Ultrafast multidimensional Laplace NMR for a rapid and sensitive chemical analysis

Traditional nuclear magnetic resonance (NMR) spectroscopy relies on the versatile chemical information conveyed by spectra. To complement conventional NMR, Laplace NMR explores diffusion and relaxation phenomena to reveal details on molecular motions. Under a broad concept of ultrafast multidimensional Laplace NMR, here we introduce an ultrafast diffusion-relaxation correlation experiment enhancing the resolution and information content of corresponding 1D experiments as well as reducing the experiment time by one to two orders of magnitude or more as compared with its conventional 2D counterpart. We demonstrate that the method allows one to distinguish identical molecules in different physical environments and provides chemical resolution missing in NMR spectra. Although the sensitivity of the new method is reduced due to spatial encoding, the single-scan approach enables one to use hyperpolarized substances to boost the sensitivity by several orders of magnitude, significantly enhancing the overall sensitivity of multidimensional Laplace NMR.

[1]  B. M. Goodson,et al.  Nuclear magnetic resonance of laser-polarized noble gases in molecules, materials, and organisms. , 2002, Journal of magnetic resonance.

[2]  S. Ahola,et al.  Ultrafast two-dimensional NMR relaxometry for investigating molecular processes in real time. , 2014, Chemphyschem : a European journal of chemical physics and physical chemistry.

[3]  D. J. Tomlinson,et al.  Nuclear spin relaxation and self-diffusion in the binary system, dimethylsulphoxide (DMSO)+ water , 1971 .

[4]  J. Keeler,et al.  A fast method for the measurement of diffusion coefficients: one‐dimensional DOSY , 2003 .

[5]  S. Akoka,et al.  "Multi-scan single shot" quantitative 2D NMR: a valuable alternative to fast conventional quantitative 2D NMR. , 2011, The Analyst.

[6]  Yi-Qiao Song Magnetic resonance of porous media (MRPM): a perspective. , 2013, Journal of magnetic resonance.

[7]  J. Ardenkjær-Larsen,et al.  Increase in signal-to-noise ratio of > 10,000 times in liquid-state NMR , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[8]  G. Bodenhausen,et al.  Spin echo NMR spectra without J modulation. , 2012, Chemical communications.

[9]  E. P. Lewis In perspective. , 1972, Nursing outlook.

[10]  J. E. Tanner Use of the Stimulated Echo in NMR Diffusion Studies , 1970 .

[11]  S. Meiboom,et al.  Modified Spin‐Echo Method for Measuring Nuclear Relaxation Times , 1958 .

[12]  Philippe Pelupessy,et al.  Adiabatic single scan two-dimensional NMR spectrocopy. , 2003, Journal of the American Chemical Society.

[13]  Lucio Frydman,et al.  Ultrafast two-dimensional nuclear magnetic resonance spectroscopy of hyperpolarized solutions , 2007 .

[14]  Ray Freeman,et al.  Hadamard NMR Spectroscopy , 2004 .

[15]  Acknowledgements , 1992, Experimental Gerontology.

[16]  K. Ogura,et al.  A perfect spin echo in a weakly homonuclear J-coupled two spin-1/2 system , 1989 .

[17]  S. Provencher A constrained regularization method for inverting data represented by linear algebraic or integral equations , 1982 .

[18]  Paul Strauss,et al.  Magnetic Resonance Imaging Physical Principles And Sequence Design , 2016 .

[19]  T Sun,et al.  Pulsed field gradient stimulated echo methods for improved NMR diffusion measurements in heterogeneous systems , 1989 .

[20]  J. Keeler Understanding NMR Spectroscopy , 2005 .

[21]  Lalitha Venkataramanan,et al.  Solving Fredholm integrals of the first kind with tensor product structure in 2 and 2.5 dimensions , 2002, IEEE Trans. Signal Process..

[22]  G. Morris,et al.  One-dimensional DOSY. , 2001, Journal of magnetic resonance.

[23]  G. C. Borgia,et al.  Uniform-penalty inversion of multiexponential decay data. , 1998, Journal of magnetic resonance.

[24]  Daniel Topgaard,et al.  NMR diffusion and relaxation correlation methods: New insights in heterogeneous materials , 2013 .

[25]  J C Gore,et al.  Errors in the measurements of T2 using multiple‐echo MRI techniques. I. Effects of radiofrequency pulse imperfections , 1986, Magnetic resonance in medicine.

[26]  P Mansfield,et al.  Spatial mapping of the chemical shift in NMR , 1983, Magnetic resonance in medicine.

[27]  L. Frydman,et al.  Ultrafast NMR T1 relaxation measurements: probing molecular properties in real time. , 2013, Chemphyschem : a European journal of chemical physics and physical chemistry.

[28]  L Venkataramanan,et al.  T(1)--T(2) correlation spectra obtained using a fast two-dimensional Laplace inversion. , 2002, Journal of magnetic resonance.

[29]  P. Callaghan,et al.  2D relaxation/diffusion correlations in porous media. , 2003, Magnetic resonance imaging.

[30]  Jozef Kowalewski,et al.  Nuclear spin relaxation in liquids : theory, experiments, and applications , 2006 .

[31]  Paul T. Callaghan,et al.  Translational Dynamics and Magnetic Resonance: Principles of Pulsed Gradient Spin Echo NMR , 2011 .

[32]  Robin K. Harris,et al.  Encyclopedia of nuclear magnetic resonance , 1996 .

[33]  R. Griffin,et al.  Single-scan longitudinal relaxation measurements in high-resolution NMR spectroscopy. , 2003, Journal of magnetic resonance.

[34]  D. Freed Dependence on chain length of NMR relaxation times in mixtures of alkanes. , 2007, The Journal of chemical physics.

[35]  Yi-Qiao Song,et al.  Scaling laws for diffusion coefficients in mixtures of alkanes. , 2005, Physical review letters.

[36]  Lucio Frydman,et al.  Single-scan multidimensional magnetic resonance. , 2010, Progress in nuclear magnetic resonance spectroscopy.

[37]  Josef Granwehr,et al.  Inverse Laplace Transform of Multidimensional Relaxation Data Without Non-Negativity Constraint. , 2012, Journal of chemical theory and computation.

[38]  C. Hilty,et al.  Implementation and characterization of flow injection in dissolution dynamic nuclear polarization NMR spectroscopy. , 2015, Chemphyschem : a European journal of chemical physics and physical chemistry.

[39]  Lucio Frydman,et al.  The acquisition of multidimensional NMR spectra within a single scan , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[40]  S. Ahola,et al.  Microfluidic gas-flow imaging utilizing parahydrogen-induced polarization and remote-detection NMR. , 2010, Angewandte Chemie.

[41]  M. Levitt Singlet nuclear magnetic resonance. , 2012, Annual review of physical chemistry.

[42]  V. Krishnan,et al.  Radiation damping in modern NMR experiments: progress and challenges. , 2013, Progress in nuclear magnetic resonance spectroscopy.