High-Resolution Pure Shift NMR Spectroscopy and Its Applications

doi:10.11938/cjmr20192777

Abstract

Abstract: Nuclear magnetic resonance (NMR) spectroscopy has found wide applications in fields of chemistry, biology, medicine, materials, etc, benefitting from its features of non-invasion, high resolution and high-throughput information. Recently, a high level of interest has reemerged in the development of pure shift NMR techniques which aim for significantly improving spectral resolution in overlapped regions. According to studies on new techniques and related applications by our group, herein we briefly review how pure shift technique is developed, and what would be next challenges in its development and extensive applications.

Key words: liquid-state nuclear magnetic resonance, high resolution, pure shift, review, decoupling

CLC Number:

O482.53

LIN Xiao-qing, LI Hong, ZHAN Hao-lin, DU Shi-jia, HUANG Yu-qing, CHEN Zhong. High-Resolution Pure Shift NMR Spectroscopy and Its Applications[J]. Chinese Journal of Magnetic Resonance, 2019, 36(4): 425-436.

References

[1] ZANGGER K. Pure shift NMR[J]. Prog Nucl Magn Reson Spectrosc, 2015, 86-87:1-20.
[2] CASTAÑAR L, PARELLA T. Broadband ¹H homodecoupled NMR experiments:Recent developments, methods and applications[J]. Magn Reson Chem, 2015, 53(6):399-426.
[3] LAURA C. Pure shift ¹H NMR:What's next?[J]. Magn Reson Chem, 2017, 55:47-53.
[4] ZHOU Q J, XIANG J F, TANG Y L, et al. Pure shift proton NMR spectroscopy and its applications[J]. Chinese J Magn Reson, 2016, 33(3):502-513. 周秋菊, 向俊锋, 唐亚林, 等. 纯位移核磁共振氢谱及其应用[J]. 波谱学杂志, 2016, 33(3):502-513.
[5] ERNST R R, PRIMAS H. Nuclear magnetic resonance with stochastic high-frequency fields[J]. Helv Phys Acta, 1963, 36(5):583-600.
[6] ANDERSON W A, FREEMAN R. Influence of a second radiofrequency field on high-resolution nuclear magnetic resonance spectra[J]. J Chem Phys, 1962, 37(1):85-103.
[7] 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):4226-4227.
[8] 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.
[9] SØRENSEN O W, GRIESINGER C, ERNST R R. Time-reversal of the evolution under scalar spin spin interactions in NMR-application for ω1 decoupling in two-dimensional NOE spectroscopy[J]. J Am Chem Soc, 1985, 107(25):7778-7779.
[10] PELL A J, EDDEN R A E, KEELER J. Broadband proton-decoupled proton spectra[J]. Magn Reson Chem, 2007, 45(4):296-316.
[11] GARBOW J R, WEITEKAMP D P, PINES A. Bilinear rotation decoupling of homonuclear scalar interactions[J]. Chem Phys Lett, 1982, 93(5):504-509.
[12] ZANGGER K, STERK H. Homonuclear broadband-decoupled NMR spectra[J]. J Magn Reson, 1997, 124(2):486-489.
[13] AGUILAR J A, FAULKNER S, NILSSON M, et al. Pure shift ¹H NMR:A resolution of the resolution problem?[J]. Angew Chem Int Ed, 2010, 49(23):3901-3903.
[14] LUPULESCU A, OLSEN G L, FRYDMAN L. Toward single-shot pure-shift solution ¹H NMR by trains of BIRD-based homonuclear decoupling[J]. J Magn Reson, 2012, 218:141-146.
[15] MEYER N H, ZANGGER K. Simplifying proton NMR spectra by instant homonuclear broadband decoupling[J]. Angew Chem Int Ed, 2013, 52(28):7143-7146.
[16] CASTAÑAR L, NOLIS P, VIRGILI A, et al. Full sensitivity and enhanced resolution in homodecoupled band-selective NMR[J]. Chem Eur J, 2013, 19(51):17283-17286.
[17] YING J, ROCHE J, BAX A. Homonuclear decoupling for enhancing resolution and sensitivity in NOE and RDC measurements of peptides and proteins[J]. J Magn Reson, 2014, 241:97-102.
[18] FOROOZANDEH M, ADAMS R W, MEHARRY N J, et al. Ultrahigh-resolution NMR spectroscopy[J]. Angew Chem Int Ed, 2014, 53(27):6990-6992.
[19] PAUDEL L, ADAMS R W, KIRALY P, et al. Simultaneously enhancing spectral resolution and sensitivity in heteronuclear correlation NMR spectroscopy[J]. Angew Chem Int Ed, 2013, 52(44):11616-11619.
[20] CASTAÑAR L, NOLIS P, VIRGILI A, et al. Experiments simultaneous multi-slice excitation in spatially encoded NMR experiments[J]. Chem Eur J, 2013, 19(46):15472-15475.
[21] COTTE A, JEANNERAT D. 1D NMR homodecoupled ¹H spectra with scalar coupling constants from 2D NemoZS-DIAG experiments[J]. Angew Chem Int Ed, 2015, 54(20):6016-6018.
[22] REINSPERGER T, LUY B. Homonuclear BIRD-decoupled spectra for measuring one-bond couplings with highest resolution:CLIP/CLAP-RESET and constant-time-CLIP/CLAP-RESET[J]. J Magn Reson, 2014, 239:110-120.
[23] KALTSCHNEE L, KOLMER A, TIMARI I, et al. "Perfecting" pure shift HSQC:Full homodecoupling for accurate and precise determination of heteronuclear couplings[J]. Chem Commun, 2014, 50(99):15702-15705.
[24] PEREZ-TRUJILLO M, CASTAÑAR L, MONTEAGUDO E, et al. Simultaneous ¹H and ¹³C NMR enantiodifferentiation from highly-resolved pure shift HSQC spectra[J]. Chem Commun, 2014, 50(71):10214-10217.
[25] CASTAÑAR L, ROLDAN R, CLAPES P, et al. Disentangling complex mixtures of compounds with near-identical ¹H and ¹³C NMR spectra using pure shift NMR spectroscopy[J]. Chem Eur J, 2015, 21(21):7682-7685.
[26] MARCÓ N, FREDI A, PARELLA T. Ultra high-resolution HSQC:Application to the efficient and accurate measurement of heteronuclear coupling constants[J]. Chem Commun, 2015, 51(15):3262-3265.
[27] HANSEN S U, MILLER G J, CLIFF M J, et al. Making the longest sugars:A chemical synthesis of heparin-related
[4]n oligosaccharides from 16-mer to 40-mer[J]. Chem Sci, 2015, 6(11):6158-6164.
[28] KAKITA V M, HOSUR R V. Non-uniform-sampling ultrahigh resolution TOCSY NMR:Analysis of complex mixtures at microgram levels[J]. ChemPhysChem, 2016, 17(15):2304-2308.
[29] 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):12770-12772.
[30] FOROOZANDEH M, ADAMS R W, NILSSON M, et al. Ultrahigh-resolution total correlation NMR spectroscopy[J]. J Am Chem Soc, 2014, 136(34):11867-11869.
[31] 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 Ed, 2011, 50(41):9716-9717.
[32] FOROOZANDEH M, ADAMS R W, KIRALY P, et al. Measuring couplings in crowded NMR spectra:Pure shift NMR with multiplet analysis[J]. Chem Commun, 2015, 51(84):15410-15413.
[33] ILGEN J, KALTSCHNEE L, THIELE C M. A pure shift experiment with increased sensitivity and superior performance for strongly coupled systems[J]. J Magn Reson, 2018, 286:18-29.
[34] MOUTZOURI P, CHEN Y X, FOROOZANDEH M, et al. Ultraclean pure shift NMR[J]. Chem. Commun, 2017, 53:10188.
[35] MAUHART J, GLANZER S, SAKHAII P, et al. Faster and cleaner real-time pure shift NMR experiments[J]. J Magn Reson, 2015, 259:207-215.
[36] NDUKWE I E, SHCHUKINA A, KAZIMIERCZUK K, et al. EXtended ACquisition Time (EXACT) NMR-a case for ‘burst’ non-uniform sampling[J]. ChemPhysChem, 2016, 17(18):2799-2803.
[37] KIRALY P, NILSSON M, MORRIS GA. Semi-real-time acquisition for fast pure shift NMR at maximum resolution[J]. J Magn Reson, 2018, 293:19-27.
[38] FREDI A, NOLIS P, COBAS C, et al. Exploring the use of generalized Indirect covariance to reconstruct pure shift NMR spectra:Current Pros and Cons[J]. J Magn Reson, 2016, 266:16-22.
[39] FREDI A, NOLIS P, COBAS C, et al. Access to experimentally infeasible spectra by pure-shift NMR covariance[J]. J Magn Reson, 2016, 270:161-168.
[40] LIU Y, GREEN M D, MARGUES R, et al. Using pure shift HSQC to characterize microgram samples of drug metabolites[J]. Tetrahedron Lett, 2014, 55(40):5450-5453.
[41] KALTSCHNEE L, KNOLL K, SCHMIDTS V, et al. Extraction of distance restraints from pure shift NOE experiments[J]. J Magn Reson, 2016, 271:99-109.
[42] CASTAÑAR L, PEREZ-TRUJILLO M, NOLIS P, et al. Enantiodifferentiation through frequency-selective pure shift ¹H nuclear magnetic resonance spectroscopy[J]. ChemPhysChem, 2014, 15(5):854-857.
[43] LAKSHMIPRIYA A, CHAUDHARI S R, SURYAPRAKASH N. Enantio-differentiation of molecules with diverse functionalities using a single probe[J]. Chem Commun, 2015, 51(70):13492-13495.
[44] ADAMS R W, BYRNE L, KIRALY P, et al. Diastereomeric ratio determination by high sensitivity band-selective pure shift NMR spectroscopy[J]. Chem Commun, 2014, 50(19):2512-2514.
[45] KAKITA V M R, VEMULAPALLI S P B, BHARATAM J. Band-selective excited ultrahigh resolution PSYCHE-TOCSY:Fast screening of organic molecules and complex mixtures[J]. Magn Reson Chem2016, 54(4):308-314.
[46] POGGETTO G D, CASTANAR L, MORRIS G A, et al. A new tool for NMR analysis of complex systems:Selective pure shift TOCSY[J]. RSC Adv, 2016, 6(102):100063-100066.
[47] NILSSON M, MORRIS G A. Pure shift proton DOSY:Diffusion-ordered ¹H spectra without multiplet structure[J]. Chem Commun, 2007, (9):933-935.
[48] HAMDOUN G, SEBBAN M, COSSOUL E, et al. 1H pure shift DOSY:A handy tool to evaluate the aggregation and solvation of organolithium derivatives[J]. Chem Commun, 2014, 50(31):4073-4075.
[49] GLANZER S, ZANGGER K. Directly decoupled diffusion-ordered NMR spectroscopy for the analysis of compound mixtures[J]. Chem Eur J, 2014, 20(35):11171-11175.
[50] LI C, ZHAN H L, YAN J, et al. A pure shift and spin echo based approach for high-resolution diffusion-ordered NMR spectroscopy[J]. J Magn Reson, 2019, 305:209-218.
[51] CASTAÑAR L, NOLIS P, VIRGILI A, et al. Measurement of T₁/T₂ relaxation times in overlapped regions from homodecoupled ¹H singlet signals[J]. J Magn Reson, 2014, 244:30-35.
[52] HUANG Y Q, ZHAN H L, YOU X Q, et al. A pure shift-based NMR method for transverse relaxation measurements on complex samples[J]. IEEE Transactions on Instrumentation and Measurement, publishing, 2019.
[53] HUANG Y Q, CAO S H, YANG Y, et al. Ultrahigh-resolution NMR spectroscopy for rapid chemical and biological applications inhomogeneous magnetic fields[J]. Anal Chem, 2017, 89:7115-7122.
[54] CHEN Z, HUANG Y Q, LIN Y Q, et al. Accurate measurement of small J Couplings[J]. Annual Reports on NMR Spectroscopy. 2010, 72:157-183.
[55] LIN Y Q, ZENG Q, LIN L J, et al. High-resolution methods for the measurement of scalar coupling constants[J]. Prog Nucl Magn Reson Spectrosc, 2018, 109:135-159.
[56] CASTAÑAR L, GARCÍA M, HELLEMANN E, et al. One-shot determination of residual dipolar couplings:Application to the structural discrimination of small molecules containing multiple stereocenters[J]. J Org Chem, 2016, 81(22):11126-11131.
[57] TIMÁRI I, KALTSCHNEE L, RAICS MH, et al. Real-time broadband proton-homodecoupled CLIP/CLAP-HSQC for automated measurement of heteronuclear one-bond coupling constants[J]. RSC Adv, 2016, 6(91):87848-87855.
[58] ZENG Q, LIN L J, CHEN J Y, et al. A simultaneous multi-slice selective J-resolved experiment for fully resolved scalar coupling information[J]. J Magn Reson, 2017, 282:27-31.
[59] LIN Y L, GUAN Q S, SU J W, et al. Combining Fourier phase encoding and broadband inversion toward J-edited spectra[J]. J Magn Reson, 2018, 291:1-7.
[60] ZENG Q, LIN Y Q, CHEN Z. Pushing resolution limits for extracting ¹H-¹H scalar coupling constants by a resolution-enhanced selective refocusing method[J]. J Chem Phys, 2019, 150:184-202.
[61] DONOVAN K J, FRYDMAN L. HyperBIRD:A sensitivity-enhanced approach to collecting homonuclear-decoupled proton NMR spectra[J]. Angew Chem Int Ed, 2015, 54(2):594-598.
[62] MAUVE C, KHLIFI S, GILARD F, et al. Sensitive, highly resolved, and quantitative ¹H-¹³C NMR data in one go for tracking metabolites in vegetal extracts[J]. Chem Commun, 2016, 52(36):6142-6145.
[63] ARIANA B J, GUY C L, DUŠAN U. SHARPER reaction monitoring:Generation of a narrow linewidth NMR singlet, without X-pulses, in an inhomogeneous magnetic field[J]. Anal Chem, 2017, 89:10013-10021.
[64] ELYASHBERG M E, WILLIAMS A J, MARTIN G E. Computer-assisted structure verification and elucidation tools in NMR-based structure elucidation[J]. Prog Nucl Magn Reson Spectrosc, 2008, 53(1-2):1-104.
[65] ELYASHBERG M E, WILLIAMS A, BLINOV K. Contemporary computer-assisted approaches to molecular structure elucidation[M]. Britain:RSC Publishing, 2012.