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gNMR

Development of gradient spatially encoded NMR : toward a novel generation of correlation experiments.
Funder: French National Research Agency (ANR)Project code: ANR-11-JS08-0009
Funder Contribution: 219,457 EUR
Description

NMR spectroscopy has proved to be a unique tool for probing structure and dynamics in a wide range of molecular assemblies. Continuous methodological developments, combined with the breakthroughs which have been accomplished in probe and spectrometer hardwares have led to a variety of high-resolution experiments that have paved the way for an accurate measurement of large ensembles of spin interactions. These observables are particularly useful to constrain the most sophisticated simulations, allowing to describe complex chemical species and processes at an atomic level. Unfortunately, in most of the systems that are of interest to the scientific community nowadays, the size or the complexity of the molecular architecture which is probed often leads to overcrowded spectra whose resolution is too low to give access to their analytical content. Neither the use of very high field spectrometers, nor the development of pulse sequences that combine broadband and selective irradiations have allowed to fully address this problem. In this context, we have recently proposed to develop an original concept which consists in carrying out a parallel acquisition of different experiments using a single-receiver-coil system. We have successfully shown that this approach could be applied to run different selective echoes in different parts of an NMR sample, leading to a spin-spin coupling edition of the interaction network around a selected spin nucleus. Following up these encouraging results, the research proposal aims at providing NMR spectroscopists with a novel generation of correlation experiments based on a sample spatial frequency encoding. First, a set of simulation programs will be developed, that will target the evaluation of the NMR signal, based on the analytical calculation of the evolution of spin coherences, which results from a gradient encoded pulse sequence. Second, capitalizing on this theoretical tool, we will then focus on the methodological development of new, high-resolution correlation techniques inspired by this sample gradient encoding concept. Third, since gradient encoded spectroscopy is intrinsically less sensitive than standard NMR experiments, we will aim at exploring several techniques as potential alternatives to improve sensitivity. Among them, we will notably study in what extent the use of para-hydrogen as a polarizing agent is compatible with our experimental schemes. Our ultimate goal will be to apply the high-resolution sequences that will result from this work to address challenging systems : these sequences will first be incorporated into a structural analysis protocol that will be applied to determine the stereochemistry of synthetic oligosaccharides. Then, we will evaluate the ability of the gradient encoded selective refocusing (G-SERF) spectroscopy to simplify enantiomeric visualization when it is applied to enantiomeric mixtures dissolved in chiral liquid crystals. Finally, we will focus on quantitativity (which is an essential issue in analytical chemistry), in the frame of an accurate evaluation of enantiomeric excesses.

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