Nonuniform sampling and maximum entropy reconstruction in multidimensional NMR

Hoch, Jeffrey C., Maciejewski, Mark W., Mobli, Mehdi, Schuyler, Adam D. and Stern, Alan S. (2014) Nonuniform sampling and maximum entropy reconstruction in multidimensional NMR. Accounts of Chemical Research, 47 2: 708-717. doi:10.1021/ar400244v

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Author Hoch, Jeffrey C.
Maciejewski, Mark W.
Mobli, Mehdi
Schuyler, Adam D.
Stern, Alan S.
Title Nonuniform sampling and maximum entropy reconstruction in multidimensional NMR
Journal name Accounts of Chemical Research   Check publisher's open access policy
ISSN 0001-4842
Publication date 2014-02-18
Sub-type Article (original research)
DOI 10.1021/ar400244v
Open Access Status File (Author Post-print)
Volume 47
Issue 2
Start page 708
End page 717
Total pages 10
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Formatted abstract
NMR spectroscopy is one of the most powerful and versatile analytic tools available to chemists. The discrete Fourier transform (DFT) played a seminal role in the development of modern NMR, including the multidimensional methods that are essential for characterizing complex biomolecules. However, it suffers from well-known limitations: chiefly the difficulty in obtaining high-resolution spectral estimates from short data records. Because the time required to perform an experiment is proportional to the number of data samples, this problem imposes a sampling burden for multidimensional NMR experiments. At high magnetic field, where spectral dispersion is greatest, the problem becomes particularly acute. Consequently multidimensional NMR experiments that rely on the DFT must either sacrifice resolution in order to be completed in reasonable time or use inordinate amounts of time to achieve the potential resolution afforded by high-field magnets.

Maximum entropy (MaxEnt) reconstruction is a non-Fourier method of spectrum analysis that can provide high-resolution spectral estimates from short data records. It can also be used with nonuniformly sampled data sets. Since resolution is substantially determined by the largest evolution time sampled, nonuniform sampling enables high resolution while avoiding the need to uniformly sample at large numbers of evolution times. The Nyquist sampling theorem does not apply to nonuniformly sampled data, and artifacts that occur with the use of nonuniform sampling can be viewed as frequency-aliased signals. Strategies for suppressing nonuniform sampling artifacts include the careful design of the sampling scheme and special methods for computing the spectrum. Researchers now routinely report that they can complete an N-dimensional NMR experiment 3N–1 times faster (a 3D experiment in one ninth of the time). As a result, high-resolution three- and four-dimensional experiments that were prohibitively time consuming are now practical. Conversely, tailored sampling in the indirect dimensions has led to improved sensitivity.

Further advances in nonuniform sampling strategies could enable further reductions in sampling requirements for high resolution NMR spectra, and the combination of these strategies with robust non-Fourier methods of spectrum analysis (such as MaxEnt) represent a profound change in the way researchers conduct multidimensional experiments. The potential benefits will enable more advanced applications of multidimensional NMR spectroscopy to study biological macromolecules, metabolomics, natural products, dynamic systems, and other areas where resolution, sensitivity, or experiment time are limiting. Just as the development of multidimensional NMR methods presaged multidimensional methods in other areas of spectroscopy, we anticipate that nonuniform sampling approaches will find applications in other forms of spectroscopy.
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Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
Centre for Advanced Imaging Publications
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Citation counts: TR Web of Science Citation Count  Cited 39 times in Thomson Reuters Web of Science Article | Citations
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Created: Wed, 19 Feb 2014, 03:47:20 EST by Sandrine Ducrot on behalf of Centre for Advanced Imaging