Pure Shift Proton NMR Spectroscopy and Its Applications

doi:10.11938/cjmr20160315

Abstract

Abstract:

J coupling gives rise to spectral multiplets (i.e. resonance from one spin is split into a group of equally spaced lines placed symmetrically around the chemical shift). Such spectral splitting contains information on molecular structure, and is therefore useful for structural elucidation. However, when the number of spin increases and many spectral multiplets are present, the spectra, especially proton spectra, could become very crowded, making structural elucidation and quantitative analysis difficult. Using the pure shift (i.e., broadband homonuclear decoupling) proton NMR technique, one could collapse spectral multiplets into singlets, and obtain spectra containing only chemical shift information. In this paper, we give brief introductions to three most widely used pure shift proton NMR techniques, namely BIRD, ZS, and PSYCHE, and describe typical applications of such techniques.

Key words: ZS, PSYCHE, J coupling, pure shift (broadband homonuclear decoupling) ¹H NMR spectroscopy, BIRD

CLC Number:

O482.53

ZHOU Qiu-ju, XIANG Jun-feng, TANG Ya-lin, CUI Jie, WU Ning-ning. Pure Shift Proton NMR Spectroscopy and Its Applications[J]. Chinese Journal of Magnetic Resonance, 2016, 33(3): 502-513.

References

[1] Hansen P I, Larsen F H, Motawia S M, et al. Structure and hydration of the amylopectin trisaccharide building blocks-Synthesis, NMR, and molecular dynamics[J] . Biopolymers, 2008, 89(12): 1 179-1 193.

[2] Emsley J W, Feeney J. Forty years of progress in nuclear magnetic resonance spectroscopy[J] . Prog Nucl Magn Reson Spectrosc, 2007, 50(4): 179-198.

[3] Ernst R R, Primas H. Nuclear magnetic resonance with stochastic high-frequency fields - (a simple example to theory of systems with a stochastic hamiltonian)[J] . Helvetica Physica Acta, 1963, 36(5): 583.

[4] Shaka A J, Keeler J. Broadband spin decoupling in isotropic liquids[J]. Prog Nucl Magn Reson Spectrosc, 1987, 19: 47-129.

[5] Aue W P, Karhan J, Ernst R R. Homonuclear broad band decoupling and two-dimensional J-resolved NMR spectroscopy[J]. J Chem Phys, 1976, 64(10): 4 226-4 227.

[6] Bax A, Mehlkopf A F, Smidt J. Homonuclear broadband-decoupled absorption spectra, with linewidths which are independent of the transverse relaxation rate[J] . J Magn Reson, 1979, 35(1): 167-169.

[7] Soerensen O W, Griesinger C, Ernst R R. Time reversal of the evolution under scalar spin-spin interactions in NMR. Application for .omega.1 decoupling in two-dimensional NOE spectroscopy[J] . J Am Chem Soc, 1985, 107(25): 7 778-7 779.

[8] Garbow J R, Weitekamp D P, Pines A. Bilinear rotation decoupling of homonuclear scalar interactions[J] . Chem Phys Lett, 1982, 93(5): 504-509.

[9] Bax A. Broadband homonuclear decoupling in heteronuclear shift correlation NMR spectroscopy[J] . J Magn Reson, 1983, 53: 517-520.

[10] Zangger K, Sterk H. Homonuclear broadband-decoupled NMR spectra[J]. J Magn Reson, 1997, 124(2): 486-489.

[11] Oschkinat H, Pastore A, Pfandler P, et al. Two-dimensional correlation of directly and remotely connected transitions by zeta-filtered COSY[J]. J Magn Reson, 1986, 69(3): 559-566.

[12] Pell A J, Edden R A E, Keeler J. Broadband proton-decoupled proton spectra[J] . Magn Reson Chem, 2007, 45(4): 296-316.

[13] Pell A J, Keeler J. Two-dimensional J-spectra with absorption-mode lineshapes[J]. J Magn Reson, 2007, 189(2): 293-299.

[14] AguilarJ A, Nilsson M, Bodenhausen G, et al. Spin echo NMR spectra without J-modulation[J] . Chem Commun, 2012, 48(6): 811-813.

[15] AguilarJ A, Colbourne A A, Cassani J, et al. Decoupling two-dimensional NMR spectroscopy in both dimensions: pure shift NOESY and COSY[J] . Angew Chem Int Edit, 2012, 51(26): 6 460-6 463.

[16] Aguilar J A, Faulkner S, Nilsson M, et al. Pure shift ¹H NMR: A resolution of the resolution problem?[J]. Angew Chem Int Edit, 2010, 49(23): 3 901-3 903.

[17] Aguilar J A, Nilsson M, Morris G A. Simple proton spectra from complex spin systems: pure shift NMR spectroscopy using BIRD[J]. Angew Chem Int Edit, 2011, 50(41): 9 716-9 717.

[18] Foroozandeh M, Adams R W, Meharry N J, et al. Ultrahigh-resolution NMR spectroscopy[J] . Angew Chem Int Edit, 2014, 53(27): 6 990-6 992.

[19] Morris G A, Aguilar J A, Evans R, et al. True chemical shift correlation maps: a TOCSY experiment with pure shifts in both dimensions[J] . J Am Chem Soc, 2010, 132(37): 12 770-12 772.

[20] Foroozandeh M, Adams R W, Nilsson M, et al. Ultrahigh-resolution total correlation NMR spectroscopy[J] . J Am Chem Soc, 2014, 136(34): 11 867-11 869.

[21] Zangger K. Pure shift NMR[J] . Prog Nucl Magn Reson Spectrosc, 2015, (86, 87): 1-20.

[22] www.bruker.com/products/mr/nmr/magnets/magnets/avance-1000/overview.html[OL] .

[23] Adams R W. Pure Shift NMR Spectroscopy[M]. London: John Wiley & Sons, Ltd., 2014.

[24] Sakhaii P, Haase B, Bermel W, et al. Broadband homodecoupled NMR spectroscopy with enhanced sensitivity[J] . J Magn Reson, 2013, 233: 92-95.

[25] Meyer N H, Zangger K. Boosting the resolution of ¹H NMR spectra by homonuclear broadband decoupling[J] . Chemphyschem, 2014, 15(1): 49-55.

[26] Meyer N H, Zangger K. Viva la Resolución! Enhancing the resolution of ¹H NMR spectra by broadband homonuclear decoupling[J] . Synlett, 2014, 25(7): 920-927.

[27] Meyer N H, Zangger K. Simplifying proton NMR spectra by instant homonuclear broadband decoupling[J] . Angew Chem Int Edit, 2013, 52(28): 7 143-7 146.

[28] Meyer N H, Zangger K. Enhancing the resolution of multi-dimensional heteronuclear NMR spectra of intrinsically disordered proteins by homonuclear broadband decoupling[J] . Chem Commun, 2014, 50(12): 1 488-1 490.

[29] Sakhaii P, Haase B, Bermel W. Experimental access to HSQC spectra decoupled in all frequency dimensions[J] . J Magn Reson, 2009, 199(2): 192-198.

[30] Nilsson M, Morris G A. Pure shift proton DOSY: Diffusion-ordered ¹H spectra without multiplet structure[J] . Chem Commun, 2007, 9: 933-935.

[31] Donovan K J, Frydman L. HyperBIRD: A sensitivity-enhanced approach to collecting homonuclear-decoupled proton NMR spectra[J] . Angew Chem Int Edit, 2015, 127(2): 604-608.

[32] Aguilar J A, Nilsson M, Morris G A. Simple proton spectra from complex spin systems: pure shift NMR spectroscopy using BIRD[J] . Angew Chem Int Edit, 2011, 50(41): 9 890-9 891.

[33] Foxall P J D, Parkinson J A, Sadler I H, et al. Analysis of biological fluids using 600 MHz proton NMR spectroscopy: Application of homonuclear two-dimensional J-resolved spectroscopy to urine and blood plasma for spectral simplification and assignment[J] . J Pharmaceut Biomed, 1993, 11(1): 21-31.

[34] Wilson I D, Fromson J, Ismail I M, et al. Proton magnetic resonance spectroscopy of human urine: Excretion of 1-(3'-carboxypropyl)-3,7-dimethylxanthine by man after dosing with oxpentifylline[J]. J Pharmaceut Biomed, 1987, 5(2): 157-163.

[35] Williams S R, Iles R A, Chalmers R A. Spin-echo and two-dimensional ¹H nuclear magnetic resonance studies on urinary metabolites from patients with 2-methylacetoacetyl CoA thiolase deficiency[J] . Clin Chim Acta, 1986, 159(2): 153-161.

[36] Tanner J E. Use of the stimulated echo in NMR diffusion studies[J] . J Chem Phys, 1970, 52(5): 2 523-2 526.

[37] Morris K F, Johnson C S. Diffusion-ordered two-dimensional nuclear magnetic resonance spectroscopy[J] . J Am Chem Soc, 1992, 114(8): 3 139-3 141.

[38] Lin M F, Shapiro M J, Wareing J R. Screening mixtures by affinity NMR[J] . J Org Chem, 1997, 62(25): 8 930-8 931.

[39] Lin M F, Shapiro M J, Wareing J R. Diffusion-edited NMR-affinity NMR for direct observation of molecular interactions[J] . J Am Chem Soc, 1997, 119(22): 5 249-5 250.

[40] JohnsonJr C S. Diffusion ordered nuclear magnetic resonance spectroscopy: Principles and applications[J] . Prog Nucl Magn Reson Spectrosc, 1999, 34(3, 4): 203-256.

[41] Hodge P, Monvisade P, Morris G A, et al. A novel NMR method for screening soluble compound libraries[J] . Chem Commun, 2001, 3: 239-240.

[42] Zhou Q J, Li L, Xiang J F, et al. Screening potential antitumor agents from natural plant extracts by G-quadruplex recognition and NMR methods[J] . Angew Chem Int Edit, 2008, 47(30): 5 590-5 592.

[43] Zhou Q J, Li L, Xiang J F, et al. Fast screening and structural elucidation of G-quadruplex ligands from a mixture via G-quadruplex recognition and NMR methods[J] . Biochimie, 2009, 91(2): 304-308.

[44] Glanzer S, Zangger K. Directly decoupled diffusion-ordered NMR spectroscopy for the analysis of compound mixtures[J] . Chemistry, 2014, 20(35): 11 171-11 175.

[45] NilssonM, Gil A M, Delgadillo I, et al. Improving pulse sequences for 3D diffusion-ordered NMR spectroscopy: 2DJ-IDOSY[J] . Anal Chem, 2004, 76(18): 5 418-5 422.

[46] Lucas L H, Otto W H, Larive C K. The 2D-J-DOSY experiment: Resolving diffusion coefficients in mixtures[J] . J Magn Reson, 2002, 156(1): 138-145.

[47] CobasJC, Martin-Pastor M. A homodecoupled diffusion experiment for the analysis of complex mixtures by NMR[J] . J Magn Reson, 2004, 171(1): 20-24.

[48] Wu D H, Chen A D, Johnson C S. An improved diffusion-ordered spectroscopy experiment incorporating bipolar-gradient pulses[J]. J Magn Reson, 1995, 115(2): 260-264.