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Transcript
Antonella De Ninno
Centro Ricerche ENEA Frascati Roma (Italy)
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Water
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• 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!
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The QED reveals us the dynamical
origin of these clusters
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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 Fc, Fnc of coherent and noncoherent molecules depending on the temperature:
Fc (T )  Fnc (T )  1
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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
IR spectrum of liquid water
0
. 9
0
. 8
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OH stretching
vibration
0
A
b
. 6
0
. 4
0
. 2
Bending mode
of the isolated
molecule
s
0
- 0
. 1
4
0
0
0
3
W
0
0
a
0
v
2
e
n
u
m
b
e
r
[ c
0
m
0
- 1
0
1
]
0
0
0
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Experimental spectrum of water
T=25°C
7
6
Molecules having a strong
correlation with the
environment
coherent
intermediate
4
Abs
Monomers
and/or
2
dimers
non-coherent
0
4000
3500
W av enumber[cm-1]
ENERGY
3000
2800
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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
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Such a system will also exhibit a Van't
1.
Hoff behaviour:
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
2.
this suggests the existence of an equilibrium between two components
3.
we know from thermodynamics that at equilibrium the variation of the
Gibbs’energy, i.e., the maximum amount of useful work from a reaction is equal
to 0
G  G0  RT ln K eq
G 0   RT ln K eq
Equilibrium constant can be used to evaluate thermodynamic parameters
H 0  T S   RT ln K eq
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Which components are the at equilibrium ?
7
T1=30 °C
6
T2=40°C
Monomers and/or dimers
+ intermediate
non-coherent
T3=60°C
4
A
b
Molecules having a strong
correlation with the
environment
coherent
s
2
0
4
0
0
0
W
a
3
5
0
0
v
e
n
u
3
m
b
e
r
[ c
ENERGY
m
- 1
]
0
0
0
2
8
0
0
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A plot of Keq vs. 1/T should be a straight line with
H 0
intercept 
0,3
RT
S0
I1
E
ln( ) 
c
I2
KT
0,2
R
Ln(I1/I2)
slope  
0,4
0,1
0
-0,1
-0,2
-0,3
2,9E-03
3,0E-03
3,1E-03
3,2E-03
3,3E-03
3,4E-03
1/T (K-1)
Here the equilibrium constant is the ratio between the peak of the
coherent and non-coherent + intermediate populations
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Van’t Hoff plot
E  0.127  0.028eV
E  0.17  0.05eV
Experimental (T=300K)
Calculated (T=0)
N.B. At T≠ 0 actually, the boundaries are not sharp because of the
thermal collisions and the energy gap is decreased.
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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 noncoherent fraction and vice versa.
(The average life time of the coherent state is ~ 4·10-15 sec which is
about 2 times the vibration transition time scale)
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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?
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Is the dynamical distribution of the two phases
only function of the temperature?
NaCl solution
1,5
Coherent
1,4
Non-coherent
No, it also depends on
the concentration of solutes
1,3
1,2
A.U.
1,1
1
0,9
0,8
0,7
0,6
0,5
-1
0
1
2
3
Mol
4
5
6
Do the interaction with the environment affect
the distribution of the two phases ?
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Yes, the quality of the surface
modifies the percentage of the
coherent phase
Water near hydrophilic surfaces
Coherent bulk water
Coherent EZ water
Intermediate bulk
Intermediate EZ
Non-coherent bulk
Non-coherent EZ
Peak
position
3205
3292
3361
3494
3526
3610
Area %
58
76
37
4
5
20
t=1/Egap increased
Egap decreased
Negatively charged surface
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”.
EZ (interfacial)
─
Up to 150 mv
Bulk
+
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
Ө Ө Ө Ө Ө Ө Ө Ө Ө Ө Ө Ө
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?
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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
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Can one phase be selectively stabilized?
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)
Residues from five drops of a sample of INW. The bright-to-dark colour coding
corresponds to the height of the clusters, ranging from 0.040μm (the control - right) to
0.403μm (the sample – left). The size of the picture is 10 μm×10.
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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.
The supra molecular arrangement of
liquid water depends on:
Temperature
Solutes
Interfaces
Electromagnetic signals
Concentration
(thank to Prof. Konovalov for discussion)
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Glutamic acid
•
•
•
•
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 pKa=9.7 the amino acid is fully
deprotonated and its ionic charge is
+2
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Glutamic acid speciation scheme
pH
When submitted to a weak
ELF/static electromagnetic field
the glutamic acid loses a proton
The electric charge ranges from +1 in the fully protonated form to -2 according to the speciation scheme.
pH=1.5
pH=11.8
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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%
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Phenylalanine
We have observed that the exposure to a weak
magnetic field of an aqueous solution of L-Phe induces
a measurable shift in the acid–base equilibrium.
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Phenylalanine
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.
Exposure to a static magnetic field 1 Gauss – 30 minutes
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H 2O
modifications
aggregation
pKa shift
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We suggest that:
the size and the hydrophobicity of the R group of the amino
acids are responsible for the magnitude of the effect.
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.
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Effect of the magnetic field on water
0
water
. 3
Exposed water
0
Difference (X10)
The magnetic field may induce a
rearrangement in the structure of liquid water
and modify the ratio between the two phases
of water
0
A
b
s
. 2
. 1
0
- 0
. 1
3
8
0
0
3
6
0
0
3
W
a
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v
0
e
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n
3
u
m
b
e
2
r
0
0
[ c
m
3
- 1
0
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8
0
0
]
Chaotrope* (disorder-maker) effect of the magnetic field
(1888)
Magnetic field
Kosmotropes
Chaotropes
EMF cosmotrope effect
effect
-10
Effect on mM to M
solutions
It helps to form
structures?
Montagnier effect
EMF emission
MF
EMF chaotrope
???
0
logc
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1. Is the dynamical distribution of the two phases only
function of the temperature?
2. Do the interaction with the environment affect the
distributionkinds
of the two
Different
of phases
water ?are then possible
according
to the
exchanged with the
3. Can one phase
beinformation
selectively stabilized?
environment.
The supra
molecular
liquid watersuitable
is very sensitive
Liquid
waterstructure
has aofstructure
to to the
environment including to the electromagnetic fields.
transform those information in significance and
The appearance of stable structures that survive even to the phase
therefore in meaning.
transition from liquid to solid state implies the existence of coherent spacetime dissipative structures, capable of exchange energy and matter with the
environment and attaining a different level of organisation.
Thank you for your attention