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Contents of Previous Volumes VOLUME 1 Chapter 1 NMR of Sodium-23 and Potassium-39 in Biological Systems Mortimer M. Civan and Mordechai Shporer Chapter 2 High-Resolution NMR Studies of Histones C. Crane-Robinson Chapter 3 PMR Studies of Secondary and Tertiary Structure of Transfer RNA in Solution Philip H. Bolton and David R. Kearns Chapter 4 Fluorine Magnetic Resonance in Biochemistry J. T. Gerig Chapter 5 ESR of Free Radicals in Enzymatic Systems Dale E. Edmondson 385

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Contents of Previous Volumes

VOLUME 1

Chapter 1

NMR of Sodium-23 and Potassium-39 in Biological Systems

Mortimer M. Civan and Mordechai Shporer

Chapter 2

High-Resolution NMR Studies of Histones

C. Crane-Robinson

Chapter 3

PMR Studies of Secondary and Tertiary Structure of Transfer RNA in Solution

Philip H. Bolton and David R. Kearns

Chapter 4

Fluorine Magnetic Resonance in Biochemistry

J. T. Gerig

Chapter 5

ESR of Free Radicals in Enzymatic Systems

Dale E. Edmondson

385

386 Contents of Previous Volumes

Chapter 6

Paramagnetic Intermediates in Photosynthetic Systems

Joseph T. Warden

Chapter 7

ESR of Copper in Biological Systems

John F. Boas, John R. Pilbrow, and Thomas D. Smith

Index

VOLUME 2

Chapter 1

Phosphorus NMR of Cells, Tissues, and Organelles

Donald P. Hollis

Chapter 2

EPR of Molybdenum-Containing Enzymes

Robert C. Bray

Chapter 3

ESR of Iron Proteins

Thomas D. Smith and John R. Pilbrow

Chapter 4

Stable Imidazoline Nitroxides

Leonid B. Volodarsky, Igor A. Grigor' ev, and Renad Z. Sagdeev

Chapter 5

The Multinuclear NMR Approach to Peptides: Structures, Conformation, and Dynamics

Roxanne Deslauriers and Ian C. P. Smith

Index

Contents of Previous Volumes

VOLUME 3

Chapter 1

Multiple Irradiation IH NMR Experiments with Hemoproteins

Regula M. Keller and Kurt Wuthrich

Chapter 2

Vanadyl(IV) EPR Spin Probes: Inorganic and Biochemical Aspects

N. Dennis Chasteen

Chapter 3

ESR Studies of Calcium- and Protein-Induced Photon Separations in Phosphatidylserine-Phosphatidylcholine Mixed Membranes

Shun-ichi Ohnishi and Satoru Tokutomi

Chapter 4

EPR Crystallography of Metalloproteins and Spin-Labeled Enzymes

James C. W. Chien and L. Charles Dickinson

Chapter 5

Electron Spin Echo Spectroscopy and the Study of Metalloproteins

W. B. Mims and J. Peisach

Index

VOLUME 4

Chapter 1

Spin Labeling in Disease

D. Allan Butterfield

Chapter 2

Principles and Applications of 113Cd NMR to Biological Systems

Ian M. Armitage and James D. Otvos

387

388

Chapter 3

Photo-CIDNP Studies of Proteins

Robert Kaptein

Chapter 4

Contents of Previous Volumes

Application of Ring Current Calculations to the Proton NMR of Proteins and Transfer RNA

Stephen J. Perkins

Index

VOLUME 5

Chapter 1

CMR as a Probe for Metabolic Pathways in Vivo

R. L. Baxter, N. E. Mackenzie, and A. 1. Scott

Chapter 2

Nitrogen-IS NMR in Biological Systems

Felix Blomberg and Heinz Ruterjans

Chapter 3

Phosphorus-31 Nuclear Magnetic Resonance Investigations of Enzyme Systems

B. D. Nageswara Rao

Chapter 4

NMR Methods Involving Oxygen Isotopes in Biophosphates

Ming-Daw Tsai and Larol Bruzik

Chapter 5

ESR and NMR Studies of Lipid-Protein Interactions in Membranes

Philippe F. Devaux

Index

Contents of Previous Volumes

VOLUME 6

Chapter 1

Two-Dimensional Spectroscopy as a Conformational Probe of Cellular Phosphates

Philip H. Bolton

Chapter 2

Lanthanide Complexes of Peptides and Proteins

Robert E. Lenkinski

Chapter 3

EPR of Mn(II) Complexes with Enzymes and Other Proteins

George H. Reed and George D. Markham

Chapter 4

Biological Applications of Time Domain ESR

Hans Thomann, Larry R. Dalton, and Lauraine A. Dalton

Chapter 5

Techniques, Theory, and Biological Applications of Optically Detected Magnetic Resonance (ODMR)

August H. Maki

Index

VOLUME 7

Chapter 1

NMR Spectroscopy of the Intact Heart

Gabriel A. Elgavish

Chapter 2

NMR Methods for Studying Enzyme Kinetics in Cells and Tissue

K. M. Brindle, 1. D. Campbell, and R. 1. Simpson

389

390 Contents of Previous Volnmes

Chapter 3

Endor Spectroscopy in Photobiology and Biochemistry

Klaus Mobius and Wolfgang Lubitz

Chapter 4

NMR Studies of Calcium-Binding Proteins

Hans 1. Vogel and Sture Forsen

Index

VOLUME 8

Chapter 1

Calculating Slow Motional Magnetic Resonance Spectra: A User's Guide

David 1. Schneider and Jack H. Freed

Chapter 2

Inhomogeneously Broadened Spin-Label Spectra

Barney Bales

Chapter 3

Saturation Transfer Spectroscopy of Spin Labels: Techniques and Interpretation of Spectra

M. A. Hemminga and P. A. de Jager

Chapter 4

Nitrogen-IS and Deuterium Substituted Spin Labels for Studies of Very Slow Rotational Motion

Albert H. Beth and Bruce H. Robinson

Chapter 5

Experimental Methods in Spin-Label Spectral Analysis

Derek Marsh

Contents of Previous Volumes

Chapter 6

Electron-Electron Double Resonance

James S. Hyde and Jim B. Feix

Chapter 7

Resolved Electron-Electron Spin-Spin Splittings in EPR Spectra

Gareth R. Eaton and Sandra S. Eaton

Chapter 8

Spin-Label Oximetry

James S. Hyde and Witold K. Subczynski

Chapter 9

391

Chemistry of Spin-Labeled Amino Acids and Peptides: Some New Mono- and Bifunctionalized Nitroxide Free Radicals

Kalman Hideg and Olga H. Hankovsky

Chapter 10

Nitroxide Radical Adducts in Biology: Chemistry, Applications, and Pitfalls

Carolyn Mottley and Ronald P. Mason

Chapter 11

Advantages of 15N and Deuterium Spin Probes for Biomedical Electron Paramagnetic Resonance Investigations

Jane H. Park and Wolfgang E. Trommer

Chapter 12

Magnetic Resonance Study of the Combining Site Structure of a Monoclonal Anti-Spin-Label Antibody

Jacob Anglister

392 Contents of Previous Volumes

Appendix

Approaches to the Chemical Synthesis of 15N and Deuterium Substituted Spin Labels

Jane H. Park and Wolfgang E. Trommer

Index

VOLUME 9

Chapter 1

Phosphorus NMR of Membranes

Philip L. Yeagle

Chapter 2

Investigation of Ribosomal 5S Ribonucleic Acid Solution Structure and Dynamics by Means of High-Resolution Nuclear Magnetic Resonance Spectroscopy

Alan G. Marshall and Jiejun Wu

Chapter 3

Structure Determination via Complete Relaxation Matrix Analysis (CORMA) of Two-Dimensional Nuclear Overhauser Effect Spectra: DNA Fragments

Brandan A. Borgias and Thomas L. James

Chapter 4

Methods of Proton Resonance Assignment for Proteins

Andrew D. Robertson and John L. Markley

Chapter 5

Solid-State NMR Spectroscopy of Proteins

Stanley 1. Opella

Contents of Previous Volumes 393

Chapter 6

Methods for Suppression of the H20 Signal in Proton Ff INMR Spectroscopy: A Review

Joseph E. Meier and Alan G. Marshall

Index

VOLUME 10

Chapter 1

High-Resolution IH-Nuclear Magnetic Resonance Spectroscopy of Oligosaccharide-Alditols Released from Mucin-Type O-Glycoproteins

Johannis P. Kamerling and Johannes F. G. Vliegenthart

Chapter 2

NMR Studies of Nucleic Acids and Their Complexes

David E. Wemmer

Index

VOLUME 11

Chapter 1

Localization in Clinical NMR Spectroscopy

Lizann Bolinger and Robert E. Lenkinski

Chapter 2

Off-Resonance Rotating Frame Spin-Lattice Relaxation: Theory, and in Vivo MRS and MRI Applications

Thomas Schleich, G. Herbert Caines, and Jan M. Rydzewski

Chapter 3

NMR Methods in Studies of Brain Ischemia

Lee-Hong Chang and Thomas L. James

394 Contents of Previous Volumes

Chapter 4

Shift-Reagent-Aided 23Na NMR Spectroscopy in Cellular, Tissue, and Whole-Organ Systems

Sandra K. Miller and Gabriel A. Elgavish

Chapter 5

In Vivo 19F NMR

Barry S. Selinski and C. Tyler Burt

Chapter 6

In Vivo 2H NMR Studies of Cellular Metabolism

Robert E. London

Chapter 7

Some Applications of ESR to in Vivo Animal Studies and EPR Imaging

Lawrence J. Berliner and Hirotada Fujii

Index

VOLUME 12

Chapter 1

NMR Methodology for Paramagnetic Proteins

Gerd N. La Mar and Jeffrey S. de Ropp

Chapter 2

Nuclear Relaxation in Paramagnetic Metalloproteins

Lucia Banci

Chapter 3

Paramagnetic Relaxation of Water Protons

Cathy Coolbaugh Lester and Robert G. Bryant

Contents of Previous Volumes

Chapter 4

Proton NMR Spectroscopy of Model Hemes

F. Ann Walker and Ursula Simonis

Chapter 5

Proton NMR Studies of Selected Paramagnetic Heme Proteins

J. D. Satterlee, S. Alam, Q. Yi, J. E. Erman, I. Constantinidis, D. J. Russell, and S. J. Moench

Chapter 6

395

Heteronuclear Magnetic Resonance: Applications to Biological and Related Paramagnetic Molecules

Joel Mispelter, Michel Momenteau, and Jean-Marc Lhoste

Chapter 7

NMR of Polymetallic Systems in Proteins

Claudio Luchinat and Stefano Ciurli

Index

Index

Aconitase, 72, 183-195 Actin, 329-330, 333-334 Active sites, 275 Albumin (BSA), 126, 128-129, 134 Amide nitrogen, 318 Anisotropic hyperfine interaction, 283 Axial symmetry, 17, 36, 224 Azide substituted SOD, 246 Azurin, 129-130, 145, 165-171,278

Benzosemiquinone anion radical, 255 Bleomycin, 136 Blind spots, 289, 296-297 Blue copper proteins, 164-171 Bovine SOD, 247

Caged ATP, 326-329 Caged compounds, 325-329 Calcium ATPase, 340-347 Cancellation effects, 311, 313 Cobalt-myoglobin, 241 Cobalt-porphyrin complexes, 237 Cobaltous hemoglobin, 237 Coherence transfer, 286, 307 Combination frequencies, 313-314 Continuous wave, 277, 305 Continuous-wave (CW) ENDOR, 160-162 Contractile proteins, 329-339 Copper complexes, blue, 105-107, 121,

129-131,277-278 Copper complexes, square planar, 105-107,

113, 125-126, 129-131, 139 Copper ENDOR, 305, 307-309 Copper tetraimidazole complex, 243-246 Copper thiosemicarbazones, 134-136

Copper (11) bis(diisopropylsalicilate), 137 Correlation times, 109-110, 112, 132-133,

136 Cross-relaxation, 283, 306 Crystal field, 11 Cyanide binding, 248 Cytochrome c oxidase, 130-132 Cyotchrome c peroxidase, 195-196 Cytochrome P-450, 80

Deoxyhemoglobin models, 239 Deuterium ENDOR, 175, 190-193 Deuterium exchange, 174 Di-p-anisyl-nitroxide (DANO), 263 Di-I-butyl nitroxide, 355-358 Dioxygen adducts, 84 Dioxygen ligand, 240 Distant ENDOR, 154 Distributed spin-density, 223 Dithiocarbamate, 132 DMPOX, 370 Doppler shift, second order, 61 Dynamic line-shape model, 76 Dynamic shift, 110, 112, 114, 132, 147

Effective g-value, 4 Electron spin echo (ESE) ENDOR, 162-164 Electron spin echo envelope modulation

(ESEEM), 243 EMR of crystals, 37 ENDOR amplitudes, 302-305,309-310,313 ENDOR analysis, 199-214 ENDOR at Wband, 257 ENDOR enhancement, 299, 306 ENDOR experiment, 152, 154-164

397

398

ENDOR frequencies, theory, 200-208 ENDOR frequency, 276, 281-284 ENDOR spectra, simulation of, 209-213 Ene-addition, 370 Energy levels, 12,27 EPR selection, 153 EPR spectrometer at Wband, 260 EPR, theory, 199-200 ESEEM frequency, 276, 302 Excitation bandwidth, 292-295, 302-305,

310

Fast fluctuation limit, 68 Fenton reaction, 356, 374 Ferric ion, 370 Ferryl hemeproteins, 75, 78 Field-swept linewidth, 28 Fine structure, 7 Flash photolysis, 326-327, 333, 336-338,

342, 344 Fluidity of lipids, 341 Four-level model, II Frequency-swept linewidth, 28

Galactose oxidase, 197-198 Gas chromatography, 363 Glutathione peroxidase, 373

Hemeproteins, I, 75-84 Hemoglobin, 35 Hemoglobin, structure-function relationship,

229 High-spin ferric, I Hole burning, 291-292, 316 Horseradish peroxidase, 76 Horseradish peroxidase, compound I, 78 HPLC, 359, 363, 370 Hydrogen bonds, 175 Hydrogenase, 277, 280, 298, 311 Hydroxylamine, 357, 365, 370, 376, 377 Hyperfine contrast selectivity, 294, 296, 307,

310,315 Hyperfine enhancement, 290, 296, 298-302,

317 Hyperfine interaction, 275, 276, 278 Hyperfine selective ENDOR, 164,316-318 Hyperfine tensor, 159

Imidazole nitrogen, 295, 307, 317 Indanedione spin label, 328, 342 Indirect detection, 290

Index

Inhomogeneous broadening, 275, 276, 311 Iodoacetamide spin label, 328, 334-336,

338-339, 343-347 Iron chelation, 367, 370, 371, 376 Iron, 2 Iron, adventitious, 372, 374, 375 Iron-57 electric quadrupole interaction, 62 Iron-57 ENDOR, 185-1897 Iron-57 hyperfine interactions, 61 Iron-57 isomer shift, 62 Iron-57 magnetic dipole interaction, 62 Iron-57-radical coupling, 76, 78, 85, 96 Iron-containing proteins, I Iron-hydrogenase, 171-172 Iron-sulfur clusters, 171-195 Iron-sulfur enzyme, 277, 311 Iron-sulfur proteins, 67-74 Isopenicillin N synthase, 90-92 Isotopic exchange, 64, 72 Isotopically labeled proteins, 176-182 Isotropic hyperfine interaction, 281

L-band EPR, 48 Laccase, 129-131, 134, 165-170 Lactoferrin, 37 Laser photolysis: see Flash photolysis Line broadening in EPR, 255 Line shape, 28 Lipid spin labels, 328, 341 Lipoxygenase, 4, 50 Local ENDOR, 155-160 Longitudinal magnetization, 289-290 Longitudinal relaxation from spin-state

fluctuations, 78 Loop-gap resonators, 117, 132

Maleimide spin label, 328, 332-334, 336-338, 342-343

Mass spectrometry, 359, 363, 370 Matrix ENDOR, 155 Metal-ion ligand complex, 221 Metalloenzyme, 275, 276 Metalloenzyme active site, 153 Metalloprotein, 275, 276 Methemoglobin, I Metmyoglobin, 1,35 Mixing pulse, 289 Molecular dynamics, 323 Motional resolution, 328, 334-336, 338-339,

343-347 Multifrequency EPR, 107

Index

Muscle contraction, 329-339 Myeloperoxidase, 373 Myoglobin, 183 Myosin, 329-339

Nafion/Cu, 139 Nitrogen superhyperfine structure, 105, 127 Nitrogen-14 ENDOR, 182,228 Nitrogen-14 hyperfine coupling, 240 Nitrogen-14 hyperfine coupling constants,

167 Nitrogen-14 quadrupole tensors, 182 Nitrogen-I 5 hyperfine tensors, 180-182 Nitrous oxide reductase, 131-132 Nitroxide radicals, 258 NO-heme complexes, 230 Nuclear hyperfine interaction, 156 Nuclear modulation effect, 279, 302, 304,

311-314 Nuclear quadrupole frequencies, 284, 311 Nuclear quadrupole splitting, 284 Nuclear spin alignment, 289 Nutation angie, 289, 298-301, 310

Orientation selection, 159 Orientation selectivity, 285, 303, 312-313 Orientation-dependent spectra, 2 Orientational resolution, 328, 336-338 Oxy-complexes, 240 Oxygen-17 ENDOR, 190-194 Oxygen-bridged dinuclear clusters, 92-98

Partial excitation effects, 303-304 Passage effects, 309-310 Peroxide radicals, 258 Phenylalanine hydrolase, 4, 45 Phenylalanine hydroxylase, 119-120 Phorbol myristate acetate, 373, 374, 377 Photosynthesis reaction centers, 85-88, 266 Photosystem II, 196-197 Phthalate dioxygenase, 176-183 Phyllosemiquinone anion radical, 264 Plastocyanin, 165-170 Polarization displacement, 293, 296 Polarization transfer, 162, 283, 286, 299, 306 POSHE,164 Power broadening, 286, 287, 307, 311 Preparation pulse, 287-288 Protein crystals, I Protocatechuate dixoygenase, 83-90 Proton ENDOR, 222

Proton hyperfine coupling constants, 167 Pulse periods, 287 Purple acid phosphatase, 93-96 Putidaredoxin, 70

Q-band ENDOR, 157, 165-168 Quadrupole coupling, 157

Rabi oscillations, 299-301 Rapid passage, 52 Recoilless fraction, 60 Relaxation rates, 277, 305, 306, 309 Rhombic coordinate system, 7 Rhombic distortion, 10

399

Rhombic symmetry, 19,38,225 Ribonucleotide reductase, 96-98, 196-197 Rieske iron-sulfur centers, 176-183 Rubredoxin, 68

Sband,48, 125-126, 128-129, 131-132, 134, 136-138, 146

Saturation hole, 292-293, 296, 310, 316 Saturation transfer, 328, 332-334, 342-343 Second harmonic, 52 Second-order shifts, 109-110, 132, 147 Selection rules, 281-282 Selective detection, 290 Selective excitation, 284, 288, 291, 306, 309 Self-ENDOR, 164 Semiforbidden EPR transitions, 276, 302-

305,319 Sensitivity analysis, 122-123 Signal averaging, 119 Single-crystal EMR, 2 Site specificity, 153 SOD, structure function relationship, 242 Solvent effect, 363 Spectral diffusion, 292, 309-310 Spin-echo, 278-280 Spin Hamiltonian, 6, 63, 220 Spin Hamiltonian, diagonalization, 66 Spin Hamiltonian, limit of applicability, 88 Spin labels, 324, 328, 332-347 Spin-orbit interaction, 8 Spin-spin interactions, 64 Spin-state fluctuations, 61 Spin-trap adduct quantitation, 364 Spin-trap extraction, 356, 357, 363, 364 Spin-trap radical adducts

alkoxyl, 368 CCl., 356, 363

400

Spin-trap radical adducts (Cont.) CCI)02' , 356, 365 cumene hydroperoxide, 358 ethanol, 366, 371, 375 linoleic acid, 367 lipoprotein, 366 nitric oxides, 360 paraquat, 367 peroxyl, 364, 368 phenelzine, 366 procarbazine, 366 sulfur trioxide anion, 361 t-butyl hydroperoxide, 357, 359

Spin-trap systemic effects anoxia, 368 cardiovascular, 358, 365, 366 cerebral ischemia, 365 ischemia-reperfusion, 378 vasodilation, 368

Stellacyanin, 165-169,277-278,294,297, 299,304,307-308,317,319

Stochastic Liouville equation, 112 Strong coupling limit, 65 Sublevel free induction, 311 Sublevel polarization, 281, 288-289, 306 Subspectra, 318-320

Substrate binding, 192-194 Sulfur-33 ENDOR, 187-190 Superoxide dismutase (SOD), 242

t-butyl hydroaminoxyl, 365 t-butyl hydronitroxide, 375 Tertiary structural transition, 235 Tetragonal distortion, 10

Index

Thiolate methylene protons, 295-296, 301, 304, 307

Time-resolved EPR: see Transient EPR Transferrin, 4, 37,126 Transient ENDOR, 161 Transient EPR, 323-351 Transient nutations, 300-301 Transition dipole, 16 Transition probability, 16,27 Two-level systems, 288-289 Tyrosine radicals, 196-198

W-band EPR, 255

X-band ENDOR, 157 X-ray structure, 6

Zero-field limit, 12, 16 Zymosan,373,377