Enantiomeric Fractions Research Articles

Enantioselective Bioaccumulation of the Chiral Insecticide Indoxacarb in Zebrafish (Danio rerio)

Indoxacarb is a typical chiral insecticide widely used in agricultural pest control. In the present study, zebrafish was used as a model animal to explore the enantioselective bioaccumulation behavior of indoxacarb to nontarget species in aquatic environments. Zebrafish were exposed to 0.025 and 0.1 mg/L rac-indoxacarb solution for 12 d under the semistatic method, and the bioconcentration factor (BCF) and enantiomeric fraction of zebrafish were investigated. The results showed that the (-)-R-indoxacarb preferentially accumulated in zebrafish. The BCF values at 0.025 mg/L exposure levels were 1079.8 and 83.4 L/kg for (-)-R-indoxacarb and (+)-S-indoxacarb after 12 d, respectively. The BCF values at 0.1 mg/L exposure levels were 1752.1 and 137.0 L/kg for (-)-R-indoxacarb and (+)-S-indoxacarb after 10 d, respectively. The half-life values of (-)-R-indoxacarb and (+)-S-indoxacarb were 3.47 and 2.05 d for 0.025 mg/L concentration exposure and 4.95 and 2.66 d for 0.1 mg/L concentration exposure, respectively. The enantiomeric fraction values were in the range of 0.48 to 0.55 and 0.89 to 1.00 for water and zebrafish samples, respectively. Studies on the enantioselective bioaccumulation behavior of indoxacarb will provide data for assessing the environmental fate and potential toxic effects of indoxacarb on aquatic organisms. Environ Toxicol Chem 2021;40:1007-1016. © 2020 SETAC.

Uptake, Acropetal Translocation, and Enantioselectivity of Perfluorooctane Sulfonate in Maize Coexisting with Copper.

Plant uptake and translocation of perfluorooctane sulfonate (PFOS) are critical for food safety and raise major concerns. However, those processes are associated with many undisclosed mechanisms, especially when PFOS coexist with heavy metals. In this study, we investigated the effect of copper (Cu) on PFOS distribution in maize tissues by assessing the PFOS concentration and enantioselectivity. The presence of <100 μmol/L Cu exerted a limited effect on PFOS bioaccumulation, while >100 μmol/L Cu damaged the root cell membrane and increased root permeability, resulting in a higher PFOS concentration in roots. The suppression of acropetal translocation might be attributed to Cu inhibition of carrier proteins. The enantiomer fraction (EF) of 1m-PFOS at <100 μmol/L Cu was higher than that in a commercial product (0.5). Racemic PFOS was detected at >100 μmol/L Cu in roots and the EF variation changed from positive to negative in shoots. These EF results evidenced the existence of a protein-mediated uptake pathway. Besides, this study indicated the challenge of chiral signature application in PFOS source identification, given the effects of heavy metals and plants on PFOS enantioselectivity. The findings provide insight into PFOS bioaccumulation in plants cocontaminated with Cu and will facilitate environmental risk assessment.

Enantioselective fate of famoxadone during processing of apple cider and grape wine.

Famoxadone enantiomers were separated on Lux Amylose-1 chiral column and determined by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). The half-lives of R-(-)-famoxadone and S-(+)-famoxadone were 69.3 and 86.6 h in apple cider, 231.0 and 346.5 h in apple pomace, 69.3 and 77.0 h in grape wine, and 231.0 and 346.5 h in grape pomace, respectively. The enantiomeric fraction (EF) values decreased gradually from 0.498, 0.499, and 0.500 (0 h) to 0.404, 0.374, and 0.427 (144 h) and then increased gradually to 0.474, 0.427, and 0.422 (312 h) in apple cider, grape wine, and grape pomace. The EF value in apple pomace decreased gradually from 0.499 (0 h) to 0.450 (168 h) and then increased gradually to 0.482 (312 h). The processing factors (PFs) for famoxadone ranged from 0.014 to 0.024 in the overall process. The residue of famoxadone reduced 94.7-97.4% after the fermentation process.

Seasonal occurrence and source analysis of pharmaceutically active compounds (PhACs) in aquatic environment in a small and medium-sized city, China

Pharmaceutically active compounds (PhACs) have been widely reported in most megacities in China but seldom in small and median-sized cities. The aim of this study is to investigate occurrence and distribution characteristics of PhACs in a typical small and medium-sized city in China and analyze their sources. 33 PhACs and 4 chiral drugs were selected for a four-season monitoring campaign in Wujin District, Jiangsu Province, a typical small and median-sized city, in 2018. PhACs concentration level in surface water, ranging from ng L−1 to μg L−1, was lower than in large-sized cities and areas in China. Impact from agricultural sources should be concerned in the study area: (1) Significant correlation between concentrations of antibiotics and NH4-N in surface water indicated the potential impact from agricultural sources (fishponds and livestock farms); (2) Government regulating measures on livestock and poultry farms since January 2018 have effectively decreased macrolides and lincosamides emissions into surface water. As for source analysis, CF/CBZ (Caffeine/Carbamazepine) was a feasible indicator to trace untreated wastewater and enantiomeric fraction values of metoprolol (MTP) were also suggested to be helpful for identifying untreated wastewater. The results of both two indicators indicated more input of untreated wastewater to surface water in the northeast area and upstream of Wuyi Canal. To our best knowledge, this is the first study to systematically analyze PhACs in aquatic environment for a small and medium-sized city in China.

The enantiomer-selective metabolism of hexabromocyclododecanes (HBCDs) by human HepG2 cells

Although hepatic metabolism of hexabromocyclododecanes (HBCDs) played critical roles in the selective bioaccumulation of HBCDs in humans, the hepatic metabolism patterns of its enantiomers remained ambiguous. Aiming to elucidate the mechanism on hepatic metabolism of hexabromocyclododecanes (HBCDs) enantiomers, the enantiomers ((+)-α-HBCD, (−)-α-HBCD, (+)-γ-HBCD, and (−)-γ-HBCD), the diastereoisomers (α-, β-, and γ-HBCDs) and the mixed of α- and γ-HBCDs were incubated with human HepG2 cell under different exposure levels in the present study. The clearance percentages ranked as γ-HBCD enantiomers >β-HBCD enantiomers >α-HBCD enantiomers at the same exposure levels. The clearance percentages of (+)- and (−)-α-HBCDs increased when cells were exposed to racemic α-HBCD and the mixture of racemic α- and γ-HBCDs (p < 0.05). (−)-γ-HBCD was more resistant to human hepatic metabolism than (+)-γ-HBCD, leading to the enantiomer fractions (EFs) of γ-HBCD lower than 0.50. (−)-α-HBCD was slightly more metabolized when independently exposed to α-HBCD, while (+)-α-HBCD was more preferentially metabolized after exposure to α- and γ-HBCD mixtures. Hydroxylation and debromination HBCD metabolites were identified. In addition, the different EFs of HBCDs in cells and mediums suggested the selective transfer of chiral HBCDs and HBCD metabolites through the cell membrane. This study provided new insight into the enantiomer-selective metabolism of HBCDs.

Enantioselective accumulation, elimination and metabolism of fenbuconazole in lizards (Eremias argus)

The enantioselective accumulation, elimination and metabolism of fenbuconazole in lizards were determined following a single-dose (25 mg/kgbw) exposure to racemic or enantiomeric fenbuconazole. Accumulation of fenbuconazole was found in lizard fat with rac-form > enantiopure enantiomers. The enantiomer fractions (EFs) were higher than 0.5 in the blood, while EFs were less than 0.5 in the liver, brain, skin and stomach. There was conversion from (+)-fenbuconazole to (−)-fenbuconazole in lizard liver and conversion from (−)-fenbuconazole to (+)-fenbuconazole in lizard liver and blood. The results showed that enantioselective accumulation appeared in lizards, but the direction varied among blood and different tissues. The elimination half-lives (t1/2) of (+)-fenbuconazole were higher than those of (−)-fenbuconazole in the blood and liver, suggesting that (−)-fenbuconazole eliminated faster than (+)-fenbuconazole in these tissues. In addition, both (+)-fenbuconazole and (−)-fenbuconazole eliminated faster in the liver and stomach exposed to racemate than those exposed to enantiopure enantiomers. On the contrary, the form of racemate decreased the elimination rate of fenbuconazole in lizard fat. Synergistic elimination may occur when two enantiomers coexisted in lizard liver and stomach, while the racemate produced antagonistic elimination in lizard fat. Simultaneously, three metabolites, RH-6467, RH-9029&RH-9030 and keto-mchlorophenol, were discovered in lizard liver. Only two metabolites, RH-6467 and RH-9029&RH-9030, were found in lizard blood. RH-9029&RH-9030 were the major metabolites. The discovered enantiomers of (+)-fenbuconazole metabolites were different from those of (−)-fenbuconazole. The findings of this study may provide a better understanding of the enantioselective behaviors of chiral triazole fungicides in reptiles.

Different Degradation Patterns of Chiral Contaminant Enantiomers: Paclobutrazol as a Case Study

Studies often neglect the different trends between enantiomers in soil chiral contaminants. In the present study, paclobutrazol was chosen as the target analyte and the selective degradation patterns of this chiral pesticide were investigated in soils. After 14 days of culture, the degradation kinetics results demonstrated the degradation process of the two enantiomers conforms to first‑order degradation kinetics equation, and the degradation rates were significantly different (paired t-test, P &lt; 0.05). The degradation rate of (2S,3S)-paclobutrazol (S-paclobutrazol) was higher than that of (2R,3R)-paclobutrazol (R-paclobutrazol), with the concentration decrease of 42.6 and 28.7%, respectively. Meanwhile, the enantiomer fraction (EF) was 0.43 at final sampling point, and the half-life (t1/2) of S-paclobutrazol and R-paclobutrazol were 17.3 and 28.9 days,which demonstrated significant enantioselective degradation. Results from this study served to enhance our understanding about the enantioselective degradation behaviors of chiral pesticides, which provided some scientific basis for the potential risk assessment of chiral pesticides in the environment.

Simultaneous enantiomeric determination of multiple triazole fungicides in fruits and vegetables by chiral liquid chromatography/tandem mass spectrometry on a bridged bis(β-cyclodextrin)-bonded chiral stationary phase

A LC-MS/MS method for simultaneous determination of twelve triazole enantiomers (hexaconazole, tebuconazole, triticonazole, flutriafol, diniconazole, paclobutrazol) in six fruits and vegetables was established based on a stable and self-made bridged bis(β-cyclodextrin)-bonded chiral stationary phase. Simultaneous enantio-separation of multiple analytes was achieved with resolution ca. 1.67–2.14. Magnetically assisted QuECHERS was used to simplify and optimize sample pre-treatment. The new method was validated (accuracy, precision, matrix effect, etc.). Good linearity (0.5–20 μg/L, R2 > 0.99) and high recoveries (76.1–103.4%) based on intra- and inter-day relative standard deviation (RSDs) (2.6–11.9%), were obtained. Furthermore, a total of 90 samples were analyzed using this method and enantiomeric fractions (EF) for tebuconazole in strawberry and cucumber (0.63 and 0.43, respectively) were determined as well as 0.57 for flutriafol in tomato. This high-throughput detection method supported a convenient enantiomeric monitoring for chiral pesticides in fruits and vegetables.

Low-dose cadmium stress increases the bioaccumulation and toxicity of dinotefuran enantiomers in zebrafish (Danio rerio)?

Co-occurrence of pesticides and heavy metals has attracted extensive attention. The enantioselective behaviors of dinotefuran to aquatic organisms have not been reported, and the effects of cadmium (Cd) was absent, which were investigated in this study at environmentally relevant concentrations. The enantioselective accumulation and elimination of dinotefuran enantiomers were observed in zebrafish, and it had tissue specificity. The S-dinotefuran concentrations were higher than R-dinotefuran in heads and viscera, but it was opposite in muscles. There existed competition between S-dinotefuran and R-dinotefuran, and the existence of S-dinotefuran might decrease the accumulation and elimination of the R-dinotefuran in zebrafish. When co-exposure to Cd and dinotefuran, the accumulation concentrations of dinotefuran enantiomers increased in zebrafish at the initial stage, which were opposite latterly. The accumulation concentrations of R-dinotefuran in R+Cd treatment in fish were 3.4 times higher than those in R-dinotefuran treatment, and the enantiomer fraction (EF) values changed from 0.484 to 0.195. The oxidative stress of S-dinotefuran on zebrafish was highest, followed by rac- and R-dinotefuran. Co-exposure to Cd led to toxicity increase for R-dinotefuran, the malonaldehyde (MDA) content decreased significantly in R+Cd treatment during 7-28 days, while obvious declination of MDA contents was found on the 28th day in R-dinotefuran treatment. Furthermore, compared to R-dinotefuran treatment, Cd increased the relative expression of cz-sod (3.4 times), cas3 (1.6 times) and p53 (5.7 times) in R+Cd treatment. The co-exposure of Cd might alter the environmental behaviors and toxicity effects of dinotefuran enantiomers in zebrafish, including the enantioselectivity. The effects of Cd on accumulation and toxicity of R-dinotefuran were greater than those on S-dinotefuran. Thus, it is necessary to consider the effects of coexistent metals to chiral pesticides in ecological risk. SUMMARIZES: The enantioselective accumulation and elimination of dinotefuran enantiomers had tissue specificity. Cd increased the accumulation and toxicity of R-dinotefuran in zebrafish.

Evaluation of Enantioselective Capillary Electrophoretic Approach for the Enantiomeric Separation of Abscisic Acid

Background: The application of enantioselective capillary electrophoresis approach for the assessment of the enantiomeric purity of chiral molecules is receiving increased attention. Abscisic acid is one of the chiral sesquiterpenic plant growth regulators that regulate various ecological and physiological roles in higher plants. Enantiomeric determination of ABA is of great concern because of the different biological activity of its enantiomers. Materials and Methods: In this study, we investigated the enantioseparation selectivity of ABA by incorporating native β-cyclodextrins (β-CD) and its derivatives as chiral modifiers in the background electrolyte of an enantioselective capillary zone electrophoresis system. Electrophoretic aspects that affect the enantiomeric separation, such as pH, types of β-CD and its concentration, applied voltage, injection pressure and time, were studied and optimised. Results and Discussions: An enhancement in enantioseparation was achieved in a bare fused-silica capillary (64.5 cm × 50 mm i.d.) using a background electrolyte solution consisting of (2-hydroxypropyl)- β-CD (80 mM) solubilised in 100 mM phosphate buffer adjusted to pH 5.9 with NaOH, operated under normal polarity mode (25 kV) at 25°C, and using hydrodynamic injection (75 mbar for 10s). Relative standard deviations of (intra- and inter-day) ≤ 3.23% and ≤ 1.39% for migration times and enantiomeric fractions (EF) were achieved using the proposed method. Conclusion: The proposed chiral capillary electrophoretic method offers advantages in terms of enantioselectivity and analysis times, which can serve as a reliable platform for the stereoisomeric analysis of ABA.

Characterizing the biotransformation of hexachlorocyclohexanes in wheat using compound-specific stable isotope analysis and enantiomer fraction analysis

Hexachlorocyclohexane isomers (HCHs) are persistent organic pollutants being responsible for environmental contamination worldwide. In order to characterize transformation of HCHs in different plant compartments during uptake, a hydroponic experimental setup was designed using wheat as the test plant. The extent of transformation was determined by using compound-specific isotope analysis (CSIA) and enantiomer fraction (EF) analysis. In nutrient solutions, no change of carbon (δ13C) and chlorine isotope ratios (δ37Cl) of α-HCH and β-HCH was detected throughout the experiment indicating no transformation there. In wheat leaves, stems and roots, however, transformation of α-HCH due to a C‒Cl bond cleavage was indicated by increasing δ13C and δ37Cl compared to the nutrient solution. In addition, 1,3,4,5,6-pentachlorocyclohexene (PCCH) was identified as the major metabolite of α-HCH transformation. For β-HCH, in contrast, no transformation was detected. The evaluation of enantiomer fraction analysis revealed no change of the EF(-) in the nutrient solution or on root surface but a decrease in the wheat compartments, providing an evidence for the preferential biological transformation of (-)α-HCH in wheat. The current study provides the first experimental evidence for biotransformation of α-HCH in wheat using CSIA and EF and provides a concept to evaluate processes during phytoremediation.

Atropselective Partitioning of Polychlorinated Biphenyls in a HepG2 Cell Culture System: Experimental and Modeling Results.

Cell culture models are used to study the toxicity of polychlorinated biphenyls (PCBs); however, it is typically unknown how much PCB enters the cells and, for chiral PCBs, if the partitioning is atropselective. We investigated the partitioning of racemic PCB 91, PCB 95, PCB 132, and PCB 136 in HepG2 cells following a 72 h incubation. PCBs were present in the cell culture medium (60.7-88.8%), cells (8.0-14.6%), and dishes (2.3-7.8%) and displayed atropisomeric enrichment in the cells (enantiomeric fraction [EF] = 0.55-0.77) and dishes (EF = 0.53-0.68). Polyparameter linear free energy relationships coupled with a composition-based model provided a good estimate of the PCB levels in the cells and cell culture medium. The free concentration was subsequently used to extrapolate from the nominal cell culture concentration to PCB tissue levels and vice versa. This approach can be used for in vitro-in vivo extrapolations for all 209 PCB congeners. However, this model (and modified models based on descriptors incorporating atropselective interactions, i.e., relative retention times on chiral columns) did not predict the atropselective partitioning in the cell culture system. Improved chemical descriptors that account for the atropselective binding of PCBs to biological macromolecules are, therefore, needed to predict the atropselective partitioning of PCBs in biological systems.

Impact of long-term irrigation with municipal reclaimed wastewater on the uptake and degradation of organic contaminants in lettuce and leek

A two years drip irrigation of lettuce and leek crops with treated municipal wastewater without and with spiking with fourteen wastewater relevant contaminants at 10 μg/L concentration level was conducted under greenhouse cultivation conditions to investigate their potential accumulation in soil and leaves and to assess human health related risks. Lettuce and leek crops were selected as a worse-case scenario since leafy green vegetable has a high potential for organic contaminants uptake. The results revealed limited accumulation of contaminants in soil and plant leaves, their concentration levels being in the range of 1–30 ng/g and 1–660 ng/g range in soil and leaves, respectively. This was likely related to abiotic and biotic transformation or simply binding processes in soil, which limited contaminants plant uptake. This assumption was underpinned by studies of the enantiomeric fractionation of chiral compounds (e.g. climbazole and metoprolol) in soil as pieces of evidence of biodegradation and by the identification of transformation products or metabolites in leaves by means of liquid chromatography - high resolution - mass spectrometry using a suspect screening workflow. The high bioconcentration factors were not limited to compounds with intermediate Dow (100 to 1000) such as carbamazepine but also observed for hydrophilic compounds such as clarithromycin, hydrochlorothiazide and the food additives acesulfame and sucralose. This result assumed that accumulation was not only driven by passive processes (e.g. lipoidal diffusion through lipid bilayer cell membranes or Casparian strip) but might be supported by carrier-mediated transporters. As a whole, this study confirmed earlier reports on the a de minimis human health risk related to the consumption of raw leafy green vegetable irrigated with domestic TWW containing organic contaminants residues.

Enantioseparation and stereoselective dissipation of the novel chiral fungicide pydiflumetofen by ultra-high-performance liquid chromatography tandem mass spectrometry

Pydiflumetofen is a novel and efficient broad-spectrum chiral fungicide consisting of a pair of enantiomers. A simple and sensitive chiral analytical method was established to determine the enantiomers of this chiral fungicide in food and environmental samples by ultra-high-performance liquid chromatography tandem triple quadrupole mass spectrometry (UHPLC-MS/MS) using QuEChERS method coupled with octadecylsilane-dispersive solid-phase extraction (C18-dSPE) as extraction procedure. The specific optical rotation and the absolute configuration of the enantiomers were identified by polarimetry and electronic circular dichroism (ECD). The elution order of the pydiflumetofen enantiomers on Lux Cellulose-2 was S-(−)-pydiflumetofen and R-(+)-pydiflumetofen. The average recoveries of eleven matrices ranged from 71.3% to 107.4%. The intraday relative standard deviations (RSDs) were less than 11.8%, and the interday RSDs were less than 12.6% for the two enantiomers. Stereoselective dissipation in pakchoi and soil were observed: S-(−)-pydiflumetofen was degraded faster than R-(+)-pydiflumetofen in pakchoi, causing the enantiomer fraction (EF) of the enantiomers to change from 0.50 to 0.42 in 7 days. However, R-(+)-pydiflumetofen was degraded faster than S-(−)-pydiflumetofen in soil, causing the EF of the enantiomers to change from 0.49 to 0.52 in 21 days. This study provides a method for monitoring pydiflumetofen enantiomer residues, which is crucial for improving risk assessments and the development of chiral pesticides.

Tetrabromobisphenol A and hexabromocyclododecanes in sediments and biota from two typical mangrove wetlands of South China: Distribution, bioaccumulation and biomagnification

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) were examined in sediments and biota species from two mangrove wetlands of the Pearl River Estuary (PRE) and the Jiulong River Estuary (JRE), South China, to investigate their distribution, bioaccumulation and biomagnification in mangrove food webs. Levels of TBBPA and ΣHBCD (sum of α-, β- and γ-HBCDs) ranged from 0.003 to 0.31 and not detected (nd) to 1.11 ng/g dry weight in the sediments, and from 0.56 to 22.1 and nd to 56.3 ng/g lipid weight in the biota species, respectively. γ-HBCD was the major diastereoisomer in the PRE sediments, while α- and γ-HBCDs predominated in the JRE sediments. In contrast, α-HBCD was dominant in the biota. Mean enantiomeric fractions (EFs) of α-, β- and γ-HBCDs in the sediments all followed the trend of JRE > racemic standard > PRE. A significant enrichment of (−)-α-HBCD was found in the biota (p = 0.04), with EFs in the range of 0.297–0.485. Bioaccumulations were seen for TBBPA and α-HBCD as their biota-sediment accumulation factors (BSAFs) were greater than 1. (−)-α-HBCD had significantly greater BSAFs than (+)-α-HBCD (p = 0.04), indicating the preferential bioaccumulation of (−)-α-HBCD. Biomagnification factors (BMFs) of TBBPA ranged from 0.83 to 1.51, which varied among feeding relationships and mangroves. Positive relationships were found between TBBPA concentrations and trophic levels of the biota species with trophic magnification factors of 2.17 for the PRE and 1.22 for the JRE, suggesting that TBBPA biomagnifies in the mangrove food webs. No biomagnifications were observed for ΣHBCD, α-HBCD and its enantiomers.

Impact of dichlorprop on soil microbial community structure and diversity during its enantioselective biodegradation in agricultural soils

Enantioselective biodegradation of racemic dichlorprop in two soils was investigated in the laboratory. Chiral separation of racemic dichlorprop was achieved by using HPLC with Phenomenex Lux Amylose-2. The first-order kinetic model fitted well the dissipation data of racemic dichlorprop and its pure R- and S-enantiomers. S-dichlorprop was preferentially degraded in both soils and enantioselectivity was affected by soil pH. The half-lives (DT50) of S-dichlorprop were 8.22 days in soil A and 8.06 days in soil D, while R-dichlorprop was more persistent with DT50 of 12.93 days in soil A and 12.38 days in soil D, respectively. Dichlorprop dissipated faster in soil D with lower organic matter content. In sterilized soils, neglected dissipation was observed and enantiomer fraction values remained constant, indicating that the enantioselective degradation was mainly controlled by soil microorganisms. Soil microbial community structure and diversity was assessed by Illumina MiSeq sequencing of 16S rRNA genes from dichlorprop and no dichlorprop contaminated microcosms. Compared with controls, dichlorprop application had no significant effect on microbial community structures at phylum level, but increased bacterial diversity and dichlorprop degradation related taxa in both soils. S-dichlorprop preferential degradation might be attributed to the S-enantiomer preferred degraders in the family of Sphingomonadaceae.

Enantiomeric fraction of hexabromocyclododecanes in foodstuff from the Belgian market

Diet is considered a major route of human exposure to hexabromocyclododecane, a chiral environmental contaminant. A previous study reported on the occurrence of hexabromocyclododecane diastereoisomers in food items of animal origin collected in Belgium. The present study reports further results on corresponding enantiomeric fractions of the same samples. None of the samples could be considered as racemic for the α-isomer suggesting that foodstuff contamination occurred prior to death of the corresponding producing animal and was not the result of the food item being in contact with technical HBCDD. Non-racemic chiral signatures were also observed for β- and γ-isomers. We conclude that, depending on their dietary habits, different individuals might be overall exposed to non-racemic profiles. Considering that toxicological effects are enantiomer-dependent, this could modulate potential adverse effects.

Chiral determination of nornicotine, anatabine and anabasine in tobacco by achiral gas chromatography with (1S)-(-)-camphanic chloride derivatization: Application to enantiomeric profiling of cultivars and curing processes.

The alkaloid enantiomers are well-known to have different physiological and pharmacological effects, and to play an important role in enantioselectivity metabolism with enzymes catalysis in tobacco plants. Here, we developed an improved method for simultaneous and high-precision determination of the individual enantiomers of nornicotine, anatabine and anabasine in four tobacco matrices, based on an achiral gas chromatography-nitrogen phosphorus detector (GCNPD) with commonly available Rtx-200 column using (1S)-(-)-camphanic chloride derivatization. The method development consists of the optimization of extraction and derivatization, screening of achiral column, analysis of the fragmentation mechanisms and evaluation of matrix effect (ME). Under the optimized experimental conditions, the current method exhibited excellent detection capability for the alkaloid enantiomers, with coefficients of determination (R2) > 0.9989 and normality test of residuals P > 0.05 in linear regression parameters. The ME can be neglected for the camphanic derivatives. The limit of detection (LOD) and limit of quantitation (LOQ) ranged from 0.087 to 0.24 μg g-1 and 0.29 to 0.81 μg g-1, respectively. The recoveries and within-laboratory relative standard deviations (RSDR) were 94.3%~104.2% and 0.51%~3.89%, respectively. The developed method was successfully applied to determine the enantiomeric profiling of cultivars and curing processes. Tobacco cultivars had a significant impact on the nornicotine, anatabine, anabasine concentration and enantiomeric fraction (EF) of (R)-nornicotine, whereas the only significant change induced by the curing processes was an increase in the EF of (R)-anabasine.

Stereoselective behaviors of the fungicide triadimefon and its metabolite triadimenol during malt storage and beer brewing

The stereoselective behaviors of triadimefon (TF) and its metabolite triadimenol (TN) during barley storage and beer brewing were studied by supercritical fluid chromatography-tandem mass spectrometry to shed light on potential security risks. Matrix-matched calibration curves were constructed for barley and beer, with determination coefficients (r2) ≥ 0.9991. Average recoveries of 77.2–107.5 % and relative standard deviations within 15.0 % were observed. The degradation of the TF enantiomers during storage followed pseudo-first-order kinetics, and S-TF was degraded in preference to R-TF with the half-life ranges 18.5–36.5 d and 20.4–69.3 d, respectively. During beer brewing, the TF enantiomers (enantiomer fraction, 0.44−0.56) were selectively metabolized into TN stereoisomers (diastereomer fraction, 0.43−0.58). The total pesticide content of beer was 93.3 % lower than that of raw grain, whereby the TF content declined by up to 100 % and the TN stereoisomers were reduced by 35.1 %. The processing factors of all the brewing steps were less than one, illustrating that beer consumption is safer after its commercial processing. Furthermore, the TF enantiomers showed different behaviors upon fermentation by two yeast strains. Thus, this work is a useful reference for assessing the food safety risk posed by individual pesticide enantiomers and their contribution to environmental pollution.

Compound-Specific Isotope Analysis and Enantiomer Fractionation to Characterize the Transformation of Hexachlorocyclohexane Isomers in a Soil-Wheat Pot System.

The uptake by plants from soil is one of the first steps for hexachlorocyclohexane (HCH) isomers to enter the food web. However, the HCH transformation associated with the uptake process is still not well understood. Therefore, a soil-wheat pot experiment was conducted to characterize the HCH transformation during wheat growth using compound-specific isotope analysis (CSIA) and enantiomer fractionation. The results showed that the δ13C and δ37Cl values of β-HCH remained stable in soil and wheat, revealing no transformation. In contrast, an increase of δ13C and δ37Cl values of α-HCH indicated its transformation in soil and wheat. A shift of the enantiomer fraction (EF) (-) from 0.50 to 0.35 in soil at the jointing stage and 0.35 to 0.57 at the harvest stage suggested that the preferential transformation of enantiomers varied at different growth stages. Based on the dual element isotope analysis, the transformation mechanism in the soil-wheat system was different from that in wheat in hydroponic systems. The high abundance of HCH degraders, Sphingomonas sp. and Novosphingobium sp., was detected in the α-HCH-treated rhizosphere soil, supporting the potential for biotransformation. The application of CSIA and EF allows characterizing the transformation of organic pollutants such as HCHs in the complex soil-plant systems.