| | Contents | |
| | | |
| |
| | Preface | v |
| | Chapter 1
The NMR Spectrometer | 1 |
| 1. | Components of an NMR Spectrometer | 1 |
| 1.1. | The Magnet | 1 |
| 1.1.2 | The Spectrometer Cabinet | 2 |
| 1.1.3 | The Computer | 3 |
| 1.1.4 | Maintenance | 3 |
| 1.2 | Tuning a Probe-Head | 3 |
| 1.3 | The Lock Channel | 4 |
| 1.4 | The Art of Shimming | 6 |
| 1.4 | The Shim Gradients | 6 |
| 1.4.2 | The Shimming Procedure | 8 |
| 1.4.3 | Gradient Shimming | 11 |
| | Chapter 2
Determination of Pulse-Duration | 14 |
| Exp. 2.1 | Determination of the 90° 1H Transmitter Pulse-Duration | 15 |
| Exp. 2.2 | Determination of the 90° 13C Transmitter Pulse-Duration | 18 |
| Exp. 2.3 | Determination of the 90° 1H Decoupler Pulse-Duration | 21 |
| Exp. 2.4 | The 90° 1H Pulse with Inverse Spectrometer Configuration | 24 |
| Exp. 2.5 | The 90° 13C Decoupler Pulse with Inverse Configuration | 27 |
| Exp. 2.6 | Composite Pulses | 30 |
| Exp. 2.7 | Radiation Damping | 33 |
| Exp. 2.8 | Pulse and Receiver Phases | 36 |
| Exp. 2.9 | Determination of Radiofrequency Power | 39 |
| | Chapter 3
Routine NMR Spectroscopy and Standard Tests | 43 |
| Exp. 3.1 | The Standard 1H NMR Experiment | 44 |
| Exp. 3.2 | The Standard 13C NMR Experiment | 49 |
| Exp. 3.3 | The Application of Window Functions | 54 |
| Exp. 3.4 | Computer-Aided Spectral Analysis | 58 |
| Exp. 3.5 | Line Shape Test for 1H NMR Spectroscopy | 61 |
| Exp. 3.6 | Resolution Test for 1H NMR Spectroscopy | 64 |
| Exp. 3.7 | Sensitivity Test for 11H NMR Spectroscopy | 67 |
| Exp. 3.8 | Line Shape Test for 13C NMR Spectroscopy | 70 |
| Exp. 3.9 | ASTM Sensitivity Test for 13C NMR Spectroscopy | 73 |
| Exp. 3.10 | Sensitivity Test for 13C NMR Spectroscopy | 76 |
| Exp. 3.11 | Quadrature Image Test | 79 |
| Exp. 3.12 | Dynamic Range Test for Signal Amplitudes | 82 |
| Exp. 3.13 | 13° Phase Stability Test | 85 |
| Exp. 3.14 | Radiofrequency Field Homogeneity | 88 |
| | Chapter 4
Decoupling Techniques | 91 |
| Exp. 4.1 | Decoupler Calibration for Homonuclear Decoupling | 92 |
| Exp. 4.2 | Decoupler Calibration for Heteronuclear Decoupling | 95 |
| Exp. 4.3 | Low-Power Calibration for Heteronuclear Decoupling | 98 |
| Exp. 4.4 | Homonuclear Decoupling | 101 |
| Exp. 4.5 | Homonuclear Decoupling at Two Frequencies | 104 |
| Exp. 4.6 | The Homonuclear SPT Experiment | 107 |
| Exp. 4.7 | The Heteronuclear SPT Experiment | 110 |
| Exp. 4.8 | The Basic Homonuclear NOE Difference Experiment | 113 |
| Exp. 4.9 | 1D Nuclear Overhauser Difference Spectroscopy | 116 |
| Exp. 4.10 | 1D NOE Spectroscopy with Multiple Selective Irradiation | 119 |
| Exp. 4.11 | 1H Off-Resonance Decoupled 13C NMR Spectra | 122 |
| Exp. 4.12 | The Gated 1H-Decoupling Technique | 125 |
| Exp. 4.13 | The Inverse Gated 1H-Decoupling Technique | 128 |
| Exp. 4.14 | 1H Single-Frequency Decoupling of 13C NMR Spectra | 131 |
| Exp. 4.15 | 1H Low-Power Decoupling of 13C NMR Spectra | 134 |
| Exp. 4.16 | Measurement of the Heteronuclear Overhauser Effect | 137 |
| | Chapter 5
Dynamic NMR Spectroscopy | 140 |
| Exp. 5.1 | Low-Temperature Calibration Using Methanol | 141 |
| Exp. 5.2 | High-Temperature Calibration Using 1,2-Ethanediol | 145 |
| Exp. 5.3 | Dynamic 1H NMR Spectroscopy on Dimethylformamide | 149 |
| Exp. 5.4 | The Saturation Transfer Experiment | 152 |
| Exp. 5.5 | Measurement of the Rotating-Frame Relaxation Time T1p | 155 |
| | Chapter 6
1D Multipulse Sequences | 159 |
| Exp. 6.1 | Measurement of the Spin-Lattice Relaxation Time T1 | 160 |
| Exp. 6.2 | Measurement of the Spin-Spin Relaxation Time T2 | 164 |
| Exp. 6.3 | 13C NMR Spectra with SEFT | 167 |
| Exp. 6.4 | 13C NMR Spectra with APT | 170 |
| Exp. 6.5 | The Basic INEPT Technique | 173 |
| Exp. 6.6 | INEPT+ | 176 |
| Exp. 6.7 | Refocused INEPT | 179 |
| Exp. 6.8 | Reverse INEPT | 182 |
| Exp. 6.9 | DEPT-135 | 185 |
| Exp. 6.10 | Editing 13C NMR Spectra Using DEPT | 188 |
| Exp. 6.11 | DEPTQ | 191 |
| Exp. 6.12 | Multiplicity Determination Using PENDANT | 194 |
| Exp. 6.13 | 1D-INADEQUATE | 197 |
| Exp. 6.14 | The BIRD Filter | 201 |
| Exp. 6.15 | TANGO | 204 |
| Exp. 6.16 | The Heteronuclear Double-Quantum Filter | 207 |
| Exp. 6.17 | Purging with a Spin-Lock Pulse | 210 |
| Exp. 6.18 | Water Suppression by Presaturation | 213 |
| Exp. 6.19 | Water Suppression by the Jump-and-Return Method | 216 |
| | Chapter 7
NMR Spectroscopy with Selective Pulses | 219 |
| Exp. 7.1 | Determination of a Shaped 90° 1H Transmitter Pulse | 220 |
| Exp. 7.2 | Determination of a Shaped 90° 1H Decoupler Pulse | 223 |
| Exp. 7.3 | Determination of a Shaped 90° 13C Decoupler Pulse | 226 |
| Exp. 7.4 | Selective Excitation Using DANTE | 229 |
| Exp. 7.5 | SELCOSY | 232 |
| Exp. 7.6 | SELINCOR: Selective Inverse H,C Correlation via 1J(C,H) | 235 |
| Exp. 7.7 | SELINQUATE | 238 |
| Exp. 7.8 | Selective TOCSY | 242 |
| Exp. 7.9 | INAPT | 246 |
| Exp. 7.10 | Determination of Long-Range C,H Coupling Constants | 249 |
| Exp. 7.11 | SELRESOLV | 252 |
| Exp. 7.12 | SERF | 255 |
| | Chapter 8
Auxiliary Reagents, Quantitative Determinations, and Reaction Mechanisms | 258 |
| Exp. 8.1 | Signal Separation Using a Lanthanide Shift Reagent | 259 |
| Exp. 8.2 | Signal Separation of Enantiomers Using a Chiral Shift Reagent | 262 |
| Exp. 8.3 | Signal Separation of Enantiomers Using a Chiral Solvating Agent | 265 |
| Exp. 8.4 | Determination of Enantiomeric Purity with Pirkle’s Reagent | 268 |
| Exp. 8.5 | Determination of Enantiomeric Purity by 31P NMR | 271 |
| Exp. 8.6 | Determination of Absolute Configuration by the Advanced Mosher Method | 274 |
| Exp. 8.7 | Aromatic Solvent-Induced Shift (ASIS) | 277 |
| Exp. 8.8 | NMR Spectroscopy of OH Protons and H/D Exchange | 280 |
| Exp. 8.9 | Water Suppression Using an Exchange Reagent | 283 |
| Exp. 8.10 | Isotope Effects on Chemical Shielding | 286 |
| Exp. 8.11 | pKa Determination by 13C NMR | 290 |
| Exp. 8.12 | Determination of Association Constants Ka | 293 |
| Exp. 8.13 | Saturation Transfer Difference NMR | 298 |
| Exp. 8.14 | The Relaxation Reagent Cr(acac)3 | 302 |
| Exp. 8.15 | Determination of Paramagnetic Susceptibility by NMR | 305 |
| Exp. 8.16 | 1H and 13C NMR of Paramagnetic Compounds | 308 |
| Exp. 8.17 | The CIDNP Effect | 312 |
| Exp. 8.18 | Quantitative 1H NMR Spectroscopy: Determination of the Alcohol Content of Polish Vodka | 315 |
| Exp. 8.19 | Quantitative 13C NMR Spectroscopy with Inverse Gated 1H-Decoupling | 318 |
| Exp. 8.20 | NMR Using Liquid-Crystal Solvents | 321 |
| | Chapter 9
Heteronuclear NMR Spectroscopy | 324 |
| Exp. 9.1 | 1H-Decoupled 15N NMR Spectra Using DEPT | 330 |
| Exp. 9.2 | 1H-Coupled 15N NMR Spectra Using DEPT | 333 |
| Exp. 9.3 | 19F NMR Spectroscopy | 336 |
| Exp. 9.4 | 29Si NMR Spectroscopy Using DEPT | 339 |
| Exp. 9.5 | 29Si NMR Spectroscopy Using Spin-Lock Polarization | 342 |
| Exp. 9.6 | 119Sn NMR Spectroscopy | 346 |
| Exp. 9.7 | 2H NMR Spectroscopy | 349 |
| Exp. 9.8 | 11B NMR Spectroscopy | 352 |
| Exp. 9.9 | 17O NMR Spectroscopy Using RIDE | 355 |
| Exp. 9.10 | 47/49Ti NMR Spectroscopy Using ARING | 358 |
| | Chapter 10
The Second Dimension | 362 |
| Exp. 10.1 | 2D J-Resolved 1H NMR Spectroscopy | 367 |
| Exp. 10.2 | 2D J-Resolved 13C NMR Spectroscopy | 370 |
| Exp. 10.3 | The Basic H,H-COSY Experiment | 373 |
| Exp. 10.4 | Long-Range COSY | 377 |
| Exp. 10.5 | Phase-Sensitive COSY | 380 |
| Exp. 10.6 | Exp. Phase-Sensitive COSY-45 | 383 |
| Exp.10.7 | E.COSY | 386 |
| Exp. 10.8 | Double-Quantum-Filtered COSY with Presaturation | 389 |
| Exp. 10.9 | Fully Coupled C,H Correlation (FUCOUP) | 393 |
| Exp. 10.10 | C,H-Correlation by Polarization Transfer (HETCOR) | 396 |
| Exp. 10.11 | Long-Range C,H-Correlation by Polarization Transfer | 399 |
| Exp. 10.12 | C,H Correlation via Long-Range Couplings (COLOC) | 402 |
| Exp. 10.13 | The Basic HMQC Experiment | 405 |
| Exp. 10.14 | Phase-Sensitive HMQC with BIRD Filter and GARP Decoupling | 409 |
| Exp. 10.15 | Poor Man’s Gradient HMQC | 412 |
| Exp. 10.16 | Phase-Sensitive HMBC with BIRD Filter | 415 |
| Exp. 10.17 | The Basic HSQC Experiment | 418 |
| Exp. 10.18 | The HOHAHA or TOCSY Experiment | 422 |
| Exp. 10.19 | HETLOC | 426 |
| Exp. 10.20 | The NOESY Experiment | 430 |
| Exp. 10.21 | The CAMELSPIN or ROESY Experiment | 434 |
| Exp. 10.22 | The HOESY Experiment | 438 |
| Exp. 10.23 | 2D-INADEQUATE | 441 |
| Exp. 10.24 | The EXSY Experiment | 445 |
| Exp. 10.25 | X,Y-Correlation | 448 |
| | Chapter 11
1D NMR Spectroscopy with Pulsed Field Gradients | 453 |
| Exp. 11.1 | Calibration of Pulsed Field Gradients | 455 |
| Exp. 11.2 | Gradient Pre-emphasis | 458 |
| Exp. 11.3 | Gradient Amplifier Test | 461 |
| Exp. 11.4 | Determination of Pulsed Field Gradient Ring-Down Delays | 464 |
| Exp. 11.5 | The Pulsed Field Gradient Spin-Echo Experiment | 467 |
| Exp. 11.6 | Excitation Pattern of Selective Pulses | 470 |
| Exp. 11.7 | The Gradient Heteronuclear Double-Quantum Filter | 474 |
| Exp. 11.8 | The Gradient zz-Filter | 477 |
| Exp. 11.9 | The Gradient-Selected Dual Step Low-Pass Filter | 480 |
| Exp. 11.10 | gs-SELCOSY | 484 |
| Exp. 11.11 | gs-SELTOCSY | 488 |
| Exp. 11.12 | DPFGSE-NOE | 492 |
| Exp. 11.13 | gs-SELINCOR | 496 |
| Exp. 11.14 |  / -SELINCOR-TOCSY | 499 |
| Exp. 11.15 | GRECCO | 503 |
| Exp. 11.16 | WATERGATE | 506 |
| Exp. 11.17 | Water Suppression by Excitation Sculpting | 509 |
| Exp. 11.18 | Solvent Suppression Using WET | 512 |
| Exp. 11.19 | DOSY | 515 |
| Exp. 11.20 | INEPT-DOSY | 518 |
| Exp. 11.21 | DOSY-HMQC | 521 |
| | Chapter 12
2D NMR Spectroscopy With Field Gradients | 525 |
| Exp. 12.1 | gs-COSY | 526 |
| Exp. 12.2 | Constant-Time COSY | 530 |
| Exp. 12.3 | Phase-Sensitive gs-DQF-COSY | 534 |
| Exp. 12.4 | gs-HMQC | 538 |
| Exp. 12.5 | gs-HMBC | 542 |
| Exp. 12.6 | ACCORD-HMBC | 546 |
| Exp. 12.7 | HMSC | 550 |
| Exp. 12.8 | Phase-Sensititive gs-HSQC with Sensitivity Enhancement | 554 |
| Exp. 12.9 | Edited HSQC with Sensitivity Enhancement | 558 |
| Exp. 12.10 | HSQC with Adiabatic Pulses for High-Field Instruments | 563 |
| Exp. 12.11 | gs-TOCSY | 567 |
| Exp. 12.12 | gs-HMQC-TOCSY | 571 |
| Exp. 12.13 | gs-HETLOC | 575 |
| Exp. 12.14 | gs-J-Resolved HMBC | 581 |
| Exp. 12.15 | 2Q-HMBC | 585 |
| Exp. 12.16 | 1H-Detected 2D INEPT-INADEQUATE | 589 |
| Exp. 12.17 | 1,1-ADEQUATE | 593 |
| Exp. 12.18 | 1,n-ADEQUATE | 597 |
| Exp. 12.19 | gs-NOESY | 601 |
| Exp. 12.20 | gs-HSQC-NOESY | 604 |
| Exp. 12.21 | gs-HOESY | 608 |
| Exp. 12.22 | 1H, 15N Correlation with gs-HMQC | 612 |
| | Chapter 13
The Third Dimension | 616 |
| Exp. 13.1 | 3D HMQC-COSY | 618 |
| Exp. 13.2 | 3D gs-HSQC-TOCSY | 622 |
| Exp. 13.3 | 3D H,C,P-Correlation | 626 |
| Exp. 13.4 | 3D HMBC | 630 |
| | Chapter 14
Solid-State NMR Spectroscopy | 634 |
| Exp. 14.1 | Shimming Solid-State Probe-Heads | 635 |
| Exp. 14.2 | Adjusting the Magic Angle | 639 |
| Exp. 14.3 | Hartmann-Hahn Matching | 642 |
| Exp. 14.4 | The Basic CP/MAS Experiment | 645 |
| Exp. 14.5 | TOSS | 649 |
| Exp. 14.6 | SELTICS | 653 |
| Exp. 14.7 | Connectivity Determination in the Solid State | 656 |
| Exp. 14.8 | REDOR | 659 |
| Exp. 14.9 | High-Resolution Magic-Angle Spinning | 663 |
| | Chapter 15
Protein NMR | 666 |
| Exp. 15.1 | Pulse Determination for Protein NMR | 670 |
| Exp. 15.2 | HN-HSQC | 673 |
| Exp. 15.3 | HC-HSQC | 678 |
| Exp. 15.4 | MUSIC | 682 |
| Exp. 15.5 | HN-Correlation using TROSY | 688 |
| Exp. 15.6 | HN-TOCSY-HSQC | 692 |
| Exp. 15.7 | HNCA | 698 |
| Exp. 15.8 | HN(CO)CA | 705 |
| Exp. 15.9 | HNCO | 711 |
| Exp. 15.10 | HN(CA)CO | 718 |
| Exp. 15.11 | HCACO | 725 |
| Exp. 15.12 | HCCH-TOCSY | 732 |
| Exp. 15.13 | CBCANH | 739 |
| Exp. 15.14 | CBCA(CO)NH | 746 |
| Exp. 15.15 | HBHA(CBCACO)NH | 753 |
| Exp. 15.16 | HN(CA)NNH | 760 |
| Exp. 15.17 | HN-NOESY-HSQC | 766 |
| Exp. 15.18 | HC-NOESY-HSQC | 773 |
| Exp. 15.19 | 3D HCN-NOESY | 779 |
| Exp. 15.20 | HNCA-J | 785 |
| | Appendix 1
Pulse Programs | 791 |
| | Appendix 2
Instrument Dialects | 794 |
| | Appendix 3
Classification of Experiments | 797 |
| | Appendix 4
Elementary Product Operator Formalism Rules | 799 |
| | Appendix 5
Chemical Shift and Spin-Coupling Data for Ethyl Crotonate and Strychnine | 802 |
| | Glossary and Index | 804 |
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