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Department of Applied Physics,
The Hebrew University of Jerusalem,
Israel
Yuri Feldman
1
Water in heterogeneous/biological systems
Interfacial water—from the ordered structures to the
single hydrated shell
2
Dielectric spectroscopy is sensitive to relaxation processes
Types of polarization
Electric Field
Orientation polarization:
Ionic Polarization:
+
-
--
- +
++ --
+
+-
-
+
++-
--
--
-
-
-
++ + +
+
+
+
+ +
Electric Field
+
Deformation polarization
Introduction-Dielectric Spectroscopy
~
32
Dielectric spectroscopy is sensitive to relaxation processes
Types of polarization
Electric Field
Orientation polarization:
Ionic Polarization:
+
-
--
- +
++ --
+
+-
-
+
++-
--
--
-
-
-
++ + +
+
+
+
+ +
Electric Field
Deformation polarization
~
Introduction-Dielectric Spectroscopy
4
Dielectric spectroscopy is sensitive to relaxation processes
in an extremely wide range of characteristic times ( 10 5 - 10 -12 s)
Broadband Dielectric Spectroscopy
Porous materialsand colloids
Clusters Single droplets and pores
Glass forming liquids
Macromolecules
10-210-4 0 102 104 106 108 1010 1012
Time Domain Dielectric Spectroscopy; Time Domain Reflectometry
f (Hz)
10-6
Water
ice
Dielectric response on mesoscale
Dielectric Response in Biological Systems
5
Broadband Dielectric Spectroscopy
Cells
Time Domain Dielectric Spectroscopy
f (Hz)H
H3N+ — C — COO-
R
Ala Asp Arg Asn
Cys Glu Gln His
Ile Leu Lys Met
Phe Ser Thr Trp
Tyr Val
1031020 105 106 107 108 109 101010410110-1 1011
P-
N+Head group
region
Lipids
Proteins
Water
- Dispersion
DNA, RNA
-Dispersion - Dispersion - Dispersion
Tissues
ice
Amino acids
+ =
Water as a marker in the dielectric spectroscopy measurements
1.8-3 D
(large dipole moment)
1031020 105 106 107 108 109 101010410110-1 1011
Decreasing temperature/
Confined conditions
Water is the “contrast” in dielectric measurements!!!
7
Water as a marker in the dielectric spectroscopy measurements
8
10 -110 1
10 3
10 510 7
Frequency [Hz]
10-4
10-2
100
102
Perm
ittivity''
[]
-200 0 200 400
Temperature [°C]
10 1
10 3
10 5
10 7
Frequency [Hz]
10-4
10-2
100
102
Pe
rmitt
ivity
'' []
0100
200300
Temperature [°C]
Water as a marker in the dielectric spectroscopy measurements
Hydrated sampleDehydrated sample
1031020 105 106 107 108 109 101010410110-1 1011
Decreasing temperature/
Confined conditions
Water is the “contrast” in dielectric measurements!!!
9
1) Silica glasses
a. 62.6% SiO2, 30.4% B2O3,7%Na2O
b. 70% SiO2, 23% B2O3, 7% Na2O,
2) The study of confined water dynamics in clay
minerals with different doped ions (K, Co, Ni)
a. Montmorillonite
b. Kaolinite
Clays and Clay Minerals (2014), Vol. 62, pp. 62–73
Water in non organic systems:
Microporous and Mesoporous Materials
58 (2003) 237–254
PRL (2010) Vol. 105, pp. 037601-4
10
L-defects D-defects OH- OH3+
Orientation defectsIonic defects
Dielectric relaxation in ice and water
Si
OO
O
10 -110 1
10 310 5
10 7
Frequency [Hz]
10-4
10-2
100
102
Perm
ittivity''
[]
-200 0 200 400
Temperature [°C]
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Local motion
Inter center
motion
Porous glasses: Relaxation Mechanism
12
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
Si
OOO
10 -110 1
10 310 5
10 7
Frequency [Hz]
10-4
10-2
100
102
Perm
ittivity''
[]
-200 0 200 400
Temperature [°C]
Si
OOO
Si
OOO
Si
OOO
Porous glasses: Relaxation Mechanism
𝑴 =
𝑖
𝑁
𝑒𝑖𝒓𝑖
10 1
10 3
10 5
10 7
Frequency [Hz]
10-4
10-2
100
102
Pe
rmitt
ivity
'' []
0100
200300
Temperature [°C]
10 -110 1
10 3
10 510 7
Frequency [Hz]
10-4
10-2
100
102
Perm
ittivity''
[]
-200 0 200 400
Temperature [°C]
SamplesHumidity h, %
II 0 .63
A 1 .2
B 1 .4
D 1 .6
C 3 .2
III 3 .39
I 3 .6
Porous glasses
14
A - 50 kJ/mol
B - 42 kJ/mol
C - 67 kJ/mol
D - 19 kJ/mol
Ice - 60 kJ/mol
15
Porous glasses
4.6 4.8 5.0 5.2 5.4 5.6 5.8
10-7
10-6
10-5
10-4
10-3
3.5 3.7 3.9 4.1 4.3 4.5 4.7 Sample
A
B
C
D
Ice
, [
s]
1000/T, [K-1]
170 180 190 200 210 2200.01
0.1
1
A
B
C
D
Temperature, [K]
-17 -16 -15 -14 -13 -12 -11 -10 -9 -8
0.36
0.39
0.42
0.45
0.48
0.51
0.54
0.57
0.60
0.63
A
B
C
D
I
II
III
ln()
A - 50 kJ/mol
B - 42 kJ/mol
C - 67 kJ/mol
D - 19 kJ/mol
Ice - 60 kJ/mol
16
2.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.8
10-8
10-7
10-6
10-5
10-4
10-3
10-2
A
B
C
, [s]
1000/T, [K-1]
II process
I process
Porous glasses
17
Aluminosilicates: Montmorillonite Ni
10-1101
103105
107Frequency [Hz]
10
-310
-110
110
310
5
Pe
rmittivity''
-200 -100 0 100 200 300
Temperature [°C]
3
2
1
5.6 5.8 6.0 6.2 6.4 6.6
10-6
10-5
10-4
10-3
10-2
[s]
1000/T
Co Co2
Ni Ni2
Cu Cu2
18
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
10-9
10-8
10-7
10-6
10-5
10-4
10-3
10-2
10-1
II.2
II.1
I.2
I.1
Montmorillonite,
s
1000/T
I K
I K2
I Co
I Co2
I Ni
I Ni2
I Cu
I Cu2
II K
II Co
II Co2
II Ni
II Ni2
II Cu
II Cu2
Aluminosilicates: Montmorillonite Ni
19
From non organic to organic systems
Using the water as a marker in porous system we can find:
1) The dynamics of water in the regime of the tight confinement
2) The influence of the various ions on the water dynamic
3) Structural properties of the sample: percolation cluster, fractal dimension and
porosity
In organic systems additional effects appear:
Specific structure of the
protein surface
Concentration of the
hydrophilic centers in
one place
Anisotropic properties.
Ordered structures
Inert interfacial water as apposed to
the actively solvating molecule
150200
250300
350
10-1
101
103
105
0
2
4
6
MidT
Die
lectr
ic lo
sse
s, "
log(f)
Temperature, [K]
LowT
Percolation
Saddle-like
Dielectric Responses of the confined water are similar
in non organic and organic systems
10 -110 1
10 310 5
10 7
Frequency [Hz]
10-4
10-2
100
102
Perm
ittiv
ity''
[]
-200 0 200 400
Temperature [°C]
[Clays and Clay Minerals
(2014), Vol. 62, pp. 62–73]
PCCP (2016),
V.18, pp. 10992-
10999
Microporous and Mesoporous
Materials 58 (2003) 237–254
Hydrated
proteins
(Lysozyme)
Porous glasses
Clays
21
Protein functionality
Protein structure
Protein hydration
shell
22
Water in organic systems. Hydration shell dynamics in proteins:
1) Hydration shell dynamics of a fibril protein
(Collagen type 1).
2) Hydration shell dynamics of a globular protein
(Lysozyme).
3) Hydration shell dynamics of a ring like protein
(Phycocyanin).
23
Introduction to collagen: General structure
Collagen is a protein consisted of (X-Y-Gly)n repeating sequences
Gly is the Glycine X or Y is the Proline or 4-HydroxyProline
HO
Steric effect stabilizes the
extended nature of the
individual chains
Hydrogen bonds (Gly: NH∙∙∙O=C: X)
leads to triple helixes organization Stable triple
helixes structure
24
Introduction to collagen: Water bridges
Water molecules embed into triple helixes
creating water bridges, that stabilizes collagen
structure [J. Bella et al Science, 1994]
Water bridges appear as a
surface bridges surround the triple helixes.
25
The problem: What is the differences
between hydration shell of globular
and fibrillar proteins
Introduction to collagen: Water bridges
The hydration shells connect between each
other creating stabilized collagen filaments
[K. Kawahara et al, Biochemistry, 2005]
26
Dielectric measurements of the hydrated collagen powders
S. A. Lusceac, et al Proteins and
Proteomics, 2010
3D plot of dielectric losses of the hydrated
collagen powders
h=0.16 =0.26 =0.33
Low temperature process
27
Main processIce process
S. A. Lusceac, et al J. Non-Cryst.
Solids (2011)
Dielectric measurements of the hydrated collagen powders
Ice process appears at high hydration level h>0.4
1. Main process doesn’t depend on the shape of the protein and is observed in
the various proteins.
2. It is attributed to the large-angle jumps of the water molecule
3. The present models are ignored the excess wing at the high frequency
S. A. Lusceac, et al Proteins and
Proteomics, 2010
28
New approach in the data description: Excess wing explanation
The proposed large-angle jumps can be corresponded with the migration of the H-bond
network defect [I. Popov, A. Puzenko, A. Khamzin and Y. Feldman PCCP, 2015]
*
12 *2
0
( )( )
16
or
B
i nq r
k T
2 2( ) /or
or hr t t
1*2 ( ) ~
or
orr i
*( )
1or
ori
If we take into account an ionic defect
Orientation defect
Ionic defect
*
12
2 *2
10
( )
1 ( )6
i i i
iB
in q r
k T
*
1( )
1or ion
or ioni i
29
*
1( )
1or ion
or ioni i
Collagen data treatment
30
Relaxation in ice
log τ
1000/T
Orientation
defect
Ionic
defect
I. Popov, A. Puzenko, A. Khamzin
and Y. Feldman PCCP, 2015
???
Orientation
Ionic
Additional delay due to
correlation with L-D defects
31
Relaxation in ice
log τ
1000/T
Independent defect migration
H3O+ defect
L- defect Blockage of the ionic defect
H3O+ defect
L- defectL-D defects
ionic defects
The low-temperature dynamic crossover in dielectric
relaxation behavior of ice Ih
Popov I., Lunev I., Khamzin A., Greenbaum A, Feldman Yu.
(2017, Paper in preparation)
32
Relaxation in ice
K.Goto et al Japanese J.
of Applied Phys. (1986)
pp.351-357
At low temperature the crack
appearance leads to the suppression of
the ionic defect and transition back to
the mechanism of the orientation
defect.
33
Collagen data treatment
H3O+
H3O+
Relaxation by ionic defect cannot be faster than relaxation by orientation defect
Hydration water ~ Distorted ice
Dehydrothermal Treatment:
34
After Heating and Keeping the
collagen at 120 0C for 30 min, proton
hopping mechanism slows down
Chains tilting prevents the
formation of the long range
water structure.
Relaxation occurs in local
compartments, where
contribution of the L-D and
ionic defect are comparable
Lysozyme: Surface charge plot[Christopher D. Cooper at el. 2013]
Charged active center
Lysozyme
35
~20Å
BDS Measurements: Lysozyme h=0.28 and h=0.16
150200
250300
350
10-1
101
103
105
0
2
4
6
MidT
Die
lectr
ic lo
sse
s, "
log(f)
Temperature, [K]
LowT
Percolation
Saddle-like
(a)
The typical dielectric spectra
[Khodadadi and A.P.Sokolov 2015] 36
37
5.0 5.5 6.0 6.5 7.0 7.5
-7
-6
-5
-4
-3
-2
-1
0 h=0.16
h=0.28
1000/T, [K-1]
log[
], [s]
T=184K
Ea=30kJ/mol
Ea=50kJ/mol
The typical dielectric spectra
[Khodadadi and A.P.Sokolov 2015]
4.5 5.0 5.5 6.0 6.5 7.010
-8
10-7
10-6
10-5
10-4
10-3
10-2
10-1
Lysozyme (h~0.37)
Myoglobin (h~0.33)
log[
], [s]
1000/T, [K-1]
Swenson and CerVeny 2015
BDS Measurements: Lysozyme h=0.28 and h=0.16
Temperature
solid like
behavior
liquid like
behavior
non-
correlated
system
Entropy and
Static Dielectric Permittivity
E=0
Dielectric Polarization and Entropy of the System
2 2
0 0
( ) ( )( ) (T) (T)
8 8
s T E T ES T S S
T T
ሻΔε(𝑇
Solid (Ordered system) Liquid (Disordered system)
E=0 E≠0
Decrease ordering Increase ordering
( )0s T
T
( )0s T
T
Τ𝑑Δε 𝑑𝑇>0 tendency tosolid-like dipole orientation
Τ𝑑Δε 𝑑𝑇<0 tendency points to a liquid-like behavior.
Tm of the extremum of 𝛥𝜀(T), the reorientation transition temperature.
T<155K 155K<T<187K T>187K
Short-range antiparallel orientation of the water dipoles, typical for the amorphous system
Tendency to solid like behavior
Tendency to liquid like behavior
39
BDS Measurements: Lysozyme h=0.28 and h=0.16
0 10 20 30 40
120
160
200
240
280
320
Tem
pera
ture
[K]
Time [minutes]
140 150 160 170 180 190 200 210 220
155 K
Cooling with no annealing
H
eat F
low
, [W
g-1]
Temperature, [K]
Exo 155K
DSC Measurements: Lysozyme h=0.2
150 175 200 225
Heat
Flo
w
Temperature, [K]
Exo
40
Protocol
140 150 160 170 180 190 200 210 220
155 K
Cooling with no annealing
Cooling with annealing
H
eat F
low
, [W
g-1]
Temperature, [K]
Exo
186.5K
155K
Lysozyme: Surface charge plot[Christopher D. Cooper at el. 2013]
Charged active center
Explanation of the Results
41
~20Å
∆𝑻𝒇(𝑹ሻ = 𝑪𝑮𝑻/(𝑹 − 𝒓ሻ
∆𝑇𝑓 = 𝑇𝑓 𝑏𝑢𝑙𝑘 − 𝑇𝑓 𝑝𝑜𝑟𝑒 - The depression of the confined water melting temperature.
𝐶𝐺𝑇-The Gibbs-Thompson Coefficient. R - The radius of the pore. r - The thickness of a liquid-like layer at the relevant melting temperature.
42
Gibbs-Thompson Fit for Silica Nano pores
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.50
20
40
60
80
100
GT equation
MCM-41 (Findenegg, G. H. et al, 2008)
MCM-41 (Schmidt, R. et al, 1995)
SBA-15 (Findenegg, G. H. et al, 2008)
[
R, [nm]
𝒓𝑹
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
-10
-9
-8
-7
-6
-5
-4
-3
-2
-1
0 Hydrated silica nanopores
Hydrated lysozyme
log[
], [s]
1000/T, [K-1]
43
Relaxation Times of Hydrated Lysozyme and Confined Water in Silica Nanopores
20Å
Silica nanopore with pore diameter equaled to 20A
Lysozyme with diameter cavity inside equaled to 20A
Crossover Tc
[Eliodoro Chiavazzoet al 2014] [Christopher D. Cooper at el. 2013]
Glass-state water
T=155K
Temperature, [K]
T=184K
Glass solution
T=155K:
1) Glass transition of the
solution
2) Onset of the crystallization
Nucleation growth
of the ice particles
….Gradual
growth of the ice
particles…..
T=184K:
Phase Transition of the
ice inside the pore.
Ice
melting…
Ice particle inside
the pore
The Model
5.0 5.5 6.0 6.5 7.0 7.5
-7
-6
-5
-4
-3
-2
-1
0 h=0.16
h=0.28
1000/T, [K-1]
log[
], [s]
T=184K
Conclusions
45
2) Water can be considered as a marker or a contrast
in Dielectric Spectroscopy. The structural and
dynamical properties of the matriex can be studied via
its hydrating.
3) Defect migration model can be used as an universal
approach in description of the dynamic of the
hydration process.
1) The morphology, dynamics and the dielectric properties of the
matrixes will have an influence on the nature of the relaxation of
hydrated water.
I would like to thank my PhD student Mrs Yael Segev,for the
generation of the data and the deep discussion of obtained
results.
I would like also to appreciate Dr. Paul Ben Ishai, Dr Anna
Greenbaum, Dr. Ivan Popov and Dr. Evegenia Levy for their
extremely helpful contribution to this work
This work has been supported by the Israel Science
Foundation (ISF) (Grant No. 465/11);
46
Acknowledgements
47
Acknowledgements