Test for solute distribution - UW Courses Web Servercourses.washington.edu/.../4_Pollack_Water.pdf · Gerald H. Pollack, PhD University of Washington Seattle, Washington Water is

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


• Surfaces

• Solutes


• 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




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




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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

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3.5

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4.5

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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 (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)


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


imparts energyfor building orderand separating charge


sun

water


imparts energyfor building orderand separating charge


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

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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

Documents

Test for solute distribution - UW Courses Web Servercourses.washington.edu/.../4_Pollack_Water.pdf · Gerald H. Pollack, PhD University of Washington Seattle, Washington Water is