Session: Parallel session 10 - Lipidomics, Metabolomics, and Small molecules
High resolution mass spectrometry-based untargeted approach: a cutting-edge analytical technique for the detection and identification of organophosphorus synthesis sources
The reported uses of chemical warfare agents (CWA) over the last years emphasize the need for analytical tools to support forensic investigations by enabling the identification of the toxic compounds, the samples comparison (batch-matching) and the sourcing of the agent employed. Chemical profiling approaches based on untargeted can provide further information to identify the source or the synthesis route of CWA. Nerve agents, a class of CWA, include mainly organophosphorus compounds that can be produced by various synthesis routes.
An original untargeted metabolomic high-resolution mass spectrometry-based approach for the sourcing of synthetic chemicals based on the specificity of synthesis by-products, impurities, and other compounds is presented. Crude chlorpyrifos (an organophosphorus pesticide) samples produced using 7 different synthesis protocols were used as a first use case, analyzed on a Bruker timsTOF fleX mass spectrometer coupled to liquid chromatography and using positive electrospray ionization. Data were extracted and processed using the collaborative portal workflow4metabolomics.
Statistical analyses highlighted a set of significant features discriminating each synthetic route thanks to rich annotation using retention times, accurate mass measurement, isotopic patterns, and ion mobility analyses (CCS values) to propose putative structures. MS/MS analyses were then conducted for unambiguous identification of the various discriminant compounds allowing to reveal the synthetic route used.
Chlorpyrifos chemical attribution signatures-based profiling can be used to readily differentiate samples of material and associate them with a particular source of reagents and/or synthetic pathway. This workflow proved to be efficient in the chlorpyrifos use case. It will be used to classify unknown samples based on the discriminating compounds and opens the way for extending this approach to the sourcing of various CWAs.
An original untargeted metabolomic high-resolution mass spectrometry-based approach for the sourcing of synthetic chemicals based on the specificity of synthesis by-products, impurities, and other compounds is presented. Crude chlorpyrifos (an organophosphorus pesticide) samples produced using 7 different synthesis protocols were used as a first use case, analyzed on a Bruker timsTOF fleX mass spectrometer coupled to liquid chromatography and using positive electrospray ionization. Data were extracted and processed using the collaborative portal workflow4metabolomics.
Statistical analyses highlighted a set of significant features discriminating each synthetic route thanks to rich annotation using retention times, accurate mass measurement, isotopic patterns, and ion mobility analyses (CCS values) to propose putative structures. MS/MS analyses were then conducted for unambiguous identification of the various discriminant compounds allowing to reveal the synthetic route used.
Chlorpyrifos chemical attribution signatures-based profiling can be used to readily differentiate samples of material and associate them with a particular source of reagents and/or synthetic pathway. This workflow proved to be efficient in the chlorpyrifos use case. It will be used to classify unknown samples based on the discriminating compounds and opens the way for extending this approach to the sourcing of various CWAs.