Novel Nuclear Magnetic Resonance Method for Position-Specific Carbon Isotope Analysis of Organic Molecules with Significant Impurities

Rasmussen, Cornelia; Hoffman, David W.

doi:10.1021/acs.analchem.2c03356

Novel Nuclear Magnetic Resonance Method for Position-Specific Carbon Isotope Analysis of Organic Molecules with Significant Impurities

Journal Article · Thu Oct 20 00:00:00 EDT 2022 · Analytical Chemistry

DOI:https://doi.org/10.1021/acs.analchem.2c03356· OSTI ID:1922646

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Univ. of Texas at Austin, TX (United States); University of Texas at Austin, Austin, TX (United States), Jackson School of Geoscience
Univ. of Texas at Austin, TX (United States)

We introduce a novel nuclear magnetic resonance (NMR) tool for determining position-specific carbon (¹³C/¹²C) isotope ratios within complex organic molecules. This analytical advancement allows us to measure position-specific isotope ratios of samples that contain impurities with NMR peaks that overlap with the signals of interest. The method involves collecting a series of alternating ¹³C-coupled and ¹³C-decoupled ¹H NMR spectra using an NMR pulse sequence designed to optimize temperature stability, followed by a data reduction scheme that allows the signals of interest to be isolated from signals of impurities. The method was validated using glycine reference materials with known ¹³C/¹²C ratios from the US Geological Survey (USGS) into which impurities typically found in amino acid samples were intentionally introduced. Following validation, the method was used to determine position-specific ¹³C/¹²C ratios in a set of USGS l-valine materials (USGS73, -74, -75) that contain significant impurities associated with their biological origin. The l-valines were found to contain distinct intramolecular isotope variability, and the ¹³Cα isotope spikes in USGS74 and USGS75 were clearly detected, where they preserve carbon isotope ratios of –4.8 ± 0.9‰ and +11.5 ± 0.8‰, respectively. Carbon isotope abundance at the beta and gamma positions indicates that the USGS73 l-valine was obtained from a different source than USGS74 and -75. Furthermore, this analytical approach is a significant step forward in the field of position-specific isotope analysis at natural abundance via NMR because it enables the investigation of samples that contain impurities which are typically present in samples derived from natural sources.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Texas at Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022524

OSTI ID:: 1922646

Journal Information:: Analytical Chemistry, Journal Name: Analytical Chemistry Journal Issue: 43 Vol. 94; ISSN 0003-2700

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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