8 th annual water conference CONFERENCE ON PHYSICS, CHEMISTRY AND BIOLOGY OF WATER Bulgaria, October...
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Transcript of 8 th annual water conference CONFERENCE ON PHYSICS, CHEMISTRY AND BIOLOGY OF WATER Bulgaria, October...
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; [email protected] Institute Bion, Stegne 21, Ljubljana, Slovenia
CONTENT
1. EXPERIMENTAL BACKGROUND
2. METHOD
3. RESULTS
4. DISCUSSION
5. CONCLUSIONS
•2
Imprint of molecular informationUnusual properties of water
EXPERIMENTAL BACKGROUND
•3
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.
•4
EXPERIMENTAL BACKGROUND
Electrical conductivity
•5
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
•6
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
•7
METHOD
REPEATABILITY•8
METHOD
bitter - sweet
RESULTS•9
bitter
INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY
•10
INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY
•11
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)
•18
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)
•19
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)
•20
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)
•21
DISCUSSION
LONG-RANGE HYDRATING
EPITAXY NEXT TO HYDROPHILIC SURFACES AND SOME SOLUTES (Zheng et al. 2006, Chai et al. 2008)
•22
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
•23
DISCUSSION
REAL DISCRETE OBJECTS
aqueous solution of urea – NTA
(Sedlák & Rak, J. Phys. Chem. B, 2013)
Further confirmation of the autothixotropic phenomenon?
•24
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
•25
DISCUSSION
What do experiments tell us about epitaxy?
•26
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.
•30
PUBLISHED WORK
THANK YOU FOR YOUR ATTENTION!
•31
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
•35
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)
•36
DISCUSSION
Verdel et al. Submitted in 2013.
EPITAXY RESEARCH
1. mechanical: alternation of dynamization and dilution
2. electric field
•37
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.
•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
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.
•41
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 …
•42