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POSSIBLE FURTHER EVIDENCE FOR THE „AUTOTHIXOTROPIC“ PHENOMENON

8 th annual water conference CONFERENCE ON PHYSICS, CHEMISTRY AND BIOLOGY OF WATER Bulgaria, October 22-25, 2013. POSSIBLE FURTHER EVIDENCE FOR THE „AUTOTHIXOTROPIC“ PHENOMENON Nada VERDEL 1 , Igor JERMAN 2 , Peter BUKOVEC 1

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POSSIBLE FURTHER EVIDENCE FOR THE „AUTOTHIXOTROPIC“ PHENOMENON

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  1. 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 1Faculty of Chemistry and Chemical Techonolgy, University of Ljubljana, Aškerčeva 5, Ljubljana, Slovenia; nadaverdel@gmail.com 2 Institute Bion, Stegne 21, Ljubljana, Slovenia

  2. CONTENT • EXPERIMENTAL BACKGROUND • METHOD • RESULTS • DISCUSSION • CONCLUSIONS

  3. EXPERIMENTAL BACKGROUND Imprint of molecular information Unusual properties of water

  4. EXPERIMENTAL BACKGROUND VITTORIO ELIA ET AL. Aged extremely diluted and succussed NaHCO3 solutions have • Higher conductivities than chemically analogous solutions • Higher enthalpies of mixing with NaOH • Elia& Niccoli. Ann NY Acad Sci.1999,879, 241-248. • Eliaet al.J. Mol. Liq. 2009, 148, 45-50. • Cacaceet al. J. Mol. Liq. 2009, 146, 122-126. • Eliaet al.J. Therm. Anal. Calorim. 2010, 102, 1111-1118. • Yinnon & Elia. Int. J. Mod. Phys. B2013, 27, 1350005-1350040.

  5. Electrical conductivity METHOD

  6. METHOD CONDUCTIVITY MEASUREMENTS • T = 25 and 5 °C • at 120, 1000, 10,000 and 100,000 Hz • ageing of solutions: 310 and 370 days • CC: conductivity= f ([NaHCO3]) • chemical analysis of Na, (K, Ca, Mg, Si) in aged solutions by ICP-MS (inductively coupled plasma mass spectrometry) • σ/σCC

  7. 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

  8. METHOD REPEATABILITY

  9. RESULTS bitter - sweet

  10. INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY bitter

  11. RESULTS INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY Holandino C. et al. International Journal of High Dilution Research2008, 7, 165-73.

  12. INFLUENCE OF AGEING sweet

  13. RESULTS INTERACTION T vs. FREQUENCY Verdel et al.J. Phys.: Conf. Ser.2011.

  14. RESULTS INFLUENCE OF S/V σE= 20 × S/V− 33 R2 = 0.999

  15. RESULTS INFLUENCE OF CONDITION ST σE/σ= 43 %; PR σE/σ = 42 %; MD σE/σ = -17 %; Verdel etal.Int. J. Mol. Sci. 2012.

  16. RESULTS INFLUENCE OF IONS Verdel etal.Int. J. Mol. Sci. 2012.

  17. DISCUSSION the time domain of water + large-scale inhomogeneities in aqueous systems and/or exclusion zones = autothixotropy of water

  18. DISCUSSION 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) Verdel et al. Int. J. Mol. Sci. 2011.

  19. DISCUSSION SELF-ORGANIZING PROPERTIES QUANTUM ELECTRODYNAMIC INTERACTIONS μm-SIZED DOMAINS: CD • two-structured model (Röntgen, 1892) • inhomogeneous structure (Huang et al., PNAS 2009) Del Giudice, Preparata, Vitiello. Phys. Rev. Lett. ,1988.

  20. DISCUSSION 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)

  21. 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)

  22. DISCUSSION LONG-RANGE HYDRATING EPITAXY NEXT TO HYDROPHILIC SURFACES AND SOME SOLUTES (Zheng et al. 2006, Chai et al. 2008) 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.

  23. 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 inhomogeneities not nanobubbles in all cases

  24. DISCUSSION REAL DISCRETE OBJECTS aqueous solution of urea – NTA (Sedlák & Rak, J. Phys. Chem. B, 2013) Further confirmation of the autothixotropic phenomenon?

  25. 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: • the dielectric constant, • conductivity

  26. What do experiments tell us about epitaxy? CONCLUSIONS What do results tell us about ageing of solutions?

  27. CONCLUSIONS INFLUENCE OF EPITAXY • Epitaxially (mechanically and electrically) imprinted KCl does not effect conductivity • Epitaxial imprint of hydrophilic glass surface may be significant: higher values of S/V gave higher excess conductivities

  28. CONCLUSIONS THE AUTOTHIXOTROPY OF WATER • 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 • no excess conductivity values were found in frozen samples due to diminished translational mobility of water molecules in the solid state • higher conductivities cannot be attributed to other ions than sodium neither to absorption of CO2 Verdel etal.Int. J. Mol. Sci. 2012.

  29. CONCLUSIONS NEW QUESTIONS • Could excess conductivites be attributed to autothixotropy? • May quantum field theory explain the occurrence of the autothixotropic phenomenon? • Could large-scale inhomogeneities form due to increase of effective particle sizes by growth of EZ?

  30. 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. PUBLISHED WORK

  31. THANK YOU FOR YOUR ATTENTION!

  32. RESULTS INFLUENCE OF DISSOLVED CO2 N=28 N=8 N=10 N=10

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

  34. RESULTS INFLUENCE OF TEMPERATURE Verdel etal.Int. J. Mol. Sci. 2012.

  35. DISCUSSION THE MAGNETIC EFFECT • properexperimental conditions • increases the structuring of the hydration shells of structure-breaking ionsand hydrophobic molecules • easily destroyed by external disturbances • more with discontinuous magnetic radiation Higashitani et al. J. Colloid Interface Sci. 1992-1995

  36. DISCUSSION 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) Verdel et al. Submitted in 2013.

  37. Epitaxy research • mechanical: alternation of dynamization and dilution • electric field Peter.Bukovec@fkkt.uni-lj.si

  38. 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.

  39. 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.

  40. THE AIM Examine the effect of epitaxy

  41. 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.

  42. NENAVADNE LASTNOSTI VODE • 4 tetraedrično razporejeni sp3-hibridizirani elektronski pari • vodikove vezi • 63 nenavadnih lastnosti vode • visoko tališče in vrelišče • maksimalna gostota v tekočem stanju • toplo vodo prej zamrznemo kot hladno • zlahka jo podhladimo …

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