Multidimensional NMR Methods for the Solution State E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: EMR Books
• Sprache: Englisch

Seitenzahl: 1399

Veröffentlichungsjahr: 2012

Beschreibung

The content of this volume has been added to eMagRes (formerly Encyclopedia of Magnetic Resonance) - the ultimate online resource for NMR and MRI.

The literature of multidimensional NMR began with the publication of three papers in 1975, then nine in 1976 and fifteen in 1977, and now contains many tens of thousands of papers. Any attempt to survey the field must therefore necessarily be very selective, not to say partial. In assembling this handbook, the Editors have sought to provide both the new researcher and the established scientist with a solid foundation for the understanding of multidimensional NMR, a representative if inevitably limited survey of its applications, an authoritative account of classic techniques such as COSY, NOESY and TOSCY, and an account of the latest progress in the development of multidimensional techniques.

This handbook is structured in four parts. The first opens with an historical introduction to, and a brief account of, the practicalities and applications of multidimensional NMR methods, followed by a definitive survey of their conceptual basis and a series of articles setting out the generic principles of methods for acquiring and processing multidimensional NMR data. In the second part, the main families of multidimensional techniques, arranged in approximate order of increasing complexity, are described in detail, from simple J-resolved spectroscopy through to the powerful heteronuclear 3D and 4D methods that now dominate the study of structural biology in solution. The third part offers and illustrative selection from the very wide range of applications of multidimensional NMR methods, including some of the most recent developments in protein NMR. Finally, the fourth part introduces the idea of multidimensional spectra containing non-frequency dimensions, in which properties such as diffusion and relaxation are correlated.

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The Encyclopedia of Magnetic Resonance (up to 2012) and eMagRes (from 2013 onward) publish a wide range of online articles on all aspects of magnetic resonance in physics, chemistry, biology and medicine. The existence of this large number of articles, written by experts in various fields, is enabling the publication of a series of EMR Handbooks / eMagRes Handbooks on specific areas of NMR and MRI. The chapters of each of these handbooks will comprise a carefully chosen selection of articles from eMagRes. In consultation with the eMagRes Editorial Board, the EMR Handbooks / eMagRes Handbooks  are coherently planned in advance by specially-selected Editors, and new articles are written (together with updates of some already existing articles) to give appropriate complete coverage. The handbooks are intended to be of value and interest to research students, postdoctoral fellows and other researchers learning about the scientific area in question and undertaking relevant experiments, whether in academia or industry.

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Based on the Encyclopedia of Magnetic Resonance (EMR), this monograph series focuses on hot topics and major developments in modern magnetic resonance and its many applications. Each volume in the series will have a specific focus in either general NMR or MRI, with coverage of applications in the key scientific disciplines of physics, chemistry, biology or medicine. All the material published in this series, plus additional content, will be available in the online version of EMR, although in a slightly different format.

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Encyclopedia of Magnetic Resonance

Edited by Robin K. Harris, Roderick E. Wasylishen, Edwin D. Becker, John R. Griffiths, Vivian S. Lee, Ian R. Young, Ann E. McDermott, Tatyana Polenova, James W. Emsley, George A. Gray, Gareth A. Morris, Melinda J. Duer and Bernard C. Gerstein.

The Encyclopedia of Magnetic Resonance (EMR) is based on the original printed Encyclopedia of Nuclear Magnetic Resonance, which was first published in 1996 with an update volume added in 2000. EMR was launched online in 2007 with all the material that had previously appeared in print. New updates have since been and will be added on a regular basis throughout the year to keep the content up to date with current developments. Nuclear was dropped from the title to reflect the increasing prominence of MRI and other medical applications. This allows the editors to expand beyond the traditional borders of NMR to MRI and MRS, as well as to EPR and other modalities. EMR covers all aspects of magnetic resonance, with articles on the fundamental principles, the techniques and their applications in all areas of physics, chemistry, biology and medicine for both general NMR and MRI. Additionally, articles on the history of the subject are included.

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Library of Congress Cataloging-in-Publication Data

Multidimensional NMR methods for the solution state / editors, Gareth A. Morris, James W. Emsley.

    p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-77075-7 (cloth)

1. Liquids—Spectra. 2. Nuclear magnetic resonance spectroscopy. 3. Nuclear magnetic resonance. I. Morris, Gareth A. II. Emsley, J. W. (James William)

QC145.4.O6M85 2010

543’.66—dc22

2009054386

A catalogue record for this book is available from the British Library.

ISBN-13: 978-0-470-77075-7

Set in 9.5/11.5 pt Times by Laserwords (Private) Limited, Chennai, India Printed and bound in Singapore by Markono Print Media Pte Ltd

Encyclopedia of Magnetic Resonance

Editorial Board

Editors-in-Chief

Robin K. HarrisUniversity of DurhamDurhamUK

Roderick E. WasylishenUniversity of AlbertaEdmonton, AlbertaCanada

Section EditorsSOLID-STATE NMR & PHYSICS

Melinda J. DuerUniversity of CambridgeCambridgeUK

Bernard C. GersteinAmes, IAUSA

SOLUTION-STATE NMR & CHEMISTRY

James W. EmsleyUniversity of SouthamptonSouthamptonUK

George A. GrayVarian Inc.Palo Alto, CAUSA

Gareth A. MorrisUniversity of ManchesterManchesterUK

BIOCHEMICAL NMR

Ann E. McDermottColumbia UniversityNew York, NYUSA

Tatyana PolenovaUniversity of DelawareNewark, DEUSA

MRI & MRS

John R. GriffithsCancer Research UK   Cambridge Research   InstituteCambridgeUK

Vivian S. LeeNYU Langone Medical   CenterNew York, NYUSA

Ian R. YoungImperial CollegeLondonUK

HISTORICAL PERSPECTIVES

Edwin D. BeckerNational Institutes of HealthBethesda, MDUSA

International Advisory Board

David M. Grant (Chairman)University of UtahSalt Lake City, UTUSA

Isao AndoTokyo Institute   of TechnologyTokyoJapan

Adriaan BaxNational Institutes of HealthBethesda, MDUSA

Chris BoeschUniversity BernBernSwitzerland

Paul A. BottomleyJohns Hopkins UniversityBaltimore, MDUSA

William G. BradleyUCSD Medical CenterSan Diego, CAUSA

Graeme M. BydderUCSD Medical CenterSan Diego, CAUSA

Paul T. CallaghanVictoria University   of WellingtonWellingtonNew Zealand

Richard R. ErnstEidgenössische Technische   Hochschule (ETH)ZürichSwitzerland

Ray FreemanUniversity of CambridgeCambridgeUK

Lucio FrydmanWeizmann Institute   of ScienceRehovotIsrael

Maurice GoldmanVillebon sur YvetteFrance

Harald GüntherUniversität SiegenSiegenGermany

Herbert Y. KresselHarvard Medical SchoolBoston, MAUSA

C. Leon PartainVanderbilt University Medical   CenterNashville, TNUSA

Alexander PinesUniversity of California   at BerkeleyBerkeley, CAUSA

George K. RaddaUniversity of OxfordOxfordUK

Hans Wolfgang SpiessMax-Planck Institute   of Polymer ResearchMainzGermany

Charles P. SlichterUniversity of Illinois   at Urbana-ChampaignUrbana, ILUSA

John S. WaughMassachusetts Institute   of Technology (MIT)Cambridge, MAUSA

Bernd WrackmeyerUniversität BayreuthBayreuthGermany

Kurt WüthrichThe Scripps Research   InstituteLa Jolla, CAUSAandETH ZürichZürichSwitzerland

Contents

Title

Copyright

Contributors

Series Preface

Volume Preface

Part A: Principles

1 Multidimensional NMR: an Introduction

2 Multidimensional Spectroscopy: Concepts

3 Ultrafast Multidimensional NMR: Principles and Practice of Single-Scan Methods

4 Fast Multidimensional NMR by Hadamard Spectroscopy

5 Multidimensional NMR by Projection-Reconstruction

6 Rapid Multidimensional NMR: Decomposition Methods and their Applications

7 Multidimensional Correlation Spectroscopy by Covariance NMR

8 Maximum Entropy Methods in Multidimensional NMR

9 Filter Diagonalization Methods for Time-Domain Signals

10 Fourier Transform and Linear Prediction Methods

Part B: Techniques

11 Two-Dimensional J-Resolved Spectroscopy

12 COSY

13 COSY: Quantitative Analysis

14 E.COSY: Determination of Coupling Constants

15 Relayed Coherence Transfer Experiments

16 TOCSY

17 Multiple Quantum Spectroscopy of Liquid Samples

18 NOESY

19 ROESY

20 TOCSY in ROESY and ROESY in TOCSY

21 2D Methods of Monitoring Exchange

22 Heteronuclear Shift Correlation Spectroscopy

23 2D Methods for the Measurement of Long-Range Proton–Carbon Coupling Constants

24 Homonuclear 3D NMR of Biomolecules

25 3D HMQC-NOESY, NOESY-HMQC, and NOESY-HSQC

26 3D and 4D Heteronuclear Magnetic Resonance

Part C: Applications

27 2D Carbon–Heteroelement Correlation

28 Multidimensional NMR in Organotin Chemistry and Catalysis

29 2D NMR of Molecules Oriented in Liquid Crystalline Phases

30 2D NMR of Molecules Oriented in Liquid Crystals—Recent Developments

31 Local Field Experiments in Liquid Crystals

32 Multiple Quantum Spectroscopy in Liquid Crystalline Solvents

33 Biological Macromolecules: Structure Determination in Solution

34 Structures of Larger Proteins, Protein–Ligand, and Protein–DNA Complexes by Multidimensional Heteronuclear NMR

35 Rapid Multidimensional NMR: Fast Pulsing Techniques and their Applications to Proteins

Part D: Related Techniques

36 Diffusion-Ordered Spectroscopy

37 2D Relaxometry

Index

Contributors

Alex D. Bain

Department of Chemistry, McMaster University, Hamilton L8S 4M1, Ontario, Canada

Chapter 13: COSY: Quantitative Analysis

Ad Bax

National Institutes of Health, DHHS NIDDK LCP, Building 5, Room 126, 9000 Rockville Pike, Bethesda, MD 20892-0520, USA

Chapter 19: ROESY

Stefan Berger

Philipps University Marburg, Marburg, Germany

Chapter 27: 2D Carbon–Heteroelement Correlation

Monique Biesemans

High Resolution NMR Centre (HNMR), Department of Materials and Chemistry (MACH) Pleinlaan 2, B-1050, Brussels, Belgium

Chapter 28: Multidimensional NMR in Organotin Chemistry and Catalysis

Martin Billeter

Department of Chemistry, Biochemistry and Biophysics, Gothenburg University, P.O. Box 462, SE-405 30, Gothenburg, Sweden

Chapter 6: Rapid Multidimensional NMR: Decomposition Methods and their Applications

Rolf Boelens

NMR Spectroscopy Research Group, Bijvoet Center for Biomolecular Research, Utrecht University, Bloembergengebouw, Padualaan 8, 3584 CH Utrecht, The Netherlands

Chapter 24: Homonuclear 3D NMR of Biomolecules

Philip H. Bolton

Hall-Atwater Laboratories, Department of Chemistry, Wesleyan University, 237 Church Street, Middletown, CT 06459-0180, USA

Chapter 15: Relayed Coherence Transfer Experiments

Rafael Brüschweiler

Chemical Sciences Laboratory, Department of Chemistry and Biochemistry & National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32306, USA

Chapter 7: Multidimensional Correlation Spectroscopy by Covariance NMR

Bernhard Brutscher

Institut de Biologie Structurale - Jean-Pierre Ebel, UMR5075 CNRS-CEA-UJF, 41, rue Jules Horowitz - 38027, Grenoble Cedex, France

Chapter 35: Rapid Multidimensional NMR: Fast Pulsing Techniques and their Applications to Proteins

Stefano Caldarelli

Equipe Chimiométrie et Spectroscopie, Institut des Sciences Moléculaires de Marseille, Université Paul Cézanne (Aix-Marseille III), ISM2-UMR-CNRS-6263, Marseille, FranceFaculté des Sciences et Techniques, Service 512,13397 Marseille cedex 20, France

Chapter 31: Local Field Experiments in Liquid Crystals

Timothy D. W. Claridge

Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK

Chapter 16: TOCSY

G. Marius Clore

Laboratory of Chemical Physics, Bldg 5/B1-30I, Protein NMR Section, NIDDK, National Institutes of Health, Bethesda, MD 20892-0520, USA

Chapter 26: 3D and 4D Heteronuclear Magnetic ResonanceChapter 34: Structures of Larger Proteins, Protein–Ligand, and Protein–DNA Complexes by Multidimensional Heteronuclear NMR

David M. Doddrell

Centre for Magnetic Resonance, University of Queensland, 4072, Australia

Chapter 12: COSY

James W. Emsley

School of Chemistry, University of Southampton, Southampton, S017 1BJ, UK

Chapter 1: Multidimensional NMR: an Introduction

Richard R. Ernst

Laboratorium für Physikalische Chemie, Eidgenössische Technische Hochschule, 8093 Zürich, Switzerland

Chapter 2: Multidimensional Spectroscopy: Concepts

Leslie D. Field

School of Chemistry, University of New South Wales, Room 205, The Chancellery, Kensington 2052, Australia

Chapter 32: Multiple Quantum Spectroscopy in Liquid Crystalline Solvents

Ray Freeman

Jesus College, Cambridge University, Cambridge, CB5 8BP, UK

Chapter 4: Fast Multidimensional NMR by Hadamard SpectroscopyChapter 5: Multidimensional NMR by Projection-Reconstruction

Lucio Frydman

Department of Chemical Physics, Weizmann Institute of Science, 76100 Rehovot, Israel

Chapter 3: Ultrafast Multidimensional NMR: Principles and Practice of Single-Scan Methods

Maayan Gal

Department of Chemical Physics, Weizmann Institute of Science, 76100 Rehovot, Israel

Chapter 3: Ultrafast Multidimensional NMR: Principles and Practice of Single-Scan Methods

Henrik Gesmar

Chemistry Department, University of Copenhagen, Unversitetsparken 5, DK-2100, København Ø, Denmark

Chapter 10: Fourier Transform and Linear Prediction Methods

S. J. Glaser

Department of Chemistry, Umeå University, KBC Building, S-90187 Umeå, Sweden

Chapter 20: TOCSY in ROESY and ROESY in TOCSY

Christian Griesinger

Institut für Organische Chemie, Johann Wolfgang Goethe-University, Max-von-Laue-Str. 7, 60438 Frankfurt, Germany

Chapter 14: E.COSY: Determination of Coupling ConstantsChapter 20: TOCSY in ROESY and ROESY in TOCSY

Angela M. Gronenborn

Laboratory of Chemical Physics, Bldg 5/B1-30I, Protein NMR Section, NIDDK, National Institutes of Health, Bethesda, MD 20892-0520, USA

Chapter 26: 3D and 4D Heteronuclear Magnetic ResonanceChapter 34: Structures of Larger Proteins, Protein–Ligand, and Protein–DNA Complexes by Multidimensional Heteronuclear NMR

Stephan Grzesiek

National Institutes of Health, DHHS NIDDK LCP, Building 5, Room 126, 9000 Rockville Pike, Bethesda, MD 20892-0520, USA

Chapter 19: ROESY

Brian P. Hills

Institute of Food Research, Norwich Research Park, Colney, NR4 7UA, UK

Chapter 37: 2D Relaxometry

Jeffrey C. Hoch

University of Connecticut Health Center, Farmington, CT, USA

Chapter 8: Maximum Entropy Methods in Multidimensional NMR

Robert Kaptein

NMR Spectroscopy Research Group, Bijvoet Center for Biomolecular Research, Utrecht University, Bloembergengebouw, Padualaan 8, 3584 CH Utrecht, The Netherlands

Chapter 24: Homonuclear 3D NMR of Biomolecules

Lewis E. Kay

Department of Medical Genetics & Microbiology, University of Toronto, Medical Sciences Building, Room 1233, 1 King’s College Circle, Toronto M5S 1A8, Canada

Chapter 25: 3D HMQC-NOESY, NOESY-HMQC, and NOESY-HSQC

Anil Kumar

Department of Physics and NMR Research Centre, Indian Institute of Science, Bangalore, Karnataka 560012, India

Chapter 29: 2D NMR of Molecules Oriented in Liquid Crystalline PhasesChapter 30: 2D NMR of Molecules Oriented in Liquid Crystals—Recent Developments

Ēriks Kupče

Varian Ltd, 6 Mead Road, Yarnton, Oxford, OX5 1QU, UK

Chapter 4: Fast Multidimensional NMR by Hadamard SpectroscopyChapter 5: Multidimensional NMR by Projection-Reconstruction

Jens J. Led

Chemistry Department, University of Copenhagen, Unversitetsparken 5, DK-2100, København Ø, Denmark

Chapter 10: Fourier Transform and Linear Prediction Methods

Vladimir A. Mandelshtam

Chemistry Department, University of California at Irvine, 4134 Natural Sciences Building 1, Mail Code: 2025, Irvine, CA 92697, USA

Chapter 9: Filter Diagonalization Methods for Time-Domain Signals

R. E. D. McClung

Gunning/Lemieux Chemistry Centre, Department of Chemistry, Room E3-24, University of Alberta, Edmonton, Alberta T6G 2G2, Canada

Chapter 22: Heteronuclear Shift Correlation Spectroscopy

Mehdi Mobli

University of Queensland, St. Lucia, Queensland, Australia

Chapter 8: Maximum Entropy Methods in Multidimensional NMR

Gareth A. Morris

Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

Chapter 1: Multidimensional NMR: an IntroductionChapter 11: Two-Dimensional J-Resolved SpectroscopyChapter 36: Diffusion-Ordered Spectroscopy

Ranjith Muhandiram

Department of Medical Genetics & Microbiology, University of Toronto, Medical Sciences Building, Room 1233, 1 King’s College Circle, Toronto M5S 1A8, Canada

Chapter 25: 3D HMQC-NOESY, NOESY-HMQC, and NOESY-HSQC

Thomas T. Nakashima

Gunning/Lemieux Chemistry Centre, Department of Chemistry, Room E3-24, University of Alberta, Edmonton, Alberta T6G 2G2, Canada

Chapter 22: Heteronuclear Shift Correlation Spectroscopy

Timothy J. Norwood

Leicester University, UK

Chapter 17: Multiple Quantum Spectroscopy of Liquid Samples

Keith G. Orrell

University of Exeter, Exeter, UK

Chapter 21: 2D Methods of Monitoring Exchange

Teodor Parella

Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona, E-08193, Bellaterra, Barcelona, Spain

Chapter 23: 2D Methods for the Measurement of Long-Range Proton-Carbon Coupling Constants

J Quant

Department of Chemistry, Umeå University, KBC Building, S-90187 Umeå, Sweden

Chapter 20: TOCSY in ROESY and ROESY in TOCSY

Paul Schanda

Laboratorium für Physikalische Chemie, ETH Hönggerberg, CH-8093 Zürich, Switzerland

Chapter 35: Rapid Multidimensional NMR: Fast Pulsing Techniques and their Applications to Proteins

J Schleucher

Department of Chemistry, Umeå University, KBC Building, S-90187 Umeå, Sweden

Chapter 20: TOCSY in ROESY and ROESY in TOCSY

P Schmidt

Institut für Organische Chemie, Johann Wolfgang Goethe-University, Max-von-Laue-Str. 7, 60438 Frankfurt, Germany

Chapter 14: E.COSY: Determination of Coupling Constants

Harald Schwalbe

Institut für Organische Chemie, Johann Wolfgang Goethe-University, Max-von-Laue-Str. 7, 60438 Frankfurt, Germany

Chapter 14: E.COSY: Determination of Coupling Constants

A. J. Shaka

Chemistry Department, University of California at Irvine, 4134 Natural Sciences Building 1, Mail Code: 2025, Irvine, CA 92697, USA

Chapter 9: Filter Diagonalization Methods for Time-Domain Signals

David A. Snyder

Department of Chemistry, William Paterson University, 300 Pompton Road, Wayne, NJ 07470, USA

Chapter 7: Multidimensional Correlation Spectroscopy by Covariance NMR

Doroteya K. Staykova

Department of Chemistry, Biochemistry and Biophysics, Gothenburg University, P.O. Box 462, SE-405 30, Gothenburg, Sweden

Chapter 6: Rapid Multidimensional NMR: Decomposition Methods and their Applications

N Suryaprakash

NMR Research Centre, Indian Institute of Science, Bangalore, Karnataka 560012, India

Chapter 30: 2D NMR of Molecules Oriented in Liquid Crystals—Recent Developments

Rudolph Willem

High Resolution NMR Centre (HNMR), Department of Materials and Chemistry (MACH) Pleinlaan 2, B-1050, Brussels, Belgium

Chapter 28: Multidimensional NMR in Organotin Chemistry and Catalysis

Michael P. Williamson

Department of Molecular Biology and Biotechnology, University of Sheffield, Firth Court, Western Bank, Sheffield S10 2TN, UK

Chapter 18: NOESY

Kurt Wüthrich

Inst. f. Molekularbiologie u. Biophysik, Eidgenössische Technische Hochschule Zürich, HPK G 17, Schafmattstr. 20, 8093 Zürich, Switzerland

Chapter 33: Biological Macromolecules: Structure Determination in Solution

Series Preface

The Encyclopedia of Nuclear Magnetic Resonance was published in eight volumes in 1996, in part to celebrate the fiftieth anniversary of the first publications in NMR in January 1946. Volume 1 contained an historical overview and ca. 200 short personal articles by prominent NMR practitioners, while the remaining seven volumes comprise ca. 500 articles on a wide variety of topics in NMR (including MRI). Two “spin-off” volumes incorporating the articles on MRI and MRS (together with some new ones) were published in 2000 and a ninth volume was brought out in 2002. In 2006, the decision was taken to publish all the articles electronically (i.e. on the World Wide Web) and this was carried out in 2007. Since then, new articles have been placed on the web every three months and a number of the original articles have been updated. This process is continuing. The overall title has been changed to the Encyclopedia of Magnetic Resonance to allow for future articles on EPR and to accommodate the sensitivities of medical applications.

The existence of this large number of articles, written by experts in various fields, is enabling a new concept to be implemented, namely the publication of a series of printed handbooks on specific areas of NMR and MRI. The chapters of each of these handbooks will comprise a carefully chosen selection of Encyclopedia articles relevant to the area in question. In consultation with the Editorial Board, the handbooks are coherently planned in advance by specially selected editors. New articles are written and existing articles are updated to give appropriate complete coverage of the total area. The handbooks are intended to be of value and interest to research students, postdoctoral fellows, and other researchers learning about the topic in question and undertaking relevant experiments, whether in academia or industry.

Robin K. Harris

University of Durham, Durham, UK

Roderick E. Wasylishen

University of Alberta, Edmonton, Alberta, Canada

November 2009

Volume Preface

Over ten years passed between the first recognition of the potential of NMR methods based on Fourier transformation of the response to a radiofrequency pulse and the practical realization of that potential, by Ernst and Anderson, in 1966. The effect on the practice of NMR was rapid and profound, with pulse-Fourier transform equipment quickly supplanting continuous wave spectrometers. The great improvement in sensitivity achieved by this method opened up areas of the periodic table that had until then been largely unexplored by NMR, and the chemical application of multiple pulse experiments such as inversion recovery and the spin echo began in earnest.

It was only five years later, in 1971, that Jean Jeener proposed another technique, two-dimensional or 2D NMR spectroscopy, that was to have equally far-reaching implications. This time it took just four years for the first successful experiments to be reported, again by Richard Ernst and his colleagues, and once again the new methods were rapidly and widely adopted. Multidimensional NMR methods have since transformed the way NMR is used in chemistry, biology, physics, and medicine, to the extent that they are now part of the routine vocabulary of chemistry and of structural biology.

One of the most engaging features of NMR is its continuing ability to surprise. Despite over half a century of intensive study of the phenomenon of magnetic resonance, new discoveries and new developments in technique are still being made, and the flow of new ideas continues unabated. One of the most fruitful areas of development in recent years has been in methods for speeding up 2D and high-dimensionality experiments. Thus it is now possible in some cases to acquire a complete 2D spectrum in a few seconds, or to acquire data correlating five or six spectral dimensions overnight, with time savings of several orders of magnitude. Thus while this handbook contains authoritative accounts of techniques such as COSY, NOESY, and TOCSY that have acquired the status of classics, it also includes a range of articles on techniques that have been developed within the last few years, each written by the leader of the relevant field.

This handbook is structured in four parts. The first opens with a historical introduction to, and a brief account of, the practicalities and applications of multidimensional NMR methods, followed by a definitive survey of their conceptual basis and a series of articles setting out the generic principles of methods for acquiring and processing multidimensional NMR data. In the second part, the main families of multidimensional techniques, arranged in approximate order of increasing complexity, are described in detail, from simple J-resolved spectroscopy through to the powerful heteronuclear 3D and 4D methods that now dominate the study of structural biology in solution. The third part offers an illustrative selection from the very wide range of applications of multidimensional NMR methods, including some of the most recent developments in protein NMR. Finally, the fourth part introduces the idea of multidimensional spectra containing nonfrequency dimensions, in which properties such as diffusion and relaxation are correlated.

The literature of multidimensional NMR began with three papers in 1975, then nine in 1976, and fifteen in 1977, and now contains many tens of thousands of papers. Any attempt to survey the field must therefore necessarily be very selective, not to say partial. In assembling this handbook, and the Encyclopedia of Magnetic Resonance with which its component articles are shared, we have sought to provide both the new researcher and the established scientist with a solid foundation for the understanding of multidimensional NMR, a representative if inevitably limited survey of its applications, and an authoritative account of the latest progress in the development of multidimensional techniques.

Gareth A. Morris

University of Manchester, Manchester, UK

James W. Emsley

University of Southampton, Southampton, UK

April 2010

Abbreviations and Acronyms

AR

Autoregression

BIRD

Bilinear Rotation Decoupling

BPTI

Bovine Pancreatic Trypsin Inhibitor

CAMELSPIN

Cross Relaxation Appropriate for Minimolecules Emulated by Locked Spins

CP

Cross Polarization

CPD

Composite Pulse Decoupling

CPFO

Cesium Perfluorooctanoate

CPMG

Carr-Purcell pulse sequence, Meiboom-Gill modification

CRINEPT

Cross-Relaxation Enhanced Polarization Transfer

CRIPT

Cross-Relaxation Induced Polarization Transfer

CT

Constant Time

CTEF

Coherence Transfer Echo Filtering

CW

Continuous Wave

DAPT

Dipolar Assisted Polarization Transfer

DFT

Discrete Fourier Transformation

1D

One-dimensional

2D

Two-dimensional

DNA

Deoxyribonucleic Acid

DQC

Double Quantum Coherence

DQFC

Double Quantum Filtered COSY

E.COSY

Exclusive Correlation Spectroscopy

EXSY

Exchange Spectroscopy

FDM

Filter Diagonalization Method

FFLG

Flip-Flop Lee-Goldburg

FID

Free Induction Decay

FSLG

Frequency-Switched Lee-Goldburg

FT

Fourier Transform

FTA

Fluid-Turbulence-Adapted

FWHM

Full-Width at Half-Maximum Height

GEXSY

Gradient-Enhanced Exchange Spectroscopy

GFT

G-matrix Fourier Transform

GHZ

Greenberger-Horne-Zeilinger

2′-GMP

2′-Guanosine Monophosphate

HETCOR

Heteronuclear Correlation

HIP

Harmonic Inversion Problem

HMBC

Heteronuclear Multiple Bond Correlation

HMQC

Heteronuclear Multiple Quantum Coherence

HOHAHA

Homonuclear Hartmann–Hahn

HSQC

Heteronuclear Single Quantum Correlation

LG

Lee-Goldburg

LP

Linear Prediction

LPSVD

Linear Prediction Singular Value Decomposition Method

LPZ

Linear Prediction

z

-Transformation

LRE

Longitudinal Relaxation Enhancement

MAS

Magic-Angle Sample Spinning

mD, nD

Multidimensional

MDD

Multidimensional Decomposition

MQ NMR

Multiple Quantum NMR

MQCs

Multiple Quantum Coherences

MUSEX

Multiplet-Selective Excitation

NAD

Nicotinamide Adenine Dinucleotide

NOE

Nuclear Overhauser Effect, Nuclear Overhauser Enhancement

NOESY

Nuclear Overhauser Effect Spectroscopy

NUS

Nonuniform Sampling

PBLG

Poly-γ-benzyl-L-glutamate

PCBLL

Poly-ɛ-carbobenzyloxy-L-lysine

PELF

Proton-Encoded Local Field

PISEMA

Polarization Inversion Spin Exchange at the Magic Angle

PMLG

Phase-Modulated Lee-Goldberg

POPS

Pair of Pure States

PPS

Pseudopure State

PSF

Point Spread Function

RF, rf

Radiofrequency

RMSD

Root Mean Square Deviation

RNA

Ribonucleic Acid

ROESY

Rotating Frame Overhauser Enhancement Spectroscopy

RRT

Regularized Resolvent Transform

SECSY

Spin Echo Correlated Spectroscopy

SERF

Selective Refocusing

SFORD

Single Frequency Off-Resonance Proton Decoupling

SLF

Separated Local Field

SNR

Signal-to-Noise Ratio

SOFAST

Selective Optimized Flip-Angle Short Transient

SQ

Single Quantum

SS-MQ NMR

Spin-Selected Multiple-Quantum Excitation

ST

Single Transition

STD

Saturation Transfer Difference

STOCSY

Statistical Total Correlation Spectroscopy

SVD

Singular Value Decomposition

TAN

Time-Averaged Nutation

TE

Total Echo Time

TOCSY

Total Correlation Spectroscopy

TPPI

Time-Proportional Phase Incrementation

TQ

Triple Quantum

XFT

Extended Fourier Transform

ZQ

Zero Quantum

ZQC

Zero Quantum Coherence

PART A

Principles

Chapter 1

Multidimensional NMR: an Introduction

Gareth A. Morris1and James W. Emsley2

1Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

2School of Chemistry, University of Southampton, Southampton, SO17 1BJ, UK

1.1 INTRODUCTION

The first demonstration of pulse Fourier transform NMR spectroscopy brought a great improvement in the sensitivity of NMR,1 and a corresponding widening of its range of applications. Although it was far from obvious at the time, the introduction of FT methods had another, even more profound, consequence for the scope and power of NMR spectroscopy. The change from experiments in which NMR signals were excited and measured simultaneously, as in continuous wave (CW) NMR, to pulsed methods, in which excitation and detection are separated in time, gave the experimenter freedom to manipulate the chemical or physical information content of the data measured, and initiated a florid growth in experimental NMR techniques that has lasted 40 years and shows no sign of abating.