Phosphorus-31 NMR. Pnnciples and Applications. Edited by David G. Gorenstein

Transcription

1 Phosphorus-31 NMR Pnnciples and Applications Edited by Department of Chemistry University of Illinois at Chicago Chicago, ACADEMIC PRESS, INC. Harcourt Brace Jovanovich, Publishers Orlando San Diego New York Austin Boston London Sydney Tokyo Toronto

2 Contents Contributors Preface xiii xi Introduction Text 1 References 3 PART 1. Phosphorus-31 Chemical Shifts and Spin-Spin Coupling Constants: Principles and Empirical Observations 1. Phosphorus-31 Chemical Shifts: Principles and Empirical Observations I. Introduction and Basic Principles 7 II. Applications of 3, P Chemical-Shift Theory and Empirical Observations 9 References Phosphorus-31 Spin-Spin Coupling Constants: Principles and Applications I. Introduction 37 II. Directly Bonded Coupling Constants: '7 PX 38 III. Two-Bond Coupling Constants: 2 J PX 42 IV. Three-Bond Coupling Constants: 3 J PX 43 References 51 v

3 PART 2. Theory and Applications of Phosphorus-31 NMR to Biochemistry 3. Phosphoras-31 NMR of Enzyme Complexes B. D. Nageswara Rao I. Introduction 57 II. Theoretical and Experimental Considerations 59 III. Experimental Studies of Specific Enzyme Systems 69 IV. Computer Calculation of NMR Line Shapes under the Influence of Exchange 96 V. Conclusion 100 References P-NMR Studies of Phosphoproteins Hans J. Vogel I. Introduction 105 II. Classification of Phosphoproteins 106 III. Theoretical and Experimental Considerations 113 IV. NMR Studies 123 V. Conclusions 144 References Paramagnetic Probes of Enzyme Complexes with Phosphorus-Containing Compounds Joseph J. Villafranca I. Introduction 155 II. General Considerations 156 III. Properties of Cr(III)- and Co(III)-Nucleotide Complexes 157 IV. Studies with Co(III)-Nucleotide Complexes 160 V. Studies with Cr(III)-Nucleotide Complexes 166 VI. Studies with Cr(III)- and Co(III)-Pyrophosphate Complexes References Use of Chiral Thiophosphates and the Stereochemistry of Enzymatic Phosphoryl Transfer Ming-Daw Tsai I. Stereochemical Problems Studied with Phosphorothioates 175 II Isotope Shifts in 31 P NMR 178 III Quadrupolar Effects in 31 P NMR 181 IV. Prochiral Centers: 31 P NMR 185 V. Pro-Prochiral Centers: 31 P( 18 0) NMR or 31 P( n O) NMR 187 VI. Pro-Pro-Prochiral Centers: 31 P( 18 0) NMR and 31 P( 17 0) NMR References 196

4 7. Use of Chiral [ 16 0, 17 0, 18 0]Phosphate Esters to Determine the Stereochemical Course of Enzymatic Phosphoryl Transfer Reactions John A. Gerlt I. Introduction 199 II. Syntheses of Oxygen Chiral Phosphate Esters 201 III. Configurational Analyses of Oxygen Chiral Phosphate Esters 210 IV. Selected Examples 220 V. Summary 230 References DNA and RNA Conformations Chi-Wan Chen and Jack S. Cohen I. Introduction 233 II. Helix-Coil Transitions 234 III. Sequence Dependence of Double-Stranded DNA Conformations 239 IV. Conformational Transitions of Double-Stranded DNA 253 V. Dynamic Behavior of RNA and DNA 255 VI. Nucleosomal DNA 256 VII. Biological and Genetic Significance 259 References High-Resolution 31 P-NMR Spectroscopy of Transfer Ribonucleic Acids I. Introduction 265 II. Spectral Comparison of Different Acceptor trnas 268 III. Mg 2+ Dependence of 31 P Spectra of trna phe 276 IV. Mn 2+ Effects on 31 P Spectra of trna* 280 V. Assignment of 31 P Signals 281 VI. Conformational Transitions 287 VII. Spermine Effects 291 VIII. 31 P NMR of Yeast trna"" E. coli trna* Complex: Spectral Changes 292 IX. Conclusions 294 References Phosphorus-31 NMR of Drug-Nucleic Acid Complexes and Evelyn M. Goldfield I. Introduction 299 II. Drug-Double-Helical Nucleic Acid Complexes: Intercalation 300 III. Electrostatic Mode of Interaction 310 IV. trn A-Ethidium 3 ' P Spectra 311 References 315

5 VIII Contents 11. Phosphorus Relaxation Methods: Conformation and Dynamics of Nucleic Acids and Phosphoproteins Phillip A. Hart I. Introduction 317 II. General Considerations 319 III. The Phosphorus-Proton Nuclear Overhauser Effect 322 IV. Phosphorus Relaxation Times 328 V. Summary 344 References Relaxation Behavior of Nucleic Acids: Dynamics and Structure Thomas L. James I. Introduction 349 II. Theory 350 III. Structure and Possible Molecular Motions in Nucleic Acids IV. Considerations for Nucleic Acid Dynamics and Structure V. Relaxation Studies of Nucleic Acids 377 References Solid-State Phosphorus-31 NMR: Theory and Application to Nucleic Acids Heisaburo Shindo I. Introduction 401 II. Basic Concepts of Solid-State 3I P NMR 402 III. Studies of Oriented DNA Fibers 408 IV. Studies of DNA Complexes 418 V. Concluding Remarks 421 References Phosphorus-31 NMR of Phospholipids in Micelles Edward A. Dennis and Andreas Plückthun I. Introduction and Perspective 423 II. Spectral Characteristics of Phospholipids in Mixed Micelles with Detergents 425 III. 7"i, Nuclear Overhauser Effect, and Quantitative Analysis 431 IV. Solubilization of Phospholipids by Detergents 433 V. Critical Micelle Concentration Determinations and Micellization of Monomeric Phospholipids by Detergents 435 VI. Lysophospholipids: Acyl and Phosphoryl Migration 438 VII. Phospholipases: Specificity and Kinetics 442 References 444

6 Contents IX 15. Phosphorus-31 NMR of Phospholipids in Membranes lan C. P. Smith and Irena H. Ekiel I. Properties of Membranes 447 II. 3I P-NMR Spectra of Ordered Systems 449 III. Obtaining 31 P-NMR Spectra 457 IV. Applications to Biomembranes 461 V. Conclusion 472 References 472 PART 3. Application to Biology and Medicine: Future Directions 16. Two-Dimensional Phosphorus-31 NMR William C. Hutton I. Introduction 479 II. General Principles of Two-Dimensional NMR: The Homonuclear, J-Correlated Experiment 484 III. Applications of Two-Dimensional Spectroscopy to 3I P NMR 492 IV. Concluding Remarks 509 References Identification of Diseased States by Phosphorus-31 NMR Michael Bäräny and Thomas Glonek I. Introduction 512 II. Skeletal Muscle 513 III. Heart 530 IV. Kidney 533 V. Brain 534 VI. Eye 537 VII. Mammalian Fluids 540 VIII. Perspectives 543 References 544 PART 4. Selected Data 18. Appendixes: Selected Compilation of 31 P-NMR Data and Dinesh O. Shah Appendix I. Doubly Connected Phosphorus (PC) 550 Appendix II. Triply Connected Phosphorus (PO 551 Appendix III. Quadruply Connected Phosphorus (^PC) 563

7 X Contents Appendix IV. Quintuply Connected Phosphorus (^PC) 586 Appendix V. Sextuply Connected Phosphorus (^P^r) 588 References 589 Index 593