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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/461daf2a-7d69-4594-9405-44fe077144c4
- author
- Carlström, Göran
LU
; Elvander, Filip
LU
; Swärd, Johan
LU
; Jakobsson, Andreas
LU
and Akke, Mikael
LU
- organization
- publishing date
- 2019-06-13
- 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
- 2022-04-26 01:45:52
@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}},
}