Royal Society of Chemistry Paramagnetism in Experimental Biomolecular NMR: Volume 16 (New Developments in NMR)

Paramagnetic NMR is a growing technique that represents an increasingly important tool for the investigation of biomolecules. This book presents an update and overview of the paramagnetic NMR phenomena and effects as well as guidelines for practical implementation of state-of-the-art experiments. All experiments are supported by a solid theoretical foundation. Areas mentioned are the development of solid state NMR, the use of paramagnetic tags providing information on the structure and mobility of the investigated systems, and dynamic nuclear polarization to increase sensitivity. Compiled by experts in the field, this book has international appeal for researchers as well as students interested in magnetic resonance and structural biology who require experimental support and accessible information. From the Back Cover Paramagnetic NMR is a growing technique that represents an increasingly important tool for the investigation of biomolecules. This book presents an update and overview of the paramagnetic NMR phenomena and effects as well as guidelines for practical implementation of state-of-the-art experiments. All experiments are supported by a solid theoretical foundation. Areas mentioned are the development of solid state NMR, the use of paramagnetic tags providing information on the structure and mobility of the investigated systems, and dynamic nuclear polarization to increase sensitivity. Compiled by experts in the field, this book has international appeal for researchers as well as students interested in magnetic resonance and structural biology who require experimental support and accessible information. Excerpt. © Reprinted by permission. All rights reserved. Paramagnetism in Experimental Biomolecular NMR By Claudio Luchinat, Giacomo Parigi, Enrico Ravera The Royal Society of Chemistry Copyright © 2018 The Royal Society of Chemistry All rights reserved. ISBN: 978-1-78801-086-3 Contents Chapter 1 NMR Consequences of the Nucleus–Electron Spin Interactions Giacomo Parigi and Claudio Luchinat, Chapter 2 Intrinsic and Extrinsic Paramagnetic Probes Christoph Nitsche and Gottfried Otting, Chapter 3 Structural and Dynamic Characterization of Protein Domains using Paramagnetic Data James H. Prestegard and Monique J. Rogals, Chapter 4 Treating Biomacromolecular Conformational Variability Witold Andralojc and Enrico Ravera, Chapter 5 Protein–Protein Interactions Marcellus Ubbink and Antonella Di Savino, Chapter 6 Solid-state NMR of Paramagnetic Proteins Andrea Bertarello and Guido Pintacuda, Chapter 7 Relaxometry and Contrast Agents Silvio Aime, Eliana Gianolio and Alessandra Viale, Chapter 8 Dynamic Nuclear Polarization Björn Corzilius, Chapter 9 Paramagnetic NMR in Drug Discovery Erhan C. Cetiner and Harald Schwalbe, Chapter 10 Small Paramagnetic Co-solute Molecules Tobias Madl and Frans A. A. Mulder, Subject Index, CHAPTER 1 NMR Consequences of the Nucleus–Electron Spin Interactions GIACOMO PARIGI AND CLAUDIO LUCHINAT 1.1 The Effect of Paramagnetism on NMR Spectra The presence of unpaired electrons in molecules makes them paramagnetic and largely affects their NMR spectra. The main effects related to the presence of a paramagnetic center, i.e., of atoms or ions with unpaired electrons, are (see Figure 1.1): (1) the NMR shifts are perturbed, so that the shifts measured for the paramagnetic molecule (δ) and for a diamagnetic analogue (δdia) (i.e., for the same molecule without the paramagnetic center or with the paramagnetic metal ion substituted by a diamagnetic one) differ. These differences are called hyperfine shifts (δhs): δ = δdia + δhs (1.1) (2) the nuclear relaxation rates of the paramagnetic molecule (R1 longitudinal; R2 transverse) are increased with respect to those of a diamagnetic analogue (Rdia1 and Rdia2). This difference is called paramagnetic relaxation enhancement (R1M and R2M): [MATHEMATICAL EXPRESSION OMITTED] (1.2) (3) the probabilities for the different orientations