Journal
JOURNAL OF MAGNETIC RESONANCE
Volume 272, Issue -, Pages 123-128Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jmr.2016.09.006
Keywords
Dissolution dynamic nuclear polarization; Nuclear magnetic resonance; Correlation spectroscopy; Optimal control methods
Funding
- Welch Foundation [A-1658]
- National Science Foundation [CHE-1362691]
- Ji and Li Family Foundation
- Deutsche Forschungsgemeinschaft (DFG) [GI 203/7-2]
- Alexander von Humboldt Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1362691] Funding Source: National Science Foundation
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Off-resonance decoupling using the method of Scaling of Heteronuclear Couplings by Optimal Tracking (SHOT) enables determination of heteronuclear correlations of chemical shifts in single scan NMR spectra. Through modulation of J-coupling evolution by shaped radio frequency pulses, off resonance decoupling using SHOT pulses causes a user-defined dependence of the observed J-splitting, such as the splitting of C-13 peaks, on the chemical shift offset of coupled nuclei, such as H-1. Because a decoupling experiment requires only a single scan, this method is suitable for characterizing on-going chemical reactions using hyperpolarization by dissolution dynamic nuclear polarization (D-DNP). We demonstrate the calculation of [C-13, H-1] chemical shift correlations of the carbanionic active sites from hyperpolarized styrene polymerized using sodium naphthalene as an initiator. While off resonance decoupling by SHOT pulses does not enhance the resolution in the same way as a 2D NMR spectrum would, the ability to obtain the correlations in single scans makes this method ideal for determination of chemical shifts in on-going reactions on the second time scale. In addition, we present a novel SHOT pulse that allows to scale J-splittings 50% larger than the respective J-coupling constant. This feature can be used to enhance the resolution of the indirectly detected chemical shift and reduce peak overlap, as demonstrated in a model reaction between p-anisaldehyde and isobutylamine. For both pulses, the accuracy is evaluated under changing signal-to-noise ratios (SNR) of the peaks from reactants and reaction products, with an overall standard deviation of chemical shift differences compared to reference spectra of 0.02 ppm when measured on a 400 MHz NMR spectrometer. Notably, the appearance of decoupling side-bands, which scale with peak intensity, appears to be of secondary importance. (C) 2016 Elsevier Inc. All rights reserved.
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