Enantiomerization and stereoselectivity in bioaccumulation of furalaxyl in Tenebrio molitor larvae

Abstract

Furalaxyl is a chiral pesticide and widely used in modern agriculture as racemate mixture. The enantiomerization and enantioselecive bioaccumulation by a single dose of furalaxyl to Tenebrio molitor larvae under laboratory conditions were studied using a high-performance liquid chromatography tandem mass spectroscopy method based on a ChiralPAK IC column. Our results showed that a significant enantiomerization (interconversion between R-enantiomer and S-enantiomer) was observed in Tenebrio molitor larvae under R- or S-furalaxyl exposure. Though the two furalaxyl enantiomers exhibited low-capacity of bioaccumulation in Tenebrio molitor larvae, bioaccumulation of rac-furalaxyl was enantioselective with a preferential accumulation of S-furalaxyl at 10mg/kg dosage exposure. In addition, enantiomerization and enantioselective degradation of the two enantiomers was not observed in wheat bran. These results showed that enantioselectivtiy of furalaxyl enantiomers was an important process combined with degradation, metabolism and enatiomerization in organisms.

Determination of Ethofumesate‐2‐hydroxy Stereolability by Dynamic HPLC

“…Stereolability has also been observed in vivo for two pesticides benalaxyl and furalaxyl . The authors reported that when exposing organisms to the enantiomers, separately, of both pesticides, conversion of S into R enantiomer and vice versa was observed.…”

“…In the latter study, Yin et al. (2017) described that stereochemical inversion in vivo may be performed by racemases and epimerases via C‐H bond breaking and forming or oxidation‐reduction enzyme mediated reactions at the chiral center. This fact, along with ETO‐OH intrinsic stereolability may suggest a potential scenario for racemization of its enantiomers in vivo .…”

State-of-the-art and recent developments of immobilized polysaccharide-based chiral stationary phases for enantioseparations by high-performance liquid chromatography (2013–2017)

“…Many papers are aimed to the determination of herbicides [103,104,108,110], insecticides [48,100,97,107,105], fungicides [102,109,106,101,99] or antiviral drugs [98] from many different chemical families, including aryloxyphenoxy propionic acids, pyridines, oxadiazines, phenylpyrazoles, acylalanines, pyrethroids, triazoles, α-aminophosphonates, sulfoxides, etc. have been determinated in environmental or food samples (soil, natural waters, fruits, vegetables, etc.).…”

“…have also been determined, especially in commercial products or biological samples (pharmaceutical formulations, human urine, human or animal blood, human plasma, animal serum, etc.). Another heterogeneous group of analytes, including connectors for building metal-organic frameworks [116,117,124], intermediates for the synthesis of pharmaceuticals [111], natural and synthetic compounds [39,113,121,120], biological compounds [82,112,58,71,78,86,[61][62][63]77,75], natural alkaloids [121], biomolecules [115,54], organometallic compounds [119] and chiral metabolites [103,108,100,97,102,59,63,52] has been enantioseparated with these immobilized polysaccharides CSPs (see Table 2-4). Fig.…”

“…All chiral applications were found in the LC reversed-phase mode using tandem mass spectrometry (LC-MS/MS), which is attributed to its compatibility with API-based MS ionization techniques. Pharmaceutical [81,96,76,89,70], biomedical [61,54] and agrochemical [103,104,107,102,101] applications were the dominant separation fields, and to a lesser extent are other industries such as fragrances and food, and also environmental studies.…”