Magnetic Resonance In Studying Natural And Synthetic Materials

244 Pages·2018·10.63 MB·English

by  Victor V. Rodin

Magnetic Resonance in Studying
Natural and Synthetic Materials
Authored by
Victor V. Rodin
Institute of Organic Chemistry, Johannes Kepler University Linz, 4040 Linz,
Austria
Magnetic Resonance in Studying Natural and Synthetic Materials
Author: Victor V. Rodin
ISBN (Online): 978-1-68108-629-3
ISBN (Print): 978-1-68108-630-9
© 2018, Bentham eBooks imprint.
Published by Bentham Science Publishers – Sharjah, UAE. All Rights Reserved.
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CONTENTS
FOREWORD 1 .......................................................................................................................................... i
FOREWORD 2 .......................................................................................................................................... ii
FOREWORD 3 .......................................................................................................................................... iii
FOREWORD 4 .......................................................................................................................................... iv
PREFACE ................................................................................................................................................ v
CONFLICT OF INTEREST ......................................................................................................... vii
ACKNOWLEDGEMENT ............................................................................................................. vii
DEDICATION ......................................................................................................................................... viii
CHAPTER 1 BASIC PRINCIPLES OF NMR AND EXPERIMENTAL TECHNIQUES ............ 1
INTRODUCTION TO NMR ......................................................................................................... 1
SPIN-LATTICE AND SPIN-SPIN NMR RELAXATION ......................................................... 5
Spin-Lattice (Longitudinal) Relaxation .................................................................................. 6
Spin-Spin (Transverse) Relaxation ......................................................................................... 8
EXPERIMENTAL MATERIALS AND METHODS ................................................................. 10
NMR Techniques for Studying T,,, T, a nd Cross-Relaxation ................................................ 12
1 2
Pulsed Field Gradient (PFG) NMR in One- and Two-Dimensional Studies .......................... 15
Cross-Relaxation in PFG NMR Studies ................................................................................. 16
Double-Quantum-Filtered (DQF) NMR Spectroscopy .......................................................... 18
CONCLUDING REMARKS ......................................................................................................... 21
REFERENCES ............................................................................................................................... 21
CHAPTER 2 DYNAMIC PROPERTIES OF BOUND WATER IN NATURAL POLYMERS AS
STUDIED BY NMR RELAXATION .................................................................................................... 26
NATURAL SILK BOMBYX MORI WITH LOW WATER CONTENT ................................. 26
NMR RELAXATION IN NONORIENTED AND ORIENTED COLLAGEN FIBERS ......... 35
NMR Relaxation in ECSD (Randomly Oriented) Collagen Samples .................................... 35
NMR Relaxation in Oriented Collagen Fibers ........................................................................ 41
CONCLUDING REMARKS ......................................................................................................... 47
REFERENCES ............................................................................................................................... 48
CHAPTER 3 NMR DIFFUSION STUDIES OF WATER IN NATURAL BIOPOLYMERS ....... 54
1H NMR STUDY OF THE SELF-DIFFUSION OF WATER IN CROSS-LINKED
COLLAGENS ................................................................................................................................. 54
SELF-DIFFUSION OF WATER IN BOMBYX MORI SILK AS STUDIED BY NMR ........... 59
CONCLUDING REMARKS ......................................................................................................... 64
REFERENCES ............................................................................................................................... 64
CHAPTER 4 COLLAGEN TISSUES WITH DIFFERENT DEGREE OF CROSS-LINKS AND
NATURAL SILK AS STUDIED BY 1H DQF NMR ........................................................................... 68
1H DQF NMR SPECTROSCOPY IN STUDYING COLLAGENS WITH DIFFERENT
DEGREE OF CROSS-LINKS ....................................................................................................... 68
1H DQF NMR STUDY OF BOMBYX MORI SILK ..................................................................... 77
CONCLUDING REMARKS ......................................................................................................... 80
REFERENCES ............................................................................................................................... 80
CHAPTER 5 NMR RELAXATION AND RESTRICTED SELF-DIFFUSION OF WATER IN
WOOD ...................................................................................................................................................... 82
INTRODUCTION: WATER IN WOOD ..................................................................................... 82
STUDYING NMR RELAXATION IN WOOD: FROM WET TO DRIED WOOD ............... 83
RESTRICTED DIFFUSION OF WATER IN WOOD: ONE-DIMENSIONAL PFG NMR
STUDIES ......................................................................................................................................... 87
CONCLUDING REMARKS ......................................................................................................... 93
ACKNOWLEDGEMENTS ........................................................................................................... 94
REFERENCES ............................................................................................................................... 94
CHAPTER 6 2D DIFFUSION-DIFFUSION CORRELATION NMR SPECTROSCOPY IN
STUDY OF DIFFUSION ANISOTROPY IN WOOD ......................................................................... 97
INTRODUCTION .......................................................................................................................... 97
THEORY AND MODELS IN DIFFUSION-DIFFUSION CORRELATION
SPECTROSCOPY (DDCOSY) ..................................................................................................... 98
DDCOSY WITH PARALLEL ORIENTED PAIRS OF GRADIENTS. SIMULATIONS
AND EXPERIMENTS ON WOOD .............................................................................................. 101
2D DDCOSY WITH PERPENDICULAR PAIRS OF GRADIENTS. INVERSE LAPLACE
TRANSFORM IN STUDYING DIFFUSION ANISOTROPY IN WOOD ............................... 102
CONCLUSION ............................................................................................................................... 106
ACKNOWLEDGEMENTS ........................................................................................................... 107
REFERENCES ............................................................................................................................... 107
CHAPTER 7 PFG NMR IN STUDYING SOLUTIONS OF CARBOXYLATED ACRYLIC
POLYMERS ............................................................................................................................................ 110
INTRODUCTION: CARBOXYLATED ACRYLIC POLYMERS ........................................... 111
SELF-DIFFUSION OF SOLVENT AND POLYMER IN SOLUTIONS OF RANDOM
COPOLYMERS IN ISOPROPANOL .......................................................................................... 112
EFFECT OF POLYMER CONCENTRATION AND BMA/MAA MOLAR RATIO ON
HYDROGEN BONDING IN NEUTRALISED COPOLYMERS ............................................. 115
SOLVENT AND POLYMER DIFFUSION STUDIES IN NEUTRALISED COPOLYMERS 119
Solvent Diffusion: Effect of mol% BMA in BMA-MAA Random Copolymers and Polymer
Concentration at Neutralisation Level TEA:COOH = 1:1 ...................................................... 119
Polymer Diffusion: Effect of BMA/MAA Molar Ratio at Neutralisation Level
TEA:COOH=1:1 ..................................................................................................................... 122
Polymer and Solvent Diffusion: Different Neutralisation Level (TEA:COOH = 1:1; 0.75:1
and 0.5:1) ................................................................................................................................ 123
CONCLUDING REMARKS ......................................................................................................... 125
ACKNOWLEDGEMENTS ........................................................................................................... 126
REFERENCES ............................................................................................................................... 126
CHAPTER 8 COPOLYMER FILMS SWOLLEN IN WATER: NMR R ELAXATION AND PFG
NMR TECHNIQUES IN STUDYING POLYMER-WATER INTERACTIONS ............................. 130
POLYMER FILMS AND WATER .............................................................................................. 130
DRIED AND WET POLYMER FILMS: 1H NMR SPECTRA AND T2 STUDIES OF
WATER-POLYMER INTERACTIONS ...................................................................................... 132
Films in Experimental Conditions .......................................................................................... 132
Dried and Wet Polymer Films: NMR Spectra, FIDs and NMR relaxation Times ................. 132
WATER SELF-DIFFUSION IN THE COPOLYMER FILMS ................................................. 143
CONCLUDING REMARKS ......................................................................................................... 145
ACKNOWLEDGEMENTS ........................................................................................................... 146
REFERENCES ............................................................................................................................... 146
CHAPTER 9 MAGNETIC RESONANCE IMAGING IN CHARACTERISATION OF
POLYMER FILMS ................................................................................................................................. 150
INTRODUCTION .......................................................................................................................... 150
POLYMER FILMS SWOLLEN IN WATER AS STUDIED BY FIDS, T AND MRI .......... 151
2
NMR AND MRI IN STUDYING EVAPORATION OF WATER FROM THE FILMS ........ 157
CONCLUDING REMARKS ......................................................................................................... 160
ACKNOWLEDGEMENTS ........................................................................................................... 160
REFERENCES ............................................................................................................................... 160
CHAPTER 10 SELF-DIFFUSION OF WATER IN CEMENT PASTES AS STUDIED BY 1H
PFG NMR AND DDCOSY NMR .......................................................................................................... 163
INTRODUCTION .......................................................................................................................... 163
METHODS AND MODELS .......................................................................................................... 164
Methods of Spin-Echo and Stimulated Echo in PFG Experiments ......................................... 165
DDCOSY Experiments in Studying Anisotropy .................................................................... 168
COMPARISON OF PULSE SEQUENCES IN CEMENT STUDIES ....................................... 170
SELF-DIFFUSION OF WATER IN CEMENT PASTE ............................................................ 171
Early Hydration of Cement Paste as Studied by 1-dimensional PFG NMR ........................... 171
DDCOSY in Studying Early Cement Hydration .................................................................... 173
Pore Size Distribution and Self-diffusion of Water in Mature Cement Paste ........................ 174
CONCLUDING REMARKS ......................................................................................................... 176
ACKNOWLEDGEMENTS ........................................................................................................... 176
REFERENCES ............................................................................................................................... 176
CHAPTER 11 CHARACTERISATION OF HYDRATED CEMENT PASTES BY 1 H D QF
NMR SPECTROSCOPY ........................................................................................................................ 180
1D AND 2D 1H NMR RELAXATION .......................................................................................... 180
METHODS AND THEORY: MODEL STUDIES ...................................................................... 188
DOUBLE-QUANTUM-FILTERED (DQF) SIGNALS: DEPENDENCE ON SAMPLE
CURING AND ON CREATION TIME. PAKE DOUBLET ...................................................... 194
DQF LINE SHAPE ......................................................................................................................... 202
DQF AND DRYING THE SAMPLES: EXCHANGEABLE WATER ..................................... 205
CONCLUDING REMARKS ......................................................................................................... 209
ACKNOWLEDGEMENTS ........................................................................................................... 210
REFERENCES ............................................................................................................................... 210
SUBJECT INDEX . .................................................................................................................................... 214
i
FOREWORD 1
"Water, Water, Everywhere" begins a famous quatrain by the English poet Samuel Taylor
Coleridge. Indeed, there is no chemical compound more ubiquitous or more crucial to all
aspects of life on Earth. Most familiar is water in its liquid form, a material that is a near-
universal solvent. Sea water, a solution of inorganic salts in water, represents more than 95%
of the water on the surface of the planet. While water molecules are essential to life, many
aspects of their involvement in biological structures and processes are not fully understood.
Formed from a single oxygen atom and two hydrogens, the physical and chemical properties
of water are often anomalous if the hydrogen compounds of the elements surrounding oxygen
in the periodic table are considered. For example, water (H O) is a liquid at room temperature
2
and atmospheric pressure while the compounds NH , HF and H S are gases under the same
3 2
conditions. The anomalous properties of water result from intermolecular dipolar and
hydrogen-bonded interactions that are peculiarly potent in pure water and account for this
liquid's ability to function so effectively as a solvent. The same types of interactions often
lead to water molecules being found within organized three-dimensional structures of living
and inanimate materials where they have specific structural roles that go beyond those of a
mere solvent.
Many experimental methods have been applied to the study of water as a solvent or as a part
of an assembled structure. Given that water contains hydrogen atoms with their spin ½ nuclei,
it is no surprise that proton nuclear magnetic resonance (1H NMR) has been at the forefront of
efforts to understand the chemistry of water wherever it is found. Proton NMR can provide
information about the stability of organized structures and indications of the time rate(s) of
change of these. Such changes might include rearrangement of three-dimensional aspects
(such as conformational motions) or change in relative positions through rotational and
translational diffusion.
In this volume, Dr. Rodin presents results from his laboratory and those of others that
exemplify information that can be obtained about water molecules contained within organized
but non-crystalline materials using proton NMR. These efforts appropriately have employed
various relaxation, multiple quantum filtered, translational diffusion and imaging
experiments. The systems examined range from synthetic (polyacrylates) and natural
polymers (collagen and silk) to intact wood and inorganic cements. These reports nicely
demonstrate to the reader the current state of the art in applying these powerful NMR
experiments to the systems mentioned.
J. T. Gerig, Professor Emeritus
University of California
Santa Barbara
USA
ii
FOREWORD 2
Nuclear Magnetic Resonance (NMR) is an indispensable technique for investigating the
structure, functionality and dynamics of molecules. It is used widely in physics, chemistry,
biology, medicine and other sciences. In this book, Dr. Victor Rodin describes NMR
experiments and techniques for consideration and discussion. This book is a great addition to
the analysis of NMR methods which Dr. Victor Rodin applied in studying the translational
dynamics of molecules in porous and heterogeneous systems: synthetic polymers and
materials, collagens and natural silk, and wood and cement pastes.
Dr. Rodin graduated from the Moscow Institute of Physics and Technology (MIPT-State
University), Faculty of Molecular & Chemical Physics. He received a PhD in Biophysics
(with specialization in Mathematics & Physics) at the Research Institute of Biophysics
(Russian Academy of Sciences). He also earned a PhD in Macromolecular and Colloid
Chemistry at the Department of Chemistry of Moscow State University. He has worked in
excellent NMR research centers, including the University of California, Santa Barbara, USA;
the University of East Anglia; the University of Bristol; the University of Surrey, UK; INRA,
Clermont-Ferrand, France; Johannes Kepler University of Linz, Austria. Dr. Rodin has
published more than 60 publications in peer-reviewed scientific journals and delivered
approximately 70 presentations at international scientific meetings and conferences. He has
been a member of the Research Council on Colloid Chemistry at Moscow State University,
and a member of the International Society of Magnetic Resonance in Medicine, USA. He has
refereed papers for scientific journals including Colloid Journal, Material Science, Polymer,
Food Chemistry, and a special issue of Magnetic Resonance in Porous Media.
Dr. Rodin has considerable experience in the development of different magnetic resonance
methods, including new methodologies. His research experience focuses on the development
and application of MR methods and analysis to study solutions and heterogeneous materials,
including biomaterials and drugs, blood and microbiological suspensions, polymer solutions,
gels and films, xenon gas clathrate hydrates, collagen tissues, natural silk, skin, wood, cement
etc. He has taught in many universities. Based on his research results he has delivered lectures
to students in physics, physical chemistry, mathematics, natural biopolymers and synthetic
materials.
Dr. Rodin illustrates the current state of numerous special NMR experiments applied to
porous heterogeneous materials. Readers with an interest in NMR will find useful information
in this volume. Potential roles of NMR to future applications are also discussed. The
examples are taken from real research results. Problems and solutions are also considered.
Syed F. Akber, PhD, DABR
Radiological Physicist
Cleveland/ Lorain, OHIO
USA