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Gerald H. Pollack, PhD
University of Washington
Seattle, Washington
Water is a dipolei. klyuzhin
Test for solute distribution
Initial experimental approach:
solutes excluded
solutes included
PVAgel
10 µm200 µm
PAAPAA gel Exclusion zone
(EZ)
Basic finding confirmed
• Felix Blyakhman (Ural State Univ)• Wei-Chun Chin (U. Cal. Merced)• Toshio Hirai (Shinshu University)• Mark Banaszak Holl (Univ. of Michigan)• Tom Lowell (Vermont Photonics)• Diedrich Schmidt (Tsukuba)• Gerhard Artmann (Aachen)• David Maughan (U. Vermont)• Miklos Kellermayer (Budapest)• Fettah Kosar (Harvard)
Seems to imply very long range ordering
May provide fresh basis for understanding
Questions to Answer
• Is the exclusion phenomenon general?
• Does it really arise from water ordering?
• Can water ordering explain anomalies?
• What energy creates this order?
• Might these findings apply more broadly?
Getting to the basis…
Question #1:Generality
• Surfaces
• Solutes
Question #1:Generality
• Surfaces
• Solutes
Question #1:Generality
• Surfaces: hydrophobic vs. hydrophilic
• Solutes
hydrophobic hydrophilic
Hydrophilic gel surfaces do exclude
• Polyvinyl alcohol
• Polyacrylic acid
• Polyacrylamide
• PolyHEMA
• Collagen
• Agarose m us cle
mi crosphe res
Biological specimens excludeBiological specimens excludeBiological specimens exclude
50 µm
monolayerMonolayers exclude
200 µm
Polymers exclude
Generality?
• Surfaces: Numerous hydrophilic surfaces show exclusion
• Solutes
Generality?
• Surfaces: Numerous hydrophilic surfaces show exclusion
• Solutes
Excluded particles
• Polystyrene microspheres
• Silica microspheres
• Erythrocytes
• Bacteria
• Colloidal gold (4 - 7 nm)
• Quantum dots
• Ash, dirt
fluorophore-labeled albumin
Excluded solutes…
Nafion
pH-sensitive dye(s)
H+
H+
H+
dye excluded
Smaller solutes excluded…
many solutes excluded
many hydrophilic surfaces generate exclusion zones
Answer to Q1: Generality
Question #2
Is this zone physically different from bulk water? EZ
Evidence that exclusion-zone (EZ) wateris physically different from bulk water
• EZ water molecules more constrained (NMR)• EZ molecules more stable (infrared radiation)• EZ has negative charge (electrical potential)• EZ absorbs at 270 nm (light-absorption spectrum)• EZ is more viscous (falling ball viscometry)• EZ molecules aligned (polarizing microscopy)• EZ molecular structure different (IR absorption)
Zheng et al., Adv. Colloid and Interface Sci, 127: 19-27, 2006Chai et al., J Phys Chem, 112: 2242 – 2247, 2008Zheng et al., J. Coll. Interface Sci, 332: 511–514, 2009
Evidence that exclusion-zone (EZ) wateris physically different from bulk water
• EZ water molecules more constrained (NMR)• EZ molecules more stable (infrared radiation)• EZ has negative charge (electrical potential)• EZ absorbs at 270 nm (light-absorption spectrum)• EZ is more viscous (falling ball viscometry)• EZ molecules aligned (polarizing microscopy)• EZ molecular structure different (IR absorption)
Zheng et al., Adv. Colloid and Interface Sci, 127: 19-27, 2006Chai et al., J Phys Chem, 112: 2242 – 2247, 2008Zheng et al., J. Coll. Interface Sci, 332: 511–514, 2009
light
slit 1
slit 2
cuvetteNafion
100 µm
spectrophotometer
UV-VIS absorption spectrum
0
0.5
1
1.5
2
2.5
3
200 250 300 350 400 450 500
Absorb
ance
Wavelength (nm)
400 µm
300 µm
200 µm
100 µm
d=0
Evidence that exclusion-zone (EZ) wateris physically different from bulk water
• EZ water molecules more constrained (NMR)• EZ molecules more stable (infrared radiation)• EZ has negative charge (electrical potential)• EZ absorbs at 270 nm (light-absorption spectrum)• EZ is more viscous (falling ball viscometry)• EZ molecules aligned (polarizing microscopy)• EZ molecular structure different (IR absorption)
Zheng et al., Adv. Colloid and Interface Sci, 127: 19-27, 2006Chai et al., J Phys Chem, 112: 2242 – 2247, 2008Zheng et al., J. Coll. Interface Sci, 332: 511–514, 2009
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Nafion
H+ H+ H+
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from previous slide
pH-sensitive dye
Control Current vs. Time
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 50 100 150 200 250 300 350 400 450 500
Time (s)
Current (uA)
Confirms charge separationConfirms charge separation
Current flow between exclusion zone and water beyond
exclusion beyond
A charged battery in waterA charged battery in water
exclusion beyond
Another charged battery in water…Evidence that exclusion-zone (EZ) wateris physically different from bulk water
• EZ water molecules more constrained (NMR)• EZ molecules more stable (infrared radiation)• EZ has negative charge (electrical potential)• EZ absorbs at 270 nm (light-absorption spectrum)• EZ is more viscous (falling ball viscometry)• EZ molecules aligned (polarizing microscopy)• EZ molecular structure different (IR absorption)
Zheng et al., Adv. Colloid and Interface Sci, 127: 19-27, 2006Chai et al., J Phys Chem, 112: 2242 – 2247, 2008Zheng et al., J. Coll. Interface Sci, 332: 511–514, 2009
Evidence that exclusion-zone (EZ) wateris physically different from bulk water
• EZ water molecules more constrained (NMR)• EZ molecules more stable (infrared radiation)• EZ has negative charge (potential measurement)• EZ absorbs at 270 nm (light-absorption spectrum)• EZ is more viscous (falling ball viscometry)• EZ molecules aligned (polarizing microscopy) • EZ molecular structure different (IR absorption)
Zheng et al., Adv. Colloid and Interface Sci, 127: 19-27, 2006Chai et al., J Phys Chem, 112: 2242 – 2247, 2008Zheng et al., J. Coll. Interface Sci, 332: 511–514, 2009
Summary, so farmay extend far
very
Liquid crystalline
Negative charge
Fourth phase of water?(Sir Wm. Hardy, 1912)
Excludes solutes
(Non-dipolar?)
Summary, so farmay extend far
very
Liquid crystalline
Negative charge
Fourth phase of water?(Sir Wm. Hardy, 1912)
Excludes solutes
(Non-dipolar?)
Non-dipolar EZ Structure?
• Negative charge (dipoles neutral)
• 270-nm absorption (ring-like structures)
• Amenable to shear thinning (layers?)
• Structure should have precedent
Precedent: ICE
remove protons = non solid
-1
Advantages of Non-dipolar EZ
• Precedent ✔• Negative charge ✔• Ring-like structures (270-nm absorption) ✔• Able to accommodate helical structures ✔• Amenable to shear thinning ✔• Large sheets eliminate Brownian instability ✔
Problem: POLYWATER
Polywater structure
Lippincott et al.Science, 1969
Answer to Question #2Is EZ physically distinct from bulk?
YesLiquid crystalline
Layered honeycomb structure ?
Question #3: Can crystalline water explain counter-intuitive anomalies?
What behavior do we expect from a crystal?
Crystalline elements stick together
gelatin dessert (95% water)gelatin dessert (95% water)gelatin dessert (95% water)………
Why doesnWhy doesnWhy doesn’’’t the water dribble out?t the water dribble out?t the water dribble out?
Crevices are filled with liquid crystal
Crystalline water is gel-like.
Crystalline water grows at air-water interface
air meniscus clear zone water + microspheres
2 mm
Clear zone similar to EZ
Thick gel-like band
Negative potential
ManyManyMany structured layersstructured layersstructured layerscreate high surface tensioncreate high surface tensioncreate high surface tension
Water surface
Crystals can be pretty stiff
Water structure stiff enoughWater structure stiff enoughto keep bridge from collapsingto keep bridge from collapsing
Elmar Fuchs, Wetsus
Crystalline zone keeps protons (hydronium ions) out
Battery charge remains separatedBattery charge remains separated
EZ
Answer to Question #3
Yes
Liquid crystalline water explains many anomalies It explains why water batteryIt explains why water battery
charges remain separatedcharges remain separated
Question #4
What charges the water battery?
(Incident radiant energy)(Incident radiant energy)100 µm
IR radiation (Right)
Nafion
Light point source here
Exclusion zone
100 µm
Near infrared illumination
nafion
100 µm
Control
Nafion
EZ
temperature rise < 1°
With illumination – 5 min
EZ
0 200 400 600 800 2000 3000 4000 5000
1.2
1.6
2.0
2.4
2.8
3.2
Effect of Wavelength on EZ Size(5 min exposure)
control (low intensity)
visible infrared
exclusion beyond
Incident radiant energy Incident radiant energy builds exclusion zone builds exclusion zone and separates chargeand separates charge
exclusion beyond
Answer to Question #4Energy?
EZ buildup powered by photonic energy…
Orders water
Charges the water battery
water
generates heat(conventional)
impartschemical energyfor building orderand separating charge
Possible Energy Flow in Universe
sun
water
generates heat(conventional)
imparts energyfor building orderand separating charge
Possible Energy Flow in Universe
sun
water
generates heat(conventional)
imparts energyfor building orderand separating charge
Possible Energy Flow in Universe
sun
Can this energy be harvested?
Nafion tube or PAA-gel tube
Energy can be harvested…
water
nafion
exclusion zone
exclusion zone
nafion
Polyacrylic acid gel
EZ
Incident radiant energy harvested to do work
higher waterlower water
Evidence that incident energy MUST be absorbed water
Light energy in
Motion energy out
Incident energy might drive Brownian excursions
(E = H2O)
Question #5Why is all of this important?
• Foundational for any/all science involving water and light– physics– chemistry– biology
Examples:water,light,particles
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charged particleor molecule
liquid crystalline water
in all aqueous chemical reactionsin all aqueous chemical reactions
including chemical reactions in cells…
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+likelike--likeslikes--like (Feynman)like (Feynman)
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attractive force = repulsive force: Stability
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Why does water vapor coalesce into discrete units?Why does water vapor coalesce into discrete units?Why does water vapor coalesce into discrete units?
Why does water vapor coalesce into discrete units?Why does water vapor coalesce into discrete units?Why does water vapor coalesce into discrete units?
aerosol droplets attract because like-likes-like
(powered by light)
A special example of like-likes-like…
Origin of LifeOrigin of Life
Step 1?
dispersed molecules coalesce
+
Aggregate keeps growing (like cell) self assemblyHas negative charge (like cell)Has potential energy (like cell)Has capacity to divide (like cell)
=
Step 1 in origin of life may belight-induced aggregation
*Is life being created continually?*
the sun’s energymoleculeswater
All that’s needed:
Final Issues: non-liquid states
• Vapor state
• Solid state
Evaporation
Rising vapor, imaged just above warm water
Corresponding structure in water?
Infrared-camera image of water surfaceMosaic lines extend down
Visible light image of warm waterWater-surface rings = real material
Evaporative process
• Mosaic rings rise to create visible vapor
• Mosaic rings: probably EZ-containing structures
• Evaporation is discrete event
vapor patterns come from liquid patterns
Final Issues: non-liquid states
• Vapor state
• Solid state
EZ Structure Ice Structure
EZ + protons = Ice exclusion beyond
exclusion beyond
cooled copper microspheres in water
turns to ice
Possible freezing process
• Water cools
• EZ builds; charge separates
• Proton concentration builds to threshold
• Protons rush into negative EZ
• EZ becomes ice
EZ Ice+ ProtonsFinal Issue Summary
• Water’s solid state: EZ-to-ice transition
• Water’s vapor state: EZ-ring to vapor-ring transition
EZ is critical intermediate state
Question #5:Why is all of this important?
EZ may provide unifying basis for understanding
Many thanks!
The interface is interesting