31P-Edited Diffusion-Ordered 1H NMR Spectroscopy for the Spectral Isolation and Identification of Organophosphorus Compounds Related to Chemical Weapons Agents and Their Degradat

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• 作者：Brian P. Mayer ; Carlos A. Valdez ; Saphon Hok ; Sarah C. Chinn ; Bradley R. Hart
• 刊名：Analytical Chemistry
• 出版年：2012
• 出版时间：December 4, 2012
• 年：2012
• 卷：84
• 期：23
• 页码：10478-10484
• 全文大小：277K
• 年卷期：v.84,no.23(December 4, 2012)
• ISSN：1520-6882

文摘

Organophosphorus compounds represent a large class of molecules that include pesticides, flame-retardants, biologically relevant molecules, and chemical weapons agents (CWAs). The detection and identification of organophosphorus molecules, particularly in the cases of pesticides and CWAs, are paramount to the verification of international treaties by various organizations. To that end, novel analytical methodologies that can provide additional support to traditional analyses are important for unambiguous identification of these compounds. We have developed an NMR method that selectively edits for organophosphorus compounds via ³¹P鈥?sup>1H heteronuclear single quantum correlation (HSQC) and provides an additional chromatographic-like separation based on self-diffusivities of the individual species via ¹H diffusion-ordered spectroscopy (DOSY): ¹H鈥?sup>31P HSQC-DOSY. The technique is first validated using the CWA VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) by traditional two-dimensional DOSY spectra. We then extend this technique to a complex mixture of VX degradation products and identify all the main phosphorus-containing byproducts generated after exposure to a zinc-cyclen organometallic homogeneous catalyst.