Identification of organic micro-pollutants in surface water using MS-based infrared ion spectroscopy

Houthuijs, Kas J.; Horn, Marijke; Vughs, Dennis; Martens, Jonathan; Brunner, Andrea M.; Oomens, Jos; Berden, Giel

doi:10.1016/j.chemosphere.2023.140046

Cited by 1 publication

(1 citation statement)

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“…It is challenging to assign a single isomer due to the similarity of several of the computed reference spectra and the sheer number of computed spectra. Therefore, we also examine one of the MS/MS fragment ions of MB to reduce the size of the ion and potentially simplify its IR spectrum. , When we examine the MS/MS spectrum in Figure B, we observe an ion at m / z 309. This indicates a fragment with the chemical formula C 14 H 22 O 6 (+Na + ), which fits with an oxidation of the geraniol tail.…”

Section: Resultsmentioning

confidence: 99%

Structural Elucidation of Agrochemical Metabolic Transformation Products Based on Infrared Ion Spectroscopy to Improve In Silico Toxicity Assessment

Vink,

Alarcan,

Martens

et al. 2023

Chem. Res. Toxicol.

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Toxicological assessments of newly developed agrochemical agents consider chemical modifications and their metabolic and biotransformation products. To carry out an in silico hazard assessment, understanding the type of chemical modification and its location on the original compound can greatly enhance the reliability of the evaluation. Here, we present and apply a method based on liquid chromatography−mass spectrometry (LC−MS) enhanced with infrared ion spectroscopy (IRIS) to better delineate the molecular structures of transformation products before in silico toxicology evaluation. IRIS facilitates the recording of IR spectra directly in the mass spectrometer for features selected by retention time and mass-to-charge ratio. By utilizing quantum-chemically predicted IR spectra for candidate molecular structures, one can either derive the actual structure or significantly reduce the number of (isomeric) candidate structures. This approach can assist in making informed decisions. We apply this method to a plant growth stimulant, digeraniol sinapoyl malate (DGSM), that is currently under development. Incubation of the compound in Caco-2 and HepaRG cell lines in multiwell plates and analysis by LC−MS reveals oxidation, glucuronidation, and sulfonation metabolic products, whose structures were elucidated by IRIS and used as input for an in silico toxicology assessment. The toxicity of isomeric metabolites predicted by in silico tools was also assessed, which revealed that assigning the right metabolite structure is an important step in the overall toxicity assessment of the agrochemical. We believe this identification approach can be advantageous when specific isomers are significantly more hazardous than others and can help better understand metabolic pathways.

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Section: Resultsmentioning

confidence: 99%