Pure-shift NMR experiments provide highly resolved spectra, which could be perfect for precise monitoring of chemical shift variations under different conditions, such as temperature or concentration. However, their sensitivity is relatively low and signal sampling is time-consuming, which leads to long experimental times, making such serial acquisition problematic. In this paper we present a new method of NMR spectroscopy which improves the speed and sensitivity of serial pseudo-two-dimensional pure-shift experiments. The example of variable-temperature study of atorvastatin reveals the potential of the method in verifying the theoretical predictions of solvent-dependent spectral effects.
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http://dx.doi.org/10.1039/c9cp03921j | DOI Listing |
Anal Chim Acta
January 2025
Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance, Department of Electronic Science, State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, 361005, China. Electronic address:
Background: Relaxation time provides invaluable insights into the molecular structure, interactions, and dynamics in nuclear magnetic resonance spectroscopy. However, conventional relaxation-time measurement techniques produce inaccurate relaxation times when the spectral peaks overlap because of the narrow chemical-shift range and J-coupled splitting. While the combination of pure-shift methods can solve this issue, they are not widely used due to their inherent drawbacks such as low sensitivity and long acquisition time.
View Article and Find Full Text PDFJ Magn Reson
November 2024
Department of Chemistry, The University of Manchester, Oxford Rd, Manchester M13 9PL, United Kingdom. Electronic address:
Slice-selective refocusing pulses are powerful building blocks in contemporary magnetic resonance experiments, but their use in quantitative applications is complicated by the site-dependent signal loss they introduce. One source of this attenuation is the spin relaxation that occurs during such pulses, which causes losses that depend on the specific longitudinal and transverse relaxation time constants for a given resonance. This dependence is complicated both by any amplitude shaping of the radiofrequency pulse, and by the presence of the spatial encoding pulsed field gradient.
View Article and Find Full Text PDFChemistry
January 2025
Nantes Université, CNRS, CEISAM UMR6230, Nantes, France.
Flow NMR is an expanding analytical approach with applications that include in-line analysis for process control and optimisation, and real-time reaction monitoring. The samples monitored by flow NMR are typically mixtures that yield complex 1D H spectra. "Pure shift" NMR is a powerful approach to simplifying H NMR spectra, but its standard implementation is not compatible with continuous flow because of interference between sample motion and the position-dependent spin manipulations that are required in pure shift NMR.
View Article and Find Full Text PDFMagn Reson Chem
December 2024
Department of Chemistry, Indian Institute of Technology Delhi, New Delhi, India.
Measurement of scalar couplings between protons is a very challenging task because of complex multiplet patterns and severe overlapping of these multiplets in congested 1D spectra. Numerous 2D J-resolved sequences now exist that utilize either the Zangger-Sterk or PSYCHE or z-filter elements along with selective refocusing and pure-shift schemes to generate high-resolution phase-sensitive spectra with simple doublets in dimension. Herein, we present a 2D J-resolved sequence that employs a simple element consisting of hard pulses and inter-pulse delays to generate phase-sensitive spectra.
View Article and Find Full Text PDFAnal Chem
August 2024
Department of Electronic Science, Fujian Provincial Key Laboratory of Plasma and Magnetic Resonance, State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China.
As one of the commonly used intact detection techniques, liquid NMR spectroscopy offers unparalleled insights into the chemical environments, structures, and dynamics of molecules. However, it generally encounters the challenges of crowded or even overlapped spectra, especially when probing complex sample systems containing numerous components and complicated molecular structures. Herein, we exploit a general NMR protocol for efficient NMR analysis of complex systems by combining fast pure shift NMR and GEMSTONE-based selective TOCSY.
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