Analysis of NAD 2D-NMR Spectra of Saturated Fatty Acids in Polypeptide Aligning Media by Experimental and Modeling Approaches

Abstract : The overall and detailed elucidation (including the stereochemical aspects) of enzymatic mechanisms requires the access to all reliable information related to the natural isotopic fractionation of both precursors and products. Natural abundance deuterium (NAD) 2D-NMR experiments in polypeptide liquid-crystalline solutions are a new, suitable tool for analyzing site-specific deuterium isotopic distribution profiles. Here this method is utilized for analyzing saturated C14 to C18 fatty acid methyl esters (FAMEs), which are challenging because of the crowding of signals in a narrow spectral region. Experiments in achiral and chiral oriented solutions were performed. The spectral analysis is supplemented by the theoretical prediction of quadrupolar splittings as a function of the geometry and flexibility of FAMEs, based on a novel computational methodology. This allows us to confirm the spectral assignments, while providing insights into the mechanism of solute ordering in liquid-crystalline polypeptide solutions. This is found to be dominated by steric repulsions between FAMEs and polypeptides.
Document type :
Journal articles
Complete list of metadatas

https://hal.archives-ouvertes.fr/hal-02143143
Contributor : Jean Michel Bouler <>
Submitted on : Wednesday, May 29, 2019 - 10:41:16 AM
Last modification on : Saturday, October 26, 2019 - 2:04:45 AM

Links full text

Identifiers

Citation

Zeinab Serhan, Andrea Borgogno, Isabelle Billault, Alberta Ferrarini, Philippe Lesot. Analysis of NAD 2D-NMR Spectra of Saturated Fatty Acids in Polypeptide Aligning Media by Experimental and Modeling Approaches. Chemistry - A European Journal, Wiley-VCH Verlag, 2012, 18 (1), pp.117-126. ⟨10.1002/chem.201102775⟩. ⟨hal-02143143⟩

Share

Metrics

Record views

23