8th annual water conferenceCONFERENCE ON PHYSICS, CHEMISTRY AND BIOLOGY OF WATERBulgaria, October 22-25, 2013

POSSIBLE FURTHER EVIDENCE FOR THE „AUTOTHIXOTROPIC“ PHENOMENON

Nada VERDEL1, Igor JERMAN 2, Peter BUKOVEC 1

1 Faculty of Chemistry and Chemical Techonolgy, University of Ljubljana, Aškerčeva 5, Ljubljana, Slovenia; nadaverdel@gmail.com2 Institute Bion, Stegne 21, Ljubljana, Slovenia

CONTENT

1. EXPERIMENTAL BACKGROUND

2. METHOD

3. RESULTS

4. DISCUSSION

5. CONCLUSIONS

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Imprint of molecular informationUnusual properties of water

EXPERIMENTAL BACKGROUND

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VITTORIO ELIA ET AL.

Aged extremely diluted and succussed NaHCO3 solutions haveHigher conductivities than chemically analogous solutions

Higher enthalpies of mixing with NaOH

Elia & Niccoli. Ann NY Acad Sci. 1999, 879, 241-248. Elia et al. J. Mol. Liq. 2009, 148, 45-50. Cacace et al. J. Mol. Liq. 2009, 146, 122-126. Elia et al. J. Therm. Anal. Calorim. 2010, 102, 1111-1118. Yinnon & Elia. Int. J. Mod. Phys. B 2013, 27, 1350005-1350040.

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EXPERIMENTAL BACKGROUND

Electrical conductivity

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METHOD

CONDUCTIVITY MEASUREMENTS

1. T = 25 and 5 °C

2. at 120, 1000, 10,000 and 100,000 Hz

3. ageing of solutions: 310 and 370 days

4. CC: conductivity= f ([NaHCO3])

5. chemical analysis of Na, (K, Ca, Mg, Si) in aged solutions by ICP-MS (inductively coupled plasma mass spectrometry)

6. σ/σCC

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METHOD

AGEING OF SOLUTIONS

ageing: 310 days

•2 mL•2,5-mL vials

AGEING CONDITIONS•MD -20 °C•ST protected from day-light•PR exposed to day-light

ageing: 370 days

•20-mL vials

AGEING VOLUMES•2 mL•5 mL•10 mL

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METHOD

REPEATABILITY•8

METHOD

bitter - sweet

RESULTS•9

bitter

INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY

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INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY

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RESULTS

Holandino C. et al. International Journal of High Dilution Research 2008, 7, 165-73.

sweet

INFLUENCE OF AGEING•12

INTERACTION T VS. FREQUENCY•13

RESULTS

Verdel et al. J. Phys.: Conf. Ser. 2011.

INFLUENCE OF S/V•14

RESULTS

σE = 20 × S/V − 33

R2 = 0.999

INFLUENCE OF CONDITION•15

ST σE/σ = 43 %;

PR σE/σ = 42 %;

MD σE/σ = -17 %;

Verdel et al. Int. J. Mol. Sci. 2012.

RESULTS

INFLUENCE OF IONS•16

RESULTS

Verdel et al. Int. J. Mol. Sci. 2012.

the time domain of water+

large-scale inhomogeneities in aqueous systems and/or exclusion zones

=

autothixotropy of water

DISCUSSION•17

INCREASED CONDUCTIVITY

aged extremely dilute solutions (Elia et al. & Verdel et al. ) lateral conductivity of ultrathin water films (Guckenberger et

al., Science, 1994) aqueous solutions under constrained conditions (Sasaki,

Biopolymers, 1984) nanoconfinement of water induces thermal enhancement (Hu

et al., Nano Lett., 2009)

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DISCUSSION

Verdel et al. Int. J. Mol. Sci. 2011.

SELF-ORGANIZING PROPERTIES

QUANTUM ELECTRODYNAMIC INTERACTIONS

μm- SIZED DOMAINS: CD

two-structured model (Röntgen, 1892) inhomogeneous structure (Huang et al., PNAS 2009)

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DISCUSSION

Del Giudice, Preparata, Vitiello. Phys. Rev. Lett. ,1988.

THE TIME-DOMAIN OF WATER

change of spectral parameters of water even when the source of radiation is removed or switched off enhancement of intensities upon radiation(Lobyshev et al. 1999; Quickenden & Que Hee 1971; Belovolova et al. 2009; Gudkov et al. 2011)duration of storage increases intensitiy of bands in the emission spectra of water (Lobyshev et al., J. Mol. Liq., 1999) the magnetic memory (Deng & Pang, Chin. Sci. Bull. 2007; Higashitani et al., J. Colloid Interface Sci. 1995)

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DISCUSSION

AUTO-OSCILLATORY FEATURES

WATER: AN ACTIVE EXCITABLE MEDIUM ORP, pH luminescence

(Yamashita et al. Langmuir, 2003,

Gudkov et al. J. Phys. Chem. B, 2011)

WATER ESTABLISHES CONDITIONS FOR SELF-ORGANIZATION

(Marchettini et al. J. Theor. Biol., 2010)

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DISCUSSION

LONG-RANGE HYDRATING

EPITAXY NEXT TO HYDROPHILIC SURFACES AND SOME SOLUTES (Zheng et al. 2006, Chai et al. 2008)

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The properties of EZ water vs. bulk:150-200 mV near the nucleating surface, higher dynamic viscosity, lower IR emissivity, shorter T2 relaxation times,expanded by light,peak at ~270 nm.

DISCUSSION

LARGE-SCALE INHOMOGENEITIES

LLS experiments: slow relaxation modes in aqueous solutions of

organic and inorganic molecules (Sedlák 2006, Subramanian et al. 2011, Liu 2003,

Dixit et al. 2002, Bowron & Moreno 2003) ordinary and degassed solvent(Sedlák & Rak 2013)

100 nm sized inhomogeneitiesnot nanobubbles in all cases

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DISCUSSION

REAL DISCRETE OBJECTS

aqueous solution of urea – NTA

(Sedlák & Rak, J. Phys. Chem. B, 2013)

Further confirmation of the autothixotropic phenomenon?

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DISCUSSION

THIXOTROPY

Greek: thixis (shaking) and trepo (changing) thixotropic effect: paints, vanadium pentoxide & aluminium oxide

sols, clays, creams, human blood ... thick albumen:

dye excluding gel dye non-excluding sol

upon shaking infinite rest time: change of non-rheological features:

o the dielectric constant, o conductivity

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DISCUSSION

What do experiments tell us about epitaxy?

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CONCLUSIONS

What do results tell us about ageing of solutions?

INFLUENCE OF EPITAXY•27

1. Epitaxially (mechanically and electrically) imprinted KCl does not effect conductivity

2. Epitaxial imprint of hydrophilic glass surface may be significant: higher values of S/V gave higher excess conductivities

CONCLUSIONS

THE AUTOTHIXOTROPY OF WATER•28

3.in all 310 and 370 days old solutions except for those stored frozen significantly higher conductivity values than in chemically analogous fresh (one day old) solutions were measured

4.no excess conductivity values were found in frozen samples due to diminished translational mobility of water molecules in the solid state

5.higher conductivities cannot be attributed to other ions than sodium neither to absorption of CO2

CONCLUSIONS

Verdel et al. Int. J. Mol. Sci. 2012.

NEW QUESTIONS•29

1. Could excess conductivites be attributed to autothixotropy?

2. May quantum field theory explain the occurrence of the autothixotropic phenomenon?

3. Could large-scale inhomogeneities form due to increase of effective particle sizes by growth of EZ?

CONCLUSIONS

Verdel et al. The “Autothixotropic” phenomenon of water and its role in proton transfer. Int. J. Mol. Sci. 2011, 12, 7481-7494.

Verdel et al. Possible time-dependent effect of ions and hydrophilic surfaces on the electrical conductivity of aqueous solutions. Int. J. Mol. Sci. 2012, 13, 4048-68.

Verdel et al. Conductivity measurements as a possible means to measure the degree of water ordering. J. Phys.: Conf. Ser., 2011, 329, 012005.

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PUBLISHED WORK

THANK YOU FOR YOUR ATTENTION!

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INFLUENCE OF DISSOLVED CO2•32

RESULTS

N=28

N=10

N=10

N=8

EPITAXY•33

EXPERIMENTAL BACKGROUND

Transfer of molecular „information“ from one substance to the other without mass transfer or chemical reactions.

INFLUENCE OF TEMPERATURE•34

RESULTS

Verdel et al. Int. J. Mol. Sci. 2012.

THE MAGNETIC EFFECT

proper experimental conditionsincreases the structuring of the hydration shells of

structure-breaking ions and hydrophobic moleculeseasily destroyed by external disturbances more with discontinuous magnetic radiation

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DISCUSSION

Higashitani et al. J. Colloid Interface Sci. 1992-1995

COHERENCE

fast resonant intermolecular transfer (Woutersen & Bakker, Nature, 1999) delocalized H+ (Bakker & Nienhuys, Science, 2002)delocalization of H+ over the protein surface (Pagnotta et al., Biophysical J., 2009)coherent energy transfer in water spectra (Yang & Skinner, PCCP, 2010)

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DISCUSSION

Verdel et al. Submitted in 2013.

EPITAXY RESEARCH

1. mechanical: alternation of dynamization and dilution

2. electric field

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Peter.Bukovec@fkkt.uni-lj.si

WORKING HYPOTHESIS

When water is left to stand undisturbed, its properties change to “autothixotropic”, which plays a major role in the proton conducting properties of water. Previous mechanical or electrical treatment has no influence on the conductivity values of aged solutions. We expect higher values of excess conductivity in smaller volumes. The same would be expected from exposure to light. Whereas thixotropic properties cannot be established if solutions are aged frozen.

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WORKING HYPOTHESIS

When water is left to stand undisturbed, its properties change to “autothixotropic”, which plays a major role in the proton conducting properties of water. Previous mechanical or electrical treatment has no influence on the conductivity values of aged solutions. We expect higher values of excess conductivity in smaller volumes. The same would be expected from exposure to light. Whereas thixotropic properties cannot be established if solutions are aged frozen.

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Examine the effect of epitaxy

THE AIM•40

IZKLJUČITVENE CONE

Zheng J. M. and Pollack G. H. Phys. Rev. E Stat. Nonlin. Soft Matter Phys., 2003, 68, 031408-1-7.

Chai B. et al. J. Phys. Chem. A, 2008, 112, 2242-47. Chai B. et al. J. Phys. Chem. B, 2009, 113, 13953-58. Figueroa X., Pollack G. H. v tisku Design and Nature, 2011. Klimov A. Pollack G. H. Langmuir, 2007, 23, 11890-11895. Klyuzhin I. et al. Environ. Sci. Techn., 2008, 42, 6160-6166. Klyuzhin I. S. et al. J. Phys. Chem. B, 2010, 114, 14020-14027. Nagornyak E. et al. Soft Matter, 2009, 5, 3850-3857. Nhan D. T. and Pollack G. H. Int. J. Design Nature, 2011, 6, 139–144. Ovchinnikova K. and Pollack G. H. Langmuir, 2008, 25, 542–547. Ovchinnikova K. and Pollack G. H. Phys. Rev. E, 2009, 79, 036117-1-

10. Pollack G. H. et al. Int. J. Mol. Sci., 2009, 10, 1419–1429. O'Rourke C. et al. Phys. Rev. E, 2011, 83, 056305-1-5. Zhao Q. et al. Langmuir, 2008, 24, 1750–1755. Zhao Q. et al. J. Phys. Chem. B, 2009, 113, 10708–10714. Zheng J.-M. et al. Adv. Colloid Interface Sci., 2006, 127, 19–27. Zheng J.-M. et al. J. Colloid Interface Sci., 2009, 332, 511-514. Yoo H. et al. J. Phys. Chem. Letters, 2011, 2, 532-536.

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