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Antonella De Ninno

Centro Ricerche ENEA Frascati Roma (Italy)


antonella.deninno@enea.it
Water
Gases are fully non coherent systems
Liquids are systems where electron clouds are coherent
Solids are systems where nuclei, too, are coherent

Liquid water is peculiar, since the coherent oscillation connects
two electronic configurations that have extreme features:

1) The ground configuration where all electrons are tightly bound
(the ionization potential is 12.60 eV, corresponding to soft X-rays and
to an excitation temperature of 145.000 C !)

2) The excited configuration has an energy E=12.06 eV, only 0.54 eV
below the ionization threshold. So for each molecule there is an
almost free electron!
antonella.deninno@enea.it
antonella.deninno@enea.it
The QED reveals us the dynamical
origin of these clusters
In liquid water two phases exist.
The interplay between the electrodynamic attraction and
thermal disruption produces a continuous crossover of
molecules between the two regimes.
The QED theory foresees a dynamical distribution
between the two phases F
c
, F
nc
of coherent and non-
coherent molecules depending on the temperature:


( ) ( ) 1
c nc
F T F T
antonella.deninno@enea.it
How can we observe experimentally
the two phases in liquid water at room
temperature and pressure ?
Measuring the energy differences between the two populations
via FT-IR spectroscopy we can measure the energy
difference between the more correlated and the less
correlated kind of molecules and compare the result with the
amount calculated by QED
antonella.deninno@enea.it
IR spectrum of liquid water

- 0 . 1
0 . 9
0
0 . 2
0 . 4
0 . 6
0 . 8
4 0 0 0 1 0 0 0 2 0 0 0 3 0 0 0
A b s
W a v e n u m b e r [ c m - 1 ]
OH stretching
vibration
Bending mode
of the isolated
molecule
antonella.deninno@enea.it
0
7
2
4
6
4000 2800 3000 3500
Abs
Wavenumber[cm-1]
Experimental spectrum of water
T=25C
intermediate
Molecules having a strong
correlation with the
environment coherent
Monomers and/or
dimers
non-coherent
ENERGY
antonella.deninno@enea.it
antonella.deninno@enea.it
Comparison of the gas, liquid and solid spectra of the same
amount of water. From Martin Chaplin: Water Structure and
Science web page http://www.lsbu.ac.uk/water/vibrat.html
antonella.deninno@enea.it
Such a system will also exhibit a Van't Hoff behaviour:

1. we can observe experimentally that our system (liquid water)
exhibits an equilibrium point upon changing the temperature, in
fact exists a point in the IR spectrum where the absorption is
always the same
0
0
ln
ln
eq
eq
G G RT K
G RT K


0
ln
eq
H T S RT K
Equilibrium constant can be used to evaluate thermodynamic parameters
3. we know from thermodynamics that at equilibrium the variation of the
Gibbsenergy, i.e., the maximum amount of useful work from a reaction is equal
to 0
2. this suggests the existence of an equilibrium between two components
Which components are the at equilibrium ?

0
7
2
4
6
4 0 0 0 2 8 0 0 3 0 0 0 3 5 0 0
A b s
W a v e n u m b e r [ c m - 1 ]
ENERGY
T
1
=30 C
T
2
=40C
T
3
=60C
Molecules having a strong
correlation with the
environment coherent
Monomers and/or dimers
+ intermediate
non-coherent
antonella.deninno@enea.it
-0,3
-0,2
-0,1
0
0,1
0,2
0,3
0,4
2,9E-03 3,0E-03 3,1E-03 3,2E-03 3,3E-03 3,4E-03
1/T (K
-1
)
L
n
(
I
1
/
I
2
)
A plot of K
eq
vs. 1/T should be a straight line with



0
0
H
slope
RT
S
intercept
R

Here the equilibrium constant is the ratio between the peak of the
coherent and non-coherent + intermediate populations
antonella.deninno@enea.it
1
2
ln( )
I E
c
I KT


Vant Hoff plot
Experimental (T=300K)
Calculated (T=0) 0.17 0.05 E eV
0.127 0.028 E eV
antonella.deninno@enea.it
N.B. At T 0 actually, the boundaries are not sharp because of the
thermal collisions and the energy gap is decreased.
antonella.deninno@enea.it
In such a picture, even the so called intermediate population could
find a rationale:

the measured spectrum emerges from a dipole-dipole
transition between two specific quantum states

the intermediate peak is naturally assigned to the transitions where the
initial state is in the coherent fraction and the final state is in the non-
coherent fraction and vice versa.
(The average life time of the coherent state is ~ 410
-15
sec which is
about 2 times the vibration transition time scale)


antonella.deninno@enea.it
antonella.deninno@enea.it

1.Is the dynamical distribution of the two
phases only function of the temperature?
2.Is it affected by the interaction with the
environment?
3.Can one phase be selectively stabilized?
antonella.deninno@enea.it
0,5
0,6
0,7
0,8
0,9
1
1,1
1,2
1,3
1,4
1,5
-1 0 1 2 3 4 5 6
Mol
A
.
U
.
Coherent
Non-coherent
Is the dynamical distribution of the two phases
only function of the temperature?
No, it also depends on
the concentration of solutes
antonella.deninno@enea.it
NaCl solution
antonella.deninno@enea.it
Water near hydrophilic surfaces
Do the interaction with the environment affect
the distribution of the two phases ?
Yes, the quality of the surface
modifies the percentage of the
coherent phase
Peak
position
Area %
Coherent bulk water
3205 58
Coherent EZ water
3292 76
Intermediate bulk
3361 37
Intermediate EZ
3494 4
Non-coherent bulk
3526 5
Non-coherent EZ
3610 20
E
gap
decreased
t=1/E
gap
increased
EZ (interfacial) Bulk
Water is a heterogeneous (at least a two-phase) system in
which charge separation occurs between two phases :
low entropy (organized) interfacial and less organized bulk.
Up to 150 mv
+
N
e
g
a
t
i
v
e
l
y

c
h
a
r
g
e
d

s
u
r
f
a
c
e

EZ-water may be charged
negatively or positively
depending on the charge
of the surface forming it
Zheng JM, Wexler A, Pollack GH.. J Colloid Interface Sci. 2009
However, we are dealing here with fixed charges
Negatively charged surface

Positively charged surface
Like charges repel each other, but as they are
covalently fixed to a matrix,
they all cannot but vibrate
Their collective vibration could become
coherent due to the principle of minimization
of energy
Interactions with the environment, in
this case the interaction with the
surface just acts like external trigger.
Water appears to contain in itself the
informations.
This may explain why the biologic
message is NOT deterministic.

Can one phase be selectively stabilized?
antonella.deninno@enea.it
antonella.deninno@enea.it
Light Scattering on water
Light scattering gives information
about the presence of large size
aggregates into the liquid provided
that a certain number of hypothesis
in support of the Mie scattering
theory are verified
antonella.deninno@enea.it
antonella.deninno@enea.it
Residues from five drops of a sample of INW. The bright-to-dark colour coding
corresponds to the height of the clusters, ranging from 0.040m (the control - right) to
0.403m (the sample left). The size of the picture is 10 m10.
3-5 drops of the liquid have been evaporated, at room temperature and
pressure, on mica substrates forming solid deposits. Atomic Force Microscopy
images of these deposits were taken in non-contact mode
Yes, a long lasting change in the structure of
liquid water
can be induced by the iterative contact with
Nafion membranes (not only)
Can one phase be selectively stabilized?
The supra molecular arrangement of
liquid water depends on:
Temperature
Solutes
Interfaces
antonella.deninno@enea.it
We have observed the formation of stable structures ongoing
after the removal of the perturbation. This suggests the
formation of a stable far from- equilibrium state achieved trough
the dissipation of energy subtracted to the environment.
Electromagnetic signals
Concentration
(thank to Prof. Konovalov for discussion)
pH<3.2 both carboxylic and amine
groups are protonated and its ionic
charge is -1
deprotonated species appear
increasing pH
isoelectric point = 3.2 pH, its ionic
charge is 0
above pK
a
=9.7 the amino acid is fully
deprotonated and its ionic charge is
+2

Glutamic acid
antonella.deninno@enea.it
The electric charge ranges from +1 in the fully protonated form to -2 according to the speciation scheme.
Glutamic acid speciation scheme
pH
antonella.deninno@enea.it
pH=1.5
pH=11.8
When submitted to a weak
ELF/static electromagnetic field
the glutamic acid loses a proton
antonella.deninno@enea.it
antonella.deninno@enea.it
When submitted to a magnetic field
from 3 to 10 times higher than the
geomagnetic field the kinetic of the
reaction is increased up to 50%

Phenylalanine
antonella.deninno@enea.it
We have observed that the exposure to a weak
magnetic field of an aqueous solution of L-Phe induces
a measurable shift in the acidbase equilibrium.
Phenylalanine
Exposure to a static magnetic field 1 Gauss 30 minutes
antonella.deninno@enea.it
The exposure of L-Phe to the magnetic field has an effect
similar to the exposure to NIR radiation, which is known to
cause significant changes in the hydration properties of such
molecules.
H
2
O
modifications
aggregation
pK
a
shift
antonella.deninno@enea.it
We suggest that:

the magnetic field acts as a chaotrope (disorder maker) agent,
presumably acting upon the water supra-molecular structure. A
major degree of aggregation between two amino acids is
allowed whenever this layer is decreased by a magnetic
field.
the size and the hydrophobicity of the R group of the amino
acids are responsible for the magnitude of the effect.
antonella.deninno@enea.it
antonella.deninno@enea.it
- 0 . 1
0 . 3
0
0 . 1
0 . 2
3 8 0 0 2 8 0 0 3 0 0 0 3 2 0 0 3 4 0 0 3 6 0 0
A b s
W a v e n u m b e r [ c m - 1 ]
water
Exposed water
Difference (X10)
Effect of the magnetic field on water
Chaotrope* (disorder-maker) effect of the magnetic field
The magnetic field may induce a
rearrangement in the structure of liquid water
and modify the ratio between the two phases
of water
antonella.deninno@enea.it
Kosmotropes
Chaotropes
Magnetic field
(1888)
logc
0
-10
EMF chaotrope
effect
M
o
n
t
a
g
n
i
e
r

e
f
f
e
c
t


E
M
F

e
m
i
s
s
i
o
n

E
f
f
e
c
t

o
n

m
M

t
o

M

s
o
l
u
t
i
o
n
s

MF
EMF cosmotrope effect
It helps to form
structures?
???
1. Is the dynamical distribution of the two phases only
function of the temperature?
2. Do the interaction with the environment affect the
distribution of the two phases ?
3. Can one phase be selectively stabilized?
The supra molecular structure of liquid water is very sensitive to the
environment including to the electromagnetic fields.
The appearance of stable structures that survive even to the phase
transition from liquid to solid state implies the existence of coherent space-
time dissipative structures, capable of exchange energy and matter with the
environment and attaining a different level of organisation.


antonella.deninno@enea.it
Different kinds of water are then possible
according to the information exchanged with the
environment.
Liquid water has a structure suitable to
transform those information in significance and
therefore in meaning.
Thank you for your attention

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