NMR of Ordered Liquids

464 Pages·2003·20.7 MB·English

by  C. A. de Lange, E. E. Burnell (auth.), E. Elliott Burnell, Cornelis A. de Lange (eds.)

NMR of Ordered Liquids
NMR of Ordered Liquids
Edited by
E. Elliott Burnell
University of British Columbia,
Canada
and
Comelis A. de Lange
University ofA msterdam,
The Netherlands
Springer-Science+Business Media, B.Y.
A c.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-90-481-6305-2 ISBN 978-94-017-0221-8 (eBook)
DOI 10.1007/978-94-017-0221-8
Printed on acid-free paper
All Rights Reserved
© 2003 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 2003.
Softcover reprint of the hardcover 1s t edition 2003
No part of this work may be reproduced, stored in a retrieval system, or transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or
otherwise, without written permission from the Publisher, with the exception
of any material supplied specifically for the purpose of being entered
and executed on a computer system, for exclusive use by the purchaser of the work.
This book is dedicated to our
dear wives Bonnie and
Annette who put up with the
many hours and late
evenings, not to mention the
early mornings, spent
discussing and arguing
about the various details of
this project
Contents
Contributing Authors xiii
Preface XXI
Introduction XXv
E.E. Burnell and CA. de Lange
Part I Basics
Basics ofNMR of molecules in uniaxial anisotropic environments 5
CA. de Lange and E.E. Burnell
1 Introduction 5
2 General Hamiltonian in uniaxial anisotropic liquids 6
3 The high-field approximation 9
4 Transformation to molecule-fixed axes 11
5 Orientation parameters 12
6 Molecular symmetry 15
7 Simple examples ofNMR spectra of orientationally ordered molecules 17
8 Orientational order induced by anisotropic solvents 21
9 Orientational order induced by strong electric fields 22
10 Orientational order induced by strong magnetic fields 23
11 Internal motion 24
12 Summary 26
2
Density matrix methods in NMR 27
M. Bloom, E.E. Burnell and CA. de Lange
1 Introduction 27
2 Brief introduction to the density matrix 27
3 PuisedNMR 30
4 Summary 43
3
Coherent averaging and correlation of anisotropic spin interactions in oriented 45
molecules
Malgorzata Marjanska, Robert H. Havlin and Dimitris Sakellariou
1 Introduction 45
2 Spatial reorientation techniques 45
Vll
viii NMR OF ORDERED LIQUIDS
3 Two-dimensional dynamic director correlations 50
4 Spin manipulation based techniques 51
5 Multidimensional techniques 57
6 Conclusions 63
4
Multiple Quantum NMR Spectroscopy in Orientationally Ordered Fluids 67
Leslie D. Field
1 NMR in orientationally ordered fluids 67
2 Spectral simplification by MQNMR 68
3 Excitation and detection of multiple quantum coherence 69
4 Selective deuteration for spectral simplification 76
5 Spectral analysis and simulation 77
6 Structural studies using MQNMR 77
7 Structural studies by 1H MQNMR 80
8 Heteronuclear MQNMR 84
9 Other applications ofMQNMR in liquid crystalline solvents 84
5
Spectral Analysis of Orientationally Ordered Molecules 89
Raymond T Syvitski
1 Introduction 89
2 Tools of the trade 90
3 Some examples of putting it together 96
4 Summary 103
Part II NMR of solute atoms and molecules
6
NMR of Noble Gases Dissolved in Liquid Crystals 109
Jukka Jokisaari
1 Introduction 109
2 NMR properties of noble gases 109
3 Chemical shift 110
4 Quadrupole coupling 121
5 Relaxation 127
6 129Xe self-diffusion 130
7 Conclusions 133
7
NMR of partially ordered solutes with emphasis on structure determination 137
c.L. Khetrapal and G.A. Nagana Gowda
1 Introduction 137
2 Basic principles 138
3 Spectral analysis 141
4 Scope and limitations 142
5 Practical considerations for deriving precise molecular structural information 142
6 Aids for spectral analysis 145
7 Emerging developments and possible future directions 153
8 Conclusions 158
Contents IX
8
Observation and interpretation of residual dipolar couplings in biomolecules 163
Jean-Franr;ois Trempe and Kalle Gehring
1 Introduction 163
2 Theory 164
3 Measurement of residual dipolar couplings 166
4 Interpretation and applications of dipolar couplings and CSA in structural
biology 177
5 Summary 186
9
The search for high-resolution NMR methods for membrane peptide structure 191
Christophe Fares and James H. Davis
1 Introduction: NMR of orientationally ordered systems 191
2 Theoretical background 193
3 Separated local field spectroscopy 197
4 High-resolution 1 H MAS NMR of small membrane proteins 209
5 Conclusions 210
Part III Theory, models, and simulations
10
Solutes as probes of simplified models of orientational order 221
E.E. Burnell and CA. de Lange
I Introduction 221
2 Obtaining a self-consistent set of solute orientational order parameters 224
3 Factors affecting solute orientational order 226
4 Orientational order of solutes in "magic mixtures" 230
5 Comparison of experimental and calculated orientational order in "pure"
liquid crystals and "magic mixtures" 234
6 Conclusions 239
11
Molecular Models of Orientational Order 241
Alberta Ferrarini and Giorgio J Mora
1 Phenomenological models for short-range interactions 242
2 Modeling electrostatic interactions 246
3 Density functional theory 251
4 Conclusion 256
Appendix: Polarization induced by a charge distribution in a dielectric 256
12
Molecular theory of orientational order 259
Demetri J Photinos
1 Introduction 259
2 Order parameters, molecular structure and interactions 260
3 Approximation schemes for the potential of mean torque 268
4 Molecular models 273
5 Summary. 281
x NMR OF ORDERED LIQUIDS
13
Very Flexible Solutes: Alkyl Chains and Derivatives 285
Edward T. Samulski
1 Introduction 285
2 Chronology ofNMR studies of flexible solutes 289
3 Models of flexible molecules 293
4 Conclusions 303
14
NMR Studies of Solutes in Liquid Crystals: Small Flexible Molecules 305
Giorgio Celebre and Marcello Longeri
1 Introduction 305
2 Theoretical background 306
3 The conformational problem 307
4 Selected examples 312
5 Conclusions 322
15
Simulations of Orientational Order of Solutes in Liquid Crystals 325
James M Polson
1 Introduction 325
2 Orientational distribution functions and mean-field potentials 327
3 Conformational behaviour of flexible solutes 333
4 Electrostatic interactions 337
5 Conclusions 343
Part IV Dynamic aspects and relaxation
16
Spin relaxation in orientationally ordered molecules 349
Ronald Y. Dong
1 Introduction 349
2 Average Hamiltonian 350
3 Spin relaxation theory 354
4 Motional models 356
5 Applications of spin relaxation 360
17
Low-frequency NMR relaxometry of spatially constrained liquid crystals 375
F Grinberg, M Vilfan and E. Anoardo
1 Introduction 375
2 Field-cycling relaxometry 378
3 Low-field proton relaxometry of confined liquid crystals 380
4 The dipolar-correlation effect 384
5 Deuteron NMR relaxometry of confined liquid crystals 391
18
NMR on macroscopically oriented lyotropic systems 399
G. Oriidd and G. Lindblom
1 Introduction 399
2 Orientation dependent NMR interactions 399
3 Lipid translational diffusion 404
4 Preparation of macroscopically oriented lamellar systems 407
Contents Xl
5 Examples 411
19
Dynamic NMR in liquid crystals and liquid crystalline solutions 419
Zeev Luz
1 Introduction 419
2 Dynamic proton NMR of solutes in nematic solvents 420
3 Dynamic deuterium NMR spectra 428
4 Dynamic carbon-13 MAS NMR 439
5 Concluding remarks 447
Contributing Authors
Esteban Anoardo (