Abstract
Chemical exchange in solution state has been investigated traditionally by both 1D and 2D NMR, permitting the extraction of kinetic parameters (e.g. the spin-lattice relaxation time T 1, the exchange rate constant k and the activation parameters). This work demonstrates a simple 1D NMR approach employing multiply selective excitation to study multi-site exchange processes in solution, applying it to systems that exhibit three-site exchange. This approach involves simultaneous excitation of all — or a chosen subset of — the exchanging sites by using an appropriately modulated shaped radiofrequency pulse. The pulse sequence, as well as analysis is summarized. Significant features of the experiment, which relies on sign labelling of the exchanging sites, include considerably shorter experiment time compared to standard 2D exchange work, clear definition of the exchange time window and uniform pulse non-ideality effects for all the exchanging sites. Complete kinetic information is reported in the study of dynamic processes in superacid solutions of two weak bases, studied by 1H NMR. An analytical solution, leading to the determination of four rate parameters, is presented for proton exchange studies on these systems, which involve a mixture of two weak bases in arbitrary concentration ratio, and stoichiometric excess of the superacid.
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References
Gutowsky H S and Saika A 1953 J. Chem. Phys. 21 1688
Jackmann L M and Cotton F A (eds) 1975 Dynamic NMR spectroscopy (New York: Academic Press)
Forsén S and Hoffman R A 1963 J. Chem. Phys. 39 2892
Forsén S and Hoffman R A 1964 J. Chem. Phys. 40 1189
Inglefield P T, Krakower E, Reevs L W and Stewart R 1968 Mol. Phys. 15 65
Dahlquist W, Longmuir K J and DuVernet R B 1975 J. Magn. Reson. 17 406
Campbell D, Dobson C M and Ratcliffe R G 1977 J. Magn. Reson. 27 455
Gutowsky S, Vold R L and Wells E J 1965 J. Chem. Phys. 43 4107
Muhandiram D R and McClung R E D 1987 J. Magn. Reson. 71 187
Levy G C and Nelson G 1972 J. Am. Chem. Soc. 94 4897
Spencer R G S 2000 J. Magn. Reson. 142 120
Jeener J, Meier B H, Bachmann P and Ernst R R 1979 J. Chem. Phys. 71 4546
Macura S and Ernst R R 1982 J. Magn. Reson. 46 269
Perrin C L 1989 J. Magn. Reson. 82 619
Abel E W, Coston T P J, Orrell K G, Šik V and Stephenson D 1986 J. Magn. Reson. 70 34
Yarnykh V L and Ustynyuk Y A 1993 J. Magn. Reson. A102 131
Bremer J 1984 J. Am. Chem. Soc. 106 4691
Campbell D, Dobson C M, Ratcliffe R G and Williams R J P 1978 J. Magn. Reson. 29 397
Rabinovitz M and Pines A 1969 J. Am. Chem. Soc. 91 1585
Mann B E 1976 J. Magn. Reson. 21 17
Mann B E 1977 J. Magn. Reson. 25 91
Grassi M, Mann B E, Pickup B T and Spencer C M 1986 J. Magn. Reson. 69 92
McClung R E D and Aarts G H M 1995 J. Magn. Reson. A115 145
Bain A D and Cramer J A 1993 J. Magn. Reson. A103 217
Bain A D and Cramer J A 1996 J. Magn. Reson. A118 21
Cavanagh J, Fairbrother W J, Palmer A G and Skelton N J 1996 Protein NMR spectroscopy. Principles and practice (San Diego, CA: Academic Press)
Zhou J and van Ziji P C 2006 Prog. Nucl. Magn. Reson. Spectroc. 48 109
Galban J and Spencer R G 2007 Magn. Reson. Med. 58 8
Lucchini V, Borsato G, Canovese L, Santo C, Visentin F and Zambon A 2009 Inorg. Chim. Acta 362 2715
Hirose K, Ishibashi K, Shiba Y, Doi Y and Tobe Y 2008 Chem. Eur. J. 14 5803
Bodenhausen G, Zwahlen C, Vincent S J F and Schwager M 1996 Chem. Eur. J. 2 45
Shapira B and Frydman L 2003 J. Magn. Reson. 165 320
Perrin C L and Engler R E 1996 J. Magn. Reson. A123 188
Bain A D, Bell R A, Fletcher D A, Hazendonk P, Maharajh R A, Rigby S and Valliant J F 1999 J. Chem. Soc., Perkin Trans. II 144 7
Heaton B T, Jacob C, Podkorytov I S and Tunik S P 2006 Inorg. Chim. Acta 359 3557
Gold V, Laali K, Morris K P and Zdunek L Z 1981 J. Chem. Soc. Chem. Comm. 769
Gold V, Laali K, Morris K P and Zdunek, L Z 1985 J. Chem. Soc., Perkin Trans. II 859
Bauer C, Freeman R, Frenkiel T, Keeler J and Shaka A J 1984 J. Magn. Reson. 58 442
Hadamard J 1893 Bull. Sci. Math. 17 240
Olah G A and Schlosberg R H 1968 J. Am. Chem. Soc. 90 2726
Olah G A 2005 J. Org. Chem. 70 2413
McConnell H M 1958 J. Chem. Phys. 28 430
Bain A D and Cramer J A 1993 J. Phys. Chem. 97 2884
Steigel A 1978 NMR Basic principles and progress (eds) P Diehl, E Fluck and R Kosfeld (Heidelberg: Springer-Verlag: Berlin) p. 15
Perrin C L and Gipe R K 1984 J. Am. Chem. Soc. 106 4036
Perrin C L and Johnston E R 1979 J. Magn. Reson. 33 619
Ugurbil K 1985 J. Magn. Reson. 64 207
Ernst R R, Bodenhausen G and Wokaun W 1987 Principles of nuclear magnetic resonance in one and two dimensions (Oxford: Oxford University Press)
Bain A D 2003 Prog. Nucl. Magn. Reson. 43 63
Bain A D 2008 Ann. Rep. NMR Spectroc. 63 23
Gold V, Laali K, Morris K P and Zdunek L Z 1985 J. Chem. Soc. Perkin Trans. II 865
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Pal, S. Study of multi-site chemical exchange in solution state by NMR: 1D experiments with multiply selective excitation. J Chem Sci 122, 471–480 (2010). https://doi.org/10.1007/s12039-010-0082-z
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DOI: https://doi.org/10.1007/s12039-010-0082-z