In Vivo NMR Spectroscopy E-Book

Robin A. de Graaf

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

Seitenzahl: 1130

Veröffentlichungsjahr: 2013

Beschreibung

This is the second edition of a unique book in the field of in vivo NMR covering in detail the technical and biophysical aspects of the technique.

The contents of the book are appropriate to both beginners and experienced users of in vivo NMR spectroscopy. The new edition is focussed on bringing the reader practical insights and advice, but is also geared towards use as a study aid and in NMR courses. Recent advances in NMR spectroscopy, like high field NMR, hyperpolarized NMR and new localization and editing techniques have been included. An extensive and updated treatment of radiofrequency pulses is given, together with several tables and recipes for their generation.

Solutions to the exercises within this text can be found here

Leseprobe

Contents

Preface

List of Abbreviations and Symbols

1 Basic Principles

1.1 Introduction

1.2 Classical Description

1.3 Quantum Mechanical Description

1.4 Macroscopic Magnetization

1.5 Excitation

1.6 Bloch Equations

1.7 Fourier Transform NMR

1.8 Chemical Shift

1.9 Digital Fourier Transform NMR

1.10 Spin-spin Coupling

1.11 T1 Relaxation

1.12 T2 Relaxation and Spin-echoes

1.13 Exercises

2 In Vivo NMR Spectroscopy – Static Aspects

2.1 Introduction

2.2 Proton NMR Spectroscopy

2.3 Phosphorus-31 NMR Spectroscopy

2.4 Carbon-13 NMR Spectroscopy

2.5 Sodium-23 and Potassium-39 NMR Spectroscopy

2.6 Fluorine-19 NMR Spectroscopy

2.7 Exercises

3 In Vivo NMR Spectroscopy – Dynamic Aspects

3.1 Introduction

3.2 Relaxation

3.3 Magnetization Transfer

3.4 Diffusion

3.5 Dynamic Carbon-13 NMR Spectroscopy

3.6 Hyperpolarization

3.7 Exercises

4 Magnetic Resonance Imaging

4.1 Introduction

4.2 Magnetic Field Gradients

4.3 Slice Selection

4.4 Frequency Encoding

4.5 Phase Encoding

4.6 Spatial Frequency Space

4.7 Fast MRI Sequences

4.8 Contrast in MRI

4.9 Parallel MRI

4.10 Exercises

5 Radiofrequency Pulses

5.1 Introduction

5.2 Square RF Pulses

5.3 Selective RF Pulses

5.4 Pulse Optimization

5.5 DANTE RF Pulses

5.6 Composite RF Pulses

5.7 Adiabatic RF Pulses

5.8 Pulse Imperfections and Relaxation

5.9 Power Deposition

5.10 Multidimensional RF Pulses

5.11 Spectral-spatial RF Pulses

5.12 Exercises

6 Single Volume Localization and Water Suppression

6.1 Introduction

6.2 Single Volume Localization

6.3 Water Suppression

6.4 Exercises

7 Spectroscopic Imaging and Multivolume Localization

7.1 Introduction

7.2 Principles of Spectroscopic Imaging

7.3 Spatial Resolution in MRSI

7.4 Temporal Resolution in MRSI

7.5 Lipid Suppression

7.6 Spectroscopic Imaging Processing and Display

7.7 Multivolume Localization

7.8 Exercises

8 Spectral Editing and Two-dimensional NMR

8.1 Introduction

8.2 Scalar Evolution

8.3 J-difference Editing

8.4 Practical Considerations of J-difference Editing

8.5 Multiple Quantum Coherence Editing

8.6 Heteronuclear Spectral Editing

8.7 Polarization Transfer – INEPT and DEPT

8.8 Sensitivity

8.9 Broadband Decoupling

8.10 Two-dimensional NMR Spectroscopy

8.11 Exercises

9 Spectral Quantification

9.1 Introduction

9.2 Data Acquisition

9.3 Data Pre-processing

9.4 Data Quantification

9.5 Data Calibration

9.6 Exercises

10 Hardware

10.1 Introduction

10.2 Magnets

10.3 Magnetic Field Homogeneity

10.4 Magnetic Field Gradients

10.5 Radiofrequency Coils

10.6 Radiofrequency Coil Types

10.7 Complete MR System

10.8 Exercises

Appendix

A1 Matrix Calculations

A2 Trigonometric Equations

A3 Fourier Transformation

A4 Product Operator Formalism

Index

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Library of Congress Cataloging-in-Publication Data

De Graaf, Robin A.

In vivo NMR spectroscopy : principles and techniques / Robin de Graaf. – 2nd ed.

p. ; cm.

Includes bibliographical references and index.

ISBN 978-0-470-02670-0 (cloth : alk. paper)

1. Nuclear magnetic resonance spectroscopy. 2. Magnetic resonance imaging. I. Title.

[DNLM: 1. Magnetic Resonance Spectroscopy–diagnostic use. 2. Magnetic Resonance Spectroscopy–methods. QU 25 D321i 2007]

QP519.9.N83D4 2007

616.07′548–dc22

2007018548

British Library Cataloguing in Publication Data

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

ISBN 978-0470-026700

Preface

Since the first edition of this textbook, published in 1998, the field of in vivo NMR spectroscopy has seen continued development of new techniques and applications, while at the same time some of the older techniques have become obsolete. One of the driving forces to write a second edition was to review some of these novel developments, such as hyperpolarized NMR, dynamic 13C NMR, automated shimming and parallel acquisitions. To maintain the flow of the book, several of the older techniques that have limited merits in modern in vivo NMR were removed. A second driving force was provided by the need for a textbook to be used in conjunction with a teaching course on in vivo NMR. In order to pursue this objective, most techniques are described from an educational point of view, without losing the practical aspects appreciated by experimental NMR spectroscopists. Furthermore, each chapter is concluded with a number of exercises designed to review, but often also to extend, the presented NMR principles and techniques.

Many of the ideas and changes that formed the basis for this second edition came from numerous discussions with colleagues. I would like to thank Douglas Rothman, Terry Nixon, Graeme Mason, Kevin Behar, Peter Brown and Kevin Koch for many fruitful discussions. Special thanks go to Christoph Juchem for his many insightful comments and careful reading of all chapters.

Finally, I would like to acknowledge the contributions of original data from Dan Green and Simon Pittard (Magnex Scientific), Andrew Maudsley (University of Miami), Gerald Shulman (Yale University) and Graeme Mason (Yale University).

Robin A. de GraafNew Haven, USAJanuary, 2007

Companion website URL: www.spectroscopynow.com/degraaf

Abbreviations and Symbols

1

Basic Principles

1.1 Introduction

The field of spectroscopy is in general concerned with the interaction between matter and electromagnetic radiation. Atoms and molecules have a range of discrete energy levels corresponding to different electronic, vibrational or rotational states. The interaction between atoms and electromagnetic radiation is characterized by the absorption and emission of photons, such that the energy of the photons exactly matches an energy level difference in the atom. Since the energy of a photon is proportional to the frequency, the different forms of spectroscopy are often distinguished on the basis of the frequencies involved. For instance, absorption and emission between electronic states of the outer electrons typically require frequencies in the ultraviolet (UV) range, hence giving rise to UV spectroscopy. Molecular vibrational modes are characterized by frequencies just below visible red light and are thus studied with infrared (IR) spectroscopy. Nuclear magnetic resonance (NMR) spectroscopy uses radiofrequencies, which are typically in the range of 10–800 MHz.

NMR is the study of the magnetic properties (and energies) of nuclei. The absorption and emission of electromagnetic radiation can be observed when the nuclei are placed in a (strong) external magnetic field. Purcell, Torrey and Pound [1] at MIT, Cambridge and Bloch, Hansen and Packard [2] at Stanford simultaneously, but independently discovered NMR in 1946. In 1952 Bloch and Purcell shared the Nobel Prize for physics in recognition of their pioneering achievements [1–4]. At this stage, NMR was purely an experiment for physicists to determine the nuclear magnetic moments of nuclei. NMR could only develop into one of the most versatile forms of spectroscopy after the discovery that nuclei within the same molecule absorb energy at different resonance frequencies. These so-called chemical shift effects, which are directly related to the chemical environment of the nuclei, were first observed in 1950 by Proctor and Yu [5], and independently by Dickinson [6].

In the first two decades, NMR spectra were recorded in a continuous wave mode in which the magnetic field strength or the radiofrequency (RF) was swept through the spectral area of interest, whilst keeping the other fixed. In 1966, NMR was revolutionized by Ernst and Anderson [7] who introduced pulsed NMR in combination with Fourier transformation. Pulsed or Fourier transform NMR is at the heart of all modern NMR experiments.

The induced energy level difference of nuclei in an external magnetic field is very small when compared with the thermal energy, making it that the energy levels are almost equally populated. As a result the absorption of photons is very low, making NMR a very insensitive technique when compared with the other forms of spectroscopy. However, the low energy absorption makes NMR also a noninvasive and nondestructive technique, ideally suited for in vivo measurements. It is believed that, by observing the water signal from his own finger, Bloch was the first to use NMR on a living system. Soon after the discovery of NMR, others showed the utility of using NMR to study living objects. In 1950, Shaw and Elsken [8] used proton NMR to investigate the water content of vegetable material. Odebald and Lindstrom [9] obtained proton NMR signals from a number of mammalian preparations in 1955. Continued interest in defining and explaining the properties of water in biological tissues led to the promising report of Damadian in 1971 [10] that NMR properties (relaxation times) of malignant tumorous tissue significantly differs from normal tissue, suggesting that (proton) NMR may have diagnostic value. In the early 1970s, the first experiments of NMR spectroscopy on intact living tissues were reported. Moon and Richards [11] used P NMR on intact red blood cells and showed how the intracellular pH can be determined from chemical shift differences. In 1974, Hoult [12] reported the first study of P NMR to study intact, excised rat hind leg.