Biological Magnetic Resonance: Volume 2

ISBN-13: 9781461565390 / Angielski / Miękka / 2012 / 351 str.

Lawrence J. Berliner

Opis

We are pleased to present this second volume of a series that has already received much interest. The application of magnetic resonance methods to the study of actual biological systems as contrasted to cell-free samples, although not entirely novel, as demonstrated by Civan and Shporer in Volume I, has taken on new dimensions with the use of phosphorus-31 and carbon-13 NMR in studying cells, tissues, and organelles. The applications of 31 P NMR to such systems is reviewed in this volume, while carbon-13 will be covered in a later one. The use of nitroxide spin labels has grown to the point where it now may be considered a common biological technique. The synthesis and applications of a new class of nitroxides is described in this volume. ESR spectroscopy of paramagnetic ions is a powerful approach to studying molecular and structural details, as the chapter by Boas, Pilbrow, and Smith on the ESR of copper in Volume 1 has shown. In this volume the ESR of molybdenum and iron is treated in a comparable fashion. In the first volume some aspects of 1 H NMR spectroscopy of certain classes of In this volume the high-resolu biological macromolecules were discussed.. tion multinuclear NMR spectra of peptides, including the physiologically significant peptide hormones, are reviewed."

Spis treści

1 Phosphorus NMR of Cells, Tissues, and Organelles.- 1. Introduction.- 2. Methods.- 2.1. Oxygenation and Perfusion.- 2.2. 31P NMR for pH Measurements.- 2.3. Saturation Transfer.- 3. Applications.- 3.1. Cellular Suspensions.- 3.2. Muscle.- 3.3. Brain, Liver, and Kidney.- 3.4. Other Systems.- 4. Summary.- References.- 2 EPR of Molybdenum-Containing Enzymes.- 1. Introduction.- 2. Enzymes to be Considered and Their General Properties.- 3. Relationship of Molybdenum to Other Constituents in the Enzymes and its Interactions with These Constituents.- 4. Multiple Species of Mo(V) and the Estimation of EPR Parameters.- 5. General Survey of the EPR Parameters of Mo(V) Species in Enzymes.- 6. Discussion of the Parameters.- 7. Conditions Governing Generation and Interconversion of the Signals.- 7.1. Introduction and Nomenclature; Functional and Desulfo Xanthine Oxidase.- 7.2. Oxidation-Reduction Potentials Associated with Molybdenum in Enzymes.- 7.3. Binding of Anions, Substrates, and Products.- 7.4. Equilibrium between EPR-Detectable Protonated and Deprotonated Forms.- 7.5. Rates of Exchange of the Interacting Protons; Direct » Hydrogen Transfer from the Substrate.- 7.6. Very Rapid Intermediate.- 7.7. Signals from Reactions of Alcohols with Xanthine Oxidases and Dehydrogenases.- 8. Conclusions on Structures and Enzymatic Mechanisms.- 8.1. Structures.- 8.2. Enzymatic Mechanisms.- References.- 3 ESR of Iron Proteins.- 1. Introduction.- 2. Electron Spin Resonance Caused by Iron Proteins.- 2.1. Introduction.- 2.2. Paramagnetic States of Fe Proteins.- 3. Heme Proteins.- 3.1. Hemoglobin.- 3.2. Methemoglobin.- 3.3. Hemichromes.- 3.4. Nitrosylhemoglobins.- 3.5. Myoglobin.- 3.6. Leghemoglobin.- 3.7. Cytochrome c Oxidase.- 3.8. Cytochromes.- 3.9. Cytochromes P450.- 3.10. L-Tryptophan-2,3-dioxygenase.- 3.11. Cytochrome c Peroxidase.- 3.12. Horseradish Peroxidase.- 3.13. Chloroperoxidase.- 3.14. Myeloperoxidase.- 3.15. Catalase.- 3.16. Flavocytochrome b2.- 3.17. Sulfite Oxidase.- 4. Nonheme Proteins.- 4.1. Hemerythrin.- 4.2. Iron Dismutase.- 4.3. Ferritin and Hemosiderin.- 4.4. Transferrins.- 4.5. The Iron-Sulfur Proteins.- 4.6. Protocatechuate 3,4-Dioxygenäse.- 4.7. Lipoxygenase.- 4.8. Ribonucleotide Reductase.- 4.9. Uterine Purple Phosphatase.- References.- 4 Stable Imidazoline Nitroxides.- 1. Introduction.- 2. Synthesis of Imidazoline and Imidazolidine Nitroxides.- 2.1. Synthesis of 3-Imidazoline-3-oxide Derivatives.- 2.2. Synthesis of 2,2,4,5,5-Pentasubstituted-3-imidazolines.- 2.3. Synthesis of Imidazolidine Derivatives.- 2.4. Synthesis of 4-Oxoimidazolidine Derivatives.- 3. Properties of Imidazoline Nitroxides and 1 -Hydroxy-3-imidazolines.- 3.1. Stability of Imidazoline Nitroxides in Acid Media.- 3.2. Quaternary Immonium Salts of Imidazoline Nitroxides.- 3.3. Interaction of Imidazoline Derivatives with Nucleophilic Reagents.- 3.4. Interaction of Imidazoline Derivatives with Electrophilic Reagents.- 3.5. Interaction of 4-Haloalkyl-3-imidazoline-3-oxides with Nucleophilic Reagents.- 3.6. Interaction of 4-Dihaloalkyl-3-imidazoline-3-oxides with Nucleophilic Reagents.- 3.7. Properties of Derivatives of Imidazoline Aldehydes and Ketones.- 3.8. Properties of Derivatives of Imidazoline Carboxylic Acids.- 3.9. Imidazoline Nitroxides as Chelating Reagents.- 4. Spectra of Imidazoline Nitroxides.- 4.1. UV Spectra and Visible Spectra.- 4.2. Vibrational Spectra.- 4.3. Mass Spectra.- 5. Magnetic Properties of Imidazoline Nitroxides.- 5.1. NMR Spectra. Regularities of Long-Range Hyperfine Interactions.- 5.2. Complexes of Transition Metals with Imidazoline Nitroxides.- 6. Applications in Analytical and Structural Chemistry.- 7. Imidazoline Spin Labels in Biology.- 8. Syntheses of Some Imidazoline Nitroxides and Important Intermediates.- References.- 5 The Multinuclear NMR Approach to Peptides: Structures, Conformations, and Dynamics.- 1. A Multinuclear Approach.- 1.1. Introduction.- 1.2. Nuclei Studied.- 2. Chemical Shifts.- 2.1. Magnetic Anisotropy.- 2.2. Chemical Exchange.- 2.3. Assignment Methods.- 2.4. Paramagnetic Reagents.- 2.5. Structural and Conformational Sensitivity of Chemical Shifts.- 3. Spin-Spin Coupling Constants.- 3.1. Proton-Proton Couplings.- 3.2. Carbon-Proton Couplings.- 3.3. Carbon-Carbon Couplings.- 3.4. Nitrogen-Proton Couplings.- 3.5. Nitrogen-Carbon Couplings.- 4. Relaxation Times.- 4.1. Measurement of Relaxation Times.- 4.2. Mechanisms of Relaxation.- 5. Concluding Remarks.- References.

O autorze

Dr. Lawrence J. Berliner is currently Professor and Chair of the Department of Chemistry and Biochemistry at the University of Denver after retiring from Ohio State University, where he spent a 32-year career in the area of biological magnetic resonance (EPR and NMR).