Knowledge (XXG)

Phosphorus-31 nuclear magnetic resonance

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The ordinary range of chemical shifts ranges from about δ250 to −δ250, which is much wider than typical for H-NMR. Unlike H-NMR spectroscopy, P-NMR shifts are primarily not determined by the magnitude of the diamagnetic shielding, but are dominated by the so-called paramagnetic shielding tensor
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P-NMR spectroscopy is useful to assay purity and to assign structures of phosphorus-containing compounds because these signals are well resolved and often occur at characteristic frequencies. Chemical shifts and coupling constants span a large range but sometimes are not readily predictable. The
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are an order of magnitude smaller. The situation for phosphorus-carbon couplings are more complicated since the two-bond couplings are often larger than one-bond couplings. The J(C,P) values for triphenylphosphine are respectively −12.5, 19.6, 6.8, and 0.3 for one-, two-, three-, and four-bond
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The convention surrounding P-NMR (and other nuclei) changed convention in 1975: "The dimensionless scale should be defined as positive in the high frequency (low field) direction." Therefore, note that manuscripts published before 1976 will generally have the opposite sign.
271:(gel phase, physiological liquid crystal phase, ripple phases, non bilayer phases), lipid head group orientation/dynamics, and elastic properties of pure lipid bilayer and as a result of binding of proteins and other biomolecules. 428:
Dubinnyi MA; Lesovoy DM; Dubovskii PV; Chupin VV; Arseniev AS (Jun 2006). "Modeling of P-NMR spectra of magnetically oriented phospholipid liposomes: A new analytical solution".
38:) in toluene solution. In addition to P–P coupling between the two types of phosphine centers, Rh–P coupling is also evident. The chemical shifts are referenced to external 85% 543: 533: 267:
and biological membranes in native conditions. The analysis of P-NMR spectra of lipids could provide a wide range of information about lipid bilayer packing,
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IUPAC 1975 Presentation of NMR data for publication in chemical journals - B. conventions relating to spectra from nuclei other than protons
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between amine protons of protein to phosphate of lipid headgroups, which is useful in studies of protein/membrane interactions.
143:, which is assigned the chemical shift of 0, and appear at positive values (downfield of the standard). Due to the inconsistent 393:
D. G. Gorenstein "Nonbiological Aspects of Phosphorus-31 NMR Spectroscopy" Progress in NMR Spectroscopy 1983, vol. 16, pp. 98.
356: 583: 573: 548: 538: 588: 523: 563: 474: 189:, and bond overlap. Illustrative of the effects lead to big changes in chemical shifts, the chemical shifts of the two 64: 144: 467: 24: 161: 135:
With a gyromagnetic ratio 40.5% of that for H, P-NMR signals are observed near 202 MHz on an 11.7-
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magnet (used for 500 MHz H-NMR measurements). Chemical shifts are typically referenced to 85%
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In addition, a specific N-H...(O)-P experiment (INEPT transfer using three-bond scalar coupling J
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PO in conjunction with P-NMR spectroscopy to assess the Lewis acidity of molecular species.
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PO (δ-13.3). More dramatic are the shifts for phosphine derivatives H
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O. Kühl "Phosphorus-31 NMR Spectroscopy" Springer, Berlin, 2008.
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Spectroscopy technique for molecules containing phosphorus
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where J(P,H) is 189 Hz. Two-bond couplings, e.g.
501: 127:that are monoisotopic (or nearly so) are H and F. 263:P-NMR spectroscopy is widely used for studies of 347:Harris, Robin Kingsley; Mann, Brian E. (1978). 475: 8: 482: 468: 460: 370: 368: 326:, but have very low magnetogyric ratios. 181:). The paramagnetic shielding tensor, σ 45: 41: 34: 30: 339: 291: 7: 75:. Phosphorus is commonly found in 14: 310:are also monoisotopic and spin 79:and coordination complexes (as 351:. Academic Press. p. 13. 87:of 100% and a relatively high 1: 442:10.1016/j.ssnmr.2005.10.009 430:Solid State Nucl Magn Reson 91:. The P nucleus also has a 631: 610:Nuclear magnetic resonance 349:NMR and the periodic table 65:nuclear magnetic resonance 259:Biomolecular applications 155:Applications in chemistry 145:nuclear Overhauser effect 162:Gutmann-Beckett method 50: 265:phospholipid bilayers 197:PO (δ2.1) and (t-BuO) 22: 375:Roy Hoffman (2007). 233:is illustrated by PH 63:technique that uses 61:analytical chemistry 25:Wilkinson's catalyst 217:P (δ20), and (t-Bu) 131:Operational aspects 225:Coupling constants 89:gyromagnetic ratio 85:isotopic abundance 69:chemical compounds 51: 23:P-NMR spectrum of 597: 596: 408:978-3-540-79118-8 381:Hebrew University 269:phase transitions 77:organic compounds 54:Phosphorus-31 NMR 622: 491:NMR spectroscopy 484: 477: 470: 461: 454: 453: 425: 419: 416: 410: 400: 394: 391: 385: 384: 377:"Phosphorus NMR" 372: 363: 362: 344: 327: 325: 323: 322: 319: 316: 296: 213:P (δ-62), (i-Pr) 191:phosphate esters 126: 124: 123: 120: 117: 110: 108: 107: 104: 101: 48: 37: 630: 629: 625: 624: 623: 621: 620: 619: 600: 599: 598: 593: 497: 488: 458: 457: 427: 426: 422: 417: 413: 401: 397: 392: 388: 374: 373: 366: 359: 346: 345: 341: 336: 331: 330: 320: 317: 314: 313: 311: 297: 293: 288: 277: 261: 252: 250:Historical note 236: 227: 220: 216: 212: 208: 204: 200: 196: 184: 174: 172:Chemical shifts 167: 157: 141:phosphoric acid 133: 121: 118: 115: 114: 112: 105: 102: 99: 98: 96: 67:(NMR) to study 47: 43: 39: 36: 32: 28: 17: 12: 11: 5: 628: 626: 618: 617: 612: 602: 601: 595: 594: 592: 591: 586: 581: 576: 571: 566: 561: 556: 551: 546: 541: 536: 531: 526: 521: 516: 511: 505: 503: 499: 498: 489: 487: 486: 479: 472: 464: 456: 455: 436:(4): 305–311. 420: 411: 395: 386: 364: 357: 338: 337: 335: 332: 329: 328: 290: 289: 287: 284: 280:hydrogen bonds 275: 260: 257: 251: 248: 234: 226: 223: 218: 214: 210: 206: 205:P (δ-240), (CH 202: 198: 194: 187:excited states 182: 177:(unrelated to 173: 170: 165: 156: 153: 132: 129: 15: 13: 10: 9: 6: 4: 3: 2: 627: 616: 613: 611: 608: 607: 605: 590: 587: 585: 582: 580: 577: 575: 572: 570: 567: 565: 562: 560: 557: 555: 552: 550: 547: 545: 542: 540: 537: 535: 532: 530: 527: 525: 522: 520: 517: 515: 512: 510: 507: 506: 504: 500: 496: 492: 485: 480: 478: 473: 471: 466: 465: 462: 451: 447: 443: 439: 435: 431: 424: 421: 415: 412: 409: 405: 399: 396: 390: 387: 382: 378: 371: 369: 365: 360: 354: 350: 343: 340: 333: 309: 305: 301: 295: 292: 285: 283: 281: 272: 270: 266: 258: 256: 249: 247: 244: 240: 232: 224: 222: 192: 188: 180: 179:paramagnetism 171: 169: 163: 154: 152: 150: 146: 142: 138: 130: 128: 94: 90: 86: 82: 78: 74: 71:that contain 70: 66: 62: 58: 55: 26: 21: 553: 433: 429: 423: 414: 398: 389: 348: 342: 294: 273: 262: 253: 242: 238: 228: 175: 158: 134: 57:spectroscopy 53: 52: 298:The nuclei 246:couplings. 221:P (δ61.9). 615:Phosphorus 604:Categories 358:0123276500 334:References 81:phosphines 73:phosphorus 229:One-bond 149:decoupled 450:16298110 231:coupling 29:RhCl(PPh 502:Isotope 495:isotope 324:⁠ 312:⁠ 164:uses Et 125:⁠ 113:⁠ 109:⁠ 97:⁠ 448:  406:  355:  59:is an 286:Notes 193:(MeO) 137:Tesla 446:PMID 404:ISBN 353:ISBN 306:and 93:spin 493:by 438:doi 276:N-P 95:of 606:: 589:Pb 584:Hg 579:Pt 574:Se 569:Co 564:Fe 549:Si 519:He 444:. 434:29 432:. 379:. 367:^ 308:Tm 304:Rh 302:, 151:. 44:PO 559:V 554:P 544:F 539:O 534:N 529:C 524:B 514:H 509:H 483:e 476:t 469:v 452:. 440:: 383:. 361:. 321:2 318:/ 315:1 300:Y 243:H 241:C 239:P 235:3 219:3 215:3 211:3 209:) 207:3 203:3 199:3 195:3 183:p 166:3 122:2 119:/ 116:1 106:2 103:/ 100:1 49:. 46:4 42:3 40:H 35:3 33:) 31:3 27:(

Index


Wilkinson's catalyst
spectroscopy
analytical chemistry
nuclear magnetic resonance
chemical compounds
phosphorus
organic compounds
phosphines
isotopic abundance
gyromagnetic ratio
spin
Tesla
phosphoric acid
nuclear Overhauser effect
decoupled
Gutmann-Beckett method
paramagnetism
excited states
phosphate esters
coupling
phospholipid bilayers
phase transitions
hydrogen bonds
Y
Rh
Tm
ISBN
0123276500

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