antonella de ninno centro ricerche enea frascati roma (italy) antonella.deninno@enea.it

Antonella De NinnoCentro 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!

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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 Fc, Fnc of coherent and non-coherent

molecules depending on the temperature:

( ) ( ) 1c ncF T F T

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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

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IR spectrum of liquid water

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OH stretching vibration

Bending mode of the isolated molecule

antonella.deninno@enea.it

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Experimental spectrum of water T=25°C

intermediate Molecules having a strong correlation with the environment coherent

Monomers and/or dimers non-coherent

ENERGY

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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 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

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ln

ln

eq

eq

G G RT K

G RT K

0 ln eqH 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 Gibbs’energy, 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 ?

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Wavenumber[cm-1]ENERGY

T1=30 °C

T2=40°C

T3=60°C

Molecules having a strong correlation with the environment coherent

Monomers and/or dimers + intermediate non-coherent

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1/T (K-1)

Ln(I

1/I2

)

A plot of Keq vs. 1/T should be a straight line with

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Hslope RTSintercept R

Here the equilibrium constant is the ratio between the peak of the coherent and non-coherent + intermediate populations

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1

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ln( )I E cI KT

Van’t Hoff plot

Experimental (T=300K)

Calculated (T=0)0.17 0.05E eV 0.127 0.028E eV

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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 non-coherent 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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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?

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A.U

.

Coherent

Non-coherent

Is the dynamical distribution of the two phasesonly function of the temperature?

No, it also depends on the concentration of solutes

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NaCl solution

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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 58Coherent EZ water 3292 76Intermediate bulk 3361 37Intermediate EZ 3494 4Non-coherent bulk 3526 5Non-coherent EZ 3610 20

Blue

shift

Egap decreased

=1/Egap 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─ +

Neg

ativ

ely

char

ged

surf

ace

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

Ө

ӨӨ ӨӨ Ө Ө ӨӨ ӨӨ Ө

Positively charged surface

Ө ӨӨ ӨӨ Ө Ө ӨӨ ӨӨ Ө

Like charges repel each other, but as they are covalently fixed to a matrix, they all cannot but vibrate

Ө ӨӨ ӨӨ Ө Ө ӨӨ ӨӨ Ө

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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antonella.deninno@enea.it

Light Scattering on water

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Size Distribution by Intensity

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pure water

water-Nafion

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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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.

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:

TemperatureSolutes

Interfaces

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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.

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 pKa=9.7 the amino acid is fully deprotonated and its ionic charge is +2

Glutamic acid

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The electric charge ranges from +1 in the fully protonated form to -2 according to the speciation scheme.

Glutamic acid speciation schemepH

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pH=1.5 pH=11.8

When submitted to a weak ELF/static electromagnetic fieldthe glutamic acid loses a proton

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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

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We have observed that the exposure to a weakmagnetic field of an aqueous solution of L-Phe inducesa measurable shift in the acid–base equilibrium.

Phenylalanine

Exposure to a static magnetic field 1 Gauss – 30 minutes

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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.

H2Omodifications

aggregation

pKa shift

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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 isallowed whenever this layer is decreased by a magneticfield.

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

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water

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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

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Kosmotropes Chaotropes

Magnetic field

(1888)

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EMF chaotrope effect

Mon

tagn

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emis

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Nano-associates

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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.

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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