Dynamics of water - Case study: molecular relaxations in ... TUT... · ‐ General Phenomenology (glasses, Tg, relaxations) Properties of bulk water / Phase diagram (simulations vs

Silvina Cerveny

Material Physics Center, CSIC/UPVSan Sebastian, Spain

Dynamics of water -Case study: molecular relaxations in aqueous solutions of

synthetic and biological materials

Tutorial – BDS 2018

Outline

‐ Where is water? Some fields of research - Confinements

‐ General Phenomenology (glasses, Tg, relaxations) Properties of bulk water / Phase diagram (simulations vs experiments)

-Broadband Dielectric spectroscopy and the study of water molecules

-The dynamics of water at low temperatures in:

- Solution of polymers, glasses and other materials

- Short introduction to Proteins and other biomolecules

- Summary

Where is found water? Where is found water?

Geological waterGeological water

Biological waterBiological water

Water in soft matterWater in soft matter

Where is found water? – Geological waterWhere is found water? – Geological water

Rivers, lakes, reservoirs… BULK LIQUID WATERBULK LIQUID WATER

5 - 10 nm5 - 10 nm5 - 10 nm5 - 10 nm5 - 10 nm

CONFINED WATERCONFINED WATER

Porosity

Some topics of study:

- Water in relation to the structure of rocks as clays, rocks, tobermorite, kaolinite, volcanic ash...-Water motions no crystallization (no man´s land: 150 – 230 K)-How the properties of water change at the nanoscale?

Some topics of study:

- Water in relation to the structure of rocks as clays, rocks, tobermorite, kaolinite, volcanic ash...-Water motions no crystallization (no man´s land: 150 – 230 K)-How the properties of water change at the nanoscale?

Where is found water? – Biological waterWhere is found water? – Biological water

Some topics of study : -The motions of the protein, the hydration shell and the bulk solvent ―> functionality-Analogies confined water in rocks and proteins

Some topics of study : -The motions of the protein, the hydration shell and the bulk solvent ―> functionality-Analogies confined water in rocks and proteins

Most of this water is never more than about 1 nm from other molecules

Most of this water is never more than about 1 nm from other molecules

Model of a bacterial cytoplasm J. Phys. Chem. B 2017, 121

The motions of the protein, the hydration shell and the bulk solvent are all necessary for functionalityThe motions of the protein, the hydration shell and the bulk solvent are all necessary for functionality

Proteins: molecules which perform biological functions

Hydration is necessary for functionalityat least… 0.2 (g of water)/(g of protein) Hydration is necessary for functionalityat least… 0.2 (g of water)/(g of protein)

Bulk solvent

Hydration shellProtein

Where is found water? – Water in all hydrophilic materials, nanocomposites.......Where is found water? – Water in all hydrophilic materials, nanocomposites.......

Hydrophilic polymers contain polar or charged functional groups, rendering them soluble in water.

Some topics of study: -How to dry a polymer?-Plasticization-Compatibility with fillers-……

Some topics of study: -How to dry a polymer?-Plasticization-Compatibility with fillers-……

Some hydrophilic groups:

1. Carboxylic groups: -(COOH)2. Amide: -(C=O)-N-3. Hydroxyl groups: OH-4. .....

Where is found water? Where is found water?

Geological waterGeological water- Confined water (Weathering)- Relationship with structure- Solvent/Buffer

- Confined water (Weathering)- Relationship with structure- Solvent/Buffer

Biological waterBiological water- Bulk water, hydration water,confined water relationship with functionality- Confined water

- Bulk water, hydration water,confined water relationship with functionality- Confined water

Water in soft matterWater in soft matter

- Bulk water, hydration water,confined water- Relationship with several industrial applications

- Bulk water, hydration water,confined water- Relationship with several industrial applications

In many situations water is not in its bulk form, but instead it is either in contact with surfaces or confined within small cavities

Outline

‐ Where is water? Several fields of research. Confinements






- Summary

cool down below Tm

crystallizescrystallizes

Fixed positions, minimal potentialEquilibrium state

Does not crystallizesDoes not crystallizes

Supercooled liquid

msNPoise /1010 1213 Liquid is termed a GLASS

Randomly moving

Liquid

Viscosity = (T)Viscosity = (T)

o

oo TT

TDexp Vogel-Fulcher-Tamman (VFT)

1/T

Log()

GlassesGlasses

Glasses – Glass transition temperature - Tg Glasses – Glass transition temperature - Tg

glass

Supe

rcoo

led

liquid

liquid

crystalTM

Tg

T

V

Tg/T

Log()

stron

g

frag

ile

1

o

oo TT

TDexp

T

cp

Tg

273

Supercooled Glassy

T [K]100150235

Crystallization

Bulk water – No man´s land.... Bulk water – No man´s land....

Glassy water (HGW)

106/107 K/sec

Liquid water

Low Density Amorphous ice (LDA)High Density Amorphous ice (HDA)

Vapor/crystalline

(Hallbrucker et all, 1989)

LDA: Sceats and Rice, 1982HDA: Mishima et al, 1984

106 K/sec LDA HDA

No man´s landthe region lying between the crystallization temperatures encountered when heating the glass and cooling the liquid.

??? ???Tg = 136 K?Tg = 200-160 K?

Anomalies of water/ Experiments....Anomalies of water/ Experiments....

Due to crystallization…No entering in the no man´s landDue to crystallization…No entering in the no man´s land

- To mix water with hydrophilic solutes (SOFT CONFINEMENT)

L

L

pores: 2-D confinementlayers: 1-D confinement

- Well-defined confinement systems (HARD CONFINEMENT)

Mineral Clays, Graphite Oxide, Cements, Molecular sieves, MCM 41, Silica hydrogels, Zeolites………

- Polymers - Glass formers materials

Outline

‐ Where is water? Several fields of research. Confinements






- Summary

The water moleculeThe water molecule

Water molecule

Hydrogen bond between water molecules BULK Liquid water

Broadband dielectric spectroscopyBroadband dielectric spectroscopy

1) Materials with a permanent dipolar moment

2) External static electric field (1 Volt)

Orientation Polarization

Dielectric spectroscopy can provide information about the segmental mobility of polar moleculesDielectric spectroscopy can provide information about the segmental mobility of polar molecules

3) External electric field is frequency dependent (10-3 to 1011 Hz):

“the dipole relaxation arising from the reorientational motions of molecular dipoles”

Carbon dioxideWater molecule Peptide

Polymers, proteins,….

EEP

o

o

)1(

χ = electric susceptibility = (1+ )

Broadband dielectric spectroscopyBroadband dielectric spectroscopy

100 101 102 103 104 105 106 107 108 109 1010

T1< T2

-relaxation

Hz

-relaxationT1< T2

Broadband dielectric spectroscopyBroadband dielectric spectroscopy Information obtained from the dielectric spectra

Kremer – Tutorial BDS 2016

Debye Relaxation Havriliak-Negami Relaxation

The dynamics of “water” as seen by BDSThe dynamics of “water” as seen by BDS

BDS - Broadband Dielectric SpectroscopyMaterials with a permanent dipolar momentBDS - Broadband Dielectric SpectroscopyMaterials with a permanent dipolar moment

Cellsf (Hz)f (Hz)HH

HH33NN++ —— C C —— COOCOO--

RR

1010--22

Proteins

Water

1010221010111010--11 101044 101055 101066 101077 101088 101099101033101000 10101010 10101111

Macromolecules

Molecular liquidsPolymer blends

Composites

T = 100-500 K (-173 to 230 oC)

Amino Acids

The dynamics of “water” as seen by BDSThe dynamics of “water” as seen by BDS

BDS - Broadband Dielectric SpectroscopyMaterials with a permanent dipolar momentBDS - Broadband Dielectric SpectroscopyMaterials with a permanent dipolar moment

f (Hz)f (Hz)

1010--22

Water

1010221010111010--11 101044 101055 101066 101077 101088 101099101033101000 10101010 10101111

0.1 1 10 100 10000

20

40

60

80

´,

´´

f [GHz]

T = 293K

Swenson & Bergman, Nature (2001)-2 0 2 4 6

1.5

2.0

2.5

3.0

3.5

4.0

4.5

´´

f [Hz]

T = 165K

0.1 1 10 100 10000

20

40

60

80

´

, ´´

f [GHz]

T = 293K

2 3 4 5 6 7 8-12

-10

-8

-6

-4

-2

0

2

log

()

1000/T [K-1]

Bulk Liquid

Liquid underconfinement

Bulk water - Phase diagram in the No man´s land – EXPERIMENTSBulk water - Phase diagram in the No man´s land – EXPERIMENTS

Outline

‐ Where is water? Several fields of research.






- Summary

Calorimetric response of water solutionsCalorimetric response of water solutions

General Result for several materials:

Polymers and small glass formers: 45-50 wt%Sugars: 30-35 wt%

General Result for several materials:

Polymers and small glass formers: 45-50 wt%Sugars: 30-35 wt%

Poly(vinyl methyl ether)

Mixtures from the dry polymer to 50 wt% of water

Mixtures from the dry polymer to 50 wt% of water

Macromolecules (2005)

Cw [wt%] Tg [K]

Dry PVME 0 250.0

PVME-2 2 246.3

PVME-4 4 244.6

PVME-10 15 224.07

PVME-15 10 220.4

PVME-20 20 216.71

PVME-30 30 208.39

PVME-35 35 214.2

PVME-40 40 207.57

PVME-45 45 202.09

PVME-50 50 196.22

150 200 250-10

-5

0

5

10

15

243K

2 wt%

30 wt%

40 wt%

202K

200K

T [K]

Hea

t Flo

w [a

.u.]

Tonset = 190K

50 wt%

PVME water solutions

246K

J. Chem. Phys. (submitted)


0 10 20 30 40 50150200250300350400450500

PVME

T g [K]

cw [wt%]

0 10 20 30 40 50150

200

250

300

350

400

450

500 PVP

T g [K]

cw [wt%] 0 10 20 30 40 50150

200

250

300

350

400

450

500 PVP -PLL 3-lysine

T g [K]

cw [wt%]

230 K

50 K

0 10 20 30 40 50150

200

250

300

350

400

450

500 PVME 2PG 3PG PPG 5EG

T g [K]

c [wt%]

Plasticization or other mechanism?

The dynamics of dry PVMEThe dynamics of dry PVME


10-1 100 101 102 103 104 105 1060.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

280285

275270265260

´´

f [Hz]

PVME Dry 255 K

Now we hydrated the sample with 2 wt% of water…

Tg, dry = 250 K

10-1 100 101 102 103 104 105 1060.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

PVME Dry

165 170175

160

´´

f [Hz]

155 K

Relaxation Map DRY PVME

3 4 5 6 7-8

-6

-4

-2

0

2

log

( [s

])

1000/T [K-1]

(case Tg,dry – Tg, cw,max < 50 oC)

The dynamics of water in PVME – low water contentThe dynamics of water in PVME – low water content


10-1 100 101 102 103 104 105 1060.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

280285

275270265260

´´

f [Hz]

PVME Dry 255 K

10-1 100 101 102 103 104 105 1060.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

NEW relaxation

´´

f [Hz]

PVME-2cw = 2 wt%

-relaxation

10-1 100 101 102 103 104 105 1060.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

280

285

275270265260

´´

f [Hz]

PVME-2cw = 2 wt%255 K

Tg, dry = 250 K

Tg, 2wt% = 246 K

10-1 100 101 102 103 104 105 1060.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

PVME Dry

165 170175

160

´´

f [Hz]

155 K


The dynamics of “water” in PVME – low water contentThe dynamics of “water” in PVME – low water content

At low water content (lower than cw = 5-10 wt%):

- There is a “new” relaxation (water molecules), w (T) is Arrhenius- (T) remains the same increasing water content- (T) faster increasing water content because plasticization

0.22 eV

0.45 eV

3 4 5 6 7-8

-6

-4

-2

0

2 Dry PVME PVME, cw = 2 wt%

log

( [s

])

1000/T [K-1]

3 4 5 6 7-8

-6

-4

-2

0

2 Dry PVME PVME, cw = 2 wt% PVME, cw = 4 wt%

log

( [s

])

1000/T [K-1]


The dynamics of “water” in PVME – high water contentThe dynamics of “water” in PVME – high water content

10-1 100 101 102 103 104 105 10610-2

10-1

100

101

2

20

10

3035

4045

´

´

f [Hz]

T = 170K50

dry PVME



Relaxation strength and shape factor Relaxation strength and shape factor

0 10 20 30 40 50

0.4

0.5

0.6

01020304050

cw [wt %] General Result:

Water mobility increases around 30 wt% for both polymers and small glasses and 20 wt % for sugars

General Result:

Water mobility increases around 30 wt% for both polymers and small glasses and 20 wt % for sugars

Cole-Cole function

Macromolecules (2005); J NON Crys Solid (2007); PRE (2008); J. Chem. Phys. (2008); PCCP (2010) ; JPCB (2011)

10-1 100 101 102 103 104 105 106

10-1

100

101

220210200190180170160

´´

f [Hz]

PVME - Watercw = 40 wt%

150 K

160 200 240 280

0

5

10

15

20

25

30

35

40

45

50

2

1020

3035

40

45

T [K]

50 wt%

160 200 240 280

0.4

0.5

0.6

0.7

2

T [K]

10

2030

3540

45

50 wt%


35

30

25

20

15

3 4 5 6 7-12-10

-8-6-4-202

Cp

log

()

1000/ T [K-1]

The dynamics of “water” in PVME – low water contentThe dynamics of “water” in PVME – low water content

10-1 100 101 102 103 104 105 106

10-1

100

101

220210200190180170160

´´

f [Hz]

PVME - Watercw = 40 wt%

150 K

35

30

25

20

15

3 4 5 6 7-12-10

-8-6-4-202

Cp

log

()

1000/ T [K-1]

Tg = 190KPVME

cw = 50wt%

The change from a fragile liquid to strong liquidis produced at Tg



The dynamics of water in several systems – high water contentThe dynamics of water in several systems – high water content

J. Chem. Phys. (2008)

02468

155K3PG - cw = 50wt%

0

2

4

6

175K

0

2

4

6

´´

188K

Process I

Process II

0369

194K

10-2 10-1 100 101 102 103 104 105 1060

3

6

9

f [Hz]

212K

3-propylene glycol

-2

0

2

4.5 5.0 5.5 6.0 6.5 7.0 7.5-6

-4

-2

0

2

Hea

t flo

w [a

.u.]

Tg = 185 K

log

()

1000/T [K-1]

3PGcw = 40 wt%




Interpretation of the crossover: Chemical Review (2016)

3 4 5 6 7-12

-9

-6

-3

0

3 5EG PVME glucose 3PG DNA Myoglobin 1PG 2PG 6EG PEG600 Molecular Sieves 3EG 4EG sorbitol

log

(m

ax)

1000/T [K-1]

At high water content

Ea ≈ (0.54 0.04) eV


Ea ≈ (0.54 0.04) eV

The dynamics of water in synthetic polymers – high water contentThe dynamics of water in synthetic polymers – high water content

At the highest water concentration (before crystallization)

PRL (2008), PRE (2008)

T < Tg

Local relaxation of water moleculesin soft confinements

Local relaxation of water moleculesin soft confinements


Comparison solutions at high water content/hard confinementsComparison solutions at high water content/hard confinements (case Tg,dry – Tg, cw,max < 50 oC)

J. Phys.: Cond. Matter (2015)

SOFT confinements: high water concentration (water less influenced by other molecules) HARD confinements: well-defined geometry / uniform filling

3 4 5 6 7 8-12

-10

-8

-6

-4

-2

0

2 PGME (cw = 55 wt%) Mineral Clays Molecular Sieves MCM (C10) Mb (cw = 33 wt%)

log

()

1000/T [K-1]

water in hard confinements

water in solutions


Ea ≈ (0.54 0.04) eV


Ea ≈ (0.54 0.04) eV

Different scenarios Different scenarios (case Tg,dry – Tg, cw,max < 50 oC)

Chem. Rev., 2016, 116 (13), pp 7608–7625

Summarizing dynamics of water Summarizing dynamics of water

0 10 20 30 40 50150

200

250

300

350

400

450

500 PVME

T g [K]

cw [wt%]

50 K

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

c [wt%]

A single relaxation of water molecules

0 10 20 30 40 50

0

10

20

30

40

50

cw [wt %]

35

30

25

20

15

3 4 5 6 7-12-10

-8-6-4-202

Cp

log

()

1000/ T [K-1]

3 4 5 6 7 8-12

-10

-8

-6

-4

-2

0

2 PVP (cw = 61 wt%) PGME (cw = 55 wt%) Mineral Clays Molecular Sieves MCM (C10) Mb (cw = 33 wt%)

log

()

1000/T [K-1]


Interpretations: Chem. Rev., 2016, 116 (13), pp 7608–7625


Ea ≈ (0.54 0.04) eV


Ea ≈ (0.54 0.04) eV


0 10 20 30 40 50150

200

250

300

350

400

450

500 PVME

T g [K]

cw [wt%]

0 10 20 30 40 50150

200

250

300

350

400

450

500 PVP

T g [K]

cw [wt%]

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

cw [wt%]

230 K

50 K

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

c [wt%]



J. Chem. Phys. (submitted)

The dynamics of water – high water contentThe dynamics of water – high water content (case Tg,dry – Tg, cw,max >> 50 oC)

Simultaneous fitting of real and imaginary permittivity

J. Physical Chemistry Letters 7, 4093‐4098 (2016)

100 102 104 1060

10

20

30

10-1 100 101 102 103 104 105 1060.1

1

10

Fast water relaxation

Slow water relaxation

'

Hz

T = 190 K (a)



T = 190 K (b)

''

Hz

10-2 100 102 104 10601020304050

10-2 100 102 104 106

10-1

101

103

Fast water relaxationSlow water

relaxation

(c) T = 207.5 K

'

Hz


(d) T = 207.5 K

''

Hz


100 102 104 106100

101

102

103

100 102 104 10610-1

101

103

105

-relaxation

T = 300 K(e)

'

Hz

(f) T = 300 K

''

Hz

-relaxation

Wübbenhorst and van Turnhout; Journal of Non‐Crystalline Solids 2002, 305, 40‐49

Poly (vinyl pyrrolidone)cw = 40 wt%


100 102 104 106

101

100 102 104 10610-1

100

101

10-2 100 102 104 106

101

102

100 102 104 10610-1

101

103

101 104 107

100

102

104

101 104 107100

101

102

103

T = 180 K

'

2

´´

2T = 180 K

2

3'

T = 212 K

´´

T = 212 K

23

f [Hz]´

T = 242 K

43

f [Hz]

43

'

T = 242 K

-Poly(lysine) cw = 40 wt%

Simultaneous fitting of real and imaginary permittivity



30 35 40 450

30

60

90

120

150

180

205 K 252.5 K 275 K

P3

cw wt%

P4

(a)

30 35 40 4505

101520253035

140K 170K 200K

cw wt%

(b)P2

3 4 5 6 7-12

-9

-6

-3

0

3

3

4

2

3

log

()

1000/T [K-1]

-PLL (cw = 40 wt%)

HF

[a.u

.]

Two relaxations due to water molecules

Two relaxations due to water molecules


Processes 3 and 4 are coupled!Processes 3 and 4 are coupled!

Summarizing the response of water in solutionsSummarizing the response of water in solutions

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

cw [wt%]

230 K

50 K

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

c [wt%]




Two relaxations of water molecules: the slower one

coupled to the α-relaxation

Two relaxations of water molecules: the slower one

coupled to the α-relaxation

4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

-6

-4

-2

0

2

1000/T [K-1]

log

()

3PG cw = 50 wt%

Plasticization

3 4 5 6 7-12

-9

-6

-3

0

3

-PLL (cw = 40 wt%)3

4

2

3

log

()

1000/T [K-1]

Outline







- Summary

ProteinsProteins

- Proteins are polymers made out of amino acids

Common backbone

Different side chains Different chemical properties

Amino acids – peptide bondAmino acids – peptide bond

- Proteins are polymers made out of amino acids

Primary structure

Peptides: 2 ‐ 50 amino acids

Proteins : >50 amino acids

ProteinsProteins

Tertiary structureTertiary structure

The function of a protein depends on its tertiary

structure

The function of a protein depends on its tertiary

structure Polymer

Monomer: Amino Acids

Primary structure

-pleated sheet

Secondary structure(Conformations)

-Helix

Dynamics of water in solution of biopolymersDynamics of water in solution of biopolymers

Medium irrelevant! Water solvent play crucial rolesin structure, dynamics and function

Water as a bio-molecule:No passive solvent in biology

Water as a bio-molecule:No passive solvent in biology

Calorimetric response of protein solutionsCalorimetric response of protein solutions

Tg of proteins is no longer observed below ~0.05 wt% of water

0 10 20 30 40 50150

200

250

300

350

400

450

500

0

BSA Gluten Glutenin Gliadin Gelatin Elastin Lysozyme Collagen

T g [K]

cw [wt%]

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

cw [wt%]

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

c [wt%]

Comparison with soft matter

Collection of different cases

1)Protein in a proper solution (water crystallization)2)Protein in less diluted solution (water crystallization)3)Peptides in solution (no crystallization)

Collection of different cases

1)Protein in a proper solution (water crystallization)2)Protein in less diluted solution (water crystallization)3)Peptides in solution (no crystallization)

Dielectric response of protein in well-diluted solutionsDielectric response of protein in well-diluted solutions

Shinyashiki, N. et al. J. of Phys. Chem. B 113, 14448 (2009)

3 4 5 6 7 8 9 10

-10

-8

-6

-4

-2

0

2

4

6

20BSA-80W

log

1000/T 1/K

IIbIIaIII

IbIa

II: crystallized bulk water -relaxation responsible

for the glass transition

I: uncrystallized water in the

hydration water

- Low solubility degree of proteins- Protein solutions large quantity of water crystallization

Bovine serum albumin (BSA)80 wt% of water – 20 wt% of protein

Dielectric response of protein in more concentrated solutionsDielectric response of protein in more concentrated solutions

3 4 5 6 7 8

-8

-6

-4

-2

0

2

4

40wt%

40wt%28wt%

18wt%

13wt%

process: cooperative motion of protein and water

w process: relaxation of water near the protein surface

ice2-40wt%ice1-40wt%

log

1000/T 1/K

v process: main relaxation of hydration water

cw=7wt%cw=18wt%

28wt%

40wt%cw=28wt%

At low temperatures, two relaxation of water molecules

(similar to “soft matter” with a broad Tg variation with water content)

Dielectric response of protein in more concentrated solutionsDielectric response of protein in more concentrated solutions

Dielectric response of small peptides in solutionDielectric response of small peptides in solution

J Phys. Chem Lett. 7, 4093‐4098 (2016)

3 4 5 6 7-12

-10

-8

-6

-4

-2

0

2

H

(b)

process 1 process 2 process 3 process 4 process 5 cw = 5 wt%

log

()

1000/ T [K-1]3Lys 32Lys

3 4 5 6 7

-8

-6

-4

-2

0

2

3 4 5 6 7-10

-8

-6

-4

-2

0

2

3 4 5 6 7-12

-10

-8

-6

-4

-2

0

2

1000/T [K-1]

3

1

4

2

3

log

()

3-Lys (cw = 40 wt%)

1000/T [K-1]

-helix3

4

2

3

log

()

10-Lys (cw = 40 wt%)

-sheet

3

4

23

log

()

1000/T [K-1]

-PLL (cw = 40 wt%)

Outline







- Summary

Dynamics of ordinary solutions and protein solutions - SUMMARYDynamics of ordinary solutions and protein solutions - SUMMARY

No related dynamics Coupled dynamics Coupled dynamics

SOLUTE SOLVENT ICE

1000/T

Log

()

A single water relaxation

1000/T

Log

()

Two relaxations due to water

1000/T

Log

()

At least two water dynamics

27

cw

TgSolutions of soft matter 1

cw

Tg

Solutions of soft matter 2

cw

Tg

Protein solutions

- Jan Swenson, Chalmers University of Technology

- Gustavo Schwartz, CSIC- Angel Alegria, UPV- Juan Colmenero, UPV- Fabienne Barroso-Bujans, DIPC

- Izaskun Combarro-Palacios, phD student, CFM (Now at Cidetec)- Manuel Monasterio, phD student, CFM (Now at Shenzhen Advanced Civil Engineering Technology, China)- Luciana Saiz, CFM (Now: Researcher in Conicet, Argentina)- Lokendra Singh, Profesor (Now: India)- Jorge Melillo, phD student, CFM

AcknowledgementsAcknowledgements

Travel and local expensessupported by EU

Broadband Dielectric Spectroscopy San Sebastian, SpainBroadband Dielectric Spectroscopy San Sebastian, Spain

THANK THANK YOU YOU FORFOR YOUR YOUR ATTENTIONATTENTION

Amino acid in well-diluted aqueous solutionsAmino acid in well-diluted aqueous solutions

109 10100

10

20

30

40

Water 0.04M 0.11M 0.20 M 0.28 M 0.37 M 0.48 M 0.54 M

Process 2

L-arginine

''

f [Hz]

Process 1

109 10100

20

40

60

80

100

120

Process 2

Process 1

L-arginine

f [Hz]

Water 0.04M 0.11M 0.20 M 0.28 M 0.37 M 0.48 M 0.54 M

'

400 water molecules per AA Well-diluted solutionsWell-diluted solutions

109 10100

20

40

60

80

100

120

10

20

30

40

50

'

''

' ''

L-proline / Water c = 1.07 mol L-1

f [Hz]

'''

Waterrelaxation

Amino acid relaxation

Dynamics of water in solution of biopolymersDynamics of water in solution of biopolymers

Well-diluted solutionsWell-diluted solutions

Bulk-like waterGlobal motion of protein

Origin questioned …

Sokolov et al: This relaxation is mainly due to protein atoms and hydration water relaxes at much shorter time scales

S. Khodadadi et al, J. Phys. Chem. B, 2011, S. Khodadadi,et al, J. Chem. Phys., 2008

Where is found water? – Geological water – Confined waterWhere is found water? – Geological water – Confined water

Size of confinements:- micro, d < 20 Å- meso, 20 Å < d < 500 Å; - macro, d > 500 Å

Vermiculite Clays

Swenson‐Bergman, Nature, 2001

Cerveny et al, JCP (2011)

MCM 41

21 Å or 36 ÅSjöström et al, JCP 128, 154503 (2008)

12 Å

OXIDATION

Graphite Oxide

Increasing hydration

8Ǻ6Ǻ

The dynamics of water in synthetic polymers – high water contentThe dynamics of water in synthetic polymers – high water content

10-1 100 101 102 103 104 105 10610-2

10-1

100

101

2

20

10

3035

4045

´´

f [Hz]

T = 170K50

dry PVME

Deuterated water is slower than protonated water

100 101 102 103 104 105 106 1070.1

1

10

deuterated sample protonated sample

´´

f [Hz]

Water molecules are responsible for this “new” dielectric process

Crossover strong-to-fragile? Crossover strong-to-fragile?

-2

0

2

4.5 5.0 5.5 6.0 6.5 7.0 7.5-6

-4

-2

0

2

Hea

t flo

w [a

.u.]

Tg = 185 K

log

()

1000/T [K-1]

3PGcw = 40 wt%

Chen et al PNAS (2006)Mallamace et al JCP (2007)Chu et al PRE (2008)…..

“Confined Waters exhibit a LL transition at 225 K”

“Fragile to strong transition”

“the low temperature Arrhenius process is most likely of local character”

Chen et al, PRE 2014

“the low temperature Arrhenius process is most likely of local character”

Chen et al, PRE 2014

The crossover does not represents the fragile-to-strong transition of BULK water

The crossover does not represents the fragile-to-strong transition of BULK water

Chemical Review (2016)

Resume results of dynamics of water in synthetic materialsResume results of dynamics of water in synthetic materials

Low water content (water influenced by the solute)

Low water content (water influenced by the solute)

High water content (clusters of water less influenced by the solute)

High water content (clusters of water less influenced by the solute)

Solutions of water and polymers, sugars, glass forming materials…

2

1000/T

Log

()

Tg,DSC

2

1000/T

Log

()

Tg,DSC

cw

cw

Water mobility increases around (c*):

30 wt% for both polymers and small glasses

20 wt % for sugars

Water mobility increases around (c*):

30 wt% for both polymers and small glasses

20 wt % for sugars

Ea = (0.54 ± 0.04) eV

c* c*

SummarizingSummarizing

0 10 20 30 40 50150

200

250

300

350

400

450

500 PVME

T g [K]

cw [wt%]

50 K

0 10 20 30 40 50150

200

250

300

350

400

450


T g [K]

c [wt%]

Low water content

(water influenced by the solute)

Low water content

(water influenced by the solute)

High water content (clusters of water less

influenced by the solute)

High water content (clusters of water less

influenced by the solute)

2

1000/T

Log

()

Tg,DSC

Water mobility increases at c*Water mobility increases at c*

2

1000/T

Log

()

Tg,DSC

Ea = 0.54 eV

cw

c*

case Tg,dry – Tg, cw,max < 50 oC

Water in hard confinementsWater in hard confinements

L

L

pores: 2-D confinementlayers: 1-D confinement

Well-defined confinement systems (HARD CONFINEMENT)

MCM-41: Swenson et al, Chen et al, Mallamace et al, Vogel et al…

Cement-like materials: Shinyashiki, Fratini et al, Cerveny et al…

Graphite Oxide: Cerveny et al

Minerals and Clays: Swenson et al, Feldman et al, Bruni et al,, Maheshwari et al…

Hydrogels: Bruni et al, Pissis et al, Shinyashiki at al…

Molecular Sieves: Swenson et al, Bruni et al, Oguni et al…

Disordered systems: 3-D confinement

water in hard confinementswater in hard confinements

OXIDATION

Graphite Graphite Oxide

Graphite OxideGraphite Oxide

Increasing hydration

8Ǻ6Ǻ

J. Phys. Chem C (2010)

MCM 41MCM 41

The pores are ordered in a hexagonal structure

The pore diameter is d = 2.1 nm

Sjostrom, Swenson, et al, J. Chem Phys (2008)

100 150 200 250 300 350

-0.2

0.0

0.2

heating

25 wt% dry GO

Rev

. Hea

t Flo

w [a

.u.]

T [K]

cooling

In hard confinements: -No crystallization - No observation of a glass transition by DSC

In hard confinements: -No crystallization - No observation of a glass transition by DSC


4 6 8-12-10-8-6-4-202

1000/T [K-1]

log()

5% 10% 15% 17% 20% 25%

No dependence on water contentNo dependence on water content

10-2 100 102 104 106 108

0.1

1

160

170

180

200

225K

150140

´´

f [Hz]

130

Water in Graphite Oxide

3 4 5 6 7 8-12

-10

-8

-6

-4

-2

0 GO - NS GO - cw = 25 wt% - BDS

log

()

1000/T [K-1]

Water in Graphite Oxide

4 6 8

-10

-8

-6

-4

-2

0

2

Dry 14 wt% 28 wt% 111 wt%

1000/T [K-1]

log

()

MCM41

2 4 6 8-12

-10

-8

-6

-4

-2

0

2

GO-25wt% Molecular Sieves Silica hydrogel Mineral Clays MCM (C10) C-S-H

1000/T [K-1]

log

()



Above the crossover – Both the time scale and Ea are differentfor all types of confinements

Below crossover – Ea is similar for all confinements

Ea ≈ (0.54 0.04) eV

-rela

xation

of wate

r mole

cules

in hard

confi

nement

s

-rela

xation

of wate

r mole

cules

in hard

confi

nement

s

Differences and Similarities of water in soft and hard confinementsDifferences and Similarities of water in soft and hard confinements


SOFT confinements: high water concentration (water less influenced by other molecules) HARD confinements: well-defined geometry / uniform filling

3 4 5 6 7 8-12

-10

-8

-6

-4

-2

0

2 PVP (cw = 61 wt%) PGME (cw = 55 wt%) Mineral Clays Molecular Sieves MCM (C10) Mb (cw = 33 wt%)

log

()

1000/T [K-1]

water in hard confinements

water in solutions

2 4 6 8-12-10-8-6-4-202

GO-25wt% - BDS GO - NS

log()

1000/T [K-1]

Summarizing - Water in soft and hard confinementsSummarizing - Water in soft and hard confinements

No calorimetric “Tg”

-8

-6

-4

4.5 5.0 5.5 6.0 6.5 7.0

-6

-4

-2

0

2

cw = 40 wt%5EG

log

()

1000/T [K-1]

Tg, DSC = 176K

HF

[a.u

.]

Soft confinements Hard Confinements

The change in the dynamics is produced in the temperature range (150-200) K depending on the

confinement system

The change in the water dynamics is produced at Tg.

4 5 6 7-8

-6

-4

-2

0

2

50% 40% 30% 20%

log

()

1000/T [K-1]

cw

Soft Confinements

SOFT CONFINEMENTS

Calorimetric glass transition(solvent + solute)

+

Stronger concentration dependence

SOFT CONFINEMENTS

Calorimetric glass transition(solvent + solute)

+

Stronger concentration dependence

3PG-water

HARD confinements

HARD CONFINEMENTS

No calorimetric glass transition (exception Oguni et al (2011) Tg = 210 K)

+

Almost no concentration dependence

HARD CONFINEMENTS

No calorimetric glass transition (exception Oguni et al (2011) Tg = 210 K)

+

Almost no concentration dependence

4 6 8

-10

-8

-6

-4

-2

0

2

Dry 14 wt% 28 wt% 111 wt%

1000/T [K-1]

log

()

MCM41

Summarizing - Water in soft and hard confinementsSummarizing - Water in soft and hard confinements


Origin of the crossover (hard and soft confinements)Origin of the crossover (hard and soft confinements)

“Cooperative re-arrangement regions” (CRR)

4 5 6 7 8 9 10 11

-8

-6

-4

-2

0

2

log

()

1000/T [K-1]

4 5 6 7 8 9-8

-6

-4

-2

0

log

()

1000/T [K-1]

Introduction - Protein dynamicsIntroduction - Protein dynamics

If nothing can move, nothing can functionIf nothing can move, nothing can function

Perutz (1970): described the movements hemoglobin must undergo to fulfill its function

Frauenfelder (1985): revealed a hierarchical organization of proteins motions

Perutz Nature 228, (1970)P. W. Fenimore, H. Frauenfelder et al., PNAS 110, 14408 (2004)

A protein does not exist in a unique conformation

A protein can assume a very large number of somewhat different conformations

Ec

ccEc

cc0Ec

cc1Ec

cc2

State

Tier0

Tier1

Tier2

A0 A1 A3

log

()

1/T

log

()

1/T

“solvent-slaved” motions“slaving” behaviour “solvent-slaved” motions“slaving” behaviour

Fluctuations of the protein (which follows aVFT behaviour) come from the solvent

Myoglobin: escape of CO from the interior of the protein

P. W. Fenimore et al., PNAS 110, 14408 (2004)

3 4 5 6 7 8-12

-10

-8

-6

-4

-2

0

exit

HF

[a.u

.]

1000/T [K-1]

log

()

2.5 3.0 3.5 4.0 4.5 5.0 5.5

-8

-6

-4

-2

0

2

3 Lysine-dry

log

()

1000/T [K-1]2.5 3.0 3.5 4.0 4.5 5.0 5.5

-8

-6

-4

-2

0

2

3 Lysine-dry cw < 1wt%

log

()

1000/T [K-1]

3-Lysine cw = 0 wt% cw = 40 wt%

2.5 3.0 3.5 4.0 4.5 5.0 5.5

-8

-6

-4

-2

0

2 cw = 10 wt%


log

()

1000/T [K-1]2.5 3.0 3.5 4.0 4.5 5.0 5.5

-8

-6

-4

-2

0

2 cw = 10 wt% cw = 40 wt%


log

()

1000/T [K-1]

The dynamics of water – From low to high water contentThe dynamics of water – From low to high water content (case Tg,dry – Tg, cw,max >> 50 oC)

Relaxations are coupled at water content higher than 15 wt%

At low water content, a single relaxation

These findings further corroborate the existence of a strong coupling between protein fluctuations and solvent dynamics.

Our results indicate a slowdown of solvent dynamics in the immediate vicinity of the protein. Hence, there is a mutual influence of protein

and solvent dynamics, rather than a full slaving.

“protein-solvent couplings can be different for side chain and backbone units”

The hydration dynamics change depending on the different DNA exposed sites. The waters confined in the narrow minor

groove are much more significantly retarded than in bulk and therefore it seems that the biomolecule slaves the water

which is the opposite of the slaving picture.

Introduction –Slaving or not?Introduction –Slaving or not?

“The hydration water dynamics is always faster than protein side-chain relaxations but with the same energy barriers, indicating that the

hydration shell fluctuations driving protein side-chain motions on the picosecond time scales and thus elucidating their ultimate relationship”

Bulk water - Phase diagram in the No man´s landBulk water - Phase diagram in the No man´s land

Stanley, 1992Stanley, 1992

Below -75 oC… they found a low density liquid and a high density liquid: LDL and HDL.

Liquid-liquid critical point hypothesis

Bulk water - Phase diagram in the No man´s land - SIMULATIONSBulk water - Phase diagram in the No man´s land - SIMULATIONS

Stanley, 1992Stanley, 1992

Limmer-Chandler, 2011-2013Limmer-Chandler, 2011-2013

“It is not enough to wait for the density of the system to settle down to a steady state”

The problem is the equilibration time!!!!

Debenedetti,2013Debenedetti,2013

He remains convinced that the liquid–liquid transition is real

"Our calculations are completely inconsistent with David Chandler's – we clearly see two, not one, liquid phases."

Below -75 oC… they found a low density liquid and a high density liquid: LDL and HDL.

Liquid-liquid critical point hypothesis


3 4 5 6 7-12

-9

-6

-3

0

3

3

4

2

3

log

()

1000/T [K-1]

-PLL (cw = 40 wt%)

HF

[a.u

.]

3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5-8-7-6-5-4-3-2-1012

cw=45wt%cw=40wt%cw=35wt%cw=30wt%

log

(

1000/T 1/K

PLLProcess2

3.0 3.5 4.0 4.5 5.0 5.5 6.0

-10

-8

-6

-4

-2

0

2

45 wt% 40 wt% 35 wt% 30 wt%

log

(3)

1000/T [K-1]

-PLLProcess 3

3.0 3.5 4.0 4.5 5.0-8

-6

-4

-2

0

2

-PLLProcess 4

45 wt% 40 wt% 35 wt% 30 wt%

log

(4)

1000 /T [K-1]

cwProcesses 3 and 4 are coupled!Processes 3 and 4 are coupled!


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Dynamics of water - Case study: molecular relaxations in ... TUT... · ‐ General Phenomenology (glasses, Tg, relaxations) Properties of bulk water / Phase diagram (simulations vs