Transcript Further evidence for the autothixotropic phenomenon

8th annual water conference
CONFERENCE ON PHYSICS, CHEMISTRY AND BIOLOGY OF WATER
Bulgaria, 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]
2 Institute Bion, Stegne 21, Ljubljana, Slovenia
CONTENT
•2
1. EXPERIMENTAL BACKGROUND
2. METHOD
3. RESULTS
4. DISCUSSION
5. CONCLUSIONS
EXPERIMENTAL
BACKGROUND
•3
Imprint of molecular information
Unusual properties of water
EXPERIMENTAL BACKGROUND
VITTORIO ELIA ET AL.
•4
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.
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.
METHOD
•5
Electrical conductivity
METHOD
CONDUCTIVITY MEASUREMENTS
•6
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)
6. σ/σCC
1.
2.
3.
4.
5.
METHOD
AGEING OF SOLUTIONS
•7
ageing: 310 days
AGEING CONDITIONS
•MD -20 °C
•ST protected from day-light
•PR exposed to day-light
•2 mL
•2,5-mL vials
ageing: 370 days
•20-mL vials
AGEING VOLUMES
• 2 mL
• 5 mL
• 10 mL
METHOD
REPEATABILITY
•8
Repeatability of conductivity after 310 days
of ageing
50
45
conductivity (mS/cm)
40
35
30
N=29
N=27
25
20
15
baseline
conductivity
10
5
0
PR1
preparation
PR2
RESULTS
•9
bitter - sweet
INFLUENCE OF MECHANICAL
AND ELECTRICAL EPITAXY
•10
bitter
RESULTS
INFLUENCE OF MECHANICAL AND ELECTRICAL EPITAXY
•11
Holandino C. et al. International Journal of High Dilution
60
Research 2008, 7, 165-73.
conductivity (µS/cm)
50
40
30
N=5
N=5
N=7
N=5
N=7
N=7
N=5
N=5
20
N=5
10
0
PR1
PR2
preparation
N=5
KON
MV
MK
EV
EK
INFLUENCE OF AGEING
•12
sweet
RESULTS
INTERACTION T VS. FREQUENCY
•13
160
σ/σCC/%
155
150
T
5 °C
25 °C
145
140
135
1000
10.000
100.000
f/Hz
Verdel et al. J. Phys.: Conf. Ser. 2011.
RESULTS
INFLUENCE OF S/V
•14
σE = 20 × S/V − 33
R2 = 0.999
RESULTS
INFLUENCE OF CONDITION
•15
ST σE/σ = 43 %;
PR σE/σ = 42 %;
MD σE/σ = -17 %;
80
CONDUCTIVITY (µS/cm)
70
60
50
conditions
PR
40
ST
30
CC (25 °C, 1000 Hz)
MD
20
10
0
0.0
0.1
0.2
0.3
0.4
CONCENTRATION OF NaHCO3 (mmol/L)
Verdel et al. Int. J. Mol. Sci. 2012.
0.5
RESULTS
INFLUENCE OF IONS
•16
CONDUCTIVITY (mS/cm)
120
2 mL
100
80
σ = 184 cNaHCO3
R² = 0.996
σ = 220 cNaHCO3
R² = 0.961
60
5 mL
40
10 mL
20
položaji
conditions
volumes
volumni
CC: 25 °C, 1000 Hz
0
0.0
0.2
0.4
0.6
CONCENTRATION OF NaHCO3 (mmol/L)
Verdel et al. Int. J. Mol. Sci. 2012.
DISCUSSION
•17
the time domain of water
+
large-scale inhomogeneities in aqueous
systems and/or exclusion zones
=
autothixotropy of water
DISCUSSION
INCREASED CONDUCTIVITY
•18




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.
DISCUSSION
SELF-ORGANIZING PROPERTIES
•19
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.
DISCUSSION
THE TIME-DOMAIN OF WATER
•20
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)
DISCUSSION
AUTO-OSCILLATORY FEATURES
•21
 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)
DISCUSSION
LONG-RANGE HYDRATING
•22
EPITAXY
HYDROPHILIC SURFACES
The properties
of EZ NEXT
water vs.TO
bulk:
AND SOME SOLUTES
150-200 mV near the nucleating surface,
(Zheng et al. 2006, Chai et al. 2008)
 higher dynamic viscosity,
 lower IR emissivity,
 shorter T2 relaxation times,
expanded by light,
peak at ~270 nm.
DISCUSSION
LARGE-SCALE INHOMOGENEITIES
•23
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
DISCUSSION
REAL DISCRETE OBJECTS
•24
aqueous solution of urea – NTA
(Sedlák & Rak, J. Phys. Chem. B, 2013)
Further confirmation of the autothixotropic phenomenon?
DISCUSSION
THIXOTROPY
•25
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
o
the dielectric constant,
conductivity
CONCLUSIONS
•26
What do experiments tell us about epitaxy?
What do results tell us about ageing of solutions?
CONCLUSIONS
INFLUENCE OF EPITAXY
•27
1.
2.
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
CONCLUSIONS
THE AUTOTHIXOTROPY OF WATER
•28
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
3.
Verdel et al. Int. J. Mol. Sci. 2012.
CONCLUSIONS
NEW QUESTIONS
•29
Could excess conductivites be attributed to
autothixotropy?
2. May quantum field theory explain the occurrence of the
autothixotropic phenomenon?
1.
3.
Could large-scale inhomogeneities form due to
increase of effective particle sizes by growth of EZ?
PUBLISHED WORK
•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.
THANK YOU FOR YOUR
ATTENTION!
•31
RESULTS
INFLUENCE OF DISSOLVED CO2
•32
190
180
σ/σCC (%)
170
N=28
N=8
160
N=10
150
140
130
N=10
120
110
100
0
0.1
0.2
VCO2/VSOLUTION (%)
0.3
0.4
EXPERIMENTAL BACKGROUND
EPITAXY
•33
Transfer of molecular „information“ from one
substance to the other without mass transfer or
chemical reactions.
RESULTS
INFLUENCE OF TEMPERATURE
•34
150
149
148
147
σ/σCC (%)
146
145
25 °C
5 °C
144
143
142
141
N = 29
N = 29
140
139
temperature (°C)
Verdel et al. Int. J. Mol. Sci. 2012.
DISCUSSION
THE MAGNETIC EFFECT
•35
 proper experimental conditions
 increases the structuring of the hydration shells of
structure-breaking ions and hydrophobic molecules
 easily destroyed by external disturbances
 more with discontinuous magnetic radiation
Higashitani et al. J. Colloid Interface Sci. 1992-1995
DISCUSSION
COHERENCE
•36
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.
EPITAXY RESEARCH
•37
mechanical: alternation of dynamization and
dilution
2. electric field
1.
[email protected]
WORKING HYPOTHESIS
•38
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.
WORKING HYPOTHESIS
•39
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.
THE AIM
•40
Examine the effect of epitaxy
IZKLJUČITVENE CONE
•41
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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.
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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.

NENAVADNE LASTNOSTI VODE
•42

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 …
