pH-Dependent Piecewise Linear Correlation of H-1, P-31 Chemical Shifts : Application in NMR Identification of Nerve Agent Metabolites in Urine Samples

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Koskela , H , Andjelkovic , B , Pettersson , A , Rapinoja , M-L , Kuitunen , M-L & Vanninen , P 2018 , ' pH-Dependent Piecewise Linear Correlation of H-1, P-31 Chemical Shifts : Application in NMR Identification of Nerve Agent Metabolites in Urine Samples ' , Analytical Chemistry , vol. 90 , no. 14 , pp. 8495-8500 . https://doi.org/10.1021/acs.analchem.8b01308

Title: pH-Dependent Piecewise Linear Correlation of H-1, P-31 Chemical Shifts : Application in NMR Identification of Nerve Agent Metabolites in Urine Samples
Author: Koskela, Harri; Andjelkovic, Boban; Pettersson, Annette; Rapinoja, Marja-Leena; Kuitunen, Marja-Leena; Vanninen, Paula
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
Date: 2018-07-17
Language: eng
Number of pages: 6
Belongs to series: Analytical Chemistry
ISSN: 0003-2700
URI: http://hdl.handle.net/10138/256023
Abstract: The NMR-observable nuclei of the acidic and basic compounds experience pH dependence in chemical shift. This phenomenon can be exploited in NMR titrations to deter- mine pK a values of compounds, or in pH measurement of solutions using dedicated pH reference compounds. On the other hand, this sensitivity can also cause problems in, for example, metabolomics, where slight changes in pH result in significant difficulties for peak alignment between spectra of set of samples for comparative analysis. In worst case, the pH sensitivity of chemical shifts can prevent unambiguous identification of compounds. Here, we propose an alternative approach for NMR identification of pH-sensitive analytes. The H-1 and X (C-13, N-15, P-31, ...) chemical shifts in close proximity to the acidic or basic functional group should, when presented as ordered pairs, express piecewise linear correlation with distinct slope, intercept, and range. We have studied the pH dependence of H-1 and P-31 chemical shifts of the CH3-P moiety in urinary metabolites of nerve agents sarin, soman and VX using 2D H-1-P-31 fast-HMQC spectroscopy. The H-1 and P-31 chemical shifts of these chemicals appear in very narrow range, and due to subtle changes in sample pH the identification on either H-1 or P-31 chemical shift alone is uncertain. However, if the observed H-1 and P-31 chemical shifts of the CH3-P moiety of individual compounds are presented as ordered pairs, they fall into distinct linear spaces, thus, facilitating identification with high confidence.
Subject: 116 Chemical sciences
WEAPONS CONVENTION
DISSOCIATION-CONSTANTS
DEGRADATION-PRODUCTS
SPECTROSCOPY
WATER
ACIDS
1D
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