Dihydrogen OxideDihydrogen Oxide

That means… 2 hydrogensThat means… 2 hydrogens

And one oxygen!And one oxygen!

Aka: Water, aka: H “two” OAka: Water, aka: H “two” O

All Behavior from Simple All Behavior from Simple GeometryGeometry

Odorless, Tasteless Odorless, Tasteless and Transparentand Transparent

Polar and Polar and DiamagneticDiamagnetic

70% of Earth’s 70% of Earth’s SurfaceSurface

70% of our 70% of our compositioncomposition

Electronic PropertiesElectronic Properties

•10 electrons completely filling the valence shell

•Hydrogens donate their electrons to the more electronegative Oxygen

•Oxygen has two lone pairs that make a tetrahedral arrangement with the Hydrogens below

•The bond character is “resonant”, i.e. a mixture of ionic and covalent character

•Overall dipole moment of 1.86 Debye.

* 1 Debye = 10−18 esu centimeter or about 3.336 × 10−30 coulomb meters

Orbitals of WaterOrbitals of Water

EnergiesEnergies -559 eV-559 eV

-37 eV-37 eV

-19 eV-19 eV

-15 eV-15 eV

-14 eV-14 eV

3a3a11 most contribution to H- most contribution to H-bondsbonds*Calculation of Restricted Hartree-Fock *Calculation of Restricted Hartree-Fock wave function with 6-31G** basis setwave function with 6-31G** basis set

Strange Temperature Strange Temperature DependenceDependence

• When Cold water (~ 0 D C) is increasing When Cold water (~ 0 D C) is increasing temperaturetemperature

VolumeVolume Decreases (-)Decreases (-) Gas solubilityGas solubility Decreases Decreases (-)(-)

CompressibilityCompressibility Decreases (-)Decreases (-) Heat capacityHeat capacity Decreases Decreases (-)(-)

Refractive indexRefractive index Increases (+)Increases (+) Thermal Thermal conductivityconductivity

Increases Increases (+)(+)

Speed of SoundSpeed of Sound Increases (+)Increases (+)

Strange Temperature Strange Temperature DependenceDependence

• When Hot Water is increasing temperature: When Hot Water is increasing temperature: There is a completely There is a completely oppositeopposite effect effect

VolumeVolume Increases Increases (+)(+) Gas SolubilityGas Solubility Increases Increases

(+)(+)

CompressibilityCompressibility Increases Increases (+)(+) Heat CapacityHeat Capacity Increases Increases

(+)(+)

Refractive IndexRefractive Index Decreases Decreases (-)(-)

Thermal Thermal ConductivityConductivity

Decreases Decreases (-)(-)

Speed of SoundSpeed of Sound Decreases Decreases (-)(-)

Anomalous behaviorAnomalous behavior(not predictable from Group 6A [i.e. H(not predictable from Group 6A [i.e. H22S] and Group S] and Group 4A [i.e. CH4A [i.e. CH44] hydrides)] hydrides)

Highest Heat Capacity Highest Heat Capacity besides Ammonia (1 cal/g)besides Ammonia (1 cal/g)

Highest Latent Heat of Fusion Highest Latent Heat of Fusion besides Ammoniabesides Ammonia

Regulates Temp of Earth Regulates Temp of Earth Ocean regulates many Ocean regulates many ecosystems ecosystems

LLff = 79.71 cal/g = 79.71 cal/g

Also regulating climateAlso regulating climate

Highest Latent Heat of Highest Latent Heat of Vaporization KnownVaporization Known

Highest Surface Tension Highest Surface Tension besides Mercury and few besides Mercury and few other High-T liquid metalsother High-T liquid metals

LLvv = 539.55 cal/g = 539.55 cal/g

Hurricanes as a result of Hurricanes as a result of condensationcondensation

T = 75.6 dynes/cmT = 75.6 dynes/cm

Gives rise to Capillary Gives rise to Capillary action, thus plants can action, thus plants can live…live…

Continuing Anomalous Continuing Anomalous behaviorbehavior• Expansion upon Freezing!Expansion upon Freezing!

Explained by Tetrahedral open structure when frozen. Explained by Tetrahedral open structure when frozen. Collapses while melting and water will then increase Collapses while melting and water will then increase Coordination number from 4 to 4.4 as heated from 0 to Coordination number from 4 to 4.4 as heated from 0 to 3.984 3.984 DD C. C.

Crystal structure of water includes >12 phases with new Crystal structure of water includes >12 phases with new phases still being postulated today. Many with higher phases still being postulated today. Many with higher density than liquiddensity than liquid

Ice floating and water freezing from the top down is an Ice floating and water freezing from the top down is an important consequence for ecosystems of lakes and important consequence for ecosystems of lakes and rivers.rivers.

Supercooled water has astounding properties which may Supercooled water has astounding properties which may be predicted by structures much larger than expected.be predicted by structures much larger than expected.

17 polymorphs of H17 polymorphs of H22O as IceO as Ice See See http://www.lsbu.ac.uk/water/phase.htmlhttp://www.lsbu.ac.uk/water/phase.html

What’s going on in my What’s going on in my freezer??freezer??

Potential of hydrogen bondingPotential of hydrogen bonding

• The potential as a function The potential as a function of distance between two 4-of distance between two 4-molecule tetramers of molecule tetramers of waterwater

• First minimum is from non-First minimum is from non-bonded interactions. bonded interactions. Second is highly directional Second is highly directional in naturein nature

Thus, low-T H-bonded water Thus, low-T H-bonded water networks hold molecules networks hold molecules apart as well as provide a apart as well as provide a strong geometry. More of strong geometry. More of these types of polymers these types of polymers follow.follow.

Pretty pictures of these molecular Pretty pictures of these molecular structures (one of highest possible structures (one of highest possible symmetries in nature)symmetries in nature)

Cyclic pentamer       Bicyclo-octamer       Tricyclo-decamer

Icosahedron symmetries

15 2-fold axes

10 3-fold axes

6 5-fold axes

Faces are:

12 regular pentagons

20 regular triangles

30 rectangles

Icosahedra predicted…Icosahedra predicted……and found!…and found!• Proposed by:Proposed by: M. F. Chaplin, A proposal for the structuring of water, M. F. Chaplin, A proposal for the structuring of water, Biophys. Chem.Biophys. Chem. 8383

(2000) 211-221. (2000) 211-221.

• Found from X-ray diffraction of water nanodrops by:Found from X-ray diffraction of water nanodrops by: A. Müller, H. Bögge and E. Diemann, Structure of a cavity-encapsulated A. Müller, H. Bögge and E. Diemann, Structure of a cavity-encapsulated

nanodrop of water,nanodrop of water, Inorg. Chem. Commun. Inorg. Chem. Commun. 66 (2003) 52-53; Corrigendum: (2003) 52-53; Corrigendum: A. Müller, H. Bögge and E. Diemann, A. Müller, H. Bögge and E. Diemann, Inorg. Chem. Commun.Inorg. Chem. Commun. 66 (2003) 329 (2003) 329

• The calculations with the collapsed and extended structures The calculations with the collapsed and extended structures of the icosahedral states can predict: of the icosahedral states can predict:

temperature-density and pressure-viscosity behavior, the radial distribution pattern of Oxygen-Oxygen distances, the presence of both cyclic pentamers and hexamers, the change in properties on supercooling and the solvation and hydration properties of ions, hydrophobic molecules, carbohydrates and macromolecules..

Vibrational Modes and Absorption Vibrational Modes and Absorption SpectraSpectra

Most likely the most relevant to material discussed in this class…Most likely the most relevant to material discussed in this class…

Some absorption notes…Some absorption notes…• Blue hue of water due to least absorption of blue Blue hue of water due to least absorption of blue

frequencies…frequencies…• Infrared peaks would be most notable in contribution Infrared peaks would be most notable in contribution

to biophysical processes since all living organisms to biophysical processes since all living organisms maintain autonomous thermodynamic work cycles at maintain autonomous thermodynamic work cycles at temperatures corresponding to the liquid phase of temperatures corresponding to the liquid phase of water.water.

• Farther below the scale of the plot is the microwave Farther below the scale of the plot is the microwave absorption spectrum which primarily interacts with absorption spectrum which primarily interacts with the dipole moment of the water molecule. Energy the dipole moment of the water molecule. Energy loss as friction provides the heat generated in your loss as friction provides the heat generated in your microwave.microwave.

• Note: The absorption spectra maintained in this figure Note: The absorption spectra maintained in this figure and in the following numbers is for and in the following numbers is for bulkbulk water. Some water. Some spectra calculations for nanoscale droplets will follow.spectra calculations for nanoscale droplets will follow.

WavelengtWavelength h

cmcm-1-1 AssignmentAssignment WavelengtWavelengthh

cmcm-1-1 AssignmentAssignment

0.2 mm0.2 mm 5050 Intramolecular Intramolecular bendbend

1470 nm1470 nm 68006800 avav11+bv+bv33; a+b=2; a+b=2

55 55 mm 183.4183.4 Intramolecular Intramolecular stretchstretch

1200 nm1200 nm 83308330 avav11+v+v22+bv+bv33; ; a+b=2a+b=2

25 25 mm 395.5395.5 Librations, LLibrations, L11 970 nm970 nm 1031010310 avav11+bv+bv33; a+b=3; a+b=3

15 15 mm 686.3686.3 Librations, LLibrations, L22 836 nm836 nm 1196011960 avav11+v+v22+bv+bv33; ; a+b=3a+b=3

6.08 6.08 m m 16451645 vv22, bend, bend 739 nm739 nm 1353013530 avav11+bv+bv33; a+b=4; a+b=4

4.65 4.65 mm 21502150 vv22 + L + L22 660 nm660 nm 1515015150 avav11+v+v22+bv+bv33; ; a+b=4a+b=4

3.05 3.05 mm 32773277 vv33, asymmetric , asymmetric stretchstretch

606 nm606 nm 1650016500 avav11+bv+bv33; a+b=5; a+b=5

2.87 2.87 mm 34903490 vv11, symmetric , symmetric stretchstretch

514 nm514 nm 1946019460 avav11+bv+bv33; a+b=6; a+b=6

1900 nm1900 nm 52605260 avav11+v+v22+bv+bv33; ; a+b=1a+b=1

a and b are integersa and b are integers

Nanoscale dropletsNanoscale droplets(may have far reaching consequences for biological molecules (may have far reaching consequences for biological molecules since water is ubiquitous and often is present within proteins)since water is ubiquitous and often is present within proteins)

Plot of absorption coefficient in droplets at specific radii of Plot of absorption coefficient in droplets at specific radii of micelles (water droplets stabilized in heptane by surfactant micelles (water droplets stabilized in heptane by surfactant sodium bis(2-ethylhexyl) sulfosuccinate {AOT})sodium bis(2-ethylhexyl) sulfosuccinate {AOT})

-Smallest micelles show absorption coefficient ~8 times that -Smallest micelles show absorption coefficient ~8 times that of bulk water.of bulk water.

This plot is the calculated Density This plot is the calculated Density of Modes as a function of of Modes as a function of frequencyfrequency

a) R = 2 nm, b) R = 5 nm, c) R = 9 a) R = 2 nm, b) R = 5 nm, c) R = 9 nmnm

Arrow signifies cutoff from Surface Arrow signifies cutoff from Surface Modes. Modes.

This plot shows measured This plot shows measured Peak absorption frequency Peak absorption frequency and the solid line is the and the solid line is the expected absorption due to expected absorption due to dominant surface modes.dominant surface modes.

As micelle size decreases, the As micelle size decreases, the water pool radius drops and water pool radius drops and the water inside becomes the water inside becomes more structured. This internal more structured. This internal structure seems to be structure seems to be providing the large absorption.providing the large absorption.

The integrated absorption strength of the measured spectra as a function of water pool radius.

The authors write:“It should be noted that narrow well-resolved resonances are almostunprecedented in far-infrared liquid-state spectroscopy. These observations have important implications for any chemical, biological, or catalytic processes in which sequestered water plays a role. Since solvent vibrations are crucial in determining the rates of many chemical reactions, these results raise the intriguing possibility that the design of certain active biomolecular subunits may be optimized to exploit the enhanced vibrational density of states induced by the confinement.” J. Boyd, A. Briskman, V. Colvin, and D. Mittleman, Phys. Rev. Lett. 87,

147401(2003)

Protein-Water Simulations Protein-Water Simulations inconclusive and not worth inconclusive and not worth includingincluding

• Several papers currently published suggesting that hydrogen-Several papers currently published suggesting that hydrogen-bond dynamics are correlated with protein structural bond dynamics are correlated with protein structural relaxation… ummm… yeah.relaxation… ummm… yeah.

• If we restrict the water molecules, proteins respond similar to If we restrict the water molecules, proteins respond similar to dehydration.dehydration.

• Complete structural relaxation necessitates relaxation of the Complete structural relaxation necessitates relaxation of the hydrogen-bond network. This is known to occur relative to Acid-hydrogen-bond network. This is known to occur relative to Acid-Base chemistry (pH dependence on folding). Base chemistry (pH dependence on folding). Note to self:Note to self: Acid- Acid-Base chemistry doesn’t exist without water. Base chemistry doesn’t exist without water.

• One paper in particular used Molecular Dynamics Simulations One paper in particular used Molecular Dynamics Simulations starting with RNase in a crystal at 100, 150, 200, 250, and 300K. starting with RNase in a crystal at 100, 150, 200, 250, and 300K. Also included was a powder with slight hydration at 300K. Also included was a powder with slight hydration at 300K.

M. Tarek and D.J. Tobias, Phys. Rev. Lett. M. Tarek and D.J. Tobias, Phys. Rev. Lett. 8888, 138101(2002), 138101(2002)

Reactive Oxygen Reactive Oxygen SpeciesSpecies

• Necessary for Respiration in Necessary for Respiration in Mitochondria, BUT… only a Mitochondria, BUT… only a little! Large numbers can little! Large numbers can create chains of causal create chains of causal reactions creating more and reactions creating more and more reactive species more reactive species breaking down structures of breaking down structures of nearby proteins.nearby proteins.

• Some of these reactive Some of these reactive species are :species are :

• Outside of Hypochlorite, All ROS are simple Outside of Hypochlorite, All ROS are simple Hydrogen and Oxygen inclusive molecular Hydrogen and Oxygen inclusive molecular ions.ions.

• It is known that ROS may be created in Water It is known that ROS may be created in Water through its homolytic dissociation from a mild through its homolytic dissociation from a mild impetus such as streaming, filtration, impetus such as streaming, filtration, sonication, microwave irradiation, etc.sonication, microwave irradiation, etc.

• Considering the spatio-temporal locations of Considering the spatio-temporal locations of specific biochemical reactions within a cell, it specific biochemical reactions within a cell, it is not implausible to suggest that the typical is not implausible to suggest that the typical approach to the analysis of ROS dependent approach to the analysis of ROS dependent processes is flawed considering the basis of processes is flawed considering the basis of average concentration.average concentration.

Last but Not LEAST…Last but Not LEAST…

The present belief of causation of The present belief of causation of Biological ProcessesBiological Processes

Key-Keyhole interactions…Key-Keyhole interactions…

Quantitative Structure Activity Quantitative Structure Activity Relationship (QSAR)Relationship (QSAR)

A slowly evolving belief of A slowly evolving belief of potential causation of Biological potential causation of Biological ProcessesProcesses

EM signal interactions…EM signal interactions…

Aren’t all processes outside of Aren’t all processes outside of nuclear interactions QED?nuclear interactions QED?

Water Memory and Water Memory and HomeopathyHomeopathyBack in 1988… Benveniste published results of Back in 1988… Benveniste published results of

an experiment in which he tried homeopathy.an experiment in which he tried homeopathy.

The Facts:

•A type of human white blood cell, polymorphonuclear basophils A type of human white blood cell, polymorphonuclear basophils with antibodies of the immunoglobulin E (IgE) type on its with antibodies of the immunoglobulin E (IgE) type on its surface , release histamine upon engaging anti-IgE antibodies. surface , release histamine upon engaging anti-IgE antibodies.

•From calculated dilutions from 10From calculated dilutions from 1022 through 10 through 10120120, over that , over that range, there are successive peaks of degranulation front 40 to range, there are successive peaks of degranulation front 40 to 60% of the basophils, despite the calculated absence of any 60% of the basophils, despite the calculated absence of any anti-IgE molecules at the highest dilutions. anti-IgE molecules at the highest dilutions.

•Upon publishing his findings, he was expelled from his Upon publishing his findings, he was expelled from his professorship and funding was withdrawn.professorship and funding was withdrawn.

Since that Time…Since that Time…• Benveniste has continued his research and is publishing his Benveniste has continued his research and is publishing his

findings in the FASEB Journalfindings in the FASEB Journal• His most recent claim is that he can have a solution of a His most recent claim is that he can have a solution of a

biochemical that causes a specific phenomena, wrap a biochemical that causes a specific phenomena, wrap a copper loop with a white noise signal played into it, record copper loop with a white noise signal played into it, record the signal with a second copper loop onto any data the signal with a second copper loop onto any data recording device, then take that signal, play into a second recording device, then take that signal, play into a second sample of pure water with another partnered White noise sample of pure water with another partnered White noise signal, shake vigorously, and reveal the same effect on signal, shake vigorously, and reveal the same effect on biological function that the solution in the first sample biological function that the solution in the first sample caused. caused. Science is still attempting to resolve the issue from 1988, and one Science is still attempting to resolve the issue from 1988, and one

taker, namely, Professor Madeleine Ennis of Queen's University taker, namely, Professor Madeleine Ennis of Queen's University Belfast is suggesting that Benveniste’s original results were correct. Belfast is suggesting that Benveniste’s original results were correct. She is conducting a similar basophil activation using 4 labs spread She is conducting a similar basophil activation using 4 labs spread across Europe that are receiving “ghost” solutions of an antibody across Europe that are receiving “ghost” solutions of an antibody produced in 3 completely separate labs. A final independent produced in 3 completely separate labs. A final independent researcher who coded the solutions and collated the data though researcher who coded the solutions and collated the data though having no part in the testing and analysis to prevent any bias having no part in the testing and analysis to prevent any bias whatsoever. Her Result: Histamine solutions, both at whatsoever. Her Result: Histamine solutions, both at pharmacological concentrations and diluted out of existence, lead to pharmacological concentrations and diluted out of existence, lead to statistically significant inhibition of basophile activation by aIgE, statistically significant inhibition of basophile activation by aIgE, confirming previous work in this areaconfirming previous work in this area.

SummarySummary• Water is Life… Without its anomalous behavior, Life can Water is Life… Without its anomalous behavior, Life can

potentially be negated.potentially be negated.• Water is weird… But apparently all due to hydrogen-Water is weird… But apparently all due to hydrogen-

bonding and its subsequent networks.bonding and its subsequent networks.• Vibrational modes of water still under investigation yet not Vibrational modes of water still under investigation yet not

quite accounted for in protein dynamics.quite accounted for in protein dynamics.• Reactive Oxygen Species still a burgeoning child of Reactive Oxygen Species still a burgeoning child of

BioPhysics thanks to the discovery of electron and proton BioPhysics thanks to the discovery of electron and proton transport in ATP synthase. Water will surely play a role in transport in ATP synthase. Water will surely play a role in the evolution of this subject.the evolution of this subject.

• Homeopathy still neglected by most, under investigation by Homeopathy still neglected by most, under investigation by others and blindly swallowed by many, BUT, true scientific others and blindly swallowed by many, BUT, true scientific evidence is being gathered now. evidence is being gathered now.

• An unbiased eye is necessary for true interpretation of An unbiased eye is necessary for true interpretation of water’s role in Life.water’s role in Life.