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Rapid NMR Relaxation Rate Measurements Using Optimal Non-Uniform Sampling of Multi-Dimensional Accordion Data Analyzed by a Sparse Reconstruction Method

Carlström, Göran LU ; Elvander, Filip LU ; Swärd, Johan LU ; Jakobsson, Andreas LU and Akke, Mikael LU (2019) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 123(27). p.5718-5723
Abstract
Nonuniform sampling (NUS) of multidimensional NMR data offers significant time savings while improving spectral resolution or increasing sensitivity per unit time. However, NUS has not been widely used for quantitative analysis because of the nonlinearity of most methods used to model NUS data, which leads to problems in estimating signal intensities, relaxation rate constants, and their error bounds. Here, we present an approach that avoids these limitations by combining accordion spectroscopy and NUS in the indirect dimensions of multidimensional spectra and then applying sparse exponential mode analysis, which is well suited for analyzing accordion-type relaxation data in a NUS context. By evaluating the Cramér-Rao lower bound of the... (More)
Nonuniform sampling (NUS) of multidimensional NMR data offers significant time savings while improving spectral resolution or increasing sensitivity per unit time. However, NUS has not been widely used for quantitative analysis because of the nonlinearity of most methods used to model NUS data, which leads to problems in estimating signal intensities, relaxation rate constants, and their error bounds. Here, we present an approach that avoids these limitations by combining accordion spectroscopy and NUS in the indirect dimensions of multidimensional spectra and then applying sparse exponential mode analysis, which is well suited for analyzing accordion-type relaxation data in a NUS context. By evaluating the Cramér-Rao lower bound of the variances of the estimated relaxation rate constants, we achieve a robust benchmark for the underlying reconstruction model. Furthermore, we design NUS schemes optimized with respect to the information theoretical lower bound of the error in the parameters of interest, given a specified number of sampling points. The accordion-NUS method compares favorably with conventional relaxation experiments in that it produces identical results, within error, while shortening the length of the experiment by an order of magnitude. Thus, our approach enables rapid acquisition of NMR relaxation data for optimized use of spectrometer time or accurate measurements on samples of limited lifetime. (Less)
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type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
123
issue
27
pages
6 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85069620577
  • pmid:31194551
ISSN
1089-5639
DOI
10.1021/acs.jpca.9b04152
language
English
LU publication?
yes
id
461daf2a-7d69-4594-9405-44fe077144c4
date added to LUP
2019-06-18 22:13:37
date last changed
2020-01-13 02:02:42
@article{461daf2a-7d69-4594-9405-44fe077144c4,
  abstract     = {Nonuniform sampling (NUS) of multidimensional NMR data offers significant time savings while improving spectral resolution or increasing sensitivity per unit time. However, NUS has not been widely used for quantitative analysis because of the nonlinearity of most methods used to model NUS data, which leads to problems in estimating signal intensities, relaxation rate constants, and their error bounds. Here, we present an approach that avoids these limitations by combining accordion spectroscopy and NUS in the indirect dimensions of multidimensional spectra and then applying sparse exponential mode analysis, which is well suited for analyzing accordion-type relaxation data in a NUS context. By evaluating the Cramér-Rao lower bound of the variances of the estimated relaxation rate constants, we achieve a robust benchmark for the underlying reconstruction model. Furthermore, we design NUS schemes optimized with respect to the information theoretical lower bound of the error in the parameters of interest, given a specified number of sampling points. The accordion-NUS method compares favorably with conventional relaxation experiments in that it produces identical results, within error, while shortening the length of the experiment by an order of magnitude. Thus, our approach enables rapid acquisition of NMR relaxation data for optimized use of spectrometer time or accurate measurements on samples of limited lifetime.},
  author       = {Carlström, Göran and Elvander, Filip and Swärd, Johan and Jakobsson, Andreas and Akke, Mikael},
  issn         = {1089-5639},
  language     = {eng},
  month        = {06},
  number       = {27},
  pages        = {5718--5723},
  publisher    = {The American Chemical Society (ACS)},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Rapid NMR Relaxation Rate Measurements Using Optimal Non-Uniform Sampling of Multi-Dimensional Accordion Data Analyzed by a Sparse Reconstruction Method},
  url          = {http://dx.doi.org/10.1021/acs.jpca.9b04152},
  doi          = {10.1021/acs.jpca.9b04152},
  volume       = {123},
  year         = {2019},
}