may be considered as connected by equilibria that shift with the physical conditions, and the presence of solutes and surfaces. How the interface may affect and, in turn, be affected by such equilibria will be discussed later.</p>
<p>The gas-liquid interface of water has been examined by experiment and by simulation using a number of routes. Unfortunately, these do not produce a clear picture as the resultant interpretations often play a major role in the conclusions drawn. Over the next few paragraphs, we discuss these different approaches and the problems involved in understanding these results before coming to some conclusions.</p>
<p><strong>Zeta Potentia</strong> <strong>l </strong></p>
<p><img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig1.jpg" alt="vol1_chaplin_fig1" width="500" height="211" /></p>
<p><em><strong>Figure 1:</strong> Assuming that the liquid-gas interface preferentially contains negatively charged ions (a), the negative zeta potential and surface potential are shown (b). The density given is for an average through both the liquid and gas phases of the rough surface and cannot be taken as showing a reduction in the density of just the liquid phase.</em></p>
<p>Zeta potential (ζ, Fig. 1) is exhibited by particles when there is a charge remaining on their surface when they are moved. It reflects the residual charge when counter-charges, within the overall neutral surface, are left behind beyond the slip plane. Zeta potentials are easily determined from the movement of such particles in an electric field and their magnitude depends on a number of factors including the dielectric constant and viscosity.</p>
<p>The surfaces of macroscopic particles of water certainly appear negative when their behavior is examined in an electric field. Beattie (2008) compares the many experiments going back 150 years, all showing a negatively charged aqueous surface and the lack of any experimental evidence for a positively charged aqueous surface. The simplest of experiments shows that air bubbles in neutral water are negatively charged, as they clearly always migrate towards a positive electrode.</p>
<p>Beattie (2007) found conclusive evidence for the presence of negative charges on oil droplets, gas bubbles, thin aqueous films and solid hydrophobic surfaces Experiments by many scientists and over many years have shown that air bubbles (cavities) in water move as though they are negatively charged in response to an external electrical field. In a similar manner, small water droplets in air are found to be negative (the waterfall effect) (Tammet et al. 2008) as are ice particles in water (Drzymala et al. 1999). In all cases, the isoelectric point appears to be about pH 3 with the negative charge apparent in pure neutral water. The consistently similar effects found in diverse fields, by different workers at different times and in different places, cannot be due to the presence of similar adventitious contamination in similar amounts. This is  particularly so, as all workers in this field are aware of the possible artifacts introduced by impurities and generally seek to minimize them.</p>
<p>The zeta potential of the air-deionized water bubble has been subject to considerable work and was determined by Graciaa et al. (1995) to be -65 mV; a slightly higher value than as determined by others. However, there is unanimity that the value is negative and about this order of magnitude. The zeta potential appears due to hydroxide ions as it depends on hydroxide concentration but is almost independent of the identity of any other present co-anions or counter ions. The zeta potential reduces with increasing ionic strength as expected from double-layer compression, giving zeta potentials typically varying from -46 mV for 0.1 mM NaCl to -18.8 mV for 0.1 M NaCl (Yang et al. 2001). The negative zeta potential cannot, therefore, be due to other ions binding within the surface. Hydrophobic liquid (e.g. oil) and solid (e.g. Teflon) -water interfaces have similar isoelectric points to these gas-water interfaces, confirming a structural similarity between all these aqueous surfaces.</p>
<p>The surface charge density varies from about an electron per 1000 nm <sup>2</sup> for pure water to about an electron per 10 nm<sup>2</sup> in 0.1 M NaCl. This surface charge for deionized water with air is similar to that found on small oil droplets in water. Beattie et al. (2009) found the surface-charge density at oil-water interfaces in mM salt is about an electron per 3 nm<sup>2</sup> (at pH 7-9). These charge densities are of similar magnitude to the charge required to establish stable nanobubbles in water; estimated at about an electron per 16 nm<sup>2</sup> for a 50 nm diameter nanobubble (Web ref. 2).</p>
<p>Beattie (2006) states that pH-neutral aqueous surfaces are charged due to the presence of surface hydroxide ions subsequent to enhanced autolysis of water and that positive hydroxonium ion adsorption at the surface of water is contrary to the experimental evidence (Beattie et al. 2009). This view is supported by Lützenkirchen et al. (2008) who put forward a model for the charging of hydrophobic electrolyte surfaces based upon enhanced autolysis within the structured interfacial water, with a pK <sub>w</sub> of about 7 and hence an isoelectric point of about pH 3.5. The negative charge on the surface is further supported by Hänni-Ciunel et al. (2009) who proved that the aqueous wetting film on a negatively charged surface of polystyrene sulfonate is electrostatically stabilized due to negative charges at the air water interface and by Yatsuzuka et al. (1996) who investigated the electrification of PTFE surfaces with ultrapure water. The fact that the zeta potential of strongly acid solutions is positive may be explained in a variety of ways and, as such, fails to specifically support any of the mechanisms here explained.</p>
<p>Zeta potential is different from the surface potential (Fig. 1), which is the potential existing across a deeper interface. In contrast to the zeta potential, the surface potential is conventionally defined such that a negatively charged surface relative to a more positively charged sub-surface is given a positive value for the potential. Studies concerning surface potential give contradictory results varying between positive and negative values of about a volt. Randles (1977) analyzed many experimental findings on real pure water and concluded that the surface potential of water is slightly positive (+80 mV), as conventionally defined, and therefore the surface is negatively charged.  More recently, v. Klitzing (2005) reviewed the effect of surface composition within wetting films and also concluded that the interface is negatively charged. This is in contrast to the recent work of Kathman et al. (2008) who found the surface potential to be -18 mV using <em>ab initio</em> molecular dynamics on just H<sub>2</sub>O at a vacuum interface. The surface potential computed using interaction models for water are consistently about two orders of magnitude more negative than this value (Kathman et al. 2008). The low value of -18 mV for pure H<sub>2</sub>O would still be expected to attract a small amount of hydroxide ions into the surface layer.</p>
<p>Lastly, we dismiss claims that all these experiments, demonstating that the water surface has a negative charge, contain artifacts due to the presence of impurities or vaguely defined stirring effects. (Vácha et al. 2008b). There is simply no evidence presented in support of such conjectures.</p>
<p><strong>Image Charge</strong></p>
<p><img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig2.jpg" alt="vol1_chaplin_fig2" width="500" height="306" /><br />
<em><strong>Figure 2:</strong> When an ion approaches the gas-liquid interface, it is repelled by the interface as though there was an identical charge (the image charge) equidistant from the interface on the gas side (shown at top). The effective dielectric of the medium separating the charges is that of the liquid side. If the charge lies on the outside of the interface then its image charge is attractive within the liquid phase (shown at bottom).</em></p>
<p>The gas-liquid surfaces of aqueous solutions exclude many ions due to a combination of factors. If the ions are strongly hydrated, the ionic hydration is isotropic. Such ions cannot approach too close to the interface without losing some of this strongly held hydration water; an outcome that is energetically highly unfavorable. Additionally, due to the dielectric boundary at the interface, image charge repulsion opposes the approach of the hydrated ions to the surface (Dill et al. 2003, Fig. 2). Such image charge effects depend on the square of the size of the charge and inversely depend upon both the dielectric of the medium (at higher dielectric) in the remaining surface layer and the distance from the interface. The inverse distance dependency reduces the approach of ions to the interface. Any such effect would, however, not be expected to continue right to the outer surface as here the dielectric (ε) approaches unity and the image charge, which further depends upon the factor (ε &#8211; 1)/( ε + 1), disappears. Ions at the interface are not repelled but will tend to form ion pairs or neutral species, if possible, due to the low dielectric. Doubly charged ions, such as calcium and sulfate, avoid the interface due to their strong hydration plus the greater repulsion dependency due to the square of the charge. Image charge increases surface tension at higher ionic strength due to this ion repulsion from the surface.</p>
<p>Image charge effects operate on the water molecules as well as the ions. As any repulsion depends on the square of the charge and as the water molecule&#8217;s oxygen atoms have twice the charge of the hydrogen atoms, water molecules are expected to reorient such that their dipoles, and hydrogen atoms, face the interface. However, the need for cooperative hydrogen bonding, the polarizability of the electrons and the low surface dielectric all mitigate any such tendency. The image charge may be negligible towards the gas side of the surface, or even cause attraction rather than repulsion. Thus, the charge distribution due to the image charge effect on unionized water molecules may well tend to oscillate within the reduced density surface layer.</p>
<p>The image charge affects the mobility of both hydroxonium (H <sub>3</sub>O<sup>+</sup>) and hydroxide ions due to the high mobility of their charges in an electric field. An electric field may also occur at the surface due to counter-ions and co-ions within the double layer and their image charges. The movement of the hydroxonium and, to a lesser extent, hydroxide ionic charges are expected to rapidly compensate for fluctuations in this field. In simulations (see later) the oxonium ion ends up at the interface and necessarily equidistant between the paired hydroxide ion and the hydroxide&#8217;s image charge. This arrangement is likely to be preferred due to the known more rapid mobility of the positive charge relative to the negative charge.</p>
<p>Image charge effects also help stabilize hydrogen ions at the surface of small clusters, as found in simulations. The surface is the only place where the oxonium ion feels no image charge repulsion but (in contrast to most other ions) sitting at the surface does not significantly reduce its interaction capacity with neighboring water molecules.</p>
<p><strong>Condensation Coefficient</strong></p>
<p>The condensation and evaporation coefficients govern the rate of water vapor entering and leaving the water-vapor interface. The condensation coefficient is the ratio of the condensing mass of molecules to those colliding onto the interface whereas the evaporation coefficient is the ratio of the observed evaporation rate to the theoretical maximum rate. The two coefficients should be equal. As such, both indicate the organization of the molecules at the surface, as well-ordered surfaces should have a low coefficients due to the orientation and activation energy requirements. Unfortunately, although as expected all studies give values less than unity, there have been widely different results reported for these coefficients.</p>
<p>Cappa et al. (2005) showed that the evaporation coefficient is less than unity and decreases with temperature, with the activation energy being about 10 kJ mol <sup>-1</sup> greater than the enthalpy of evaporation. This is evidence that there is a considerable barrier to free evaporation and therefore condensation, indicating considerable structuring within this surface water. Also demonstrated is that water molecules at the liquid-air interface have a tendency to form stronger, if fewer, hydrogen bonds than do those in the bulk liquid. Their later work (Smith et al. 2006) found the evaporation coefficient of water to be 0.62 +/- 0.09 and indicated the possible geometric requirements for the evaporation of a water molecule.</p>
<p>Other workers report much lower values for the condensation coefficient. Zagaynov (2000) find the condensation coefficient of water to be 0.001-0.01 for water droplets of radius 0.04 to 0.08 mm respectively. Jakubczyk et al. (2007) report higher values of between 0.054 and 0.12 over the temperature range of 0-25°C with a minimum value of 0.036 coinciding with the temperature of maximum density (4°C) and so agreeing with the thermodynamic evidence for the occurrence of a maximum in the surface structuring (see later). However, Kobayashi (2008) determines the value to be almost unity (0.85). This latter work, however, used a shock tube to achieve non-equilibrium, which may have upset the surface structure of water.</p>
<p><strong> </strong><br />
<strong>Sum Frequency Generation and Second Harmonic Generation Spectroscopy</strong></p>
<p><img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig3.jpg" alt="vol1_chaplin_fig3" width="500" height="258" /><br />
<em><strong>Figure 3: </strong>The surface spectrum for pure water O-H stretch vibrations consists of three main peaks centered at about 3150 cm-1, 3400 cm-1 and 3700 cm-1. The spectrum shown is a cartoon of those typically found and has been smoothed and simplified from that of Shultz et al. (2000). </em></p>
<p>Sum frequency generation (SFG) and second harmonic generation (SHG) surface spectra are spectroscopic methods for investigating the surface of water without interference from the bulk liquid. The output spectra derive from a combination of input beams. As both the bulk aqueous solution and the gas phase are isotropic, they are not active in this spectroscopy, leaving just the anisotropic interfacial layer to provide the spectra, due to a net orientation of surface molecular dipoles. The depth of this anisotropy governs the depth probed. As the spectra are acquired over periods of seconds, it is of interest that the surface monolayer may be exchanged millions of time during this period (Shultz, et al. 2000). It is thus surprising that any spectral features remain from within this ever-changing environment. Any surface-active ions must continue with unchanging spectra even though the surface is in continual flux.</p>
<p>SFG and SHG thus present powerful methodology for investigating the interface. Disappointingly, the data accompanying an increase in bulk concentration of an ion may be open to opposing interpretations and does not provide definitive conclusions. Current methods do not distinguish as to whether a spectroscopic change at the surface is due to the presence of the ion at the surface or due to an effect that the ion has from a distance from the surface, such as a field potential effect from within the double layer. Thus, the fact that acids interfere with the surface structure of water can be taken as support for the hydronium ions preferring the surface. Alternatively, opposing views can be taken whereby the surface effect is due to charging at the double layer and/or the presence of unionized acid at the surface. Unambiguous experimental proof that oxonium ions (e.g. H <sub>3</sub>O<sup>+</sup>) are in excess at the surface is missing. Some researchers link the spectroscopy with molecular dynamics (discussed later) in such a way that the strictly spectroscopic conclusions are overshadowed and possibly biased.</p>
<p>Fig. 3 shows a typical surface spectrum of the O-H stretch vibrations of pure water.  By general consensus, these O-H resonances are believed to mostly represent symmetric stretch of anisotropically oriented tetrahedrally hydrogen bonded water molecules (~3150 cm <sup>-1</sup>, ‘ice-like&#8217;), asymmetrically hydrogen bonded water molecules (~3400 cm<sup>-1</sup>, ‘liquid-like&#8217;) and the dangling O-H stretch, free from hydrogen bonding (~3700 cm<sup>-1</sup>, ‘gas-like&#8217;). The assignation of these peaks is probably correct but not assured as  Sovago et al (2008a, 2008b, 2009) disagree with these assignments with Tian and Shen (2008, 2009) dissenting from this view. Certainly, the model used by Sovago et al (2008a, 2009), which assumes that liquid HOD behaves no differently from H<sub>2</sub>O in its hydrogen bonding, is open to question. The dangling O-H stretch may be further explained by making use of the infrared spectra of oxonium ion clusters (Shin et al. 2004). The vibration from the single free O-H in a water molecule held by two or three hydrogen bonds were at ~ 3717 cm<sup>-1</sup> and ~3695 cm<sup>-1</sup> respectively, whereas the symmetric and asymmetric stretch of the pair of O-H bonds from single water molecules held by donated hydrogen bonds were found at ~3650 cm<sup>-1</sup> and 3740 cm<sup>-1</sup> respectively. These resonances qualitatively agree with the O-H stretch from gaseous HDO (3707 cm<sup>-1</sup>), where the O-H stretch is similarly decoupled and the peaks at 3657 cm<sup>-1 </sup>or 3756 cm<sup>-1 </sup>from the symmetric and asymmetric stretch vibrations from pairs of free O-H groups in H<sub>2</sub>O vapor. Thus, similarly sized peaks at ~3650 cm<sup>-1</sup> and 3750 cm<sup>-1</sup> would represent water molecules held in the surface only by accepted hydrogen bonds from underlying water molecules. Such peaks cannot be seen to any significant extent in water&#8217;s surface SFG spectra.</p>
<p>The peak at ~3700 cm <sup>-1</sup> shows that about a quarter of the water molecules in the surface each have a &#8216;dangling&#8217; O-H group (Wilson et al. 2002, Du et al. 1993) pointing at a slight angle out of the water (Kuo and Mundy, 2004; Gan et al. 2006) and creating a slight negative charge on the outer liquid surface. These amounts of dangling O-H groups are identical to those found in the basal plane of ice. In addition, Du et al. (1993) says the dangling O-H angle averages at about 52° to the surface plane, placing its molecular dipole almost exactly parallel to the surface. Using the value of 106° for the bond angle of the water molecule, a randomly oriented water molecule in the outer monolayer would be expected to possess at least one free O-H group 79% of the time (= (180+106)/360) and have both O-H groups free 21% of the time (= (180-106)/360). As the proportion of free O-H vibrations indicates amounts of such water molecules substantially lower than this, it appears that the surface monolayer of water molecules is part of substantially ordered arrangement and the water dipole must probably point towards the bulk liquid, giving a negatively charged surface. Random orientation of these water molecules fitted to this data, less the ~25% that are dipole-neutral, would give them a net dipole of about 40% of the H<sub>2</sub>O molecular dipole. Goh et al. (1988) also concluded, from the temperature dependence of the SHG, that water molecules are oriented with their dipole moments pointed, on average, into the bulk at the air-water interface. The water molecules hydrogen-bonded to these, lying just under the surface but within the surface monolayer, would tend to reduce this surface polarity. As the water molecule is neutral, any net charge effect can only be carried to the bulk by means of oriented hydrogen bonding and would be much reduced due to thermal randomization.</p>
<p>The free O-H stretch is a good indicator for surface perturbation whereas the symmetric stretch at ~3150 cm <sup>-1</sup> indicates a preferred orientation of the tetrahedrally hydrogen bonded water molecules in the immediate sublayer. Clearly, a surface dipole creates ordering in the sublayer extending until the effect peters out. These experimental findings are in contrast to molecular dynamics simulation results on pure H<sub>2</sub>O that show exterior water dipoles pointing out but with a stronger dipole pointing in due to water molecules deeper in the surface (Sokham and Tildesley, 1997).</p>
<p>Of key importance is the effect of acid, anions and cations on the surface. Even ions that do not reside in the surface, such as strongly hydrated metal cations, perturb the surface layer by their charge effect on the subsurface. Acids generally appear to have a greater effect than salts. However, it is not clear whether this greater effect is due to the presence of surface hydrogen ions or unionized (charge neutral) surface acid molecules. Noticeable effects are the reduction in the free O-H peak due to its replacement in the surface or re-orientation of the surface water molecules, and the increased intensity of the anisotropically oriented tetrahedrally hydrogen bonded water molecules (~3150 cm <sup>-1</sup>).</p>
<p>Direct recording of the spectra from oxonium ions (e.g. H <sub>3</sub>O<sup>+</sup>) is unlikely due to their much lower concentration and the strength of their donor hydrogen bonding red-shifting the expected O-H vibrations. No such red-shifted vibrations have been seen (Baldelli et al.1998). At a pH of 1 (or 13), the surface would only involve one oxonium ion (or hydroxyl ion) for every 550 surface water molecules, and they are therefore unlikely to contribute much directly to the spectrum. There is some support for oxonium ions lying in the surface of concentrated solutions, but not within the top monolayer, from Tarbuck et al. (2006). They show that the O-H stretching modes are affected by both OH<sup>-</sup> and H<sup>+</sup> ions, albeit more substantially by the latter. Water hydrogen bonded to hydroxide ions would behave similarly to those hydrogen bonded to oxonium ions. However, the resonances of ‘free&#8217; O-H groups, if present, from any surface hydroxide ions would be expected to overlap with those of the dangling O-H groups from H<sub>2</sub>O molecules.</p>
<p>Mucha et al. (2005) used SFG to probe the O-H stretch vibrations parallel and perpendicular to the surface but found the signal too weak except when concentrated acid or hydroxide was used. 1.2 M acid solutions gave strong increases in the tetrahedral hydrogen bonded O-H stretch (~3150 cm <sup>-1</sup>) with a smaller changes in the 3450 cm<sup>-1</sup> peak and decreases in free O-H stretch (~3700 cm<sup>-1</sup>), indicating the presence of surface hydronium ions to the authors. The spectra indicate a greater effect caused by HI than HCl, due probably to the highly polarizable and known surface-active iodide ion dragging hydrogen ions into the surface with them. No such effects were found for hydroxide ions, but these appear to give a slightly higher free O-H stretch (~3700 cm<sup>-1</sup>) that is difficult to distinguish from that of water. However, similar spectra to the above acid spectra have been obtained using neutral salts, such as sodium sulfate, which are known to be absent from the interfacial layer (Gopalakrishnan et al. 2006). Also, sulfuric acid, which is also known not to enter the surface from its affect on surface tension, shows a much enhanced SFG peak at ~3150 cm<sup>-1</sup> and reduced SFG peak at ~3700 cm<sup>-1</sup> (Gopalakrishnan et al. 2006) and must be achieving this through a double layer effect reorienting the surface water molecules. Isotope dilution experiments, involving the four sodium halides F<sup>-</sup>, Cl<sup>-</sup>, Br<sup>-</sup> and I<sup>-</sup>, have shown these to only minimally perturb the surface SFG spectra in contrast to that expected from simulations (Raymond and Richmond, 2004). However Bian et al. (2008) show, using non- resonant SHG, that the greater surface presence of the heavier halides increases the thickness of the interfacial water layer but that the electric double layer is much weaker than produced in simulations.</p>
<p>Tian, et al. (2008) also interpret their SFG spectroscopy data as due to hydroxonium ions residing at the surface. Surprisingly, they find that acid solutes  do not affect the free O-H vibrations. However, as surface oxonium ions strongly hydrogen bond to other water molecules, so reducing the further acceptor character of such water molecules, they would be expected to affect the ~3400 cm <sup>-1</sup> resonances more than the ~3150 cm<sup>-1</sup> resonances, which is not seen.</p>
<p>The differences are also discussed by Petersen and Saykally (2008) using resonant UV SHG. This method uses two identical photons directed at the surface and analyzes the emitted photons having double the energy. When the energy of molecular transitions coincides with either incident or emitted photons, resonance enhancement of the second order signal gives rise to the surface spectrum. Several anions exhibit strong charge-transfer-to-solvent (CTTS) transitions that were thought best modeled by surface depletion of hydroxide ions but with surface enhancement of oxonium ions associated with ions such as iodide. The presence of surface hydroxide was dismissed as having no theoretical base.</p>
<p>Levering et al. (2007) also examine the air-liquid interface of aqueous hydrogen-halide solutions using vibrational SFG spectroscopy. These acids caused a significant disruption in the hydrogen-bonding network at the interface, including an increase in interfacial depth and a decrease in the number of dangling O-H bonds. Levering et al. (2007) interpreted the increased resonance at frequencies below 3000 cm <sup>-1</sup> to indicate that hydrogen ions exist at the air-aqueous interface, but it is unclear whether this requires an enhancement or is simply a consequence of the high acid concentrations (0.05 mole fraction). They also found a peak at 3748 cm<sup>-1 </sup>that increases in acid solutions. This is equivalent to the asymmetric stretch of water molecules with two free O-H groups but they did not find the expected ‘twin&#8217; peak at ~3650 cm<sup>-1 </sup>for the symmetric stretch. Indeed, there was only a slight change in the ~3200 cm<sup>-1</sup> peak on increasing the acids from mole fractions of 0.015 to 0.1. This peak increases or decreases slightly dependent on the acid and, therefore, this would seem more simply resulting from forcing the molecules closer to the surface due to the concentration increase rather than a surface excess due to proposed specific surface activity of the hydroxonium ions.</p>
<p><strong>Surface Tension and Related Thermodynamics</strong></p>
<p>In a liquid, molecules within the bulk phase attract each other equally in all directions. However, at a gas-liquid interface, the surface molecules are more attracted to the molecules within the liquid than they are to molecules of the gas, so creating the surface tension. In order to achieve the greatest possible interaction energy, surface tension causes the maximum number of surface molecules to enter the bulk of the liquid and, hence, minimizes the surface area.</p>
<p>Water has an unusually high surface tension with a tightly packed surface. Water molecules at the liquid-gas surface have lost potential hydrogen bonds directed at the gas phase and are pulled towards the underlying bulk liquid water by the remaining stronger hydrogen bonds (Scatena et al. 2001). Energy is required to increase the surface area, by removing a molecule from isotropically hydrogen bonded interior bulk water to the anisotropically hydrogen bonded outer surface. This energy is minimized and the surface is held under tension. As the forces between the water molecules are several and relatively large on a per-mass basis, compared to those between most other molecules, and the water molecules are very small, the surface tension is large. Lowering the temperature greatly increases the hydrogen bonding in the bulk causing increased surface tension.</p>
<p>Surface tension measurements do not give direct information about the aqueous molecular structure of the surface, but unambiguously report the presence of other molecules within the surface layer. Unfortunately, liquid surfaces are easily contaminated and such experiments are prone to error. This not only means that they are difficult to carry out reproducibly and without artifacts but also allows critics to denigrate results they disagree with.</p>
<p>Gas at air-water and other gas-water interfaces behaves like a flattish flexible hydrophobic surface but with the difference that the van der Waals interactions between the liquid and gas are negligible and with the caveat that gas molecules can bind to the surface. It is well known that gas adsorbs preferentially at the water gas interface (Vácha et al. 2004), as proven by the lowering of surface tension with gas pressure (Massoudi and King, 1974). Such adsorption must affect the structure and properties of the surface. In the presence of methane gas, for example, its concentration within the surface layer may be almost a hundred times greater than that in the bulk liquid (Sachs and Meyn, 1995). Similarly, the surface excess of CO <sub>2</sub> may be ten times greater than its bulk concentration (Massoudi and King, 1974).</p>
<p>The aqueous surface is strongly attracted to probes approaching from the gas side at distances of about a micrometer and jumping into contact when still over 100 nm distant (Wu et al. 2007), thus showing the long range nature of the attractive forces and the likeliness an uneven surface. Atomic force microscopy at air-water interfaces has indicated that the surface polarization causes the presence of nano-sized clusters of water within about 250 nm of the interface (Teschke and de Souza, 2005). These clusters are apparently built up from ~100 H <sub>2</sub>O molecule clusters; the same size that forms the core clusters in the icosahedral model of water (Chaplin, 2000) and as found by X-ray analysis in Mo-based nanodrops (Müller et al. 2003). Teschke and de Souza (2005) describe the surface as oscillating between greater and lesser organization with sharp boundaries between them. The reduced density and stronger hydrogen bonds within the surface will both contribute to the stabilization of expanded water clusters. Small gas molecules may bind preferably to such surface clusters due to multiple van der Waals interactions, and good fit, between the gas molecules and the clusters without the possibly negative influence caused by the necessary closure of the clusters as must occur within the bulk. This is supported by the known greater solubility of the hydrophobic gasses at the interface. Also, there remains the possibility that the surface forms a different aqueous phase that extends far from the gas interface (Zheng  et al. 2006).</p>
<p>Hydrogen bonding in the surface is stronger than in the bulk (Gan et al. 2006) but some hydrogen bonds are lost, giving a more reactive environment at the surface (Kuo and Mundy, 2004) and greater ice nucleation just under the surface (Shaw et al. 2005). The increased strength of water&#8217;s hydrogen bonds in the surface is partially due to the reduced competition from neighboring water molecules and partially due to improved cooperativity and lower anticooperativity. Nevertheless, it has little effect on their vibrational lifetime (Smits et al. 2007). This stronger bonding compensates for the increased chemical potential on the loss of some bonds. The diffusion within the surface is increased for some molecules (in the surface) but decreased for others and depends on the number of hydrogen bonds and size of the water clusters (Liu et al. 2005). The refractive index of the surface of water at 22°C has been shown to be higher than that of the bulk and opposite in behavior to other normal and hydrogen-bonding liquids, ethanol  for example (Greef and Frey, 2008). Thus, the refractive index reveals the surface of water to be about 1.7 nm thick at 22°C and that it appears to behave like water at a lower temperature. This indicates higher density or greater hydrogen bond strength, at equal density. We know that more structured water has higher specific refraction and refractive index for its density (Cho et al. 2001) but the effect of density changes on the refractive index may outweigh that of the specific refraction differences due to water structuring, as well-structured hexagonal ice has a density of 91.7% of water but a refractive index of just 98.2%. Zasetsky et al. (2007) used molecular dynamics with a SPC/E based model and found enhanced local order at the liquid-gas interface at low temperatures.</p>
<p>The interactions of ions with the interface have been reviewed (Jungwirth and Tobias, 2006). As the surface has low dielectric, ions will not generally be preferred there compared with the high dielectric bulk. However, chaotropic ions with low surface charge density and/or high polarizability (such as Cl <sup>-</sup>, Br<sup>-</sup>, I<sup>-</sup>, HO<sub>2</sub><sup>-</sup> and O<sub>2</sub>·<sup>-</sup>) will favor the gas-liquid interfaces (Garrett, 2004; Jungwirth and Winter, 2008) as they only interact weakly with water but are influenced favorably by the highly polarized surface. Aqueous radicals also prefer to reside at such interfaces (Roeselová al, 2004), as do some molecular species that prefer to hydrogen bond on the outside of clathrate-like structures, like superoxide (Shi et al. 2003). Small cations are found away from the interface towards the bulk where their requirement for efficient hydration may be satisfied. Such cations may only approach the interface in response to a surface negative charge. Oxonium ions are an exception to this as they certainly have a much stronger preference for the surface than other small cations (Mucha et al. 2005). Brown et al. (2008) used X-ray photoemission spectroscopy to probe the ion distribution of concentrated KF, comparing it with that of concentrated KBr and KI, to show that fluoride ions stay away from the surface whereas the bromide and iodide ions are more concentrated at the surface, relative to their cation counterions.</p>
<p>It might be expected that much can be discovered concerning the surface of water from consideration of thermodynamics. This may well be true but thermodynamics produces some inconsistent results that require interpretation. At the liquid-gas surface the following thermodynamic relationship holds:</p>
<p>[1]                                  dG = -SdT + VdP +  γdA + ∑ <sub>ι</sub>µ<sub>ι</sub>dn<sub>ι</sub></p>
<p>where G, S, T, V, P, γ, A, μ and n <sub>i</sub> are the thermodynamic quantities Gibbs (free) energy, entropy, temperature, volume, pressure, surface tension, surface area, chemical potential and number of moles of substance i, respectively, as referring to the whole system (Vavruch, 1995a), From the properties of the differential, the definition of the surface tension may be derived</p>
<p>[2]                                  (∂G/∂A) <sub>TPn</sub> = γ</p>
<p>As can,</p>
<p>[3]                                  (∂V/∂A) <sub>TPn</sub> = (∂γ/∂P)<sub>TAn</sub></p>
<p>(Vavruch, 1995a; Rice, 1947), which relates the change in surface tension with pressure (∂γ/∂P) <sub>TAn</sub> to the change in volume associated with forming surface (∂V/∂A)<sub>TPn</sub>. The influence of pressure on the surface tension of water, as with other liquids, is not straightforward. There are two clear effects, the thermodynamic effect described here and the effect of specific binding described earlier. (∂A/∂V)<sub>TPn</sub>, the inverse of (∂V/∂A)<sub>TPn</sub>, may be taken as a measure of the difference in density of the liquid in the bulk compared with that at its surface and is therefore generally positive; that is, the surface tension should increase with pressure about +0.7 mJ m<sup>-2</sup> MPa<sup>-1</sup> for water at 25°C. (∂γ/∂P)<sub>TAn </sub>is generally much higher than for other liquids at 0.696 nm (25°C); for example, methanol (0.159 nm), diethyl ether (0.176 nm), benzene (0.178 nm) and even mercury (0.398 nm) (Vavruch, 1995b). This high value for water indicates that the density at the surface of water is more similar to the bulk liquid than occurs in most other liquids.</p>
<p>Also derived from equation 1 are</p>
<p>[4]                                 (∂S/∂A) <sub>TPn</sub> = -(∂γ/∂T)<sub>PAn</sub></p>
<p>where (∂S/∂A) <sub>TPn</sub> is the surface entropy and</p>
<p>[5]                                  (∂S/∂V) <sub>TAn</sub> = (∂P/∂T)<sub>VAn </sub> (Pitzer, 1995).</p>
<p>From these relationships, an equation for the surface enthalpy (∂H/∂A) <sub>TPn</sub> may be derived,</p>
<p>[6]                                  (∂H/∂A) <sub>TPn</sub> = γ &#8211; T(∂γ/∂T)<sub>PAn</sub> (Pitzer, 1995).</p>
<p>From inspection of the surface tension changes with temperature, it is clear that this term (the surface enthalpy) is always positive. The greater than expected drop in surface tension with temperature increase (0.155 mJ m <sup>-2</sup> K<sup>-1</sup> at 25°C) is one of the highest known and similar to that of the liquid metals. It has been quantitatively explained using spherically symmetrical water clustering (Khan et al. 2001).</p>
<p><img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig4.jpg" alt="vol1_chaplin_fig4" width="500" height="308" /><br />
<em><strong>Figure 4:</strong> The surface enthalpy/temperature curve was calculated from a combination of sixth power fits to four ranges of surface tension data, (Hacker, 1951; IAPWS, 1994). Due to noise in the data and the lack of data below 250 K, the form of the curve at very low temperatures is error-prone.</em></p>
<p>Although there is no clear anomaly in the surface tension/temperature behavior (Fig. 4), there are inflection points at about 4°C (Hacker, 1951) and 262°C (Pellicer et al. 2002). The inflection in the data at low temperatures has been explained by use of a two-state mixture model involving low-density and higher density water clusters (Hrubý and Holten, 2004). The surface enthalpy/ temperature behavior is anomalous, however, with a clear minimum at the temperature of maximum density. This is a consequence of the minimum in the surface entropy/ temperature behavior. Surface tension changes differently from bulk water properties due to surface enrichment with water clusters. These appear to be optimal at +4°C, collapsing somewhat at both higher and lower temperatures,</p>
<p>Surface enthalpy, also known as the total surface energy, may be calculated from the binding energy lost per unit surface area (= molecules per surface area times the binding energy lost per molecule). At 4°C, this is equivalent to a surface half occupied with water molecules that have lost no hydrogen bonds with the other half having lost the equivalent of about 30% of their hydrogen bonds. A freshly exposed surface of water, with many more broken hydrogen bonds, would be expected to have much higher surface energy (~180 mJ m <sup>-2</sup>; Ogawa and Matsuura, 2004) with a relaxation to the experimental value (117.9 mJ m<sup>-2</sup>, 25°C) taking place in about 3 ms (Kochurova and Rusanov, 1981).</p>
<p>The internal (cohesive) pressure ∏ <sub>ι </sub>is the work required to increase the volume at constant temperature, external pressure and solute concentrations, having the same units as pressure,</p>
<p>[7]               (∂U/∂V) <sub>TPn</sub> = Π<sub>ι</sub></p>
<p>(Leyendekker, 1983; Vavruch, 1995a).</p>
<p>As H = U + PV,</p>
<p>[8]                                  (∂H/∂A) <sub>TPn</sub> =  (∂U/∂A)<sub>TPn</sub> + P(∂V/∂A)<sub>TPn</sub></p>
<p>and also,</p>
<p>[9]                                  (∂U/∂A) <sub>TPn </sub>= (∂U/∂V)<sub>TPn</sub> * (∂V/∂A)<sub>TPn</sub></p>
<p>therefore</p>
<p>[10]                                  (∂H/∂A) <sub>TPn</sub> = (Π<sub>ι</sub> + P) * (∂V/∂A)<sub>TPn</sub></p>
<p>(Vavruch, 1995a). As dU = TdS &#8211; PdV,</p>
<p>[11]                                  (∂U/∂V) <sub>TAn</sub> = T(∂S/∂V)<sub>TAn</sub> &#8211; P = Π<sub>ι</sub></p>
<p>therefore</p>
<p>[12]                                  (∂U/∂V) <sub>TAn</sub> = T(∂P/∂T)<sub>VAn</sub> &#8211; P = Π<sub>ι</sub></p>
<p>and as</p>
<p>[13]                                  (∂P/∂T) <sub>VAn</sub> = -(∂P/∂V)<sub>TAn</sub> * (∂V/∂T)<sub>PAn </sub>= α/κ<sub>T</sub></p>
<p>the internal pressure may be calculated from</p>
<p>[14]                                  (Π <sub>i</sub> + P) = T(α/κ<sub>T</sub>)</p>
<p>where α is the coefficient of thermal expansion and κ <sub>T</sub> is the coefficient of isothermal compressibility (Leyendekker, 1983). As T(α/κ<sub>T</sub>) is zero at 3.984°C, so is (∏<sub>ι</sub> + P) and both are negative below this temperature, as must be (∂A/∂V)<sub>TPn</sub>. ∏<sub>ι</sub> is zero at 3.99°C when cohesive and repulsive components of the hydrogen bonding are equal. It follows that the densities of surface and bulk water are equal at 3.984°C as, below this temperature, the surface density increases relative to the bulk density, rather like what happens at the surface of hexagonal ice (Henson et al. 2005). Both above and below this temperature the density of the surface of water appears to change less than the changes in the bulk water density.</p>
<p>It follows that</p>
<p>[15]                                  (∂A/∂V) <sub>TPn</sub> = (Π<sub>ι</sub> + P) / {γ &#8211; T(∂γ/∂T)<sub>PAn</sub>}</p>
<p>(Vavruch, 1995a). At constant temperature and pressure, this equation can be written</p>
<p>[16]                                  (Π <sub>ι </sub>+ P)dV = {γ &#8211; T(∂γ/∂T)<sub>PAn</sub>}dA</p>
<p>where the left hand side represents the volume work done against the intermolecular forces in bringing molecules from the bulk liquid to the surface and the right hand side represents the energy cost of the extension to the surface (Vavruch, 1995a). Clearly, the work required at 3.984°C is zero (from Eq. 14), which gives rise to an inconsistency, as the right hand side of Eq. 16 is not zero. It may be that the structure of the surface of water is behaving as a different phase and so showing a change in the composition (n). The zero work does however confirm that the surface has the same density to the bulk at this temperature. At lower temperatures, the work is positive again as the bulk density drops with temperature and the thermodynamic expression changes, as here the thermodynamic work equals -pΔV (Stepanov, 2008).</p>
<p>The thermodynamic relationships do not hold for real liquid-vapor-gas systems, however, where the application of pressure will cause water vapor to condense and gas molecules to adsorb on to the liquid-gas interface. The adsorption of gas molecules to the surface of liquid water lowers the surface tension by a greater extent than the thermodynamic effect, outlined above (Eq. 3), raises it except perhaps for helium. Thus, the surface tension of water, in contact with other molecules in the gas phase, drops with increase in pressure due to the surface activity of surface-absorbed gas molecules (Rice, 1947; Massoudi and King, 1974). The extent of this lowering depends upon the gas involved and is much greater for hydrophilic gasses, such as CO <sub>2</sub> (-7.7 mJ m<sup>-2</sup> MPa<sup>-1</sup>), than nonpolar gasses such as N<sub>2</sub> and O<sub>2</sub> (-0.8 mJ m<sup>-2</sup> MPa<sup>-1</sup>). This effect of pressure does not manifest itself in the modeling simulations.</p>
<p>Changes in the surface tension of water with solute concentration indicate solute presence or absence within the surface layer. Increase in surface tension with salt concentration indicates that ions are depleted in the surface layer as given by the Gibbs adsorption equation.</p>
<p>[17]                                  dγ = -ΣιΓιdµ <sub>ι</sub></p>
<p>where Γ <sub>ι</sub> is the surface excess of solute component i and μ<sub>ι</sub> is its chemical potential . Thus, strong hydration of ions in the bulk liquid leads to increases in the surface tension as they are depleted within surface layer. Some acid and basic solutions show the opposite effect. Also, some salts show a reduction in surface tension at low concentrations, followed by an increase at higher concentrations; the Jones-Ray effect (Petersen et al. 2004b; Petersen and Saykally, 2005). Petersen et al. (2004b) showed that iodide saturates at surface at about 1 mM in agreement but this experimental Jones Ray effect has not yet been found in simulations. The Jones-Ray effect is explained by envisaging a limited number of binding sites at the expanded and weakly hydrogen bonded surface, increasing both the interfacial concentration directly and by counterion attraction. Certainly, chaotropic ions prefer this surface environment to the bulk phase where they disrupt the natural water structuring without forming the strong compensatory interactions of kosmotropic ions.</p>
<p>The increase in surface tension with higher concentrations of kosmotropic salts is due to the relative depletion of salt within the surface, which means that when ions do absorb at the surface a depletion layer must be created deeper in. Also, higher concentrations of such salts disproportionately increase the bulk salt concentration so supplementing the attractive forces on the surface water molecules, consequently adding to the increase in the surface tension. Kosmotropic cations and anions prefer to be fully hydrated in the bulk liquid water and so increase the surface tension by the latter mechanism at all concentrations. This partitioning is noticeable in NaCl solutions, such as seawater; the weakly chaotropic chloride ion occupying surface sites whereas the weakly kosmotropic sodium ion only resides deeper within the bulk water (Knipping et al. 2000). The polarizability of large chaotropic anions (such as iodide) is accentuated due to the asymmetric solvent distribution at the surface and increases the strength of chaotrope-solvent interactions when at the surface (Archontis and Leontidis, 2006). Thus, the main driving forces for the entry of such ions into the anisotropic environment of the interface are the stabilizing polarization interactions. Similarly to chaotropic ions, hydroxyl radicals also prefer to reside at air-water interfaces (Roeselová et al. 2004); the radicals donating one hydrogen bond but accepting less than two (VandeVondele and Sprik, 2005).</p>
<p>As some acid solutions (e.g. HCl, HNO <sub>3</sub> and HClO<sub>4</sub>) have reduced surface tension, this has generally been given as supporting water having an acidic surface. For example, arguments for hydrogen ions being surface active often involve the fact that the surface tensions of HCl solutions go down with increased concentration whereas those of NaCl goes up. However, the anion is also important, as the same effect is not shown by H<sub>2</sub>SO<sub>4 </sub>or H<sub>3</sub>PO<sub>4</sub> under similar conditions, where the surface tension increases with concentration even at low concentrations. The claims for it falling at very high concentrations (Mucha et al. 2005), due to the surface-active nature of less-ionized sulfuric acid, are weak as the surface tension only falls below that of water when the solution changes from one of H<sub>2</sub>SO<sub>4</sub> in water to one of water in H<sub>2</sub>SO<sub>4</sub>. As the surface tension of pure H<sub>2</sub>SO<sub>4</sub> is substantially lower than that of water, this phenomenon is best considered as the water content raising sulfuric acid&#8217;s surface tension due to relatively more water being in the surface layer of H<sub>2</sub>SO<sub>4</sub>, with water acting as the surface-active species. Overall, this argument for surface-active oxonium ions is probably fallacious. Moreover, a similar case could be made for OH<sup>-</sup></p>
<p>The reduction in surface tension that occurs with some acids and bases may be due to the surface-active nature of their uncharged acid or base forms. Certainly, this allows an easier and more consistent explanation of surface activity by the formation of uncharged species (for example, HCl, NH <sub>3</sub>) at the surface. Ammonia appears to behave quite differently at the water-gas interface than the isoelectronic oxonium ion (Simonelli et al. 1998; Gopalakrishnan et al. 2006), due to its weaker donor hydrogen bonding and stronger acceptor hydrogen bonding. The NH<sub>3</sub> molecule orients with free N-H upwards away from the liquid. Certainly some of these acids and NH<sub>4</sub>OH may be smelt (but this should be avoided) from concentrated aqueous solutions showing their volatile nature. Even very strong acids such as nitric acid and perchloric acid may act differently at the low dielectric interfaces (Shamay et al. 2007; Karelin and Tarasenko, 2003). The drop in surface tension of sulfuric acid in low to moderate concentrations at low (&lt; 18°C) to very low temperatures (Myhre et al. 1998) is unusual and needs some explanation. Clearly, a different phenomenon is acting at higher temperatures (&gt; 18°C) where the surface tension always increases with concentration.  It is probably due to the preferred presence of the highly polarizable and chaotropic bisulfate ion in the more organized surface layer apparent at low temperatures, as argued under different circumstances by Mucha et al. (2005).</p>
<p>Higher concentrations (often about 0.1M) of many, but not all, salts prevent the coalescence of small gas bubbles, as recently reviewed by Craig (2004), in contrast to the expectation from the raised surface tension and reduced surface charge double layer effects in the DLVO theory. Higher critical concentrations are required for smaller bubble size (Tsang et al. 2004). This is the reason behind the foam found on the seas (salt water) but not on lakes (fresh water). The salts do not directly follow the Hofmeister effects with both the anion and cation being important with one preferentially lying closer to the interface than the other does; for example, excess hydroxonium ions tend to negate the effect of halides (Craig et al. 1993). One explanation for this unexpected phenomenon is that bubble coalescence entails a reduction in the net gas-liquid surface, which otherwise acts as a sufficiently more favorable environment for the pair of ions rather than the bulk when their concentration is higher than a critical value. It has been proposed that anions and cations may be divided into two groups α and β with α cations (Na <sup>+</sup>, K<sup>+</sup>, Mg<sup>2+</sup>) and β anions (ClO<sub>4</sub><sup>-</sup>, CH<sub>3</sub>CO<sub>2</sub><sup>-</sup>, SCN<sup>-</sup>) avoiding the surface and α anions (OH<sup>-</sup>, Cl<sup>-</sup>, SO<sub>4</sub><sup>2-</sup>) and β cations (H<sup>+</sup>, (CH<sub>3</sub>)<sub>4</sub>N<sup>+</sup>) attracted to the interface; αα and ββ anion-cation pairs then cause inhibition of bubble coalescence whereas αβ and βα pairs do not (Henry et al. 2007). These groupings do not behave as bulk-phase ionic kosmotropes and chaotropes, which indicates the different properties for bulk water and the gas-liquid surface. It is likely that the ions reside in the interfacial region, between the exterior surface layer and interior bulk water molecules, where the hydrogen bonding is naturally most disrupted (Paul and Chandra, 2004). A similar phenomenon is the bubble (cavity) attachment to microscopic salt particles used in microflotation, where chaotropic anions encourage bubble formation (Nickolov and Miller, 2005). Further explanation for coalescence involves the effect of the ions on raising or lowering gas solubility (Weissenborn and Pugh, 1996) and this explanation may be extended to water-gas surfaces, as if some ions increase the solution of gasses at the interface, they will reduce the surface tension by this effect alone.</p>
<p>It has been proposed that the lesser hydration energy of OH <sup>-</sup> (ΔG° hydration = -437.6 kJ mol<sup>-1</sup>, Camaioni and Schwerdtfeger, 2005), relative to H<sub>3</sub>O<sup>+ </sup>(ΔG° hydration = -461.1 kJ mol<sup>-1</sup>, Camaioni and Schwerdtfeger, 2005), results in hydroxide ions, rather than the hydroxonium ions, preferring the surface (Boström et al. 2005). This phenomena, even if correct, cannot be the whole story as ions with lower hydration energies do not seem to readily replace hydroxide ions at the interface (Beattie, 2007).</p>
<p><strong>Simulations</strong></p>
<p>Due to memory and computational restraints, simulations involving H <sup>+</sup> and OH<sup>-</sup> ions effectively concern concentrated acidic or basic solutions but with few interacting ions. It is technically impossible to simulate pH 7 water or even acidic water above the proposed isoelectric point (~pH 3-3.5) and so all simulation results have lower pH and, as such, their results would be expected to depend but weakly on the acid concentration. Rarely do simulations involve or allow either the ionization of water molecules or the recombination of the ions. Additionally, the methods used have not been shown to be good predictors of the known physical chemistry of bulk liquid water. Particularly misleading may be methods based on the results for small clusters as it is known that the stability of such clusters is due to maximizing the number of hydrogen bonds and van der Waals interactions and minimizing putative links out from the cluster. Water clusters within bulk liquid water, however, are strongly influenced by the surrounding water molecules and similar effects (if anisotropic) are expected at interfaces. Overall, the results of such simulations should not be interpreted recklessly but with a caution that is not always apparent.</p>
<p>Simulations generally show lower structuring in water than reality. They may use models that give a much lower melting point for water, consequent upon their formation of less structured liquid water and hence a higher entropy change on freezing (DS), or even the wrong structure for the ice formed. It is surprising how much trust has been placed on the results of water surface simulations, when the errors encountered using current models in predicting the properties of bulk water are considered. Simulations of hydrogen ions within the surface present problems due to the high effective concentration necessarily involved and the thinness of the surface examined; both factors necessitated by the need to avoid excessive calculation time. Also, the diffusion of these ions is often dealt with in a way that is not realistic. Both ions translate preferentially through the Grotthuss mechanism when affected by electric fields and such fields are very important at interfaces. However, within many simulations they move around by conventional diffusion, which should strongly depend on what ions are used, e.g. H <sub>3</sub>O<sup>+</sup>, H<sub>5</sub>O<sub>2</sub><sup>+</sup>, H<sub>9</sub>O<sub>4</sub><sup>+</sup>, OH<sup>-</sup> , H<sub>7</sub>O<sub>4</sub><sup>-</sup>, etc. Also, image charges would place and hold a surface hydrogen ion equidistant between the two equal attractors of the hydroxide ion and its image charge. The greater mobility of hydrogen ions would ensure that it would respond to the field first and preferentially seek out the surface.</p>
<p><em>Ab initio</em> studies are particularly limited by high computational cost and cannot include more than a very few molecules. Although early Monte Carlo studies on isolated clusters indicated that the hydroxonium ion prefers the interior of the clusters (Svanberg and Pettersson, 1998), later  studies, including density functional analysis, suggest that they prefer the exterior of the cluster (Buch et al. 2007; Vácha et al. 2007). Note however that such clusters contain mainly surface molecules, are charged particles and not neutral and are acidic with a pH equivalent to less than zero; with hydrogen ion concentration at least three orders of magnitude higher than those present at the lowest isoelectric points proposed. The preference of hydrogen ions for the surface of small clusters seems mainly due to their inability to form isotropic hydrogen bonding links (see later). Buch et al. (2007) also used slab simulations with empirical potentials based on their, possibly biased and misleading, results for small clusters. They claimed that the 3 kcal mol<sup>-1</sup> stabilization of the proton at the surface, that they found, is equivalent to 150-fold increase in H<sup>+</sup> at the surface compared with the bulk and claimed a surface pH of about 4.8, with lower bound of  about 1.9. Similar calculation for hydroxide showed a weak (~1-2 kcal) preference for the bulk giving a pOH in the range 7.7-8.4 at the surface. Clearly, a combination of these values would give a pKw of about 12-13 or lower rather than the bulk  pKw of 14. However, this calculation takes no notice of the restricted sites available within the model for surface H<sup>+</sup> or the depth of the surface layer. Also, repeats of this simulation were reported to more often than not produce recombined water molecules and only certain unlikely high-energy initial configurations allowed the simulation to proceed (Buch et al. 2007).</p>
<p>The structuring of the interface at simulated solid hydrophobic walls derives, to some extent, from the prevention of the surface waves that otherwise tend to destructure time-averaged liquid-gas interfaces. Additionally, the van der Waals attraction for the surface increases the interface density, when compared to the liquid-gas interface. Kudin and Car (2008) used <em>ab initio</em><sup>-</sup> and H<sup>+</sup> are surface active with OH<sup>-</sup>(H<sub>2</sub>O)<sub>4</sub><sub>5</sub>O<sub>2</sub><sup>+</sup>(H<sub>2</sub>O)<sub>4</sub> sitting on surface with the lone pair on one, but not the other, of the O-atoms (Fig. 7b) pointing away from the bulk water. The hydrophobic surface attracts the hydroxide ions apparently in contrast to the situation supposed at the water-air hydrophobic surface. Also, the hydrogen ion delocalizes from the surface more readily due to the Grotthuss shuttle<br />
(Fig. 8b) sitting on the surface with its O-H pointing away from the bulk water and H<br />
Vácha et al. (2008c) investigated the behavior of hydronium and hydroxide at water/hydrophobic medium and water-vapor interfaces using molecular dynamics simulations. The rigid wall interface strongly structures water and weakly adsorbs hydroxide ions. In pure water, their calculations show surface enhancement of hydronium but not hydroxide, by one or two orders of magnitude. Vácha et al. (2008b) later state that the mechanism for the adsorption of hydroxide ions next to hard attractive walls may not be applicable to the water-air interface. The reasoning behind this conclusion is not clear however.</p>
<p>The charge on the surface of just theoretical water (H <sub>2</sub>O, modeled without dissociation), gives a change in the charge across the surface dependent on the depth of the surface examined (Vrbka and Jungwirth, 2006). Thus overall it is negative (relative to a positive bulk) but where the very outer layer of the interface (next to the gas) is more positive (Goh et al. 1988). They report the  probability that this outer (gas-facing) positive contribution is due to the almost-free singly-linked water molecules compensating for the negative quadrupole and dipole contributions in the denser part of the surface layer (Kuz&#8217;min, 2000). This effect, however, is not seen in the surface spectroscopy, where such water molecules would be expected to be seen but their expected resonances are very low or absent. Mucha et al. (2005) shows that there is little preference of H<sup>+</sup> over Cl<sup>-</sup> in the surface of HCl solutions, but that the hydroxonium ion is preferred more than the sodium ion in NaCl solutions. Perhaps, the hydroxonium ion can more easily exist all around surface chaotropic ions such as Br<sup>-</sup> in HBr whereas Na<sup>+</sup> ions only sit on the bulk side in NaBr. Hydroxide ions are found on surface side of Na<sup>+</sup> ions in NaOH. Petersen et al. (2004a) studied the hydrated proton at the water liquid-vapor interface using the multistate empirical valence bond (MS-EVB) methodology, which enables its migration via the Grotthuss shuttle mechanism. They found that the hydrated proton behaved as an amphiphile and displays a marked preference for water liquid-vapor interfaces. Their model included a chloride counterion but no hydroxide ions.</p>
<p><strong>Autoionization and Dielectric</strong></p>
<p>One of the unusual properties of water is its ability to self-ionize. Dissociation is a rare endothermic event normally followed by the ions recombining within a few femtoseconds. Separation of the ions is a rarer event, occurring only about twice a day for each molecule; that is, only once for every 10 <sup>16</sup> times the hydrogen bond breaks. In these cases the localized hydrogen bonding arrangement breaks before allowing the separated ions to return (Geissler, 2001) and the pair of ions (H<sup>+</sup>, OH<sup>-</sup>) hydrate independently and translate away or exchange with other water molecules.</p>
<p>2 H <sub>2</sub>O(aq) ↔ (H<sub>3</sub>O<sup>+</sup> + OH<sup>-</sup>)(aq) ↔ H<sub>3</sub>O<sup>+</sup>(aq) + OH<sup>-</sup>(aq)</p>
<p>The ions stay separated for about 70 ms before finding a partner to recombine with, but as the extra proton exchanges on the same timescale as hydrogen bond breakage, the excess proton visits up to over a millionmolecules of water during its travels. The ions tend to recombine when separated by only one or two water molecules, but the greater strength and extent of hydrogen bonding that is found at lower temperatures facilitates this process.</p>
<p>In pure bulk liquid water, the concentrations of these ions are equal and about 10 <sup>-7</sup> M, giving a pH of close to seven. There is no good reason to presuppose that the same will hold at the gas-liquid interface. Higher density within the surface causes the ionization to increase (Bandura and Lvova, 2006), but this can only have a very small effect by itself.</p>
<p><img title="vol1_chaplin_fig5.jpg" src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig5.jpg" alt="vol1_chaplin_fig5" width="500" height="231" /><em><strong><br />
Figure 5:</strong> The H2O  with ‘free&#8217; dangling O-H (a1) held by two donor and one acceptor H2O at the surface is more easily ionized in response to surface charge fluctuations including image charge repulsion. The ionization is even more preferred if a further third water donates its hydrogen bond.  Once ionized (b1) it is difficult for the hydroxide to move inwards by normal diffusion rather than by the Grotthuss mechanism.</em></p>
<p><em> </em>Beattie (2007) puts forward the case for the autoionization of water increasing by about six orders of magnitude because of surface effects. Such a shift would result in [H<sup>+</sup>] = [OH<sup>-</sup>] = 10<sup>-4</sup> M at the pure water surface. The reason for this large change is proposed to be due to a number of favorable phenomena. There is likely to be large potential drop across the interface of the order of about 10<sup>9</sup> V m<sup>-1</sup> (Beattie, 2007), although the figure from Randles (1977) and Kathmann et al. (2008), although large, would be about an order of magnitude lower. Water molecules with ‘free&#8217; dangling O-H groups pointing out and away from the interface are more easily ionized than those isotropically situated, as can be determined from the change in the charge distribution using <em>ab initio</em> simulations. This effect is more marked if the surface water molecule has accepted three hydrogen bonds plus donating one to the water molecule that accepts the proton on ionization (Fig. 5). Autoionization should, therefore, be different within the surface from in the bulk, promoted by these surface electric fields and the anisotropic surface but reduced by the lower dielectric.</p>
<p>Consider a surface with a fluctuating charge causing irregular potential gradients. Hydrogen ions will respond faster than hydroxide ions to such changeable electric fields. Also, movement of the hydrogen ion charge is less disruptive of a tetrahedral hydrogen bonding arrangement than hydroxide ion due to the latter&#8217;s need for tetra-hydrogen bond acceptance (Tuckerman et al. 2006). As the surface structuring of water involves stronger hydrogen bonding, this is likely to further accentuate the difference in response between the two ions. Thus, it seems most likely that hydrogen ions rather than hydroxyl ions will enter the bulk, via proton hopping, from any excess ionization at the surface, so leaving the surface more negative. Once connecting proton wires due to extensive hydrogen bonding are broken, hydrogen or hydroxyl ion charges leave the surface. They may only return through the much slower process of molecular diffusion until such hydrogen-bonded proton wires reconnect.</p>
<p>Image charge effects may also help the ionization, as a hydrogen ion once formed necessarily beneath the surface will be repelled away from the surface. Once displaced, such hydrogen ions are affected by their image charge and cannot so easily return. Also at the surface, the loss of water by evaporation would tend to break up hydrogen-bonded wires connecting the hydroxide with the hydrogen ion. A hydroxide that tends to leave the surface, on the vapor side, will be held to the surface by an attractive image charge. Also if the hydroxide is about to evaporate, the charge will be held at the surface while the hydroxide grabs a proton from below to evaporate leaving a resultant hydroxide ion to remain on the surface. This cannot occur with some ions but can for H <sup>+</sup>, Cl<sup>-</sup> and NH<sub>4</sub><sup>+</sup>.</p>
<p>The high fields created within the interface increase such autolysis. Surface facing hydrogen-donating water molecules, lying close to the interface would also encourage, and be encouraged by, the ionization. These water molecules could hydrogen-bond to surface hydroxide to form HO <sup>-</sup>(H<sub>2</sub>O)<sub>4</sub> and so encourage the interfacial hydroxide. Both the oxonium ions and hydroxide ions have highly anisotropic hydrogen bonding that should increase their surface activity and relatively discourage bulk hydration compared with other ions.</p>
<p>Beattie et al. (2009) reported that the concentration of hydroxide present in homogenised oil in water is much greater than in neutral water, proving that there is increased autolysis driven by the adsorption of hydroxide ions at the oil-water interface in emulsions formed in oil-water (1.1 mm diameter, with surface 1.1 x 10 <sup>6</sup> cm<sup>2</sup> L<sup>-1</sup>). Lützenkirchen et al. (2008) put forward a model for the charging of hydrophobic electrolyte surfaces based upon enhanced autolysis within the structured interfacial water, with a pK<sub>w</sub> of about 7 and hence an isoelectric point of about pH 3.5.</p>
<p>Beaglehole (1987) noted that surface heating caused a rapid change in the sign of the coefficient of ellipticity followed by a slower relaxation back, but only in the presence of dissolved gas. He attributed this to surface structural changes involving surface gas replenishment. An interesting effect of gas on ionization is shown by degassing experiments whereby degassing allows colloidal suspensions of oils to be more easily formed (Francis et al. 2006). Degassing also causes an increase in conductivity from 0.07 mS cm <sup>-1</sup> at 25°C to about 1.2 mS cm<sup>-1</sup><sub>w</sub> to 12.8. It would seem, however, that this effect may work against the greater ionization of water within the interface as this water will have greater gas content than the bulk water. However, the effect may be different at the surface where the bound gas molecules do not need to be isotropically surrounded by water molecules as they do in the bulk, with the greater energy cost so entailed.<br />
(Pashley et al. 2005). This is equivalent to a decrease in the pK<br />
<strong> </strong><br />
<strong>Hydrogen and Hydroxide Ions</strong></p>
<p>Buch et al. (2007) present a number of studies showing that the surface of neutral water is acidic. Their work has received a wide distribution but some counter-argument (Beattie, 2008). The rationale for this acidic behavior is easily understood. The hydroxonium ion only hydrogen bonds to three water molecules, which necessarily are placed to one side of the molecule. These preferentially hydrogen bond to the bulk of the liquid water whereas the non-hydrogen bonded lone-pair side points outwards into the gas phase and so interferes (disrupts) least with the normal hydrogen-bonding network found in liquid water. The anisotropic interaction of hydronium ions with the surrounding water molecules is in contrast to the isotropic behavior of other cations. Indeed, other small cations much prefer the bulk environment rather than the surface. This simple concept, which necessitates the hydronium ion being placed at the very outside of the liquid-gas interface, is backed by a number of studies. However, very similar arguments can be put forward to support the hydroxide ion also preferentially lying at the water-gas interface due to its equally anisotropic hydrogen bonding.</p>
<p>A preferred orientation of water molecules at the surface may cause a charged surface and help adsorb hydroxonium or hydroxide ions, dependent on the charge. Both OH <sup>-</sup> (Boström et al. 2005; Schechter et al. 1998) and H<sub>3</sub>O<sup>+</sup> (Petersen et al. 2004a) can sit at gas-water interfaces, although clearly not at the same time due to their rapid recombination to form H<sub>2</sub>O within this lower dielectric interface. Both ions are ionic kosmotropes, creating order and forming stronger hydrogen bonds with surrounding water molecules. The hydrogen ion donates to three strong hydrogen bonds but is a very much weaker hydrogen bond acceptor than a water molecule whereas the hydroxide ion accepts three or four strong hydrogen bonds but is a very much weaker hydrogen bond donor than a water molecule. In both cases, if the number of interacting water molecules is reduced the remaining hydrogen bonds are stronger and more linear.</p>
<p><em><strong><img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig6.jpg" alt="vol1_chaplin_fig6" width="401" height="388" /></strong></em></p>
<p><em><strong>Figure 6:</strong> The water (a), hydroxonium ion (b) and hydroxide ion (c) are drawn using ab initio calculations using the 6-31G** basis set and HyperChem 8 Professional. Bond distances, angles and atomic charges are derived from these effectively gas phase calculations. On ionization, the charge on the oxygen atom in the hydroxonium ion is reduced by 34% and the charge on the hydrogen atom in the hydroxyl ion is reduced by 63%.</em><br />
The oxonium ion (H<sub>3</sub>O<sup>+</sup>) has a flattened trigonal pyramidal structure (Fig. 6b). It forms the core of the &#8216;Eigen&#8217; cation (H<sub>9</sub>O<sub>4</sub><sup>+</sup>, Fig. 7c). The strength of the donated hydrogen bonds are over twice as strong as those between H<sub>2</sub>O molecules in bulk water (Markovitch and Agmon, 2007), such that the H<sub>3</sub>O<sup>+</sup> cation can be considered as H<sub>9</sub>O<sub>4</sub><sup>+</sup> in solution. The polarization causes these first shell water molecules to each donate two further hydrogen bonds, but poorly accept, with strengths still somewhat higher than bulk water (Markovitch and Agmon, 2007). Second shell water molecules also donate two hydrogen bonds, but accept only one with a rather weak hydrogen bond, with strengths still fractionally higher than bulk water (Markovitch and Agmon, 2007). The bias towards donated rather than accepted hydrogen bonds, within the two-shell H<sub>21</sub>O<sub>10</sub><sup>+</sup> ion cluster, requires that this hydrated ion must be surrounded by a zone of broken hydrogen bonds. This is confirmed by infrared spectra that show that the presence of an H<sub>3</sub>O<sup>+</sup> ion extends to affect the hydrogen bonding of at least 100 surrounding water molecules (Mizuse et al. 2007).<br />
<img title="vol1_chaplin_fig7.jpg" src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig7.jpg" alt="vol1_chaplin_fig7" width="500" height="226" /><strong><br />
Figure 7:</strong><em> The asymmetric (a) and symmetric (b) Zundel dihydronium ions (H5O2+) and the Eigen cation (c, H9O4+) are drawn using ab initio calculations using the 6-31G** basis set and HyperChem 8 Professional. Bond distances, angles and atomic charges are derived from these effectively gas phase calculations. The charges on the oxygen atoms are almost back to their values (95-98%) in the water molecule (Fig. 6a).</em></p>
<p>The hydroxonium ion exchanges its excess proton by binding strongly to another water molecule to form exchanging H <sub>5</sub>O<sub>2</sub><sup>+</sup>. The presence of these three minima for the proton, of similar energy, lying so close between the two H<sub>2</sub>O oxygen atoms, eases the transfer of protons between water molecules. The proton moves very quickly (&lt; 100 fs, Woutersen and Bakker , 2006) between the extremes of triply-hydrogen bonded H<sub>3</sub>O<sup>+ </sup>(H<sub>9</sub>O<sub>4</sub><sup>+</sup>, the Eigen cation, Fig. 7c) ions through symmetrical H<sub>5</sub>O<sub>2</sub><sup>+</sup>ions (the Zundel cation, Fig. 7b) (Marx et al. 1999), with the low potential energy barriers washed out by the zero-point motion of the proton (Woutersen and Bakker , 2006). Certainly, hydrogen ions at the surface of water cannot be considered as permanent features as their charges are expected to move between water molecules on a picosecond timescale. Note that the tiny movement of the proton gives rise to a much greater movement of the center of positive charge and consequent electric field shifts. Preference for the Zundel cation structure occurs when its outer hydrogen bonding is approximately isotropic as in the tetrahedral  H<sub>13</sub>O<sub>6</sub><sup>+</sup> (Headrick et al. 2005) and is, therefore thought less likely than the anisotropic Eigen cation to be naturally found at the gas-liquid interface.</p>
<p>The Eigen cation (H <sub>9</sub>O<sub>4</sub><sup>+</sup>) is the most stable hydrated proton species in liquid water, and the most likely hydrated protonated water cluster to be found at the gas-liquid interface.  As shown (Fig. 7c), it may support the presence of ‘free&#8217; dangling O-H groups on its pendant hydrogen-bonded neighboring water molecules. However, such structuring would restrict the movement of charge via the Grotthuss mechanism.</p>
<p>The hydration of the hydroxide ion (Fig. 6c) is neither as well-known nor simply described as the hydrogen ion. Most experimental structural work on this hydrated ion involves concentrated or very concentrated solutions, containing structure-controlling cations, compared with the study of acids that generally involves less-disruptive anions. Within such experimental environments, the basic tetrahedral structuring of water is destroyed and the specific effects of solvent-separated and contact ion pairs confuse any results. The hydroxide ion strongly interacts with other water molecules to give clusters and is essentially absent, as such, in aqueous solution. The extent of this hydration is, however, less clear.</p>
<p>Although many recent studies have attempted to determine the preferred hydration of the hydroxide ion in solution, there is no consensus. In particular, the hydrogen bonding capacity utilizing the donated OH <sup>-</sup> proton, remains in serious doubt. No local minima is found in <em>ab initio</em><sup>-</sup><sub>2</sub>O finds the free hydroxide O-H stretch at higher frequency indicative of very weak or absent  hydrogen bonding (Smiechowski and Stangret, 2007).<br />
calculations for a water hydrogen-bonded  to the OH<br />
It is probable, however, that a fleeting very weak hydrogen bond may facilitate the OH<sup>-</sup> transport mechanism (Botti et al. 2004a). The lack of such a weak hydrogen bond may be of importance in stabilizing such ions at the water-gas interface, as surface oriented hydroxide ions would not have any water molecules in this position. In contrast with the movement of hydrogen ions, which does not require a donor hydrogen bond to the oxonium ion, this may cause a much slower diffusion of surface hydroxide ions to the bulk relative to hydrogen ions. However, this difficulty is contra-indicated by the finding of a low energy barrier for proton transfer (~0.9 kJ mol<sup>-1</sup>) in H<sub>3</sub>O<sub>2</sub><sup>-</sup>, so allowing easy equilibration of the proton&#8217;s position (Samson and Klopper, 2002) as occurs with H<sub>5</sub>O<sub>2</sub><sup>+</sup>.<br />
<em><strong><br />
<img src="http://www.waterjournal.org/images/figs/vol1/chaplin/figures/vol1_chaplin_fig8.jpg" alt="vol1_chaplin_fig8" width="450" height="680" /><br />
Figure 8:</strong> The hydroxyl ion, hydrated by three (a) and four (b) water molecules are drawn using ab initio calculations using the 6-31G** basis set and HyperChem 8 Professional. Bond distances, angles and atomic charges are derived from these effectively gas phase calculations. The charge on the hydrogen atom of the hydroxyl ions is well below (~75%) its value in the water molecule (Fig. 6a).</em> proton unless held by an extensive, and intrinsically somewhat unlikely, network of bridging hydrogen bonds from sixteen other water molecules (Novoa et al. 1997). The nearest aqueous oxygen atom to the hydroxide proton appears to average about 0.25 nm, almost twice the distance of the hydroxide ions accepting hydrogen bonds (~0.14 nm), well outside the normal hydrogen-bond signature distance of  0.15-0.21 nm (Botti et al. 2004b) and at a distance often considered as showing the absence of a bond (Khan, 2000). The O-H stretch vibration behaves as the free hydroxyl group in small gas-phase clusters (Robertson et al. 2003) and both concentrated and more dilute hydroxide solutions (Corridoni et al. 2007). In confirmation, Fourier transform infrared (FTIR) spectroscopy of HDO isotopically diluted in H<br />
The hydroxide ion (OH<sup>-</sup>, Fig 6b) is a very good acceptor of hydrogen bonds, with three to four water molecules binding strongly to form H<sub>7</sub>O<sub>4</sub><sup>-</sup><sub>9</sub>O<sub>5</sub><sup>- </sup>(Fig 8b), as its lone-pair electron distribution around the hydroxide ion is smeared out and not tetrahedrally situated (Tuckerman et al. 2006). As the hydration increases, the hydroxide O-H bond becomes shorter, its hydrogen atom more positive and its oxygen atom less negative. The hydrogen bonds become longer and individually weaker whereas the hydrogen bonded water molecules become less polarized. The tetrahedral ion H<sub>7</sub>O<sub>4</sub><sup>-</sup>(Fig. 8a) is probably the most stable hydrated  hydroxide ion (Asthagiri et al. 2003) being slightly energetically favored over  H<sub>3</sub>O<sub>2</sub><sup>-</sup> (Agmon, 2000). It hydrogen bonds well at the surface of small clusters and even in the gas phase (Meot-Ner and Speller, 1986). Hydroxide hydrogen bonded to four water molecules have been recently reported using neutron diffraction, with empirical structure refinement, (Botti et al. 2004b), and X-ray absorption spectroscopy (Cappa et al. 2007), with both studies utilizing concentrated hydroxide solutions. It should be noted, however, that at such high concentrations most, if not all, water molecules must be within the first shell of at least one ion (Botti et al. 2004a) and the normal tetrahedral clustering of water, as found in more dilute solutions, has been destroyed. Certainly the Raman spectra of hydroxide solutions changes when the solution is diluted below OH<sup>-</sup>:H<sub>2</sub>O 1:20 (Corridoni et al. 2007). Also, HO<sup>-</sup>(··HOH)<sub>4</sub>was found to be energetically unfavorable using quasi-chemical theory (Asthagiri et al. 2003) and spectroscopic studies indicate the 4<sup>th</sup> H<sub>2</sub>O in HO<sup>-</sup>(··HOH)<sub>4</sub> to be preferably hydrogen bonded to the other three forming a second shell (Robertson  et al. 2003).<br />
(Fig 8a) and H<br />
The strong hydrogen bonding between the hydroxide ion (OH<sup>-</sup>) and its first shell water molecules is thought responsible for the very large temperature dependence of the hydroxide reorientation, with three-fold increase in activation energy at low temperatures (&lt; 290 K, Thøgersen et al. 2008). Although thought possibly due to the presence of hyper-coordinated HO<sup>-</sup>··(HOH)<sub>4</sub> clusters (Thøgersen et al. 2008), such an effect could equally well be due to dominant tetrahedral HO<sup>-</sup>··(HOH)<sub>3</sub><sup>-</sup>(··HOH)<sub>4</sub> ion (Fig. 8b) has importance in dilute solutions beyond its, perhaps transient,  formation during diffusion. It is worth noting, perhaps, that Eigen cations H<sub>9</sub>O<sub>4</sub><sup>+</sup>, but not hydrogen bonded hydroxyl ions (e.g. H<sub>7</sub>O<sub>4</sub><sup>-</sup>), can simply reorient  by inversion (like a wind-blown umbrella) with an activation energy far less than that of a hydrogen bond and this may occur as an alternative, or even preferred, pathway to rotation within dynamic hydrogen bonded clusters. Fixing the hydroxonium ion on the surface would tend to prevent this inversion and reduce its presence there.</p>
<p><strong>Conclusions</strong></p>
<p>The structure of the surface of water is not completely understood but some information has been determined. It is well-structured and contains clusters of water molecules held by strong hydrogen bonds As such it interacts better with polarizable and low surface charge density chaotropic ions but poorly with kosmotropic ions, except for hydrogen or hydroxyl ions. The ‘natural&#8217; state of such interfaces appears to be negative (Schechter et al.1998; Tammet et al.2008) as at hydrophobic surfaces (Tandon et al. 2008; Zangi and Engberts, 2005). This view is greatly influenced by the undisputedly negative zeta potential of such interfaces, which remains the only unambiguous experimental conclusion.</p>
<p>The inference that the surface of pH-neutral water is positive cannot be fairly made from current modeling studies. The pH values of the modeled systems appear to be well below the experimentally determined isoelectric point. For example, if just one hydronium ion to 71 water molecules (as Buch et al. 2007), the pH would be 0.1 and even if there were 1000 water molecules the pH (1.3) is still far below the expected isoelectric point of at least pH 3. Therefore, such modeling does not predict the effects under neutral conditions. Note that the presence of non-combining hydroxide ions, within the simulation, does not change this argument. In addition, the effects of the gas phase are not included in the modeled surface nor are the poor predictions, otherwise made using these models, generally stated. The counter-argument that all the experimental zeta potential evidence by many researchers over many years in many places (and which is self-consistent) is faulty due to adventitious negatively charged adsorbents (all coincidently apparently possessing the same properties and concentrations) has no obvious foundation apart from the wishfulness of some.</p>
<p>In acid solutions, it is likely that some oxonium ions (e.g. H <sub>3</sub>O<sup>+</sup>) are present at the surface where they preferentially orient. Their dipoles point away from the surface as they only poorly accept hydrogen bonds, but strongly donate three, with their oxygen atom pointing at the surface (Petersen et al. 2004a). This would certainly be expected to encourage these ions to sit at the interface in the absence of competing hydroxyl anions. However, there is no evidence for their excess elsewhere within the surface layer and it remains unproven whether they ever produce a net surface excess without the presence of surface-active counterions, such as iodide. At neutral pH, there is the experimental zeta potential evidence for a lower concentration of hydrogen ions than hydroxide ions at the surface.</p>
<p>Vácha et al. (2008b) has suggested that techniques scrutinizing the water-gas interface from the vapor side can see it as acidic, while those examining it from the aqueous bulk side it will appear as basic. However, there seems little evidence in support as no experimental method has unambiguously shown that the surface is positive but several show it unambiguously as being negative (Hänni-Ciunel et al. 2009; Beattie et al. 2009). As hydroxide ions seem to be preferred over hydrogen ions, above a pH of about three, this generally reinforces the interface&#8217;s negative charge compared with the bulk.</p>
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<p><strong>Web References</strong></p>
<p>1.  Chaplin M (2008a). Anomalous properties of water, <a href="http://www.lsbu.ac.uk/water/anmlies.html">http://www.lsbu.ac.uk/water/anmlies.html</a> [12-12-2008].</p>
<p>2.  Chaplin M (2008b). Nanobubbles, <a href="http://www.lsbu.ac.uk/water/nanobubble.html">http://www.lsbu.ac.uk/water/nanobubble.html</a> [12-12-2008].</p>
<p><strong>Discussion with Reviewers</strong></p>
<p><strong>James K. Beattie<sup>1</sup>: </strong> I have just one question for Dr. Chaplin, but it is a large and generic one. He concludes that the surface of neutral water is negative. How then is all of the evidence presented in the bulk of his article to be interpreted, or reinterpreted?  Perhaps it would take another article of similar length to address this question comprehensively, but some selected and significant aspects could be considered now.</p>
<p>For examples:<br />
1. How are the negative balloelectric particles generated by the splashing of rain drops consistent with a negative surface but an electrically neutral double layer within the drop?<br />
2. What alternative explanation of the results of Petersen and Saykally would be consistent with the conclusion that the surface is negative due to hydroxide ions, an interpretation that they reject?<br />
3. How would the hydroxide ions affect the refractive index of the surface?<br />
4. How does the presence of hydroxide ions affect the surface tension of water, and how does it modify the effect of other ions on the surface tension?&#8217;</p>
<p><strong>Martin Chaplin</strong> : This question is certainly ‘large.&#8217; In my paper I present a variety of evidence concerning the surface of water. I felt that the subject required me to come to a firm conclusion, rather than to ‘opt out&#8217; and leave that up to the reader. Having come to my own conclusion that the surface of neutral water is negative, Dr. Beattie wishes me to go further and present more proof. However, if there were further proof, I would have given it. Certainly, there is room for further debate. Below, I attempt to answer the particular points raised.</p>
<p>1. The key fact concerning the balloelectric effect (H. Tammet, U. Hõrrak and M. Kulmala, Negatively charged nanoparticles produced by splashing of water, <em>Atmos. Chem. Phys. Discuss</em>. <strong>8</strong> (2008) 16609-16641) is that smaller water droplets are naturally negatively charged rather than positive. These small particles possess a net charge and are not neutral; so they do not possess an electrically neutral double layer. Small droplets have a larger surface area for their mass than larger droplets such that any surface stabilization of positive or negative ions is expected to be reflected in the charge of the smaller particles. As the particles are found by experiment to be negatively charged, the stabilization offered to negatively charged ions at the surface must be greater that that for positively charged ions. Consequently, larger water droplets, produced simultaneous with the small particles, possess the residual positive charge. There remains the possibility with this phenomenon that the charges are due to other species rather than hydroxide and hydrogen ions. However the absence of positively charged nanoparticles does strongly indicate the hydrogen ions are not as surface active as others suggest.</p>
<p>2. Petersen and Saykally hit the nail on the head when they state &#8220;Our experiments are not able to directly probe the hydronium concentration at the water surface, &#8230;&#8221; (Petersen PB, Saykally RJ (2008). Is the liquid water surface basic or acidic? Macroscopic vs. molecular-scale investigations. <em>Chem Phys Lett </em><strong>458</strong> (2008) 255-261). Their conclusions are based on interpretations rather than being directly given by experiment. Some experimental data Petersen and Saykally discuss involves the behavior of the surface active iodides. Hydrogen ions and associated iodide ions are drawn more into the surface than sodium or potassium iodide. However, as we know that sodium ions (and to a lesser extent potassium ions) are certainly expelled from the surface, it is perfectly reasonable to expect their associated iodide ions to be less prevalent there. The hydroxide data presented is only significant at high hydroxide ion concentration when, naturally, the cation concentration is equally high and when there is effectively only a single shell, or less, of water around the ions. This is grossly inappropriate for the likely site concentration at the surface of neutral water. It is extremely likely that any putative adsorption sites would be  totally swamped by this excess and then the (near zero) free energy of adsorption reported merely reflects the difficulty over cramming so many ions (both cations and anions) near to the surface.</p>
<p>3. Little work seems to have been done on the refractive index of solutions or their surfaces. The refractive index would be expected to rise whether there is an increase in hydrogen bond strength or an increase in solute (accompanied by broken hydrogen bonds) at the surface, so refractive index measurements may be poor discriminators for the surface structure.</p>
<p>4. I discuss surface tension at length in my paper. Surface tension is affected by both the cations and anions present and the total effect is not simply additive. Ammonium hydroxide and hydrogen chloride both lower the surface tension, but ammonium chloride, sodium hydroxide and sulphuric acid all raise it. Thus surface tension has difficulty in discriminating individual effects. The surface tension lowering effects seem to be mainly due to the surface active neutral species known to be present in the solutions where surface tension lowering is noted. Also worthy of comment is that the modeling studies do not generally allow the formation of the neutral species such as water (from the recombination of hydrogen and hydroxide ions), hydrogen chloride or ammonia.&#8217;</p>
<p><strong>Regine von Klitzing<sup>2</sup>:</strong></p>
<p>1 <strong>. </strong>The main conclusion of your article is that the air-water interface is negatively charged. Concerning the adsorption of ions at the air-water interface the question arises: &#8220;What is the driving force for the accumulation of negatively charged ions at a negatively charged interface?&#8221;  This is contrary of what one would expect from the electrostatic point of view.</p>
<p>2. Due to the fact, that in theory only the first few layers of the interface are considered, whereas in practical experiment a bigger scale of the interface is measured, can it be, that theory and experiments are not excluding each other? Are theory and experiments compatible, if the same dimensions are considered during the analysis?&#8217;</p>
<p><strong>Chaplin:</strong></p>
<p>1. It is clear that like charges do not attract, but such a view wrongly attributes cause and effect. The reasons why the surface accumulates a negative charge are the same reasons why they may accumulate further negative charges. The actual concentration of negative charges is always quite low compared with the number of water molecules present. There will be an attraction to positively charged ions that do not enter the surface layer but will cause shrinkage of the double layer.</p>
<p>2. It would be satisfying if the theoretical and experimental approaches were to be so easily thought compatible. However, this is not the case. Theoretical approaches are basically flawed and these flaws should be more widely recognized. Until our water models can be shown to behave well in the bulk phase diagram, less reliance on them should be made at the more complex gas-liquid interface. It is true, however, that theory and experiments have vastly different scales and these differences should be additionally accommodated within the resultant discussions.&#8217;</p>
<p><sup>1</sup> <em>Associate Professor, School of Chemistry, University of Sydney, Australia.<br />
</em><sup>2 </sup><em>Professor, Technical University Berlin, Germany.</em></p>
<p>http://www.waterjournal.org/archives/72-chaplin-full-text</p>
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		<title>The Fifth Annual Conference on the Physics, Chemistry and Biology of Water</title>
		<link>http://korotkov.org/water/2010/10/the-fifth-annual-conference-on-the-physics-chemistry-and-biology-of-water/</link>
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		<pubDate>Thu, 21 Oct 2010 11:54:01 +0000</pubDate>
		<dc:creator>admin</dc:creator>
				<category><![CDATA[Articles about Water]]></category>
		<category><![CDATA[Biology of Water]]></category>
		<category><![CDATA[Chemistry and Biology of Water]]></category>
		<category><![CDATA[The Fifth Annual Conference on the Physics]]></category>

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		<description><![CDATA[The Fifth Annual Conference on the Physics, Chemistry and Biology of Water will be held on October 21-24, 2010 at the Grand Summit Resort Hotel and Conference Center in West Dover, Vermont. &#160; &#160; A DVD set of the proceedings of the Third Annual Water Conference is available at a cost of $375.00 plus shipping.<a href="http://korotkov.org/water/2010/10/the-fifth-annual-conference-on-the-physics-chemistry-and-biology-of-water/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p><strong>The Fifth Annual Conference on the Physics, Chemistry and Biology of Water will be held on October 21-24, 2010 at the Grand Summit Resort Hotel and Conference Center in West Dover, Vermont. </strong></p>
<p>&nbsp;</p>
<div id="attachment_210" class="wp-caption alignnone" style="width: 310px"><strong><a href="http://korotkov.org/water/wp-content/uploads/2010/10/Jerry.jpg"><img class="size-medium wp-image-210" title="Water conf" src="http://korotkov.org/water/wp-content/uploads/2010/10/Jerry-300x132.jpg" alt="Water conf" width="300" height="132" /></a></strong><p class="wp-caption-text">Water conf</p></div>
<p>&nbsp;</p>
<p><strong><span id="more-206"></span></strong><br />
A DVD set of the proceedings of the Third Annual Water Conference is available at a cost of $375.00 plus shipping. An order form is available at the above-mentioned website. A limited number of DVD sets of the Second Annual Water Conference&#8217;s proceedings are also available.<br />
<strong>For details, visit: </strong><a href="http://watercon.org/" target="_blank">www.watercon.org</a></p>



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		<title>Dye Exclusion and Other Physical Properties of Hen Egg White</title>
		<link>http://korotkov.org/water/2010/10/dye-exclusion-and-other-physical-properties-of-hen-egg-white/</link>
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		<pubDate>Thu, 21 Oct 2010 11:50:10 +0000</pubDate>
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				<category><![CDATA[Articles about Water]]></category>
		<category><![CDATA[Cameron]]></category>
		<category><![CDATA[Egg White]]></category>
		<category><![CDATA[Physical Properties]]></category>

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		<description><![CDATA[Dye Exclusion and Other Physical Properties of Hen Egg White Cameron, I1,* 1 University of Texas Health Science Center, Department of Cellular and Structural Biology, San Antonio, Texas 78229 * Correspondence: Tel.: (210) 567-3817; E-mail: cameron@uthscsa.eduThis e-mail address is being protected from spambots. You need JavaScript enabled to view it ; Key Words: Egg white,<a href="http://korotkov.org/water/2010/10/dye-exclusion-and-other-physical-properties-of-hen-egg-white/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p><strong>Dye Exclusion and Other Physical Properties of Hen Egg White</strong></p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig2.jpg" alt="fig2" width="570" height="279" /></p>
<p>Cameron, I<sup>1,*</sup></p>
<div><em><sup>1 </sup>University of Texas Health Science Center, Department of Cellular and Structural Biology, San Antonio, Texas 78229<sup><br />
</sup></em></div>
<div><em><sup>* </sup>Correspondence: Tel.: (210) 567-3817; E-mail: <a href="mailto:cameron@uthscsa.edu">cameron@uthscsa.edu</a>This e-mail address is being protected from spambots. You need JavaScript enabled to view it ;</em></div>
<p>Key Words: Egg white, albumen, solute exclusion, vital dye, methylene blue, gel-sol</p>
<p>Received 10 May 2010; revised 22 July; accepted 24 July. Published 19 August 2010; available online 19 August 2010</p>
<p><strong>Summary</strong></p>
<p>As reported here hen egg white can be sepa­rated by sieve filtration into thin and thick albumen fractions that remain as separate non-miscible fractions. Thick albumen but not thin albumen behaves as a gel and was found to have vital dye excluding properties. Thick albumen also demonstrates swelling and shrinking under osmotic conditions and the ability to transform from a dye ex­cluding gel to a non-dye excluding more fluid sol under the influence of pressure or agitation. Thick albumen gel that had been agitated to a sol state was observed to trans­form from the non-dye-excluding sol state back to a dye excluding gel state when al­lowed to rest without agitation. These find­ings may help explain vital dye exclusion by most but not all cells.</p>
<p>&nbsp;</p>
<p><span id="more-201"></span></p>
<p><strong>Introduction</strong></p>
<p>The research focus of this laboratory has been on the physical properties of water in cells and on proteins. These physical prop­erties of water include: motion, osmotic activity, flow, sorption and the size of the bulk and the different non-bulk water frac­tions (Cameron and Fullerton 2006, 2008, Fullerton et al. 2006, 2007 and Cameron et al.1988, 1997, 2007, 2008). One of the physical properties of water in cells and on proteins left to explore was solute (dye) ex­clusion. While preparing concentrated solu­tions of proteins like bovine serum albumen, egg white albumen and egg white lysozyme for physical measures, an alternate natural source of concentrated globular protein so­lution came to mind. The natural source is hen egg white albumen. Note that the name of the specific protein type is spelled albu­min, while albumen is a generalized word referring to egg white. Egg white is read­ily available and an inexpensive source of a concentrated globular protein solution and was therefore chosen for study. This report deals with dye exclusion from the thick vs. the thin albumen fraction of hen egg white, but the report also deals with other physical properties of thin and thick albumen.</p>
<p>It is commonly held that exposure of living cells to a vital dye, like methylene blue, does not dye the living cell interior but dead cells do dye blue. There are however, reports that viable normal cells (Harris and Peters 1953), Brooks and Brooks 1941), cells ad­jacent to wounds (Marconi and Quintian 1998), Upile et al. 2007) and pre-malignant epithelial cells adjacent to the normal epi­thelial cells all do take in methylene blue as evidenced by the fact that at least their nu­cleus turns blue (Gordon et al. 2007, Chen et al. 2007). Two possible cellular dye ex­cluding mechanisms are: the semi-permea­bility of the cell’s plasma membrane and the dye excluding properties of cell’s cytoplasm.</p>
<div>A question arises from the observations re­ported above. Does the dye excluding prop­erties of cytoplasm/protoplasm, even with­out an intact cell membrane, have the ability to exclude vital dye solutes like methylene blue or other vital dyes? In at least one case, the answer is yes. This case is illustrated in Fig. 1 from Cameron et al. (1988). None of the decapsulated and membrane disruptive detergent exposed treatments resulted in dye uptake by the lens cells. It was conclud­ed that the lens cell cytoplasm, rather than an intact cell membrane was responsible for the dye exclusion in the lens cells.<img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig1.jpg" alt="fig1" width="512" height="439" /><em><strong> </strong></em></p>
<p><em><strong>Figure 1: </strong>Photographs illustrating the result of dye exclusion tests on the lens body, lens capsule, and sclera of pig eyes with and without treatment in nonionic detergents. The round-shaped speci­mens are decapsulated lens. Above and to the right of each lens is the removed capsule of that lens, and above and to the left is a piece of the sclera. The let­ters “H” and “S” refer to the bathing solutions used (“H” = Hanks and “S” = isotonic sucrose). The let­ters “B” and “T” refer to cell membrane disruptive detergents (“B” = brig 58 and “T” = triton x 100). The letter “C” refers to the unstrained control. Spec­imens in A (top paragraph), except the unstained controls were exposed to 0.1% nigrosin. Specimens in B (middle photograph was exposed to 0.1% try­pan blue, and in C (bottom photograph, were ex­posed to 0.1% methylene blue. After one hour in the dye solutions, the intact lenses were removed and their stained capsule removed. The lens body (less the capsules) was returned to the dye solution for 2 additional hours, then removed and placed on a glass plate along with its lens capsule and a piece of sclera. As shown here, none of the treatments resulted in dye uptake or staining of the lens body, whereas all of the lens capsule and sclera speci­mens took up the dye. Figure reproduced from Cameron et al. 1988 with permission of John Wiley and Sons, Inc.</em></p>
<p><strong>Experimental Observations: Meth­ods and Results</strong></p>
</div>
<p><em><strong>Observations on the distribution and on the dye exclusion properties of thin and of thick egg white albumen fractions</strong></em></p>
<p>When an egg is cracked open and dropped on to the surface of a dark hot frying pan the egg white farthest from the yolk turns white before the thicker more viscous egg white, around the yolk, turns white. This observa­tion reveals egg white to be composed of at least two major fractions.</p>
<p>An egg was cracked open and the egg white was separated from the yolk and poured gently into a beaker. The egg white did not appear to be homogeneous. Some of the more viscous egg white tended to move to­wards the bottom. However the more vis­cous egg white did not form a separate layer at the bottom of the beaker, thus simple sed­imentation in a beaker by one times gravity could not be used as a means of separating egg white into two or more fractions. These observations raised questions: First, where are the different fractions of egg white lo­cated in an intact egg, and second, can the different fractions of egg white albumen be separated so that the properties of the frac­tions can be separately measured and ana­lyzed? These questions are addressed next.</p>
<p>Published hen egg structure gives informa­tion on the spatial distribution of the more viscous thick albumen and of the less vis­cous thin albumen. Fig. 2 illustrates a cross section through the long axis of a hen egg and reveals the clear albumen (egg white) to consist of layers (Fig. 2 Kiple and Ornelas). Fig. 2. Just under the shell’s mammilary layer is found an outer less viscous or thin albumen layer. Next inward is a thick vis­cous albumen layer, then an inner thin al­bumen layer and finally, another very small chalaziferous layer located immediately over the yolk surface. An air cell is located at the blunt end of the egg.</p>
<div>Based on the layered distribution of thin and of thick albumen an experiment was done to determine the possible solute (methylene blue dye) excluding properties of the outer thin and the thick layer of albumen. A half cm hole was made in the egg shell halfway between the blunt and the sharp pole of the egg shell. Through the hole 0.1 ml of 0.5% methylene blue solution made up in phos­phate buffered saline was injected about 1 mm into the outer thin layer of albumen lo­cated just under the shell surface. The hole in the egg shell was sealed with Scotch brand magic tape, and the eggs were revolved for 15 seconds at about one revolution per two seconds and were then allowed to rest for 4-6 hours. The eggs were then placed in a freezer at minus 20 degrees centigrade for an overnight period. The frozen eggs were transected through the site of dye injection with the use of a thin knife blade and the blow of a hammer.<img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig2.jpg" alt="fig2" width="570" height="279" /><br />
<em><strong><br />
Figure 2: </strong>Drawing of a midsagital section of a hen egg. The layers of albumen are indicated. The layers between thin and thick are not known to be separated by membranes but still have distince boundaries (modified from Kiple and Ornelas 2000).</em></p>
<p>Blue dye was observed at the site of dye injection but was also observed laterally through the outer layer of thin albumen for a radial distance of about a cm. The blue dye did not move into the underlying thick albumen layer. The blue dye was not de­tected in the inner layer of thin albumen or in the chalaziferous layer. These findings indicate that the outer thin layer of albumen is solvent to the blue dye and that the thick albumen layer excluded the blue dye. Given difference in the methylene blue properties of the thin and the thick albumen layer, it was decided to attempt a separation of the thick from the thin albumen so that their physical properties could be independently studied and analyzed.</p>
</div>
<p>The method used to separate the thick and the thin albumen was to carefully place fresh whole egg white on a plastic filter with a pore size of 2 mm diameter (Fig. 3a). Fig. 3b is a photograph of whole egg white with 5 drops of methylene blue then poured into a 15 cm Petri dish that was positioned over a lined grid paper. Thin albumen dyes blue and thick albumen remained unstained. Thin albumen passed through the pores in about 15 minutes and was collected in an underlying beaker while the thick albu­men and the two white chalazae remained on the filter surface. The two white chalazae were then removed with forceps. To further confirm the ability of the filter method to separate thin and thick albumen fractions, methylene blue was added to the whole egg white and then subjected to the filter sepa­ration procedure. The results showed that the dyed albumen passed through the filter and that the thick albumen remained al­most colorless (Fig. 4).</p>
<div><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig3.jpg" alt="fig3" width="550" height="275" /><em><strong>Figure 3: </strong>A and B, photographs of a plastic sieve used to separate thin from thick egg white. A, White albu­men fractions. B, photograph of whole egg white dyed with five drops omethylene blue then poured into a 15 cm diameter Petri dish positioned over a grid.</em></p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig4.jpg" alt="fig4" width="550" height="413" /></p>
<p><em><strong>Figure 4: </strong>Photographs of thin and thick egg white fractions separated by filtration. Two mls of methy­lene blue were added to the egg white of a single egg which was then added to the filter surface. The frac­tion that passed through the filter was dark blue (Fig. 4 right) while the fraction on the filter surface was almost colorless (Fig. 4 left).</em></p>
<p>To determine the volume fraction of thin and of thick albumen each of these two sep­arated fractions was poured into a gradu­ate cylinder and the volume measured. A bit less than half of the total egg white vol­ume was found to be thin albumen (46%) while a bit more than half, (54%) of the total egg white volume was thick albumen. The whole white of an egg was exposed to sev­eral drops of the various dyes listed in Table 1. All of the listed dyes were selectively ex­cluded by the thick albumen.</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/table1.jpg" alt="table1" width="293" height="214" />The above finding that only about half of the egg white had dye excluding properties has lead to development of another method for assessment of the volume fraction of dye excluding egg white. The test of this meth­od was to add a few drops of dye to whole egg white and then gently mix and pour the egg white from a single egg into a 15 cm diameter Petri dish. The height of the egg white in the Petri dish was about 1.5 mm. The Petri dish was placed over a white sheet of paper with thin black perpendicular grid lines. Counting the number of grid inter­cept points under the non-dark blue areas over the total number of intercept points allows determination of the volume densi­ty fraction of dark blue and non-dark blue areas (Fig. 3B). As shown in Fig. 3B there are two areas lacking the dark-colored dye. When the whole egg white is stirred or agi­tated, there was an increase in the number of smaller non-blue areas. Repeated use of a Porter-Elvehjem tissue grinder on the dye and the whole egg white resulted in a homogenous blue dye area. The mean vol­ume density fraction of the fresh blue dyed albumen fraction was found to be 50.7 ≥ 2.2% which agrees with the 54% of methy­lene blue in phosphate buffered saline was added to the top of each sample. Therefore this intercept point counting method was used to determine the dye excluding vol­ume fraction of samples as reported further on in this report.<strong><br />
<em><br />
Physical measures of thick and of thin albumen and of deionized water at 22ºC</em></strong></p>
</div>
<p>Table 2 summarizes data on six physical measures made on thick and on thin albu­men fractions in comparison to deionized water. The method used to get each mea­sure and the results are presented in the same order listed in Table 2.</p>
<p>The water content was determined by add­ing thick or thin albumen or deionized wa­ter into a pre-weighed aluminum weighing pan and then weighing. The pans were then placed in a vacuum drying oven at 90ºC. The dry weight remained constant by day six in the oven and the g water/g dry mass was then calculated. No solids were de­tected in the deionized water sample. The water content of thick albumen is 24% less than the water content of the thin albumen (Table 2). Thus, the thick albumen is less watery than the thin albumen.</p>
<p>Density of thick and of thin albumen was determined by first measuring their vol­ume in a graduate cylinder then weighing the mass of the volume in pre-weighed alu­minum weighing pans. Data in Table 2 in­dicate that the density of thin albumen to be significantly greater than the density of deionized water and significantly less dense than thick albumen.</p>
<div>The rate of methylene blue dye diffusion into test samples of: deionized water, thick and thin albumen was done by placing the samples in a tube of uniform diameter, 50 mm. A drop of the dye solution composed of methylene blue buffered saline was added to the top of each sample. The distance the blue dye diffused from the surface top was measured as a function of time. The results are presented in Fig. 5 and the statistical results of the dye diffusion rate in the thin albumen was two times slower than the dye diffusion rate in deionized water (Table 2). Linear regression analysis of the dye diffu­sion in the thick albumen indicates the dye diffusion did not give a slope value that dif­fered significantly from a diffusion rate of zero. This study indicates that significant diffusion of the dye into the thick albumen did not occur during the course of the study.<img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig5.jpg" alt="fig5" width="325" height="338" />Flow rate was measured by use of a glass funnel. The funnel contents exited the fun­nel through a 170 mm long tube with an in­side bore diameter of 3 mm. The tube exit was sealed with Scotch brand magic tape and 20 ml of sample was then added to the funnel. None of the sample entered the exit tube mouth until the tape was removed. The tape was then removed from the funnel tube exit and the time for all of the funnel contents to flow out of the tube was mea­sured with a stop watch. The flow rate of thin albumen was about 3.5 times slower than the flow rate of deionized water. Un­expectantly, the thick albumin did not flow. The thick albumen was made to flow by ro­tating a 3.5 mm wide spatula at one revolu­tion per second at the mouth of the funnel tube. These findings indicate that thick al­bumen has the property of a thixotropic gel.</p>
</div>
<p>The rate of fall of a 50 μm diameter glass sphere from the top of a 10 cm column of specimen was measured with a stop watch. The results are summarized in Table 2. The fall rate of a 50 μm diameter glass sphere with a density of 2.8 agrees with the flow rate data in Table 2 and provides additional evidence that the fresh non-agitated (non-stirred) albumen acts as a gel. The rate of fall of the glass sphere through the thin albumen was about 3-4 times slower than through deionized water. The glass sphere did not fall through the thick albumen. Al­though the glass sphere did not fall through the thick albumen a 4 mm diameter lead sphere fell through the thin albumen. Here again thick albumen demonstrates the properties of a thixotropic gel.</p>
<p>The pH of thick and thin albumen fractions and of fresh deionized water were measured with a Beckman pH meter. The pH of thick and thin albumen fractions were both in the alkaline range and were not significantly different. The mean pH of freshly deion­ized water was 7.36, which was significantly lower than the pH of the thick and the thin albumen fractions (Table 2).</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/table2.jpg" alt="table2" width="585" height="348" /></p>
<div><em><strong>Table 2: </strong>Physical measure of thick and of thin albumen and of deionized water at 22oC (mean ± SD)<sup>a</sup>.</em></div>
<p><strong><br />
</strong></p>
<p><em><strong>Centrifugal force applied to thick al­bumen decreases much of its dye ex­cluding properties</strong></em></p>
<div>It is known that most proteins have a den­sity of 1.4 g/cm<sup>3</sup>. Given the density of thick albumen is 1.027 g/cm<sup>3</sup>(Table 2) it was decided to subject thick albumen to cen­trifugal force as a means to separate a pro­tein rich denser fraction from a less dense fraction. It was postulated that some of the dye excluding properties of thick albumen would be reduced by the force of centrifuga­tion and a less dense dye solvent fraction of the thick albumen would develop towards the top of the centrifuge tube with time.<img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig6.jpg" alt="fig6" width="313" height="324" />Two cm long stoppered, volume calibrated and marked centrifuge tubes were loaded with thick albumen, placed in a centri­fuge and subjected to a centrifugal force of 14,000 x g. At intervals, the centrifuge was stoppered and one or more of the tubes was removed. To the sample tubes removed from the centrifuge was added a drop of methylene blue dye at the top of the tube contents. The total height of the sample in the stoppered tube and the distance the blue dye diffused from the top of the column was measured at 20 hours after the blue dye was added at the top of the sample in the tube. The volume of non-blue dyed sample and the volume of sample that dyed blue, was calculated and the results are summarized in Fig. 6. The volume fraction of non-blue decreased with time of centrifugation.</p>
</div>
<p>The data points in Fig. 6 gave a best fit to a one phase exponential decay, r2 = 0.97, with a half life of 89.9 minutes. These re­sults indicate that a large proportion of the blue dye excluding thick albumen was sepa­rated from the thick albumen by a centrifu­gal force of 14,000 x gravity. Clearly much of the blue dye excluding albumen can be forced to become blue dye solvent.</p>
<p><em><strong>Effect of shear force on dye excluding properties of thick albumen</strong></em></p>
<p>Thick albumen was allowed to remain on the plastic sieve used to separate thick and thin albumen for 15 minutes. Thick albu­men formed protrusions below the sieve bottom (Fig. 7A). The thick albumen was then poured into a dish with methylene blue dye. As illustrated in Fig. 7B, the rim of the thick albumen at the edge of the sieve pores dyed blue. Apparently, the shear force of the protruding drop of the thick albumen was enough to change the dye-excluding state of the thick albumen to a non-dye-excluding state.</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig7.jpg" alt="fig7" width="600" height="302" /></p>
<p><em><strong>Figure 7: </strong>A and B. Photographs of under surfaces of filter and protrusions of thick albumen (A). Effect of shear force on dye uptake at the edge of sieve pore of thick albumen fraction after removal from the filter (B).</em></p>
<p><em><strong>Conversion of the thick albumen gel state to a more fluid sol state causes loss of some of the gel’s dye excluding properties</strong></em></p>
<p>As reported above, the measured volume fractions of thick and of thin albumen agrees with the volume density of methy­lene blue dyed area when the dye was added to the whole egg white prior to placing in a 15 cm diameter Petri dish. Scoring of the number of non-blue intercept points over the total intercept points in an underlay­ing grid was the method used for this study. Separated thick albumen excluded most of the methylene blue dye while thin albumen had all of the area dark blue. The thick albu­men remained dye excluding when rested without agitation in a covered beaker for 20 or more hours. Data are summarized in Table 3. When thick albumen was made to flow through the funnel with gentle stir­ring 33% of the area in the Petri dish dyed blue. When thick albumen that had flowed through the funnel once and then returned to the funnel that was then covered tight­ly with parafilm was allowed to rest with­out agitation for 20 hours only 23% of the sample area dyed blue but with longer rest periods the percent that dyed blue further decreased to 10% by 72 hours and to 6% by 96 hours. The 96 hour rested sample failed to flow through the funnel giving evidence of gel reformation.</p>
<p>After moderate stirring of thick albumen and after three passes through the funnel 53% of the thick albumen sample dyed blue after adding two drops of the blue dye solu­tion prior to pouring into the Petri dish. Af­ter a 20 hour rest the blue dyed fraction de­creased to 40% and by 72 hours decreased to 28%.</p>
<p>These results indicate the conversion of the thick albumen gel-like state to a more fluid sol-like state caused loss of some of the gel’s blue dye exclusion properties. The results also indicate that some of the dye excluding properties of the thick albumen are recov­erable with time after mechanical agitation.</p>
<p>As noted in the previous section increased mechanical agitation caused an increase in the fraction of thick albumen that dyed blue upon exposure to methylene blue dye. The relationship between flow rate and the per­cent of thick albumen that dyed blue was therefore measured. A significant positive linear relationship between the fraction of blue dye thick albumen and the flow rate was found (p value 0.003). The greater the agitation of the thick albumen the higher the fraction that dyed blue and the faster the flow rate or decrease in viscosity.</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/table3.jpg" alt="table3" width="573" height="203" /></p>
<div><em><strong>Table 3: </strong>Mechanical agitation of thick albumen and percent of blue dye exclusion as a function of time the sample was allowed to remain without further agitation (rest).</em></div>
<p><em><strong>The thick albumen gel demonstrates osmotic “like” behavior</strong></em></p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Cameron1/fig8.jpg" alt="fig8" width="329" height="356" />It was hypothesized that the thick albu­men gel would increase volume when ex­posed to a hypotonic methylene blue dye containing solution and would decrease its volume when exposed to a hypertonic dye containing solution. Three methylene blue dye solutions were tested: the first was thin albumen, the second was thin albumen di­luted in half with deionized water and the third was thin albumen with sucrose added to give a saturated solution of sucrose in thin albumen. The experiment designed to test the hypothesis was simply to gently layer one of the three blue dye solutions to the top of a volume of thick albumen gel in a graduate cylinder and to measure the height of the undyed region with time after adding the blue solution. The thin albu­men that was saturated with sucrose had so high a density that it fell to the bottom of the column of thick albumen. This fraction was subsequently injected to the bottom of the column with a long needle and syringe. Thus, the height of blue dyed and non-blue column could be measured as a function of time. There was not a distinct boundary be­tween the blue and non-blue regions. The measurements reported in Fig. 8 were made where the height of non-blue color could just be detected. The height between blueand non-blue regions became more diffuse as time progressed. Fig. 8 illustrates the ex­perimental results. The total height of the thick albumen and the height of the blue dye bathing solution was measured. The height of the non-blue column increased af­ter exposed to the hypotonic solution and decreased after exposure to the hypertonic sucrose solution and remained unchanged after exposure to the thin albumen. These results demonstrate that thick albumen has osmotic “like” behavior.</p>
<p><strong>Discussion<a name="discussion"></a></strong></p>
<p><em><strong>Dye exclusion mechanisms in thick egg white and in cells</strong></em></p>
<p>The extent of dye exclusion of the thick al­bumen can be explained by one or by both of the following mechanisms: 1) formation of at least two layers of water molecules over the surface of the globular proteins that are solute (dye) excluding. 2) formation of cav­ities of water molecules within the individ­ual globular protein molecules or in spaces between the tightly packet globular proteins that cannot be reached by the vital dye. At this time neither possibility can be excluded as an explanation of the extent of dye exclu­sion of a vital dye by living cells. Given that these mechanisms are operational in tissue cells, then mechanical agitation (perhaps palpation or other physical perturbations) of a tumor could cause transformation of the gel state to a sol state and allow drug or dye to better diffuse throughout the tumor.</p>
<p>There are at least three possible ways to ex­plain loss of vital dye exclusion upon death of a cell: 1) a failure of membrane exclusion, 2) loss of a key cardinal adsorbent (like ATP) causing loss of a solute (dye) exclud­ing layer of polarized multilayers of water (Ling 2001), 3) change from a solute (dye) excluding gel state to a non-solute dye ex­cluding sol state as demonstrated by thick albumen. Possibility one seemed doubtful as the sole mechanism responsible for sol­ute dye exclusion because detergent or sur­gical disruption of the plasma membrane of lens fiber cells did not cause loss of dye exclusion (Cameron et al. 1988) and for more examples see Maniotis and Schliwa, 1991 and Pollack, 2001). Possibility two also seems unlikely as loss of the key cardi­nal adsorbent (ATP) after cell death did not decrease the extent of non-bulk, polarized multilayers of water, to become bulk water as Ling’s association induction theory pre­dicts (Cameron et al. 2007, 2008). Pos­sibility three remains a viable option but there is currently no direct evidence that cell death causes the cytoplasmic gel state that may exclude a vital dye, to change into a non-vital dye excluding sol state. Further studies are underway to understand the dye excluding properties of the thick egg white gel.</p>
<p><em><strong>Gel-sol-gel phase transformation in thick albumen</strong></em></p>
<p>The gel-to-sol and back to a gel phase transformation, as observed in thick albu­men, has also been observed to occur dur­ing amoeboid motion as reported by Mast in 1926 and 1930. Mast reported that cyto­plasm flowed as a sol from a region near the rear of the cell forward towards the advanc­ing pseudopod. The rear of the cell and ar­eas under the cell surface, along the length of the cell remained stationary, and were termed the gel state. Thus the gel state at the rear of the cell transformed to a sol state that then flowed forward through the tu­bular gel cell body towards the advancing pseudopod. As the flowing sol approached the tip of the advancing pseudopod it moved laterally and transformed back to a gel state. When subjected to agitation or increased hydrostatic pressure the thick egg albumen fraction demonstrates a gel to sol phase transformation that resembles the gel to sol transformation observed in the cytoplasm/protoplasm of the amoeba cell during locomotion. However the time need­ed for transformation of thick albumen sol back to the gel state was much longer than in amoeba.</p>
<p><strong>Conclusions<a name="conclusions"></a></strong></p>
<div>The hen egg white thick albumen, rich in globular protein, demonstrate the follow­ing properties: the ability of the boundary of thick albumen to act as a semi-permeable boundary with solute (vital dye) exclud­ing properties, the ability to demonstrate osmotic-“like” behavior, and the ability to transform from a gel to a sol under the in­fluence of hydrostatic pressure or mechani­cal agitation. The thick albumen can also transform from a sol state back to a dye ex­cluding gel state similar to the properties of cytoplasm observed in living cells (Pollack 2001).<br />
<strong><br />
Acknowledgements</strong></div>
<p>Thanks is given to Anthony Lanctot and James Buchanan for help with photographs and to Professors Gary D. Fullerton and William Phillips for critical review of this report and for helpful discussion on the subject. Thanks is also given to Cathy Bun­nell for typing and to Nicholas Short for manuscript preparation.</p>
<p><strong>References<a name="references"></a></strong></p>
<p>Brooks, SC, Brooks, MM. <em>The permeability of living cells.</em> 1941</p>
<p>Cameron, IL Contreras, E, Fullerton, GD, Keller­mayer, M, Ludany, A, Misetta, A. Extent and prop­erties of nonbulk “bound” water in crystalline lens cells. <em>J. Cell. Physiol. </em>1988. 137:125-132.</p>
<p>Cameron, IL and Fullerton, GD. Interfacial wa­ter compartments on tendon/collagen and in cells. 2008. Phase Transition in Cell Biology, ed. Pollack, G, Chin, WC, Springer, Dordrecht, The Netherlands. 2008, p. 43-50.</p>
<div>Cameron, IL and Fullerton GD. Non-bulk like water on cellular interfaces. <em>Water and the Cell.</em> Eds. Pol­lack, GH, Cameron, IL, and Wheatley, DN, Springer, Dordrecht, The Netherlands. 2006. 315-323.</div>
<p>Cameron, IL, Kanal, KM, Keener, CR, Fullerton, GD. A mechanistic view of non-ideal osmotic and mo­tional behavior of intracellular water. <em>Cell Biol. Int.</em> 1997. 21: 99-113.</p>
<p>Cameron, IL, Short, NJ, Fullerton, GD. A simple centrifugal dehydration force method to character­ize water compartments in fresh and post-mortem fish muscle. <em>Cell Biol.Int.</em> 2007. 31: 516-520.</p>
<p>Cameron, IL, Short, NJ, Fullerton, GD. Characteris­tics of multiple water of hydration fractions in rabbit skeletal muscle with age and time post-mortem by centrifugal dehydration force and rehydration meth­ods.<em> Cell Biol. Int. </em>2008. 32:1337-1343.</p>
<p>Chen, YW., Lin, JS, et al. Application of in-vivo stain of methylene blue as a diagnostic aid in the early detection and screening of oral squamous cell carci­noma and precancerous lesions. <em>J. Clin. Med. Assoc.</em> 2007. 70:497-503.</p>
<p>Fullerton, GD and Cameron, IL. Water compart­ments in cells. <em>Methods in Enzymology.</em> 2007. 428:2-26.</p>
<p>Fullerton, GD, Kanal, KM, Cameron, IL. Osmotical­ly unresponsive water fraction on protein. <em>Cell Biol. Int.</em> 2006. 30:86-92.</p>
<p>Gordon, DL, Airan, MC, Swanick, S,. Visual identifi­cation of insulinoma using methylene blue. <em>Brit. J. Surgery.</em> 2007. 61:363-364.</p>
<p>Harris, JE, Peters, A. Experiments on vital staining with methylene blue. <em>Quarterly J. of Microscopical Science.</em> 1953. 94:113-124.</p>
<p>Kiple, KF, Ornelas, KC. <em>The Cambridge World His­tory of Food</em> 2000. Cambridge Univ. Press, Cam­bride. P 503.</p>
<p>Ling, GN. Life at the Cell and Below Cell Level., 2001 Pacific Press, N.Y.</p>
<p>Maniotis, A, Schliwa, M. Microsurgical removal of centrosomes blocks cell reproduction and centriole generation in BSC-1 cells. <em>Cell.</em> 1991. 495-504.</p>
<p>Marconi, G, Quintian , R. Methylene blue dye of cellular nuclei during salpingoscopy, a new in-vivo method to evaluate vitality of tubal epithelium. <em>Hu­man Repro. </em>1998. 13:3414-3417.</p>
<p>Mast, SO. Structure, movement, locomotion and stimulation in amoeba. <em>J. Morphol. </em>926. 41:347-425.</p>
<p>Mast, SO. Locomotion in Amoeba proteous (Leidy) Protoplasma. 1931. 14:321-330.</p>
<p>Upile T., Fisher, C., et al. Recent technology develop­ments: in situ histopathology interrogation of surgi­cal tissue and resected margins get nuclear dye posi­tive. <em>Head and Face Med</em> 2007. 3:13-26.</p>
<p>Pollack, GH. <em>Cells, Gels and the Engines of Life.</em> 2001, Enner &amp; Sons, Seattle.</p>
<div>Upile, T, Fisher, C, et al. Recent technological devel­opments: in situ histopathological interrogation of surgical tissue and resected margins get nuclear dye positive. <em>Head and Face Med. </em>2007. 3:1-26.</div>
<p><strong>Figure Legends</strong></p>
<p><em>Figure 1: </em>Photographs illustrating vital dye exclusion from decapsulated pig lens treated with membrane disruptive deter­gents. The round-shaped specimens are decapsulated lens. Above and to the right of each lens is the removed capsule of that lens, and above and to the left is a piece of the sclera. The letters “H” and “S” refer to the bathing solutions used. H” = Hanks and “S” = isotonic sucrose). The letters “B” and “T” refer to cell membrane disruptive de­tergents (“B” = brig 58 and “T” = triton x 100). The letter “C” refers to the unstrained control. Specimens in A (top paragraph), except the unstained controls were exposed to 0.1% nigrosin. Specimens in B (middle photograph was exposed to 0.1% trypan blue, and in C (bottom photograph, were exposed to 0.1% methylene blue. After one hour in the dye solutions, the intact lenses were removed and their stained capsule re­moved. The lens body (less the capsules) was returned to the dye solution for 2 ad­ditional hours, then removed and placed on a glass plate along with its lens capsule and a piece of sclera. As shown here, none of the treatments resulted in dye uptake or staining of the lens body, whereas all of the lens capsule and sclera specimens took up the dye. Figure reproduced from Cameron et al. 1988 with permission of John Wiley and Sons, Inc.</p>
<div><em>Figure 2: </em>Drawing of a midsagital section of a hen egg. The layers of albumen are indi­cated. The layers between thin and thick arenot known to be separated by membranes but still have distinct boundaries (modified from Kiple and Ornelas 2000).</div>
<p><em>Figire 3, A and B: </em>A, photographs of a plas­tic sieve used to separate thin from thick egg white albumen fractions. B, photograph of whole egg white dyed with five drops of methylene blue then poured into a 15 cm diameter Petri dish that is positioned over a lined grid paper.</p>
<p><em>Figure 4: </em>Photographs of thin and thick egg white fractions separated by sieve fil­trations. Two mls of methylene blue were added to the egg white of a single egg which was then added to the filter surface. The fraction that passed through the filter was dark blue (Fig. 4 right) while the fraction on the filter surface was almost colorless (Fig. 4 left).</p>
<p><em>Figure 5: </em>Graph of the rate of diffusion of methylene blue into thin and thick albumen fraction compared to deionized water. The statistical analysis of slopes is summarized in Table 2. The slope of thick albumen is not significantly different than a zero slope.</p>
<p><em>Figure 6: </em>Relationship between the non-blue dyed volume fraction and the time each sample of thick albumen was centri­fuged at 14,000 x gravity prior to exposure to the dye. Centrifugation leads to loss of dye exclusion.</p>
<p><em>Figure 7, A and B: </em>Photographs of under surfaces of filter and protrusions of thick albumen (A). Effect of shear force on dye uptake at the edge of sieve pore of thick al­bumen fraction after removal from the filter (B).</p>
<p><em>Figure 8: </em>Relationship between the percent of thick albumen that dyed blue and the flow rate of the thick albumen when the al­bumen was agitated to different extents by stirring. Statistical analysis reveals a sig­nificant linear relationship</p>
<p><em>Figure 9: </em>Behavior of fresh thick albumen exposed to hypotonic (water diluted thin albumen) or to hypertonic (thin albumen saturated with sucrose). Methylene blue dye was added to the test solutions prior to being added to the undyed thick albumen. The change in volume of non-blue thick albumen was measured with time of expo­sure.</p>
<p><strong>Discussion With Reviewers<a name="discussion-with-reviewers"></a></strong></p>
<p>Mae Wan Ho<sup>1</sup>: Do you see any relationship between the dye exclusion in the gel frac­tion of albumen to the exclusion zone Pol­lack et al. have identified in water organized next to hydrophilic surfaces?</p>
<p>Ivan Cameron:<strong> </strong>The likelihood that multi­layers of water on hydrophilic surfaces, as shown by Pollack et al., can exclude solutes in an established fact. Thus it seems likely that the same mechanism operates in the fresh thick hen egg white gel. Another pos­sible mechanism for dye exclusion in the egg white gel is formation of cavities of wa­ter molecules within protein molecules or in spaces between lightly packed and/or cross linked proteins that cannot be reached by the dye (“cavity water” see Fullerton and Cameron 2007).</p>
<p>Ho: Do you see the egg albumen picture of gel and sol representative of cytoplasm in general?</p>
<p>Cameron: Yes in that both do transform from get to sol and back to gel states but no in regard to speed of conversion between states, i.e. in amoeba conversion from sol to gel is almost instantaneous but in the thick hen egg white albumen the conversion from sol to gel took days (see Table 3 in text).</p>
<div>Ho: Do you see the egg albumen picture of gel and sol representative of cytoplasm in general?</div>
<p>Cameron: Yes I do in that both cytoplasm and thick egg albumen undergo gel to sol and back to gel transformation associated with dye exclusion properties as also seen in vivo by Kite and Lepeschkin (cited in Ling 2001). Also data on thick egg gel, as reported in the current report, and data in a recent report by Fels et al. (Biophy. J. 2009 96: 4276-4285) both indicate that the egg albumen gel and that a mammalian cytoplasmic hy­drogel are osmotically responsive.</p>
<p>Ho: What do you think are the natural sig­nals for gel to sol transformation in vivo?</p>
<p>Cameron: I refer you to a monography (Phase Transition in cell Biology, Pollack, G.H. and Chin, W-C, 2008, Springer). Pos­sible signals include: ion changes during nerve excitation, stretch (shear-induced fluidization followed by slow resolidifica­tion) and perhaps ATP levels.</p>
<p>Ho: Can you say anything regarding density of water associated with the two albumen states?</p>
<p>Cameron: This is an important question but I have only indirect information to address the question. It seems that the proteins in egg albumen have both hydrophilic sur­face domains with water hydrogen bonding properties (denser water) and hydrophobic surface domains that does not allow direct hydrogen bonding of water molecules. The water over hydrophobic domains is there­fore less dense. Thus the amount of dense and less dense water is dependent on the extent of hydrophilic and hydrophobic sur­face area which can change with extent of protein folding and aggregation (polyme ization).</p>
<p><sup>1</sup> <em>Visiting Professor of Biophysics, Catania Univer­sity, Sicily</em></p>
<p>http://www.waterjournal.org/component/content/article/21-volume-2/79-cameron-1-full-text</p>



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		<title>Collective Molecular Dynamics of a Floating Water Bridge</title>
		<link>http://korotkov.org/water/2010/10/collective-molecular-dynamics-of-a-floating-water-bridge/</link>
		<comments>http://korotkov.org/water/2010/10/collective-molecular-dynamics-of-a-floating-water-bridge/#comments</comments>
		<pubDate>Thu, 21 Oct 2010 11:48:38 +0000</pubDate>
		<dc:creator>admin</dc:creator>
				<category><![CDATA[Articles about Water]]></category>
		<category><![CDATA[Biology of Water]]></category>
		<category><![CDATA[Chemistry of Water]]></category>
		<category><![CDATA[Del Giudice]]></category>
		<category><![CDATA[Fuchs]]></category>
		<category><![CDATA[G]]></category>
		<category><![CDATA[Molecular Dynamics]]></category>
		<category><![CDATA[Vitiello]]></category>
		<category><![CDATA[Water Bridge]]></category>

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		<description><![CDATA[Collective Molecular Dynamics of a Floating Water Bridge Del Giudice, E1; Fuchs, E C2,*; Vitiello, G3 1 Istituto Nazionale di Fisica Nucleare, Sezione di Milano, Milano &#8211; 20133 Italy and IIB, Neuss, Germany 2 Wetsus, Centre of Excellence for Sustainable Water Technology, Agora 1, 8900 CC Leeuwarden, The Netherlands 3 Dipartimento di Matematica e Informatica<a href="http://korotkov.org/water/2010/10/collective-molecular-dynamics-of-a-floating-water-bridge/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p><strong>Collective Molecular Dynamics of a Floating Water Bridge<br />
</strong></p>
<p>Del Giudice, E<sup><em>1</em></sup>; Fuchs, E C<sup><em>2</em></sup>,*; Vitiello, G<sup><em>3</em></sup></p>
<div><em><sup>1</sup> Istituto Nazionale di Fisica Nucleare, Sezione di Milano, Milano &#8211; 20133 Italy and IIB, Neuss, Germany</em></div>
<div><em><sup>2</sup> Wetsus, Centre of Excellence for Sustainable Water Technology, Agora 1, 8900 CC Leeuwarden, The Netherlands</em></div>
<div><em><sup>3</sup> Dipartimento di Matematica e Informatica and INFN, Università di Salerno, Fisciano (SA) &#8211; 84084 Italy</em></div>
<div>* Correspondence: Tel.: +31 (0) 58 284 3162; E-mail: <a href="mailto:elmar.fuchs@wetsus.nl">elmar.fuchs@wetsus.nl</a>This e-mail address is being protected from spambots. You need JavaScript enabled to view it</div>
<div>Key Words: floating water bridge, quantum electrodynamics, quantum field theory</div>
<div>PACS: 61.20.Gy, 47.57.jd, 47.65.Gx<span id="more-199"></span></div>
<p>Received 5 May 2010; revised 18 July; accepted 19 July. Published 30 July 2010; amended online 15 August 2010</p>
<p><strong>Summary</strong></p>
<p>When a high voltage is applied to pure water filling two beakers kept close to each other, a connection forms spontaneously, giving the impression of a floating water bridge. This phenomenon is of special interest, since it comprises a number of phenomena currently tackled in modern water science. The formation and the main properties of this floating water bridge are analyzed in the conceptual framework of quantum electrodynamics. The necessary conditions for the formation are investigated as well as the time evolution of the dynamics. The predictions are found in agreement with the observations.</p>
<p><strong>1. Introduction <a name="introduction"></a><br />
</strong></p>
<p>In 1893 Sir William Armstrong placed a cot­ton thread between two wine glasses filled with chemically pure water. After applying a high voltage, a watery connection formed between the two glasses, and after some time, the cot­ton thread was pulled into one of the glasses, leaving, for a few seconds, a rope of water sus­pended between the lips of the two glasses [1].</p>
<p>As a gimmick from the early days of electric­ity, this experiment was handed down through history until the present authors learned about it from W. Uhlig, ETH Zürich [2]. Although easy to reproduce, this watery connection between the two beakers, which is further referred to as ’floating water bridge’ holds a number of interesting static and dynamic phenomena [3,4,5,6,7,8,9].</p>
<p>At the macroscopic scale, several of these phe­nomena can be explained by modern electrohy­drodynamics, analyzing the motion of fluids in electric fields (see, e.g., the Maxwell pressure tensor considerations by Widom et al. [10], or the book of Castellanos [11]), while on the mo­lecular scale, water can be described by quan­tum mechanics (e.g., [12,13]).</p>
<p>The gap at the mesoscopic scale is bridged by a number of theories, such as quantum me­chanical entanglement and coherent struc­tures in water. These theories are currently dis­cussed (e.g., [14,21,22,17,25]). Recently, a 2D neutron-scattering study indicated a low-level long-range molecular ordering within a D<sub>2</sub>O bridge [8]. Detailed optical measurements [7] suggested the existence of a mesoscopic bubble network within the water bridge.</p>
<p>The properties of water at these scales have drawn special attention due to their suggested importance to human physiology [15]. In this paper, we consider the interaction of an applied high voltage potential with the water molecules by exploring the suitability of a quantum field theory approach. In particular, we consider a quantum electrodynamics (QED) approach to the structure of liquid water proposed in refs. [23,24,25].</p>
<p>The paper is organized as follows. In section 2 the experimental set-up and the measurement methods are described, in section 3 the appear­ance of coherent structures in liquid water as an outcome of QED is discussed. In Section 4 we analyze in the same framework the formation of a mesoscopic/macroscopic vortex in liquid wa­ter as a consequence of the application of high voltage.</p>
<p>Sections 5 and 6 are devoted to the analysis of the process of formation of the water bridge, in­cluding a comparison between theory and ex­periment, and to the understanding of some of its properties, respectively. Some conclusions are finally drawn in Section 7.</p>
<p><strong>2. Experimental <a name="experimental"></a><br />
</strong></p>
<p>For the high speed imaging experiments per­formed, flat platinum electrodes were sub­merged in the center of the beakers, one set to ground potential (cathode), the other on high voltage, up to 25kV dc (anode). For the thermo­graphic measurements, cylindrical silver elec­trodes were used. The beakers were filled with deionized H<sub>2</sub>O (‘milli-Q’ water, conductivity &lt; 1μS/cm).</p>
<p>A Phywe high–voltage (HV) power supply (’Hochspannungs–Netzgerät 25kV’, Order No 13671.93) was used with a 42nF ceramic capaci­tor connected in parallel to the electrodes. The voltage was measured by a potential divider of 500MΩ/500kΩ to ground level. Since the volt­age generator provided a limited current out­put, the electric current was stable at 0.5 mA, while the voltage continuously adapted. The images in Fig. 1 and Fig. 2 were recorded with a FLIR 620 thermographic camera (FLIR Sys­tems, Boston, MA, USA).</p>
<p>The images in Fig. 3 and 4 were recorded with a Photron SA-1 high-speed camera (Photron Ldt, Bucks, United Kingdom). Fig. 3 was recorded with 2000 fps exposure time, after 0 ms (a, ref­erence point), 198 ms (b) 268 ms (c) 306 ms (d) 536 ms (e) 551 ms (f) 626 ms (g) and 1020 ms (h). Fig. 4 was recorded with 1000 fps, 1/1000 s exposure time, after 0 ms (a), reference point), 510 ms (b) 520 ms (c) 570 ms (d) and 630 ms (e). In all cases, the high voltage was manually increased from 0 to 15 kV (+) dc, and the images were taken at the moment of bridge or vortex creation, respectively, which was between 7 and 11 kV.</p>
<p><strong>3. Coherent Structures in Liquid Water <a name="coherentstructuresinliquidwater"></a><br />
</strong></p>
<p>In this section we focus our attention on the gauge invariant properties of a system, like the water bridge, which exhibits complex dynam­ics. A key motivation for this approach arises from the fact that gauge invariance is the basic requirement to be satisfied when dealing with systems where charge density and electric po­larization density play a relevant role.</p>
<p>It is apparent that the discussion of the gauge invariant properties can be done only within a field description of the structure and dynamics of water. As a matter of fact, many models in­troduced so far to describe water are based on molecular dynamics, which is an approxima­tion that does not consider the field features of water (for reviews see e.g., [26,27]).</p>
<p>A conceptual step in this direction was the ex­perimental proof for quantum entanglement in liquid water at room temperature: Chatzi­dimitriou–Dreismann et al. (1995) did Raman light-scattering experiments [16] on liquid H<sub>2</sub>O &#8211; D<sub>2</sub>O mixtures, which provided experimental evidence for the quantum entanglement of the ion OH<sup>-</sup> (and OD<sup>-</sup>) vibrational states.</p>
<p>In 1997, a first experimental proof of nuclear quantum entanglement in liquid water [17] was published, again, by Chatzidimitriou–Dreismann et al. by the means of inelastic neu­tron scattering. The interpretation is disputed [18,19]. Another approach where water is con­sidered a ‘hot quantum liquid’ was proposed in 2006 [20].</p>
<p>In the frame of the theory of liquids, the mod­el of liquid helium proposed by Landau [28] is appealing. Within this model the liquid ap­pears as made up of two phases, one coherent (having components oscillating in phase), the wother non-coherent (having independent com­ponents as in a gas). There is no sharp space separation between the two phases since a con­tinuous crossover of molecules occurs between them. This dynamical feature makes the experi­mental detection of the two-phase structure a delicate task indeed.</p>
<p>As a matter of fact, an experimental probe &#8211; that has a resolution time longer than the typi­cal period of the particle oscillation between the two phases &#8211; produces a picture that is an aver­age of the conformations assumed by the sys­tem during this time. This produces the appear­ance of a homogenous liquid [29,30]. On the contrary, the two-phase structure would only be completely revealed by an instantaneous measurement. In a realistic situation, an obser­vation lasting a short-enough time could give evidence of the chunks of the coherent phase, which could succeed in remaining coherent during the whole time of the measurement.</p>
<p>This kind of observation would give some evi­dence of the existence of a two-phase structure, but would not be enough to give the full instan­taneous extension of the coherent region. Re­cently, two articles [31,32] in favor of the pro­posed model appeared. In ref. [31] evidence is presented of two phases of water having differ­ent densities and orderings. Ref. [32] discusses a comprehensive account of the experimental data supporting the existence in liquid water of aggregates quite larger than those accountable in terms of customary electrostatic theories. In the frame of QED [23,24,25], a description of liquid water exhibiting two interspersed phases in agreement with these last experimental find­ings has been worked out. The two phases are:</p>
<p><em>i</em>) a coherent phase made up of extended re­gions, the so-called “coherence domains” (from now on referred to as CDs) where all water mol­ecules oscillate in phase between two configura­tions.</p>
<p><em>ii</em>) ii) a non-coherent phase made up of inde­pendent molecules trapped in the interstices among the CDs.</p>
<p>The coherent oscillations of the molecules be­longing to the first phase are maintained by the electromagnetic (e.m.) field self-produced and self-trapped within the CD, and occur between two definite molecule states. So far two such processes have been identified:</p>
<p><em>a</em>) In a process analyzed in Ref. [23,24], the os­cillations occur between two rotational levels of the water molecule. This produces correlations as large as several hundred microns. This also gives rise to a common dipole orientation of the molecule electric dipoles which, as a conse­quence of the rotational invariance of the aque­ous system, gives rise to a zero net polarization. However, when the rotational symmetry is bro­ken by an externally applied polarization field, such as that which occurs near a hydrophilic membrane or near a polar molecule, a perma­nent polarization develops. The range of per­manent polarization depends on the amplitude of the external polarization field and, therefore, on the physical state of the surface. The applica­tion of a voltage would obviously increase this kind of correlation.</p>
<p><em>b</em>) In a process analyzed in Ref. [25], the os­cillations occur between the ground electronic state of the molecule and the excited 5<em>d </em>state at <em>E</em>exc=12.06 eV, just below the ionization thresh­old at 12.60 eV. Each CD has a size given by the wavelength of the resonating e.m. mode</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq0.gif" alt="eq0" width="140" height="61" />.</p>
<p>The frequency of the common oscillation of molecules and field is 0.26 eV (in energy units) at T = 0K, much lower than the frequency, 12.06 eV, of the free field. This dramatic softening of the e.m. mode is just the consequence of the nonlinear dynamics occurring in the process [23,25,24].</p>
<p>Non-aqueous molecules cannot participate in the resonant dynamics, so they are excluded from the CDs. In particular, atmospheric gases are expelled from the CD volume and give rise to nano- and/or micro-bubbles adjacent to the CD. When the dynamics causes a decoherence of a CD, such bubbles, too, would disappear, since their components are able to dissolve again in the non-coherent fraction of water.</p>
<p>The amount of the coherent fraction in the liq­uid is decreasing with temperature. At room temperature the two fractions are approximate­ly equal [25]. In the bulk water, molecules are subjected to two opposite dynamics: the elec­trodynamical attraction produced by coherence and the disruptive effect of the thermal colli­sions, so that, whereas in the average the rela­tive fractions are time independent, at a local, microscopic level each molecule is oscillating between the coherent and the non-coherent re­gime. The coherent structure is thus a flickering one, so that an experiment having a duration longer than the lifetime of a CD probes water as a homogenous medium.</p>
<p>In the coherent state in the fundamental con­figuration, whose weight is 0.87, all the elec­trons are tightly bound, whereas in the excited configuration, whose weight is 0.13, there is one quasi-free electron. Consequently, a CD con­tains a reservoir of 0.13 x <em>n </em>quasi-free electrons. At room temperature <em>n </em>is about 6 x 106. In Ref. [33] it has been shown that this reservoir can be excited, producing cold vortices of quasi-free electrons confined in the CD.</p>
<p>The energy spectrum of these vortices can be estimated following the mathematical scheme outlined in ref. [33]. Similarly, it can be seen that the lowest lying excited state has a rota­tional frequency of a few kHz and the spacing of the levels has the same order of magnitude. The lifetime of these vortices can be extremely long because coherence prevents random (ther­mal) fluctuations and because the conservation of the topological charge prevents the decay of the vortex in a topologically trivial state.</p>
<p>We finally remark that in a coherent region, the pure gauge nature of the e.m. potential field</p>
<p>(1)        <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq1.gif" alt="eq1" width="85" height="29" /></p>
<p>where <strong>λ </strong>is the gauge transformation function, implies that the applied electric potential V is proportional to the time derivative of the phase <em>Φ </em>(see below): <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq1-2.jpg" alt="eq1-2" width="53" height="22" />. Here and throughout the paper we omit the space-time dependence of the variables whenever no misunderstanding arises therefrom. When necessary we adopt the notation <em>x </em>≡ (<strong>x</strong>,<em>t</em>).</p>
<p>The two above-mentioned dynamics occur si­multaneously and produce a non-trivial inter­play that gives rise to a number of phenomeno­logical situations:</p>
<p><strong><em>1</em></strong><strong>) <em>Bulk water in normal conditions. </em></strong><em>In this case, the dynamics a) are phenomenologi­cally irrelevant due to the rotational symme­try of the system. The dynamics b) only are at work, producing instant CD structures as large as 0.1</em><em>μ</em><em>m, which are exposed to the disruption of the thermal collisions. </em></p>
<p><em>This gives rise to a Landau-like situation where water appears homogeneous in experi­ments having a long-enough resolution time and exhibiting deviations from homogeneity at smaller resolution times. Moreover, the flicker­ing nature of the coherent structure prevents the appearance of the long time features of the coherent dynamics. </em></p>
<p><em>In the case of the bulk water, the experimental check of the theory is the correct prediction of the thermodynamic processes, which do not de­pend on the space distribution of the coherent molecules, but on their total number only. The flickering space structure of CDs implies that the corresponding ensemble of microbubbles described above should be a flickering one too, as found by the experimental observations.</em></p>
<p><strong><em>2</em></strong>) <strong><em>Interfacial water</em></strong>. <em>In this case, dynam­ics a) are at work and their interplay with dy­namics b) gives rise through nonlinear dynam­ics to a stabilization of the coherent structure, which is much more protected against thermal fluctuations. </em></p>
<p><em>The equilibrium between the two phases is shifted toward coherence. Since an extra en­ergy gap is added, molecules are kept aligned by the total polarization field produced by the dynamics a) that compels the radiative dipoles produced by the dynamics b) to stay aligned. </em></p>
<p><em>The smaller CDs (0.1 </em><em>μ</em><em>m) of dynamics b) are tuned together by the much more extended co­herence produced by dynamics a), so that the global coherent region, thanks to the polariza­tion field produced by the surface, gets wid­ened up to several hundreds of microns. This is the span of the CD dynamics a). A confirma­tion of this QED prediction is provided by the </em><em>experimental findings of the group led by G. H. Pollack [34], which confirm results obtained more than sixty years earlier [35]. They show that layers of “anomalous” water (EZ water) as thick as 500 </em><em>μ</em><em>m appear on hydrophilic sur­faces. </em></p>
<p><em>The observed anomalies include the exclu­sion of solutes, a highly reducing power (cor­responding to a negative redox potential of several hundreds of millivolts), and widely dif­ferent optical and electrical properties. These anomalies are compatible with those expected from the coherence domains of dynamics b) [25]. A much more detailed discussion of this important point will be given elsewhere.</em></p>
<p><strong><em>3</em></strong><strong>) <em>Bulk water in special conditions. </em></strong><em>Ref. [36] describes the possibility of the onset of a coherence among CDs induced by the tuning of the phases of the oscillations of the CDs, which in normal water are not correlated. This tun­ing of the different CDs can also be induced by the application of an external e.m. field. </em></p>
<p><em>A recent 2D neutron scattering study indicat­ed a preferred molecular orientation within a heavy water bridge [8]. This observation can be interpreted in accordance with the dynam­ics a). Moreover, this prediction could account for the experimental observation of a so called “Neowater” produced by an Israeli group [37] and compatible with similar results of Russian [38] and Ukrainian researchers [39]. This im­portant point, too, will be discussed at length elsewhere.</em></p>
<p>The stabilization of the array of water CDs im­plies the stabilization of the corresponding en­semble of microbubbles, which therefore form a stable and ordered array. This result has been reported in Ref. [37]. Katzir et al. connect the ordered nature of the neowater structure with the appearance of the ordered network of mi­crobubbles; they report as a typical size of the single microbubble a value comparable to the CD size. Thus QED provides a rationale for this surprising phenomenon.</p>
<p>However, the cases <em>2</em>) and <em>3</em>) are different. In the case <em>2</em>) the superposition of the two coher­ent dynamics gives rise to a continuous coher­ent region, which doesn’t contain non-coherent zones. Therefore, the re are no bubbles. In case <em>3</em>) there is a coherent ensemble of CD, which al­lows the presence of interstices and microbub­bles. In this paper we concentrate on describing what happens in the particular case of the float­ing water bridge. This discussion will be done in the next section.</p>
<p><strong>4. Formation of a Mesoscopic/Mac­roscopic Vortex <a name="formationofamesoscopicmacroscopicvortex"></a><br />
</strong></p>
<p>The formation of the floating water bridge is triggered by the application of a high voltage V. Let us discuss which are the consequences of such a physical operation on a coherent struc­ture such as the one described in the previous section. We split the e.m. potential <em>A</em>μ into the electric and magnetic part. In cgs units we have</p>
<p>(2)     <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq2.jpg" alt="eq2" width="100" height="50" /></p>
<p>(3)     <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq3.jpg" alt="eq3" width="120" height="42" /></p>
<p>where <em>e </em>denotes the electron charge. According to Eq. (2) the application of a voltage implies a strong variation of the phase <em>Φ </em>which adds up to the original phase of the unperturbed CDs.</p>
<p>Should the applied potential be high, the volt­age generated phase would be dominant with respect to the original phase, which might be regarded as a small perturbation of the total phase. The new phase spans over a macroscop­ic region and is thus space-correlating all the phases of the CDs enclosed in the macroscopic region. A coherence among the CDs emerges.</p>
<p>Moreover, in this new macroscopic coherent region, a definite non-vanishing gradient of the phase has appeared, that, in turn, according to Eq. (3), produces a non-vanishing magnetic po­tential.</p>
<p>The presence of a magnetic field depends on the rotational or irrotational character of the geom­etry of the problem. One can show [40, 41] that consistency with the gauge invariance requires that</p>
<p>(4)    Φ(<em>x</em>) → Φ(<em>x</em>) &#8211; <em>e</em>α<em> f </em>(<em>x</em>)</p>
<p>where ἁ is a constant depending on the wave re­normalization constant and the transformation function <em>f</em>(<em>x</em>) is a solution of the equation ∂<sup>2</sup><em>f</em>(<em>x</em>) = 0. We use <em>x </em>≡ (<strong>x</strong>,<em>t</em>). The macroscopic current ju,cl is given by [40, 41].</p>
<p>(5)   <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq5.gif" alt="eq5" width="304" height="72" /></p>
<p>where <em>a</em><sub>μ,cl</sub>(<em>x</em>) is the classical e.m. field, which has acquired the mass <em>m</em><sub>v</sub> (the Anderson-Higgs-Kibble mechanism [42]). One has ∂<em><sub>μ</sub> </em><em>j</em><sub>μ,cl</sub>(<em>x</em>) = 0.</p>
<p>It is crucial here to stress that the presence of quasi–free electrons in the elementary CDs fully characterizes the dynamical regime of the system. Since these quasi–free electrons are confined within the CDs, their motion is neces­sarily a closed one, which implies that a mag­netic field is generated.</p>
<p>Moreover, the beaker system exhibits a lo­cal non-trivial topology. That is because the (charged) electrode in the beaker center pre­vents the paths closed around it from shrink­ing to zero. That is, of course, provided one does not draw these paths around the electrode tip. This fact produces a macroscopic vortex.</p>
<p>Such a vortex is indeed present in both beakers and can be visualized with a thermographic camera as shown in Fig. 1. Thus, an extended coherence, on a scale much larger than the original 0.1μm, is the consequence of the ap­plication of a high voltage. The extended coher­ence is also the consequence of the absence of an electric current, as can be seen in the short time just after engaging the voltage yet before the appearance of the bridge. This effect can be understood as a variant of the well-known Bohm–Aharonov effect [43].</p>
<p>Such a phenomenology is described in formal terms by the fact that the function <em>f</em>(x) may in­deed carry a topological singularity describing the occurrence of a vortex and given by</p>
<p>(6)    <em>f</em>(<em>x</em>) = arctan(<em>x</em>2/<em>x</em>1).</p>
<p>Eq. (6) shows that the phase is undefined on the line <em>r </em>= 0, with <em>r</em><sub>2</sub> = <em>x</em><sub>1</sub><sup>2</sup> + <em>x</em><sub>2</sub><sup><em>2</em></sup><em>, </em>consistently with the phase indeterminacy at the electrode site due to the specific system geometry.</p>
<p>When <em>f</em>(<em>x</em>) carries a (vortex) topological singu­larity, it means that it is path-dependent (not single-valued). When <em>f</em>(<em>x</em>) is a regular function, i.e., when it does not carry a topological singu­larity, the current <em>j<sub>u,cl</sub></em> vanishes [40,41]. This, in turn, implies zero e.m. field <em>F</em><sub>μv</sub> = ∂<sub>μ</sub><em>a</em><sub>v</sub> <em>- </em>∂<sub>v</sub><em>a</em><sub>μ</sub><em>.</em></p>
<p>In conclusion, in the dynamical scenario de­picted above, the action of turning on the high potential compels the CDs to join the observed giant vortex, whose core position is determined by the electrode position. The closer the CDs are to the vortex core (the electrode), the stronger the action pushing them to join together.</p>
<p>Since the applied potential is a decreasing func­tion of the distance from the electrode, periph­eral CDs (those nearest to the beaker wall) have a better chance to preserve their individuality. (They are, however, in a non–equilibrium re­gime due to the criticality of the dynamics going on).</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/fig1.gif" alt="fig1" width="600" height="183" /> <strong><br />
</strong></p>
<p><em><strong>Figure 1: </strong></em><em>Thermographic visualization of the macroscopic Vortex in the beakers under application of high voltage before the water bridge is formed. The time interval between the images is 5 sec, the tem­perature scale is calibrated to the emissivity of water (0.96).</em></p>
<p><strong> </strong>The presence of the other electrode in the grounded beaker—and the consequent exis­tence of a preferred radial direction on the join­ing line between the two electrodes—breaks the cylindrical symmetry around each one of the electrodes.</p>
<p>The radial velocity of the slightly (~1K) colder vortices is ~ 1°/s – 3°/s and could be observed independently of the potential applied. The rotational direction was counter-clockwise in both beakers. In Fig. 2, the symmetry break due to the influence of the second beaker is visual­ized by thermography.</p>
<p>Fig. 2a again shows the slight cooling of the vortices. After a certain threshold (between 9 and 11kV), a cooling along the joining line of the electrodes as shown in Fig.2b appears (2-3K), and the rotation stops. The cooling is then followed by electric discharges heating the bea­ker walls (Fig. 2c) and finally leads to the water bridge formation (Fig. 2d). The dark spots on the anode in Fig. 2c and d are water droplets, which were ejected from the beakers during the process.</p>
<p>The vortices occur independently of the value of the applied potential. The potential acts as a trigger inducing the phase transition. The inner dynamics of the water then control the system evolution and its vorticity. This explains the ob­served independence of the turbulent patterns of the strength of the applied potential.</p>
<p>Finally, we note that the above description which starts from the analysis of the microscopic dy­namics is consistent with the results obtainable by use of the classical electro–hydro–dynamics (EHD) field equations, originally proposed by Melcher and Taylor [44] and completed by Sav­ille [45], describing the effects of a high voltage applied onto a ”leaky dielectric.”</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/fig2.gif" alt="fig2" width="600" height="414" /></p>
<p><em><strong>Figure 2: </strong>Thermographic visualization of the bridge formation mechanism. First, the macroscopic vorti­ces appear (a), then the water cools down at the joining line of the two electrodes (b). With the first sparks (c), the water heats up, and finally forms a water bridge (d). The time interval between the images is 5s, the temperature scale is calibrated to the emissivity of water (0.96). The dark spots on the electrodes in (c) and (d) are water droplets which were ejected during the process.</em></p>
<p><strong>5. Formation of the Water Bridge <a name="formationofthewaterbridge"></a><br />
</strong></p>
<p>It is well known [42] that within a coherent re­gion a magnetic field should vanish (Meissner effect), provided that the size of the region ex­ceeds a threshold (London penetration length). Indeed, the magnetic field penetration in the coherent region decays exponentially, as de­scribed by the London equation</p>
<p>(7)   <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq7.gif" alt="eq7" width="133" height="67" /></p>
<p>where <em>λ</em>L is the London penetration length (see, e.g., Ref. [46]). This property is the consequence of the regularity of the phase in the coherent re­gion (far from the boundaries), which produces the vanishing of the magnetic field [cf. Eq. (5) and the comments following Eq. (6)]. Near the boundaries the phase acquires a singular behav­ior due to inhomogeneities and this produces a non-vanishing magnetic field [cf. Eq. (6)].</p>
<p>In the case of liquid water, <em>λ</em><sub>L</sub> has a value much larger than the size 0.1μm of the water CD, in agreement with the well-known fact that mag­netic fields are not expelled from normal water.</p>
<p>However, when the peculiar dynamics outlined in the previous section are at work, the coher­ent region could become so far extended that its size overcomes the London penetration length. In this case a phenomenon of levitation analo­gous to the one observed with superconductors might occur.</p>
<p>Actually, in the presence of the Meissner effect, a gradient of the magnetic inductance μ appears since μ = 0 in the coherent region and equals about one outside. A magnetic levitating force <strong>F</strong><sub>lH</sub> <em>= -H</em><sup>2</sup><strong>grad</strong><em>μ </em>appears, provided that <em>H</em><sup>2</sup> is in­homogeneous.</p>
<p>At the air water interface, the presence of the macroscopic vortex (described above) produc­es a high value of <em>H</em>2 below the water surfaces. Consider that, in the atmosphere above the sur­face, <em>H</em><sup>2</sup> is much lower and corresponds to the ambient magnetic field.</p>
<p>Consequently, a net upward force develops that raises the CD up. Since the extended coherent region is the one close to the beaker wall, mag­netic levitation would occur along the wall of the vessel where the size of the coherent regions is larger. These magnetic forces would occur only in the vessel with the high positive poten­tial where the vortex can develop.</p>
<p>In the grounded beaker, however, the high posi­tive potential will be absent.</p>
<p>Moreover, an electric levitation force</p>
<p>(8)<strong> F</strong><sub>le</sub> <em>= -E</em><sup>2</sup><strong>grad</strong><em>ε</em></p>
<p>may appear, since the dielectric constant <em>ε </em>is much larger in the CDs than in the non-co­herent region. As a matter of fact, if we model the non-coherent region as an ensemble of in­dependent electric dipoles, the Fröhlich for­mula would give us room temperature <em>ε </em>= 15. The dielectric constant of the CDs, in contrast, could be estimated to be 160 [47]. Since at room temperature the two fractions are almost equal, the two above estimates result in an average di­electric constant <em>ε</em><sub>obs</sub> of <em>ε</em><sub>obs</sub> = (160/2) + (15/2) = 87.5 which is in good agreement with the ex­periment.</p>
<p>Along the line joining the two electrodes, the electric field is very strong and reduced below the water surface by a factor 1/<em>ε </em>whereas it is at full strength above the air water surface. A net upward force is thus generated according to Eq. (8).</p>
<p>We conclude that the application of a high electric voltage, through the complex dynam­ics outlined above, gives rise to two levitations: electric and magnetic. These levitations occur along the wall of the vessel with the positive electrode. Only the electric levitation can occur in the grounded vessel.</p>
<p>This prediction is in agreement with the obser­vation of a larger probability of water-column formation. The water-column formation occurs in the HV vessel rather than in the grounded vessel. This is shown by high-speed visualiza­tion in the examples given in Fig. 3 and Fig. 4. For both figures, fringe projection technique is used to contour the bridge and thus enhance its visibility (for details see [7]).</p>
<p>The levitating drops of water, being coherent, are surrounded by the evanescent electromag­netic field, filtering out of the coherent cores. The tail of the evanescent field spans for a length of the same order as the CD radius, so that it could act as an interaction field among the drops within some distant. This distance is in the order of the droplet radius, namely some microns. The possibility of the formation of a string of interacting water droplets emerges and eventually gives rise to the water bridge.</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/fig3.gif" alt="fig3" width="600" height="203" /></p>
<p><em><strong>Figure 3: </strong>High speed visualization of the water bridge formation with glass beakers and fringe projec­tion. (a) shows the beakers before the voltage is applied, (b) – (d) show the levitation of the water in both beakers leading to droplet formation, (e)–(f) show the ejection of a jet from the HV beaker leading to the bridge formation (g), which is stabilized in (h). The water on the HV side (right) is levitated stronger than on the grounded side (left) due to the fact that the water is lifted both electrically and magnetically there, whereas on the grounded side, the levitation is due to electric forces only.</em></p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/fig4.gif" alt="fig4" width="600" height="118" /></p>
<p><em><strong>Figure 4: </strong></em><em>High speed visualization of the water bridge formation with Teflon beakers with fringe projec­tion. (a) shows the situation without high voltage, in (b) and (c) the fringe projection shows the rising of the surfaces, in (d) levitation and droplet formation are shown, and in (e) a connection is finally formed.</em></p>
<p><strong>6. Properties of the Water Bridge <a name="propertiesofthewaterbridge"></a><br />
</strong></p>
<p>The water bridge thus represents a sequence of interacting coherent droplets extracted from the water vessels. The electron coherence illus­trated in Section 3 points to the CDs as reser­voirs of quasi free electrons. On the CD bound­aries a ponderomotive force</p>
<p>(9)   <img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq9.gif" alt="eq9" width="174" height="63" /></p>
<p>acts upon any particle having charge <em>q </em>and mass <em>m </em>present there. Eq. (9) can be easily un­derstood considering that the Hamiltonian of a particle immersed in a vector potential gives rise to a field energy distribution</p>
<p><img src="http://www.waterjournal.org/images/figs/vol2/Fuchs/eq9-2.gif" alt="eq9-2" width="103" height="58" /></p>
<p>which produces in turn the force</p>
<p><strong>F</strong><sub>p</sub> <em>= -</em><strong>grad</strong><em>U </em></p>
<p>The ponderomotive force Eq. (9) pushes the quasi-free electrons outwards with a force many thousand times larger than that acting on the parent molecules. As a consequence, a double layer of charges appears on the boundary of the CDs. The applied strong electric field induces a twofold motion along the bridge. The positive cores of the CDs are pushed along the bridge from the anode to the cathode. This gives rise to a simultaneous transport of mass, whereas the outer, negatively charged, layer slides toward the cathode.</p>
<p>We should remember that the component drop­lets of the water bridge have been extracted from a macroscopic vortex so that their mo­tion along the bridge arises from the superpo­sition of the vortex motion and the electrically induced motion. The final result is a helicoidal motion around the axis of the bridge, a sort of traveling vortex.</p>
<p>According to the topological considerations developed in section 3, the axis of the bridge should be the site of a topological singularity. In other words, no coherence should exist on the axis. Consequently, a negative gradient of the coherent fraction should be observed when going from the outer surface to the axis of the bridge. This prediction is consistent with ob­servation of a negative gradient of the speed of sound in the same direction [9]. Actually, since the coherent region is very much correlated, the speed of sound should be larger in the coherent region than in the non-coherent one.</p>
<p>The peculiar optical properties of the bridge are described in Ref. [7], with particular regard to the change of the polarization angle of linearly polarized light passing through the bridge. As suggested in Ref. [4], this change can be con­nected to both reflection at micro-bubbles un­der the Brewster angle [7], or, as shown in a very recent work, to birefringence due to long-range low-ordering within the bridge [8]. A detailed discussion of this in the framework of QED will be given elsewhere.</p>
<p>Experimental observations [7] have shown that cooling—achieved by, e.g., the addition of ice cubes to the beakers—destabilizes the bridge. This can be easily explained within the pro­posed model. The coherent fraction increases when temperature—and the depth of the inter­stices among them—decreases.</p>
<p>Consequently, the excitation of rotational mo­tion of the CDs becomes more and more diffi­cult. This is the result of the drag produced by the interaction with neighboring CDs through the evanescent fields protruding from inside of them.</p>
<p>At the freezing point, the drag becomes so in­tense that it prevents the formation of vortices. As explained above, the existence of these vor­tices is crucial for the presented analysis; their reduction explains the destabilization of the phenomenon.</p>
<p>Finally, the suggested ordered network of mi­crobubbles would be a natural consequence of the presence of a permanent extended coher­ence as discussed in section 3.</p>
<p><strong>7. Conclusions <a name="conclusions"></a><br />
</strong></p>
<p>Much work is still needed to understand the wealth of the results revealed by the water bridge. However, in this paper we have shown that a consistent framework for understanding this surprising phenomenon can be provided by QED.</p>
<p>Without a doubt, water is one of the most com­mon and most studied substances in the world. The properties of water at mesoscopic scale have drawn special attention lately due to their suggested importance to human physiology [15].</p>
<p>Still, present theories have difficulties explain­ing more than a few of its properties at once, and no theory so far can satisfyingly explain one lately rediscovered phenomenon, the floating water bridge.</p>
<p>The QED approach to this phenomenon pro­vides a possible theoretical background for many of the bridge’s features, such as the vortex formation upon applying a potential; the occur­rence of a cold region prior to the rising of the water; the asymmetric rising of the water in the beakers; the stability of the bridge; the temper­ature dependence of this stability; the correla­tion of charge and mass transfer; the formation of micro and nanobubbles and consequently; and the findings by optical and neutron scatter­ing</p>
<p>Therefore, although unconventional in the field of electro-hydro-dynamics (EHD), quantum field theory can be a powerful tool to bridge the gap between microscopic descriptions and field theories.</p>
<p>This has, until now, been conceived as a quite difficult task [11]. Moreover, some of the de­scribed effects can be found in other experi­ments as well, such as the macroscopic vortices discussed herein.</p>
<p>These vortices, hitherto unexplained, are known as EHDs. Furthermore, an application (as a mo­tor) was discussed recently [48]. Also, the Pol­lack group suggested formation of a clear zone next to gel surfaces [15].</p>
<p>Recently, Cabane et al. stated that water has thus far been a fantastic ”graveyard” for theo­ries that are clever but wrong [27]. It may be appropriate here to stress the well-known fact that no theory can in principle describe reality in all its aspects.</p>
<p>Nevertheless, to the knowledge of the authors, no other theory has been able to describe the floating water bridge as correctly, or in as pre­cise detail, as the quantum field theory. There­fore, it may be prudent to assume that QED is a good choice to describe and understand this special interaction of water with electric fields.</p>
<p><strong>Special Acknowledgments</strong></p>
<p>The authors would like to express their grati­tude to Prof. Jakob Woisetschläger for the per­formance of the presented experiments.</p>
<p><strong>Acknowledgments</strong></p>
<p>With great pleasure, the authors wish to thank Profs. Marie-Claire Bellissent-Funel (Labora­toire Léon Brillouin, Saclay), Eshel Ben-Jacob (Tel Aviv University), Cees Buisman (Wetsus &#8211; Centre of Excellence for Sustainable Water Technology), Friedemann Freund (NASA SETI Institute, Mountain View CA), Karl Gatterer (Graz University of Technology), Franz Heit­meir (Graz University of Technology), Jan C.M. Marijnissen (Delft University of Technology), Laurence Noirez (Laboratoire Léon Brillouin, CEA-CNRS/IRAMIS, CEA-Saclay), Gerald H. Pollack (University of Washington), Alan Soper (Rutherford Appleton Laboratories, Oxford), José Teixeira (Laboratoire Léon Brillouin, CEA-CNRS/IRAMIS, CEA/Saclay), as well as Luew­ton L.F. Agostinho, Ingo Leusbrock and Astrid H. Paulitsch-Fuchs (Wetsus, Centre of Excellence for Sustainable Water Technology) for the ongoing discussion on the water bridge phenomenon (in alphabetic order). Partial financial support from University of Salerno and Istituto Nazio­nale di Fisica Nucleareis also acknowledged.</p>
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<p>[46] Feynman R P, <em>Statistical Mechanics</em>, The Benjamin/Cummings Pub. Co., INC. Reading, MA (1972).</p>
<p>[47] Del Giudice E, Preparata G, unpublished.</p>
<p>[48] Sugiyama H, Ogura H, Otsubo Y, The Society of Rheology 80th Annual Meeting. <em>AIP Conference Proceedings </em>1027 (2008) 1453-1455.</p>
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<p>[51] Chaudhary K C and Redekopp L G, J. <em>Fluid Mech</em>. 96 (1980) 267–74.</p>
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<p>[53] Eggers J and Villermaux E, <em>Rep. Prog. Phys.</em> 71 (2008) 026601 1–79.</p>
<p>[54] Rai D, Kulkarni A D, Gejji S P and Pathak R K <em>J. Chem. Phys.</em> 128 (2008) 34310.</p>
<p>[55] Choi Y C, Pak C, Kim K S, <em>J. Chem. Phys.</em> 124 (2006) 94308.</p>
<p>[56] Teixeira J, Bellissent-Funel M-C, <em>J. Phys.: Condens. Matter</em> 2 (1990) SA105-SA108.</p>
<p>[57] Némethy G, Scheraga H A, <em>J. Chem. Phys.</em> 36 3382,3401 (1962); 41, 680 (1964).</p>
<p>[58]  Walrafen G E,<em> J. Chem. Phys.</em> 47 (1967) 114.</p>
<p>[59] D’Arrigo G, Maisano G, Mallamace F, Migliardo P, Wanderlingh F, <em>J. Chem. Phys</em>. 75 (1981) 4264.</p>
<p>[60] Walrafen G E, Hokmabadi M S, Yang W-H,<em> J. Chem. Phys. </em>85 (1986) 6964.</p>
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<p><strong>Discussion With Reviewers <a name="discussionwithreviewers"></a><br />
</strong></p>
<p>John D. Swain<em><sup>1</sup> </em>: In section IV there is the claim that the beaker system has a nontrivial topol­ogy, but this can’t quite be true since the volume of water in the beaker, even with the electrode excluding some, is contractible and thus topo­logically trivial in the strict sense of the term. I’m sure what is meant is that there is, in some sense, a locally nontrivial topology near the electrode—i.e., there are loops around the elec­trode which are sort of nontrivial in the sense that they can’t be shrunk to zero in a plane that is punctured by the electrode. But one can cer­tainly shrink them if one pulls them around the tip. It might be better to say (if I understand the intention of the authors correctly) that there the topology is nontrivial in some local sense very near the electrode. (By “local” I mean that one does not allow loops drawn around the elec­trode to be pulled very far from it).</p>
<p>Emilio Del Giudice, Elmar C. Fuchs and Gi­useppe Vitiello: We perfectly agree with the referee observation. Indeed, the beaker system exhibits a local non-trivial topology since the (charged) electrode in the beaker center pre­vents the paths closed around it from shrinking to zero (provided, of course, one does not pull these paths around the electrode tip). We have included a short sentence concerning this point in the paragraph after Eq. 5.</p>
<p>Swain: Equation 9 for the ponderomotive force is often written (in tex notation) as F=-\frac{q^2}{4m\omega^2} grad |\vec{E}|^2. This has the advantage of being gauge invariant. If one wants to write it in terms of the vector potential A, I suppose what is being assumed is A oscillating at frequency omega and E=-dA/dt being used with the other factor of 1/2 coming from some time averaging.</p>
<p>Is this correct? If so, one might want to con­sider writing it gauge invariantly, mentioning that the field is oscillating, and that an average is being taken. I know the ponderomotive force assumes a time-varying field, but this may not be immediately obvious to the reader who is not a bit of an expert.</p>
<p>At the moment, one has to know a fair bit of physics to see what this might mean. As it stands, for a general case, one could think that one could make a gauge transformation and get into all sorts of trouble. For example, around a solenoid one has no B, but clearly an A which cannot be made to vanish everywhere (Aha­ronov- Bohm effect) and still there would be no force—I think the assumed time dependence (if I understand this correctly) should be noted.</p>
<p>Similarly, the energy being U=\frac{q^2}{2m}||\vec{A}|^2 would make no sense with­out the time-dependence being made clear. For example, with no time-dependence of A, there would be no electric field and this could be con­fusing to the non-expert.</p>
<p>Del Giudice, Fuchs and Vitiello: We agree with the referee also on this point. We have included in the text a sentence (see the paragraph after Eq. 1) clarifying that throughout the paper, space-time dependence of the variables is understood. Thus, when no misunderstanding arises, we omit writing them explicitly. When necessary we adopt the notation .</p>
<p>Vladimir Voeikov: Why do you look for a quan­tum explanation to the exclusion of the possi­bility of a classical one ?</p>
<p>Del Giudice, Fuchs and Vitiello: An essential step in the formation of the water bridge is the ear­ly appearance of vortices in the water, which are submitted to a high voltage. The result is a quantum feature that exists according to the general relationship coupling the electromag­netic potential to the space-time derivatives of the phase of the matter field. This relationship implies a wave-like energy transfer that does not fade with the distance. This implies a long-lasting adaptive tuning among the oscillations of molecules.</p>
<p>The motion of molecules in a classical frame­work would be diffusive and consequently would be quite random. The existence of coher­ence involving a large number of molecules is a quantum feature without a classical analogue.</p>
<p>Moreover, the ordered raising of large amounts of water—located at the origin of a stable wa­ter bridge—implies the appearance of levitating forces, such as those produced by the Meissner effect in superconductors. Classical mecha­nisms, such as those implied by field induced sprays of water, would hardly produce the for­mation of stable arches. That is due to the fact that classical mechanisms would demand a long-range attraction among the droplets of the sprayed water.</p>
<p>Voeikov: Could the dynamics of formation of the water bridge be also at work in the process of formation of living structures?</p>
<p>Del Giudice, Fuchs and Vitiello: This question could not be answered in a rigorous way at the present moment. However, in living organ­isms there are many examples of quasi one di­mensional structures, dynamically built, which disappear at death. This is the point at which, presumably, the overall coherence of the system fades away. An example is given by the cell cy­toskeleton, whose elements are made up of self-piped water coated by biomolecules resonating with the e.m. field trapped inside. A model of cytoskeleton incorporating such a feature is de­scribed in Del Giudice E., Doglia S., Milani M., Vitiello G., “A dynamical mechanism for cyto­skeleton structures” in Interfacial Phenomena in Biological Systems (Ed. M. Bender) Marcel Dekker Inc, New York (1991), pag. 279-285. Del Giudice E., Doglia S., Milani M., Vitiello G., Electromagnetic field and spontaneous symme­try breaking in biological matter, Nucl. Phys. B275 [FS 17], 185 (1986).</p>
<p>In any case, this question needs much further investigation.</p>
<p><em><sup>1</sup> Professor of Physics, Northeastern University, USA and CERN, Switzerland </em></p>
<p>http://www.waterjournal.org/component/content/article/21-volume-2/77-fuchs-full-text</p>



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		<title>Kozyrev&#8217;s Mirrors</title>
		<link>http://korotkov.org/water/2010/05/kozyrevs-mirrors/</link>
		<comments>http://korotkov.org/water/2010/05/kozyrevs-mirrors/#comments</comments>
		<pubDate>Thu, 27 May 2010 06:33:15 +0000</pubDate>
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				<category><![CDATA[Articles about Water]]></category>
		<category><![CDATA[Magic Water]]></category>
		<category><![CDATA[Physics of Water]]></category>
		<category><![CDATA[Alexander V. Trofimov]]></category>
		<category><![CDATA[Kozyrev]]></category>
		<category><![CDATA[Kozyrev's Mirrors]]></category>

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		<description><![CDATA[Kozyrev&#8217;s Mirrors and Electromagnetic Null Zones: Reflections of Russian Cosmic Science Interview with Alexander V. Trofimov, MD By Carol Hiltner Imagine standing under a vast, scintillating aurora borealis, and seeing it change colors as you changed your thoughts. This exact situation led Russian medical doctor Alexander V. Trofimov into his groundbreaking research on human consciousness,<a href="http://korotkov.org/water/2010/05/kozyrevs-mirrors/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p><strong>Kozyrev&#8217;s Mirrors and Electromagnetic Null Zones:<br />
Reflections of Russian Cosmic Science</strong></p>
<div id="attachment_113" class="wp-caption alignnone" style="width: 310px"><a href="http://korotkov.org/water/wp-content/uploads/2010/04/IMG_0781.jpg"><img class="size-medium wp-image-113" title="IMG_0781" src="http://korotkov.org/water/wp-content/uploads/2010/04/IMG_0781-300x199.jpg" alt="Kozyrev's Mirrors" width="300" height="199" /></a><p class="wp-caption-text">Kozyrev&#39;s Mirrors</p></div>
<p>Interview with Alexander V. Trofimov, MD By Carol Hiltner</p>
<p>Imagine standing under a vast, scintillating aurora borealis, and seeing it change colors as you changed your thoughts. This exact situation led Russian medical doctor Alexander V. Trofimov into his groundbreaking research on human consciousness, in collaboration with Vlail P. Kaznacheev, and following in the footsteps of the great 20th century physicist Nikolai Kozyrev.<span id="more-188"></span></p>
<p>Essentially, Kozyrev devised reproducible experiments that prove the existence of a &#8220;torsional energy field&#8221; beyond electromagnetism and gravity, which travels much faster than light. He called it the &#8220;flow of time.&#8221; Others, Einstein among them, have called it &#8220;ether.&#8221; Others call it &#8220;zero point energy.&#8221;</p>
<p>Within this &#8220;flow of time,&#8221; the past, present, and future all exist at the same time, and in every place. This discovery sets the stage for all psychic phenomena to be scientifically explainable. Trofimov and Kaznacheev have, for the past thirty years, been experimentally developing the practical explanations, and have made some surprising discoveries.</p>
<p>When I visited Trofimov&#8217;s laboratories at the International Scientific Research Institute for Cosmic Anthropo-Ecology in Novosibirsk, where he is general director, he enthusiastically showed us his two main experimental apparati — two hollow, metal, person-sized tubes, equipped with mattresses and drinking water.</p>
<p>The first, dubbed &#8220;Kozyrev&#8217;s Mirrors,&#8221; reflects thought energy (which exists within the &#8220;flow of time&#8221;) back to the thinker. This apparatus, invented by Kozyrev, gives access to intensified consciousness and altered states, including non-linear time — similar to a deep meditational state.</p>
<p>Trofimov&#8217;s work has consisted of &#8220;remote viewing&#8221; experiments across both distance and time. They discovered that results are more positive when the &#8220;sender&#8221; is in the far north, where the electromagnetic field is less powerful. So they invented a second apparatus that shields an experimental subject from the local electromagnetic field. Within this apparatus, their subjects can reliably access all place and time — past, present, and future — instantaneously. Construction specifications for these apparati are published in Russian scientific literature.</p>
<p>Among Trofimov and Kaznacheev&#8217;s conclusions are:</p>
<p>1) our planet&#8217;s electromagnetic field is actually the &#8220;veil&#8221; which filters time and place down to our everyday Newtonian reality — enabling us to have the human experience of linear time,</p>
<p>2) in the absence of an electromagnetic field, we have access to an energy field of &#8220;instantaneous locality&#8221; that underlies our reality,</p>
<p>3) that the limiting effect of the electromagnetic field on an individual is moderated by the amount of solar electromagnetic activity occurring while that person was in utero, and</p>
<p>4) that once a person has accessed these states, his or her consciousness remains so enhanced.</p>
<p>The implication is that the global electromagnetic soup of cell phones, radio, television and electric appliances actually impedes our innate communication abilities. The further implication is that expanded human consciousness is mechanically producible now, which raises the vast ethical question of how these apparati can be most beneficially used.</p>
<p>Carol: Alexander, why did you begin doing research in this field?</p>
<p>Trofimov: I very clearly remember the moment. It was March, 1975. After my post-graduate education, my first expedition as junior scientific researcher was to Dixon — a small village in the far north, which is located above 73 degrees latitude. It was to study adaptation of human organism to the conditions of the far north — a great experiment of U.S.S.R. Academy of Sciences. I worked with Kaznacheev, who was the creator of the civilian department of this Academy. I began my investigation as a cardiologist, studying the reaction of the cardiovascular system and the importance of different magnetic conditions.</p>
<p>I stepped outside our hospital to see the aurora borealis, which was like a cone over our building. This first impression was wonderful! I felt that we were interacting, that what I thought was changing the colors of the aurora borealis. I didn&#8217;t know whether it was my consciousness or cosmic consciousness. Only later did we learn about cosmic consciousness. But it was a beginning for me.</p>
<p>I continued my investigation as a doctor, and from approximately 1990, with Academician Kaznacheev, we began new cycle of work — the study of cosmic consciousness. Let me show you Kozyrev&#8217;s Mirrors. This apparatus is the grandfather of Kozyrev&#8217;s Mirrors — the first generation. Now we have seven generations. Carol: But why is this called a mirror? Where is the mirror?</p>
<p>Trofimov: We use the law of optical reflection — which also applies to streams other than light. When the surface is curved, according to this law, the energy is focused.</p>
<p>Kozyrev was also an astronomer. He created a small mirror to put inside a telescope, which he focused on one of the stars. And he programmed it for three times: one year in the past, the present, and one year in the future.</p>
<p>Carol: And how did he program that?</p>
<p>Trofimov: He simply calculated, using some mathematical methods. He had the know-how to calculate where it was, where it should be, and where it is — its projected location. So he realized that the star is present everywhere — in the past, present, and future.</p>
<p>Carol: But that is common knowledge. What was the discovery?</p>
<p>Trofimov: We wanted to prove it in a scientific way. Kozyrev proved it in astronomical terms. Our task was to prove it in biological terms. So the legacy of Kozyrev was that, if people could create such kinds of apparatus that are capable of creating density of the energy of time, from this point they could have the opportunity to visit any place in the universe.</p>
<p>We created such an apparatus, and called it Kozyrev&#8217;s Mirrors. It takes the energy not out of the stars, but out of the human being — being a star. (Carbonaceous life forms, such as those on Earth, are one stage of a star&#8217;s evolution.) And these streams coming out of human beings, they are not allowed to go everywhere in the space, but they are concentrated here, creating this density of the streams of time and energy. But a human being should be specially prepared, and when he spends some time inside, he finds himself in a particular state of mind. He can travel to any part of the planet. And there is a special &#8220;ray&#8221; enabling him to be in this or that part of the planet. We used this kind of apparatus for our experiment for distant communication with Dixon.</p>
<p>Basically, there was a person inside the mirrors who was given symbols that he was supposed to project, and there were people all around the world who were supposed to receive.</p>
<p>Carol: Were they also in mirrors?</p>
<p>Trofimov: No, they were in an ordinary life situation, but they knew the time. There were three special sessions for investigating the role of television and radio. The person inside the mirrors projected the symbols and they made a television recording of it. They showed these recording to people from Dixon. They also made television recordings of three sessions in which a person projected symbols, but was not inside the mirrors. And almost 80% of the people who took part in this experiment received the information. The results using the television recording were even better than straight from the mirrors. Another interesting detail: the people who were receiving the information were asked to simply switch on their television, without even sound or images, but just power, and it gave the opportunity to receive this information more effectively. So this space around the planet, and television and radio space interrelate. And they approached the world with special precautions so that people would know the interrelationship of space and radio waves. It was very important. So, fifteen years ago, they made this research and realized these consequences.</p>
<p>Carol: Well, the whole planet is an electronic soup, with radio waves on all frequencies.</p>
<p>Trofimov: Yes, exactly. So, to the next room … This is a &#8220;cosmobiotron&#8221; clinical device. There are two here — the only ones in the whole world. Inside this apparatus, the electromagnetic field is reduced almost to nothing, which allows us to go anywhere in space. Just to be free, out of the magnetic field of the earth.</p>
<p>Carol: How does it do that?</p>
<p>Trofimov: Inside this shell are several layers of a special steel called &#8220;permalloy&#8221; that has magnetic &#8220;receiving qualities,&#8221; that is sensitive to magnetism. Inside the tube, the magnetic field is diminished 600 times.</p>
<p>Currently, the Earth&#8217;s magnetic field has 49,000 nano-Teslas. It has been decreasing by about 50-70 nano-Teslas per year. By the end of the millennium, we&#8217;ll have only 100-200 nano-Teslas. So, this apparatus allows us to emulate the situation that we will have 1000 years in our future.</p>
<p>[He sat down on the open end of the tube]. Where I&#8217;m sitting now, the magnetic field is how it will be on Earth in 100 years. As I move further into the apparatus, the magnetic field is decreased, as it will be on Earth further into the future. We measure the results every 15 centimeters, which is equivalent to 100 years. In a thousand years, we will be somewhere in the middle of this apparatus.</p>
<p>This apparatus is the most important research instrument for assessment of the evolutionary consequences of the fluctuation of Earth&#8217;s magnetic field.</p>
<p>Carol: What is the result of that diminished magnetic field?</p>
<p>Trofimov: As the force of the magnetic field is decreased, the sun&#8217;s energies will penetrate more.</p>
<p>Carol: So the magnetic field protects us from the solar rays?</p>
<p>Trofimov: Yes, and also cosmic rays — galactic protons, for example. The less protection there is, the more particles can reach us.</p>
<p>Carol: Is the ozone layer a different mechanism?</p>
<p>Trofimov: Somewhat different. The ozone layer filters only the ultraviolet part of the spectrum.</p>
<p>So we have a profound opportunity to really emulate what will happen with any living creature or human being, century by century — how we will co-exist with these energies from space. What will happen? Either our mind reserves or extra abilities will open, or on the contrary they will be limited, and some catastrophe will happen. So basically, this is a like a theatrical stage, where we can see how the fate of human life will play in a thousand years.</p>
<p>We have been working more than 15 years, so we do have results. Part of our results have been published, and we are preparing to publish more.</p>
<p>Now I will say something important. As we investigate brain activity — either with an electro-encephalogram, or by assessing brain functions like intellect level, memory, and other functions, we realize that we currently use only 5% of the capacity of our brains throughout our whole lives. And then, after we spend some time inside the apparatus — in a space without magnetism — we repeat the same tests, and we see a drastically different picture. We see that our mind&#8217;s additional reserves and abilities are activated. We see an increase in memory capacity, increased IQ, and changing zones of electric activity of the brain.</p>
<p>Carol: Is this because of the reduction in magnetic field?</p>
<p>Trofimov: When the magnetic field is decreased, we see an increasing ability to use the reserves and capacity of the human brain, and that&#8217;s good. But there is still a question of whether it is good for everyone. How quickly should these reserves be opened in real life, and for what would these resources be used. Why should we access these resources? What is the practical use of this opportunity? Just opening the resources is not a panacea.</p>
<p>We need a scientifically rigorous forecasting model — not a purely theoretical one — about what will happen with us, and how this knowledge can be used right now to educate. For example, how long should a person be inside to increase his memory capacity without waiting a hundred years. We are now doing practical research on how to make use of this phenomenon.</p>
<p>There&#8217;s another important point. When a person is inside, his brain function is in direct correlational dependency not only with solar energies, but with galactic rays. So we thereby open a request for information from the galaxy.</p>
<p>We believe that this is the mechanism by which cosmic human consciousness is currently being opened, with the decreasing electromagnetic field. This shift is opening people&#8217;s &#8220;cosmophile&#8221; properties — properties that we are lacking right now in this &#8220;cosmophobe&#8221; world. But we cannot bring the whole of humanity onto this cosmophilic life-raft, because we are only in the experimental scientific stage that allows us to make a forecast and back it up experimentally.</p>
<p>According to the Russian writer and philosopher Gumilev, balance or imbalance in the number of cosmophobes or cosmophiles in any society or ethnic group defines the fate of this society or ethnic group.</p>
<p>So what can we do? For the survival of our civilization, we have to foster the cosmophiles. And for this, we need to open these resources. While we can give people this possibility, we cannot order or force them to be cosmophiles. We need a well-coordinated system to guide people to this source.</p>
<p>Alexander V. Trofimov, MD, is General Director of the International Scientific Research Institute for Cosmic Anthropo-Ecology, which was founded in 1994 for scientific investigation, and is located in Academic City, Novosibirsk, Russia.</p>



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		<title>RESPIRATION OF WATER</title>
		<link>http://korotkov.org/water/2010/05/respiration-of-water/</link>
		<comments>http://korotkov.org/water/2010/05/respiration-of-water/#comments</comments>
		<pubDate>Sat, 08 May 2010 16:21:08 +0000</pubDate>
		<dc:creator>admin</dc:creator>
				<category><![CDATA[Articles about Water]]></category>
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		<category><![CDATA[Vladimir Voyeykov]]></category>
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		<description><![CDATA[RESPIRATION OF WATER Vladimir L. Voeikov Faculty of Biology, Lomonosov Moscow State University, Moscow, Russia Respiration is a chemical process whereby cells use oxygen to release energy; a technical term for &#8220;breathing&#8221;. According to common knowledge aerobic respiration is restricted to glucose oxidation to carbon dioxide and water (a process reverse to photosynthesis) in which<a href="http://korotkov.org/water/2010/05/respiration-of-water/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p>RESPIRATION OF WATER</p>
<p><a title="Water" href="http://korotkov.org/water/"><img class="alignnone size-medium wp-image-127" title="IMG_3612" src="http://korotkov.org/water/wp-content/uploads/2010/04/IMG_3612-193x300.jpg" alt="" width="193" height="300" /></a> <strong>Vladimir L. Voeikov</strong><br />
Faculty of Biology, Lomonosov Moscow State University, Moscow, Russia<span id="more-170"></span></p>
<p>Respiration is a chemical process whereby cells use oxygen to release energy; a technical term for &#8220;breathing&#8221;. According to common knowledge aerobic respiration is restricted to glucose oxidation to carbon dioxide and water (a process reverse to photosynthesis) in which energy is stored in the form of ATP molecules that are used to provide energy for all vital activities. It is also generally accepted that atmospheric oxygen ensuring respiration emerged as a by-product of plant photosynthesis, while oxidizable organic compounds appeared in the course of pre-biotic evolution in oxygen-free milieu.</p>
<p>However, recently there appeared evidence that water molecules in aqueous systems may decompose to H2 and O2 under the influence of mechanical and other low density energy factors in rather mild conditions (close to neutral pH values, normal temperature, ets.). Intensity of this process is high enough to provide accumulation of oxygen in atmosphere up to contemporary levels in relatively short historical period without participation of biological photosynthesis. On the other hand there appeared evidence that oxygen can directly oxidize water to hydrogen peroxide. In many reactions of direct oxidation by oxygen of its substrates free radicals emerge as intermediate products. Such reactions are accompanied with generation of electronic excitation energy equivalent to energy of visible and even UV light photons and may be monitored by registration of ultra-weak photon emission from systems where they go on.</p>
<p>We used the method of single photon counting for the analysis of the properties of pure water, artesian waters, tap water and other kinds of aqueous systems, including aqueous solutions of simple bioorganic molecules in which processes of their spontaneous autoxidation develop. We have shown that in many kinds of artesian water contacting with air there develop a process of autoxidation of water, and that at least part of energy released as it goes on does not dissipate but rather may accumulate in water and may be released as photonic energy or used for the performance of chemical work.</p>
<p>Formally this phenomenon may be defined as “Respiration of water”. Different patterns of photon emission including non-linear oscillatory ones may be observed dependent on a particular aqueous system. The process of accumulation of energy in water equivalent to the levels of electron excitation energy, the patterns of photonic emission oscillations turned out to be highly responsive to very low intensity external factors including irradiation of aqueous systems with radiations of ultra-weak intensities. The probable role of these processes for the biological properties of drinking water and water participation in vital processes is considered.</p>
<p>Taken as a whole the new information on phenomena related to oxidation-reduction processes arising in water and aqueous systems calls for the serious re-evaluation of many currently dominating biological concepts related to all levels of organization of biological systems – from molecular to biospheric ones.</p>



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		<title>PERSPECTIVES OF DEVELOPMENT OF PHARMACEUTICAL AND COSMETIC PRODUCTS WHICH DO NO DISTURB THE WATER STRUCTURE IN HUMAN TISSUES</title>
		<link>http://korotkov.org/water/2010/05/perspectives-of-development-of-pharmaceutical-and-cosmetic-products-which-do-no-disturb-the-water-structure-in-human-tissues/</link>
		<comments>http://korotkov.org/water/2010/05/perspectives-of-development-of-pharmaceutical-and-cosmetic-products-which-do-no-disturb-the-water-structure-in-human-tissues/#comments</comments>
		<pubDate>Sat, 08 May 2010 16:19:28 +0000</pubDate>
		<dc:creator>admin</dc:creator>
				<category><![CDATA[Articles about Water]]></category>
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		<guid isPermaLink="false">http://korotkov.org/water/?p=167</guid>
		<description><![CDATA[PERSPECTIVES OF DEVELOPMENT OF PHARMACEUTICAL AND COSMETIC PRODUCTS WHICH DO NO DISTURB THE WATER STRUCTURE IN HUMAN TISSUES Semichina L.P. Russia, Tumen Federal University Proposed ideas are based on the results of the research of water properties in the tissues of animals in-vivo using dielectric L-method developed by the author [1-2]. In this approach subjects<a href="http://korotkov.org/water/2010/05/perspectives-of-development-of-pharmaceutical-and-cosmetic-products-which-do-no-disturb-the-water-structure-in-human-tissues/">&#160;&#160;[ Read More ]</a>]]></description>
			<content:encoded><![CDATA[<p>PERSPECTIVES OF DEVELOPMENT OF PHARMACEUTICAL AND COSMETIC PRODUCTS WHICH DO NO DISTURB THE WATER STRUCTURE<br />
IN HUMAN TISSUES</p>
<p>Semichina L.P.<br />
Russia, Tumen Federal University<span id="more-167"></span><br />
Proposed ideas are based on the results of the research of water properties in the tissues of animals in-vivo using dielectric L-method developed by the author [1-2]. In this approach subjects under study are placed in a weak vortex electrical field of the L-cell of the solenoid measuring coil with a field strength E = 1-100 microV/cm and fre-quency 10 kHz – 40 MHz. In accordance with [2] these fields are too weak to change the orientation of the bio-molecules. That is why L-method allows to distinguish input from polarization effect of water solutions inside the tissues of biological subjects having high moisture with the background of many polar molecules and evaluate the condition of these solutions based on frequency  , where they have maximum of dielectric loss tangent (tg). Shift of tg of water solution in any subject under the influence of different factors to the higher frequency band indicates the decrease of structurization, while shift to the lower frequency band on the contrary indicate the increase of structurization.</p>
<p>Study of the tissues of animals based on abovementioned approach revealed the increase of the level of water structurization for different organisms in the process of evolution development. The highest level of water structurization was found for mammalians and in particular humans.</p>
<p>This highly structured state of water solution is inherent only to the living animals and is disturbed under the influence of stresses, Ultra Violet, Ultra High Frequency and strong electromagnetic fields. It is well known that both stress and electromagnetic rad-iations increase the risk of oncological, cardiovascular and other diseases.  This indicate to the correlation between the health condition and the state of water in tissues. So we can tell about positive effects of restoration of damaged water structure in the tissues of animals.</p>
<p>We suggested to solve this problem using weak electromagnetic fields of the par-ticular frequency and amplitude [3]. But on a large-scale for mass-population this problems may be solved by using an appropriate food, pharmaceutical and cosmetic products.<br />
Result of investigation of food products was negative up till the latest time. Intro-duction into water of any impurities including juices and syrups of fruits, berries and vegetables led to the decrease of water structurization. The only exclusion was found to be honey. Solution of water with honey is nearer to the tissue water on their dielectric properties compared with initial water or any other solutions.</p>
<p>Testing of medications on their properties to change the condition of distilled wa-ter revealed strong difference even for one and the same drug produced by different companies. There are drugs which practically do not change the structure of water as well as others which totally destroy it. For example, the former are glucose and some antibiotics, the latter are Fervex and Coldrex. In accordance with our data the fast ef-fects of Fervex and Coldrex are provided by the strong destruction of structured state of tissue water which decreases the speed of exchange processes. But if the human or-ganism will not be able to restore the structure of water in tissues, damaged both by the illness and by medications, circumstances may be quite negative.</p>
<p>Testing of different cosmetic products (shampoo, liquid soups, balsams, and creams) produced by different companies demonstrated that all of them change the structure of water to some extend. This is illustrated by the experimental data for sev-eral creams (fig.1). As we see from the graphs the tg maximum frequency for all creams is higher compared with honey. So these cosmetic products are unable to restructure the damaged structure of tissue water.</p>
<p><img src="http://electrophotonics.net/images/stories/2000/69.jpg" alt="" border="0" /></p>
<p>It is also important to note that the amplitude of tg maximum for all cosmetics was lower compared with honey. The amplitude of tg maximum is defined by inter-molecular interactions in the particular substance, so the lower amplitude for the cosmetics may indicate the wrong choice of ingredients with low inter-molecular interaction and hence low effectiveness. Plus, this indicates the absence of synergism between components of the particular cosmetics. The synergism effect means that composition of the two or more surface- or biologically active substances is more effective compared with each individual component. This effect is related to the increase of inter-molecular interactions in the mixture and may be detected by the increase of tg for the mixture [2].</p>
<p>We believe that using developed in [2] approach it is much easier to find the syn-ergetic mixture of ingredients for different applications.</p>
<p>References<br />
1.    Семихина Л.П. Способ определения диэлектрических параметров воды и ее растворов в низкочас-тотной области с помощью L-ячейки. Патент РФ № 2234102. //БИПМ. №6. 2004.<br />
2.    Семихина Л.П. Низкочастотная диэлькометрия жидкостей в слабых вихревых электрических полях. Докторская дисс. Санкт-Петербург. 2006. 230 с.<br />
3.    Семихина Л.П. Способ изменения свойств протонсодержащих объектов и устройство для его реали-зации. Патент РФ № 2196320 // БИПМ. 2003. №1(часть II). С. 346.</p>



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