In Vivo Contaminant Monitoring and Metabolomic Profiling in Plants Exposed to Carbamates via a Novel Microextraction Fiber

Abstract

In this study, a biocompatible solid-phase microextraction (SPME) fiber with high-coverage capture capacity based on a nitrogen-rich porous polyaminal was developed. The fiber was used to track the bioaccumulation and elimination of carbamates (isoprocarb, carbofuran, and carbaryl) and their metabolites (o-cumenol, carbofuran phenol, and 1-naphthalenol) in living Chinese cabbage plants (Brassica campestris L. ssp. chinensis Makino (var. communis Tsen et Lee)). A case-and-control model was applied in the hydroponically cultured plants, with the exposed plant groups contaminated under three carbamates at 5 μg mL–1. Both bio-enrichment and elimination of carbamates and their metabolites in living plants appeared to be very fast with half-lives at ∼0.39–0.79 and ∼0.56–0.69 days, respectively. Statistical differences in the endogenous plant metabolome occurred on day 3 of carbamate exposure. In the exposed group, the plant metabolic alterations were not reversed after 5 days of contaminant-free growth, although most contaminates had been eliminated. Compared with prior nutriological and toxicological studies, >50 compounds were first identified as endogenous metabolites in cabbage plants. The contents of the glucosinolate-related metabolites demonstrated significant time-dependent dysregulations that the fold changes of these key metabolites decreased from 0.78–1.07 to 0.28–0.82 during carbamate exposure. To summarize, in vivo SPME provided new and important information regarding exogenous carbamate contamination and related metabolic dysregulation in plants.

In Vivo Profiling and Quantification of Chlorinated Paraffin Homologues in Living Fish

“…The amount extracted in the probe is governed by the mass transfer of analytes in multiphase systems. According to the non-exhaustive extraction nature of the in vivo SPME technique, we established a label-free sampling rate calibration method for the in vivo quantification of organic pollutants previously, and numerous applications have proven its feasibility and reliability. − Pre-equilibrium SPME sampling of living organisms was calibrated with the sampling-rate calibration method according to the following equation. R normals = n C normals t where R s was the defined sampling rate, n was the extracted amount of analyte in a fiber determined by injecting a series of standard solutions into the analytical instrument, C s was the analyte concentration in the sample matrix, and t was the sampling duration …”

Latest Improvements and Expanding Applications of Solid-Phase Microextraction

“…A biocompatible SPME fiber with high-coverage capture capacity based on a nitrogen-rich porous polyaminal has been developed, and it was used to track the bioaccumulation and elimination of carbamates (isoprocarb, carbofuran, and carbaryl) and their metabolites (ocumenol, carbofuran phenol, and 1-naphthalenol) in living Chinese cabbage plants (Figure 7A). 204 The MWCNTs/PANI-PPy@PDMS fiber with confirmed biocompatibility has been used for in vivo sampling and quantitative determination of three insecticides (hexachlorobenzene, fipronil, and chlorfenapyr) 205 as well as fipronil and its three metabolites 206 by directly exposing micrometer-sized fiber in living garlic (Figure 7B). In vivo extractions from soybean nodules have been carried out in a thin-film format to capture metabolic alterations occurring in the nodule under different growth phases and the generated deviations due to air temperature, soil humidity, and soybean growth.…”

“…The coating material should be nontoxic and noninjurious for a living system, and biofouling should be avoided after fiber insertion. A biocompatible SPME fiber with high-coverage capture capacity based on a nitrogen-rich porous polyaminal has been developed, and it was used to track the bioaccumulation and elimination of carbamates (isoprocarb, carbofuran, and carbaryl) and their metabolites (ocumenol, carbofuran phenol, and 1-naphthalenol) in living Chinese cabbage plants (Figure A) . The MWCNTs/PANI-PPy@PDMS fiber with confirmed biocompatibility has been used for in vivo sampling and quantitative determination of three insecticides (hexachlorobenzene, fipronil, and chlorfenapyr) as well as fipronil and its three metabolites by directly exposing micrometer-sized fiber in living garlic (Figure B).…”

Machine learning-empowered cis-diol metabolic fingerprinting enables precise diagnosis of primary liver cancer

“…Actually, glycoproteins, such as immunoglobin and transferrin which are highly abundant in serum, also belong to cis-diols, but they were hardly observed in the BESE-MS experiments. The absence of glycoproteins in our method is noteworthy, and we supposed that there are two reasons for this phenomenon: (1) in the direct immerse mode of SPME-based methods, the SPME probe can become quickly saturated with the most abundant analytes present in a given matrix (metabolites in serum), 52,53 while other analytes (glycoproteins) remain unextracted; 54 (2) even if a small amount of glycoproteins is extracted onto the probe, the detection of undesirable high molecular weight compounds will be easily interfered by matrix effects in the electrospray ionization source. 55 The above comparison of BESE-MS with the direct serum detection method and BE-MS (boronate affinity extraction-mass spectrometry) indicates that our integrated method was not only effective in selective cis-diol analysis but also a sensitive and simple approach for general use.…”