Pollack Kaqun Zuglo-Presents

Gerald H.
Pollack, PhD
University of Washington
Seattle
Vermont 2012
Albert Szent-Gyorgyi
Gilbert Ling
Role of water in cell biology
Exclusion Zone
EZ
10 m
Another example
200 m
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)
Jacques Huyghe (Eindhoven)
Nikolay Bunkin (Moscow)
Questions to Answer
Is the exclusion phenomenon general?

Does it really arise from water ordering?
What energy creates this order?
Can the ordered zone explain everyday
phenomena?
Question #1:
Generality
Surfaces: gels, polymers, biological
surfaces, monolayers
Solutes excluded: down to mw 100 and lower
Small solutes excluded
pH-sensitive dye(s)
H+
H+
Nafion
dye excluded
H+
Generality
many solutes excluded
many hydrophilic surfaces

generate exclusion zones
Question #2
Is this zone
physically different
from bulk water?
EZ
Evidence that exclusion-zone (EZ) water

is 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)
EZ optical properties different (refractive index)
Zheng et al., Adv. Colloid and Interface Sci, 127: 19-27, 2006
Chai et al., J Phys Chem, 112: 2242 2247, 2008
Zheng et al., J. Coll. Interface Sci, 332: 511514, 2009
Yoo et al. J. Phys. Chem. Letters 2: 532- 536, 2011


+
+
+
+
+
+
+
+
+
Nafion
from previous slide
H+
H+
pH-sensitive dye
H+
Control Current vs. Time
Current flow between exclusion zone and water beyond

5
4.5
4
Current (uA)
3.5
3
Confirms charge separation
2.5
2
1.5
1
0.5
0
0
50
100
150
200
250
Time (s)
300
350
400
450
500
A charged battery in water
Separated charges
should attract
Charges genuinely
separated




Summary, so far
may extend far
Liquid crystalline
very
Negative charge
Excludes solutes
(Non-dipolar?)
Fourth phase of water?

(Sir Wm. Hardy, 1912)
Summary, so far
may extend far
Liquid crystalline
very
Negative charge
Excludes solutes
(Non-dipolar?)
Fourth phase of water?

(Sir Wm. Hardy, 1912)
Non-dipolar EZ Structure?
Negative charge (dipoles neutral)
270-nm absorption (ring-like structures)
Structure should have precedent
Precedent: ICE
remove protons = negative charge; non solid
NOT
H2O
Advantages of sheet-like EZ
Precedent
Negative charge
Ring-like structures (270-nm absorption)
Able to accommodate helical structures
Large sheets eliminate Brownian instability
unstable?
stable
Precedent
Negative charge
Tight lattice keeps hydronium ions out
Crystalline zone keeps protons (hydronium ions) out
EZ
Battery charge remains separated
Precedent
Negative charge
Tight lattice keeps hydronium ions out
Is the sheet-like honeycomb actually seen?
ATP synthasesubunit c
SEM
TEM
ordered
hexagonal
sheets of water
McGeoch and McGeoch
Interface 2008
Answer to Question #2
Is EZ physically distinct from bulk?
Yes
Layered honeycomb structure
Question #3
What charges the water battery?
(Incident radiant energy)
infrared most
powerful
material
EZ
water
Reduce incident
radiant energy
Energy?
EZ buildup powered by photonic energy
Orders water
Charges the water battery
Possible Energy Flow in Universe
water
sun
generates heat
(conventional)
imparts
chemical energy
for building order
and separating charge
water
sun
generates heat
(conventional)
imparts energy
for building order
water
sun
generates heat
(conventional)
imparts energy
for building order
Can this energy be harvested?
Energy can be harvested
Nafion tube
or gel tube
water
nafion
exclusion zone
exclusion zone
nafion
Polyacrylic acid gel

PAA gel
EZ
EZ
EZ
work done
system MUST absorb energy
water transduces light energy
E = H2O
Question #4
Can EZ existence
help explain
everyday phenomena?
five examples
Charged aerosol droplets come together

because of like-likes-like mechanism
+
charged particle
or molecule
+
+
liquid
crystalline
water
+
+
+
+
+
+
+
+
+ - - --- - - + +
-- -- - - - -- -- - +
+
+
+
+
+
+
+
+
+
+
+
+
+
+
- -+
+ + +
+ - +
+
- -+ +
+
- +
-+ +
- - - +
- - +
+
+
+
+
+
-- +
+
+
+
+
+
+
-- - - - +
+
+
+
+ +
+
+
+
+
like
likes
like
(Feynman)
+
(Tale of Genji)
+
+
+
-- + +
+
+
+
+
+
+
+
-+
-- + ++ + - - +
+
+ + + +
- - -+
+
+ - +
+
+
+
Stability: attractive force = repulsive force
Particles stick together because of like-likes-like
2. Sandcastles
3. Ice
Ice Formation Paradox

Creating order
commonly requires
energy input
Creating order in ice requires energy withdrawal

Does ice violate general rule?
No
Why?
ICE
intimately tied to EZ
remove protons
exclusion zone
protons + exclusion zone

ice precursor
ice
add protons
ice
Is EZ really necessary for ice formation?
Freeze
initiates in EZ
ice
(EZ +
protons)
Testing the proton rush
replace microspheres with pH-sensitive dye
red color = many protons
cooling plate
freezing
Ice formation involves protons

EZ + protons = ice
Energy paradox resolved
Increased order DOES require energy
Reverse: Melting
Melting should produce EZ water
Absorption
spectra
melted
water
samples
270 nm =
signature of EZ
4. Low friction
Liquid layer known since Michael Faraday
EZ + protons?
Pressure
should produce EZ + protons
ice
EZ
Pressing harder should give lower friction!
5. Biological applications
Low friction: why your joints dont squeak
Should be filled
with protons
Injury-induced swelling
sprain
X
X
X
No restraint to swelling
Ouch!
Swelling arises from buildup

of large EZ layers
Obtaining energy: Can we get energy from the

environment (like plants)
Pedro Cabrales UCSD
Laboratory studies: radiant energy drives the flow
Might radiant energy help drive blood flow?
Might absorbed external energy assist blood

flow?
Radiant energy may help power cells
Cells are
full of EZ
water
Separated charges drive reactions
EZs Central for Biological Function

Anesthetics (impair function): diminish EZ size
Aspirin (enhance function): builds EZ
EZ water central to function
Practical Use of Radiant Energy?
Getting energy
from sunlight and water
Obtaining drinking water
hydrophilic
material
contaminated water
Excluded stuff
Excluded salt?
EZ
Main Conclusions
Where weve come
Water
is fascinating to study
Fun
to study
Why only one cloud when the vapor rises all over?
Elmar Fuchs, Wetsus
Water is a dipole
i. klyuzhin
Initial experimental approach:
Test for solute distribution

solutes included
solutes excluded
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
Biological specimens exclude

microspheres
muscle
Monolayers
exclude
monolayer
50 m
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
Excluded solutes
fluorophorelabeled
albumin


Takehome
message:
the shaky
edifice of
science
UV-VIS absorption spectrum

spectrophotometer
slit 2
cuvette
Nafion
slit 1
light
100 m
Another charged battery in water


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)
Why doesnt 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

Negative potential
Thick gel-like band
Many structured layers

create high surface tension
water
water
water
Crystals can be pretty stiff
Water structure stiff enough

to keep bridge from collapsing
Yes
Liquid crystalline water
explains many anomalies
It explains why water battery

charges remain separated
Near infrared illumination

With illumination 5 min
100 m
EZ
Control
nafion
EZ
Nafion
100 m
temperature rise < 1
higher water
lower water
Evidence that incident energy MUST be absorbed

Converted to work
exclusion
beyond
A charged battery in water
exclusion
beyond


EZ has negative charge (potential measurement)
including chemical reactions in cells
Possible things to include

Evaporation see older talks
Anesthetics + aspirin
Freezing
brication/friction- see Vancouver extra session
Practical Use of Radiant Energy?
Getting energy
from sunlight and water
Obtaining drinking water
hydrophilic
material
contaminated water
Excluded stuff
Excluded salt?
EZ
PAA
PAA gel
Exclusion zone
(EZ)
200 m
Effect of Wavelength on EZ Size

(5 min exposure)
3.2
EZ-size ratio
2.8
2.4
2.0
1.6
visible
1.2
control
infrared
(low incident intensity)
200
400
600
800
2000
Wavelength (nm)
3000
4000
5000
Charged aerosol droplets come together

because of like-likes-like
Injury-induced swelling
EZ water builds up next to protein surfaces

Tendency to swell tissue
Cross-links btw. proteins restrain swelling
Injury tears cross-links
EZ water builds unrestrained; tissue swells
EZ Size Modulates Function

Impairment anesthetics: diminish EZ
Enhancement aspirin: builds EZ
EZ water central to function

Pollack Kaqun Zuglo-Presents

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Gerald H.

Role of water in cell biology

Basic finding confirmed

Felix Blyakhman (Ural State Univ)

Is the exclusion phenomenon general?

Small solutes excluded

many hydrophilic surfaces

Evidence that exclusion-zone (EZ) water

EZ water molecules more constrained (NMR)

Evidence that exclusion-zone (EZ) water

EZ water molecules more constrained (NMR)

from previous slide

Control Current vs. Time

Current flow between exclusion zone and water beyond

Confirms charge separation

A charged battery in water

Evidence that exclusion-zone (EZ) water

EZ water molecules more constrained (NMR)

Evidence that exclusion-zone (EZ) water

EZ water molecules more constrained (NMR)

Fourth phase of water?

Fourth phase of water?

remove protons = negative charge; non solid

Tight lattice keeps hydronium ions out

Crystalline zone keeps protons (hydronium ions) out

Tight lattice keeps hydronium ions out

Is the sheet-like honeycomb actually seen?

(Incident radiant energy)

Possible Energy Flow in Universe

Possible Energy Flow in Universe

Possible Energy Flow in Universe

Can this energy be harvested?

Energy can be harvested

Polyacrylic acid gel

Charged aerosol droplets come together

Stability: attractive force = repulsive force

Particles stick together because of like-likes-like

Ice Formation Paradox

Creating order in ice requires energy withdrawal

protons + exclusion zone

Is EZ really necessary for ice formation?

Testing the proton rush

replace microspheres with pH-sensitive dye

red color = many protons

Ice formation involves protons

Energy paradox resolved

Increased order DOES require energy

Liquid layer known since Michael Faraday

should produce EZ + protons

Pressing harder should give lower friction!

Low friction: why your joints dont squeak

Swelling arises from buildup

Obtaining energy: Can we get energy from the

Pedro Cabrales UCSD

Laboratory studies: radiant energy drives the flow

Might radiant energy help drive blood flow?

Might absorbed external energy assist blood

Radiant energy may help power cells

EZs Central for Biological Function

EZ water central to function

Practical Use of Radiant Energy?

Obtaining drinking water

Where weve come