Abstract
1H-1H coupling constants are one of the primary sources of information for NMR structural analysis. Several selective 2DJ experiments have been proposed that allow their individual measurement at pure shift resolution. However, all these experiments fail in the not uncommon case when coupled protons have very close chemical shifts. Firstly, the coupling between protons with overlapping multiplets is inaccessible due to the inability of a frequency-selective pulse to invert just one of them. Secondly, the strong coupling condition affects the accuracy of coupling measurements involving third spins. These shortcomings impose a limit on the effectiveness of state-of-the-art experiments, such as G-SERF or PSYCHEDELIC. Here, we introduce two new and complementary selective 2DJ experiments that we coin SERFBIRD and SATASERF. These experiments overcome the aforementioned issues by utilizing the 13C satellite signals at natural isotope abundance, which resolve the chemical shift degeneracy. We demonstrate the utility of these experiments on the tetrasaccharide stachyose and the challenging case of norcamphor, for the latter achieving measurement of all JHH couplings while only few were accessible with PSYCHEDELIC. The new experiments are applicable to any organic compound and will prove valuable for configurational and conformational analyses.
Supplementary materials
Title
Supporting information
Description
The Supporting Information contains the experimental section, phase cycles and gradient amplitudes, signal-to-noise comparisons, setup guidelines for SERFBIRD and SATASERF, simulations on the impact of magnetic field strength on strong coupling involving 13C satellites, and an overview of NMR spectra and coupling data for stachyose and norcamphor.
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Title
SERFBIRD pulse sequence
Description
Bruker pulse sequence code for the SERFBIRD experiment.
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Title
SATASERF pulse sequence
Description
Bruker pulse sequence code for the SATASERF experiment.
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