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Sensitivity gains, linearity, and spectral reproducibility in nonuniformly sampled multidimensional MAS NMR spectra of high dynamic range

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Abstract

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear 13C–13C correlation spectra. We demonstrate on model compounds and on 1–73-(U-13C,15N)/74–108-(U-15N) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7–2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear 13C–13C MAS correlation experiments that yield high-quality artifact-free datasets.

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Acknowledgments

This work was supported by the National Institutes of Health (NIH Grants R01GM085306, P50GM082251, and P30GM103519 from NIGMS, and P30RR031160 from NCRR), and by Agilent University Collaborative Research award. We acknowledge the support of the National Science Foundation (NSF Grant CHE0959496) for the acquisition of the 850 MHz NMR spectrometer at the University of Delaware. The 21.1 T spectra were acquired at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the United States Department of Energy’s Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory in Richland, WA. The kind assistance of Andrew Lipton, Sarah Burton, Jesse Sears, Michael Froehlke, and Joseph Ford during our visit to EMSL is gratefully acknowledged.

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Author notes

  1. Sivakumar Paramasivam

    Present address: Department of Astrophysics, Pondicherry University, Puducherry, 605 014, India

  2. Shangjin Sun

    Present address: Structural Biophysics Laboratory, Center for Cancer Research, National Cancer Institute, Frederick, MD, USA

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716, USA

    Christopher L. Suiter, Sivakumar Paramasivam, Guangjin Hou, Shangjin Sun & Tatyana Polenova

  2. Pittsburgh Center for HIV Protein Interactions, University of Pittsburgh School of Medicine, Pittsburgh, PA, 15261, USA

    Christopher L. Suiter, Guangjin Hou & Tatyana Polenova

  3. Agilent Technologies Inc., Santa Clara, CA, 95051, USA

    David Rice

  4. Department of Molecular Biology and Biophysics, University of Connecticut Health Center, Farmington, CT, 06030-3305, USA

    Jeffrey C. Hoch

  5. Department of Chemistry, Bucknell University, Lewisburg, PA, 17837, USA

    David Rovnyak

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  1. Christopher L. Suiter
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Correspondence to Tatyana Polenova.

Electronic supplementary material

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10858_2014_9824_MOESM1_ESM.pdf

Supplementary material 1 (PDF 2347 kb): Figures for stack view of FFT and MINT reconstructions, correlation plots of absolute peak intensity vs. sensitivity enhancements, relative sensitivity enhancement vs. T2*/TSMP, correlation plots of absolute peak intensities vs. line width differences (NUS - US), correlation plots for sub-sampled NUS data, and comparison of NUS reconstructions using different λ values. Tables summarizing sensitivity and line widths for each of the ten 50 % NUS experiments acquired with equivalent experiment time compared to US for l-histidine and expanded experimental details

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Suiter, C.L., Paramasivam, S., Hou, G. et al. Sensitivity gains, linearity, and spectral reproducibility in nonuniformly sampled multidimensional MAS NMR spectra of high dynamic range. J Biomol NMR 59, 57–73 (2014). https://doi.org/10.1007/s10858-014-9824-4

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