Isomer, enantiomer and compound-specific stable isotope evidences for the transformation of dichlorodiphenyltrichloroethanes (DDTs) in soils from three typical paddy fields in China.

Chlorinated pollutants may follow distinct degradation pathways in anaerobic environments compared to aerobic settings. However, the understanding of the behaviors and fate of dichlorodiphenyltrichloroethanes (DDTs) under anaerobic conditions remains limited. To address this knowledge gap, we conducted a study on flooded soil samples collected from three typical paddy fields in China using an integrated approach of enantiomer-specific analysis and compound-specific stable carbon isotope analysis. It is unexpected that the dichlorodiphenyldichloroethane /dichlorodiphenyldichloroethylene ratios (DDD/DDE=(o,p'-DDD+p,p'-DDD)/(o,p'-DDE+p,p'-DDE)) were below 1 in over 90 % of the samples. This might be attributed to the higher recalcitrance of p,p'-DDE, which concentrations were found to be 36 times higher than p,p'-DDD on average. There were 71.7 % of the samples showing enantiomeric fractions (EFs) of o,p'-DDT below 0.5, indicating a preferential accumulation of the (-)-enantiomer. The δ13C values of the anaerobic metabolite o,p'-DDD (-24.76 ± 1.35 ‰ to -34.39 ± 0.20 ‰) all deviated negatively from the initial product, while those of the aerobic metabolite o,p'-DDE (-23.61 ± 0.48 ‰ to -38.95 ± 0.81 ‰) displayed either negative or positive deviations. This demonstrates that o,p'-DDD is the primary metabolite of o,p'-DDT under anaerobic conditions. However, no clear correlations were observed between the δ13C and EF of o,p'-DDT. This study underscores the importance of such an integrated methodology in unraveling the fate and behaviors of DDTs in complex environmental systems.

Molecular mechanism of the influence of related genes expression in synovium tissue around shoulder joint of secondary frozen shoulder model rats on angiogenesis.

The study aimed to explore the pathogenesis of secondary frozen shoulder and its influence on synovium tissue and angiogenesis by constructing a rat secondary frozen shoulder model along with transforming growth factor. 40 healthy male rats aged 8 weeks were divided into Sham group (n=10, no modeling treatment), Control group (n=10, modeling treatment), Low group (n=10, modeling treatment, and 10 mL/d transforming growth factor), and High group (n=10, modeling treatment, and 20 mL/d transforming growth factor). Hematoxylin and Eosin (HE) method was used for histological detection, and Reverse Transcription-Polymerase Chain Reaction (RT-PCR) and immunohistochemical staining method were adopted to detect the expression of Matrix metalloproteinase-14 (MMP-14), mitogen-activated protein kinase (p38MAPK), and Vascular endothelial growth factor (VEGF). Compared with Sham group, the range of abduction and external rotation of rat glenohumeral joint in Control group, Low group, and High group was significantly reduced, and High group had the smallest range. Compared with the Sham group, the synovium in the Control group, the Low group, and the High group had obvious hyperplasia, and the blood vessels were significantly increased. Immunohistochemical staining and RT-PCR results showed that compared with Sham group, MMP-14, p38 MAPK, and VEGF in Control group, Low group, and High group all increased significantly, among which High group increased most. The secondary frozen shoulder is mainly manifested as synovial hyperplasia and increased blood vessels, which are related to the induction of MMP-14, p38 MAPK, and VEGF by transforming growth factor, which reveals the pathogenesis of secondary frozen shoulder to a certain extent, and lays a foundation for subsequent clinical treatment of secondary frozen shoulder.

Dual-functional porphyrinic zirconium-based metal-organic framework for the fluorescent sensing of histidine enantiomers and Hg2.

A novel fluorescence sensor based on a porphyrinic zirconium-based metal-organic framework, L-cysteine-modified PCN-222 (L-Cys/PCN-222), was developed to selectively recognize histidine enantiomers and sensitively detect Hg2+. The dual-functional sensor was successfully prepared via the solvent-assisted ligand incorporation method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), 1H nuclear magnetic resonance (1H NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, circular dichroism (CD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption analyses. L-Cys/PCN-222 not only showed a higher quenching response for L-histidine than that for D-histidine with a fast fluorescent response rate of <40 s but also exhibited low detection limits for L- and D-histidine (2.48 µmol L-1 and 3.85 µmol L-1, respectively). Moreover, L-Cys/PCN-222 was employed as a fluorescent and visual sensor for the highly sensitive detection of Hg2+ in the linear range of 10-500 µmol L-1, and the detection limit was calculated to be 2.79 µmol L-1 in surface water. The specific and selective recognition of chiral compounds and metal ions by our probe make it suitable for real field applications.

Spatial distribution, isomer signature and air-soil exchange of legacy and emerging poly- and perfluoroalkyl substances.

Widespread occurrences of various poly- and perfluoroalkyl substances (PFAS) in terrestrial environment calls for the growing interest in their transport behaviors. However, limited studies detected PFAS with structural diversity in tree barks, which reflect the long-term contamination in atmosphere and play a vital role in air-soil exchange behaviors. In this study, 26 PFAS congeners and typical branched isomers were investigated in surface soils and tree barks at 28 sites along the Taihu Lake, Taipu River, and Huangpu River. Concentrations of total PFAS in soils and tree barks were 0.991-29.4 and 7.99-188 ng/g dw, with PFPeA and PFDoA were the largest contributors in the two matrices. The highest PFAS levels were found in the Taihu Lake watershed, where textile manufacturing and metal plating activities highly prosper. With regard to the congener and isomer signatures, short-chain homologs dominated in soils (65.5%), whereas long-chain PFAS showed a major proportion in barks (41.9%). The composition of linear isomers of PFOS, PFOA and PFHxS implied that precursor degradation might be an important source of PFAS in addition to the 3M electrochemical fluorination (ECF). Additionally, the distance from the emission source, total organic carbon (TOC), logKOA and logKOW were considered potential influencing factors in PFAS distributions. Based on the multi-media fugacity model, about 71% of the fugacity fraction (ffs) values of the PFAS were below 0.3, indicating the dominant deposition from the atmosphere to the soil. The average fluxes of air-soil exchange for PFAS were -0.700 ± 11.0 ng/(m2·h). Notably, the estimated daily exposure to PFAS ranged from 9.57 × 10-2 to 8.59 × 10-1 ng/kg·bw/day for children and 3.31 × 10-2 to 3.09 × 10-1 ng/kg·bw/day for adults, suggesting low risks from outdoor inhalation and dermal uptake. Overall, results from distribution with structural diversity, air-soil exchange and preliminary risk assessment. This study provided in-depth insight of PFAS in multi-medium environment and bridged gaps between field data and policy-making for pollution control.

Short- and medium-chain chlorinated paraffins in agricultural and industrial soils from Shanghai, China: surface and vertical distribution, penetration behavior, and health risk assessment.

The widespread contamination of chlorinated paraffins (CPs) of the soil environment has raised global concern due to their highly persistent and toxic properties. However, little information is available regarding these industrial toxicants' spatial-vertical distribution and penetration potentials. In this study, short- and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively) were analyzed in pooled surface and core soils (0-45 cm) samples collected from agricultural and industrial areas in Shanghai. ∑SCCP concentrations in agricultural and industrial surface soils ranged from 52.6 to 237.6 and 98.3 to 977.1 ng/g dry weight (dw), respectively. ∑MCCP levels were comparatively higher and ranged from 417.2 to 1690.8 and 370.9 to 10,712.7 ng/g dw in agricultural and industrial soils, respectively. C10Cl5-10 SCCPs and C14-15Cl5-7 MCCPs were the predominant homologues in all samples. Analysis of the soil vertical profiles revealed that MCCP concentrations decreased significantly with depth (P < 0.01). SCCPs more efficiently penetrated into the soils than MCCPs because of their higher water solubility and less octanol-water partition coefficient (Kow) values. A preliminary risk assessment suggested no potential health risks caused by non-dietary exposure. The daily exposure doses of CPs via ingestion were significantly (P < 0.01) higher for children (5.41 ± 2.11 × 10-3 and 1.68 ± 1.03 × 10-2 µg kg-1 day-1) and adults (2.56 ± 0.99 × 10-4 and 7.94 ± 4.87 × 10-4 µg kg-1 day-1) than dermal permeation exposure. Furthermore, CPs at current levels posed low ecological risks (0.1 ≤ RQ < 1) according to the risk quotient model. This study enhanced our understanding of the fates and behaviors of CPs in the terrestrial environment.

Concentrations and homologue patterns of SCCPs and MCCPs in the serum of the general population of adults in Hangzhou, China.

Due to their ubiquitous presence in the environment and humans, chlorinated paraffins (CPs) are a major environmental and public health concern. CPs are known to persist, bioaccumulate and potentially threaten human health, but reports on their internal exposure in the adult general population are still scarce. In this study, serum samples collected from adults living in Hangzhou, China, were quantified for SCCPs and MCCPs using GC-NCI-MS methods. A total of 150 samples were collected and subjected to analysis. ∑SCCPs were detected in 98% of the samples with a median concentration of 721 ng/g lw. MCCPs were found in all serum samples with a median concentration of 2210 ng/g lw, indicating that MCCPs were the dominant homologous group. For SCCPs and MCCPs, ∑C10 and ∑C14 were found to be the dominant carbon chain length homologues. Our results showed that age, BMI and lifestyle were not found to be significantly associated with internal exposure to CPs for the samples in this study. Based on PCA analysis, an age-specific distribution of CP homologues was observed. This suggests that internal exposure to CPs in the general population is related to exposure scenarios and history. The results of this study may contribute to a better understanding of the internal exposure to CPs in the general population and may provide a direction for the investigation of the source of exposure to CPs in the environment and daily life.

[Occurrence Characteristics of Microplastics and Metal Elements in the Surface Water of Huangpu River and Their Associations with Metal Resistance Genes].

Urban rivers have been regarded as the "hotspots" for microplastic (MPs) and metal contamination as they play important roles in pollution migration. However, as important sinks and sources of resistance genes, there has been little to no research investigating the associations between MPs, metal contaminations, and metal resistance genes (MRGs). Ten water samples were collected from the Huangpu River in situ; along with metal elements, MPs characteristics analyzed. Metal resistance genes and mobile genetic elements (MGEs) in waters and MPs were detected using metagenomic technology. As a result, the highest metal concentration was that of Sb in surface water (3.16±0.419) µg·L-1. The average abundance of MPs was (1.78±0.84) n·L-1, and the peak levels located in industrial and densely populated areas, which was significantly higher than those in agricultural and low population density areas. Fibrous, small-size (<0.5 mm), and transparent polyethylene terephthalate (PET) were the largest contributors of MPs. Eighteen MRGs were detected in all the samples. The relative abundance of MRGs in water was 1.68±0.21. The most dominant MRGs subtypes were merR and ruvB, which are subtypes resistant to mercury and Multi_metals. Correlation analysis showed that chromium and nickel in waters were significantly positively associated with MRG-Cr, MRG-Ni, and Multi_metals resistance genes. For MPs particles, the relative abundance of MRGs was 1.63±0.53. The most dominant MRGs subtypes were merT-P and copB, which also belong to mercury-resistant and Multi_metals. The Multi_metals resistance gene, ctpC, cueA, czrA, kmtR, etc., had significant positive associations with Ni, Cr, and Sb in waters. Compared with water samples, MPs selectively enriched merT-P, copB, ziaA, sodA, and dmeF. Additionally, the co-occurrence patterns of MRGs and MGEs were explored based on network analysis. In water samples, the transposases (tnpA_1 and tnpA_2), integrase (qacEdelta), and insertion sequence (IS91) were the major contributors of the horizontal gene transfer (HGT) of specific MRGs. Multiple subtypes resistant to copper and Multi_metals resistance genes on MPs were positively associated with IncFIC(FII), Rep7, rep7, and rep13, which were subtypes of plasmids. The presence of MPs exerted a significant impact on HGT of specific MRGs mediated by plasmids.

Prenatal exposure to 209 PCBs in mother-infant pairs from two cities in China: Levels, congener profiles, and transplacental transfer.

Prenatal exposure to polychlorinated biphenyls (PCBs) has been well researched, but studies covering all 209 congeners are limited. Recent literature suggests a shift in the dominant congeners and increasing levels of unintentionally-produced PCBs (UP-PCBs) in environmental samples in China. To investigate the exposure levels and profiles of PCBs in pregnant women and newborns, as well as the characteristics of transplacental transfer, we measured 209 PCBs in 80 pairs of maternal serum (MS) and cord serum (CS) from Hangzhou and Mianyang, China. The levels of ∑PCBs of participants in this study were lower than those in developed countries and followed the order of (ng/g lw): Hangzhou-MS (148) > Hangzhou-CS (107) > Mianyang-MS (63.8) > Mianyang-CS (57.9). UP-PCBs (mainly PCB-11) contributed around 50% of ∑PCBs in serum, which is consistent with the environmental samples. Environmental burden and dietary intake may account for the differences in the exposure levels, while the historical production and release may have impacted the homologue profiles. Prenatal exposure to PCB-126 was associated with increased birth weight (n = 80, adjusted ß = 0.270, p = 0.030). The body burden of dioxin-like PCBs of newborns in Hangzhou was 82.4 pg TEQ/kg bw, suggesting certain health risks under WHO tolerable daily intake of 1-4 pg TEQ/kg bw. Log10 KOW was negatively correlated with log10-transformed transplacental transfer efficiency (R2 = 0.36, p < 0.001), serving its importance for PCBs' transplacental transfer. This study is the first to investigate maternal and fetal exposure to PCBs in China based on their levels, congener and homologue profiles, and potential adverse effects. Our findings help to provide insights into the processes and factors influencing the transplacental transfer of PCBs.

Multi-omics analysis reveals cuproptosis and mitochondria-based signature for assessing prognosis and immune landscape in osteosarcoma.

Background: Osteosarcoma (OSA), the most common primary mesenchymal bone tumor, is a health threat to children and adolescents with a dismal prognosis. While cuproptosis and mitochondria dysfunction have been demonstrated to exert a crucial role in tumor progression and development, the mechanisms by which they are regulated in OSA still await clarification. Methods: Two independent OSA cohorts containing transcriptome data and clinical information were collected from public databases. The heterogeneity of OSA were evaluated by single cell RNA (scRNA) analysis. To identify a newly molecular subtype, unsupervised consensus clustering was conducted. Cox relevant regression methods were utilized to establish a prognostic gene signature. Wet lab experiments were performed to confirm the effect of model gene in OSA cells. Results: We determined 30 distinct cell clusters and assessed OSA heterogeneity and stemness scRNA analysis. Then, univariate Cox analysis identified 24 candidate genes which were greatly associated with the prognosis of OSA. Based on these prognostic genes, we obtained two molecular subgroups. After conducting step Cox regression, three model genes were selected to construct a signature showing a favorable performance to forecast clinical outcome. Our proposed signature could also evaluate the response to chemotherapy and immunotherapy of OSA cases. Conclusion: We generated a novel risk model based on cuproptosis and mitochondria-related genes in OSA with powerful predictive ability in prognosis and immune landscape.

Perfluoroalkyl Mixture Exposure in Relation to Fetal Growth: Potential Roles of Maternal Characteristics and Associations with Birth Outcomes.

Perfluoroalkyl substances (PFASs) exposure is suggested to interfere with fetal growth. However, limited investigations considered the roles of parity and delivery on PFASs distributions and the joint effects of PFASs mixture on birth outcomes. In this study, 506 birth cohorts were investigated in Hangzhou, China with 14 PFASs measured in maternal serum. Mothers with higher maternal ages who underwent cesarean section were associated with elevated PFASs burden, while parity showed a significant but diverse influence. A logarithmic unit increment in perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and perfluorononane sulfonate (PFNS) was significantly associated with a reduced birth weight of 0.153 kg (95% confidence interval (CI): -0.274, -0.031, p = 0.014), 0.217 kg (95% CI: -0.385, -0.049, p = 0.012), and 0.137 kg (95% CI: -0.270, -0.003, p = 0.044), respectively. Higher perfluoroheptanoic acid (PFHpA) and perfluoroheptane sulphonate (PFHpS) were associated with increased Apgar-1 scores. PFOA (Odds ratio (OR): 2.17, 95% CI: 1.27, 3.71, p = 0.004) and PFNS (OR:1.59, 95% CI: 1.01, 2.50, p = 0.043) were also risk factors to preterm birth. In addition, the quantile-based g-computation showed that PFASs mixture exposure was significantly associated with Apgar-1 (OR: 0.324, 95%CI: 0.068, 0.579, p = 0.013) and preterm birth (OR: 0.356, 95% CI: 0.149, 0.845, p = 0.019). In conclusion, PFASs were widely distributed in the maternal serum, which was influenced by maternal characteristics and significantly associated with several birth outcomes. Further investigation should focus on the placenta transfer and toxicities of PFASs.

Reparative effects of chronic intermittent hypobaric hypoxia pre­treatment on intervertebral disc degeneration in rats.

Previous studies have indicated that chronic intermittent hypobaric hypoxia (CIHH) preconditioning can inhibit TNF­α and other related inflammatory cytokines and exerts protective effect on intervertebral disc degeneration disease (IDD) in rats; however, the mechanism is still unclear. The present study aimed to explore the repair mechanisms of CIHH on IDD in rats. In the experiment, 48 adult Sprague­Dawley rats were selected and randomly divided into an experimental group (CIHH­IDD), a degenerative group (IDD) and a control group (CON). The CIHH­IDD group of rats (n=16) were treated with CIHH (simulated 3000 m altitude, 5 h per day, 28 days; PO2=108.8 mmHg) before disc degeneration surgery. The IDD group of rats (n=16) underwent tail­vertebral intervertebral disc surgery to establish a model of intervertebral disc degeneration. The CON group of rats (n=16) did not receive any treatments. After surgery, the disc height index was calculated using X­ray analysis of rat tail vertebrae, the degeneration process was observed and repair was evaluated by chemically staining degenerative intervertebral disc tissue slices. The expression levels of basic fibroblast growth factor (bFGF), TGFß1, Collagen I and Collagen II were measured in the intervertebral disc tissue using western blotting; while the expression levels of bFGF, TGFß1 and hypoxia­inducible factor 1­α (HIF­1α) were measured in rat serum using ELISA. The results demonstrated that: i) The degree of intervertebral disc height degeneration in CIHH­IDD rats was significantly lower compared with that in IDD rats (P<0.05); ii) the expression levels of bFGF, TGFß1 and HIF­1α were higher in CIHH­IDD rat serum compared with those in IDD rat serum (P<0.05); iii) optical microscopy revealed that the degree of disc degeneration was relatively mild in CIHH­IDD rats; and iv) the protein expression levels of bFGF, TGFß1 and collagen II were increased in CIHH­IDD rat intervertebral disc tissues compared with those of IDD rats, while the overexpression of collagen I protein was inhibited. Overall, after CIHH pre­treatment, the expression levels of bFGF and TGFß1 were up­regulated, which play notable roles in repairing degenerative intervertebral discs in rats.

Exposure patterns, chemical structural signatures, and health risks of pesticides in breast milk: A multicenter study in China.

China is the world's largest pesticide user. These chemicals are bioaccumulative in the human body, and eventually could be transferred from the mother to the fetus/infant via placental and breastfeeding transport, which might pose developmental deficiency risks. In this study, human biomonitoring of legacy pesticides was conducted in three Chinese cities using 60 breast milk samples. The patterns, chemical structural signatures, and the estimated daily intake of pesticides were assessed. The median concentration of HCB (57.8 ng g-1 lw, Interquartile range: 28.5-76.9 ng g-1 lw) was the highest among all pesticides, whereas the HCHs, DDXs, TCVP, and heptachlor were also detected. A significantly different pattern of pesticides was found among three sampling cities: the Mianyang cases were mostly DDXs oriented while the Wuhan and Hangzhou cases were under HCB, HCHs, TCVP, and heptachlor influences. Maternal age and pre-pregnancy BMI were found to be the influencing factors for the pesticides in the breast milk, and dietary preferences were an important factor in the exposure scenario. Chemical structural signatures indicated that for HCHs and DDXs the exposure was mostly historical, while the lindane and dicofol exposure may exist among the volunteering mothers. The EF for chiral pesticides did not deviate significantly from the racemic value. The risk from breastfeeding was negligible according to the Chinese and UN standard, while some cases from Hangzhou and Wuhan exceeded the Canadian restrictions. Thus, the adverse health effects of chemical exposure by dietary intake for infants need to be closely monitored in future studies.

The occurrence and sources of polychlorinated biphenyls (PCBs) in agricultural soils across China with an emphasis on unintentionally produced PCBs.

In addition to being historically intentionally manufactured as commercial products, polychlorinated biphenyls (PCBs) can be unintentionally released as by-products from industrial processes. Recent studies have emphasized the importance of unintentionally produced PCBs (UP-PCBs) and have even identified them as major contributors to atmospheric PCBs. However, little is known about contributions of UP-PCBs in current soils. In this study, all 209 PCB congeners were analyzed in agricultural soils on a national scale to investigate the influence of unintentional sources on Chinese soil. The concentration of Σ209PCBs in soils across China was in the range of 64.3-4358 pg/g. Four non-Aroclor congeners, i.e., PCB11, PCB44 + 47+65, PCB68, and PCB209, were dominant among all PCBs, averagely accounting for 26.3%, 8.83%, 3.03%, and 2.80% of total PCBs, respectively. PCB11 and PCB209 were found to be higher in East China, while PCB44 + 47+65 and PCB68 were higher in South China. Their spatial distributions were largely dependent on local sources. The results of source apportionment indicated that the legacy of historically produced and used commercial PCB mixtures was the dominant contributor to seven indicator PCBs in Chinese agricultural soils, especially high-chlorinated congeners. However, unintentional sources (i.e., pigment/paint, combustion-related sources, and polymer sealant), which contributed 57.4% of the total PCBs, are controlling PCB burdens in agricultural soils across China.

ß-Cyclodextrin-modified covalent organic framework as chiral stationary phase for the separation of amino acids and ß-blockers by capillary electrochromatography.

Covalent organic frameworks (COFs) as a novel stationary phase have attracted much attention in the field of chromatography owing to their permanent nanoscale porosity, higher surface area, and exceptional stabilities. Here, a novel isocyanate-ß-cyclodextrin-modified COF (MDI-ß-CD-modified COF) was synthesized using isocyanate-ß-cyclodextrin as the chiral selector and imine-based TpPa-1 COF as the matrix by a bottom-up strategy. The reaction condition and the structure of MDI-ß-CD-modified COF were optimized and characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectra, nitrogen adsorption/desorption (Brunauer-Emmett-Teller [BET]), and thermogravimetric analysis (TGA). And then the coated open-tubular column (OT column) was prepared using MDI-ß-CD-modified COF as chiral stationary phase (CSP) by in situ growth approach, which exhibited excellent stability and repeatability. For seven consecutive runs, the intraday and interday relative standard deviations (RSDs) were in range from 0.35% to 2.21% for the migration time of histidine. The column-to-column reproducibility ranged from 2.39% to 3.08%. Meanwhile, the separation of eight compounds including four amino acids and four ß-blockers by capillary electrochromatography sufficiently verified the favorable chiral resolution properties of the MDI-ß-CD-modified COF-coated OT column. This strategy of fabricating MDI-ß-CD-modified COF-coated OT column expanded the application of imine-based COFs in chromatographic analytical fields.

Enantioselectivity in transplacental transfer of perfluoro-1-methylheptanesulfonate (1m-PFOS): Human biomonitoring and in silico study.

Perfluorooctane sulfonates (PFOS) are one of the most prominent perfluoroalkyl contaminants in humans and wildlife. Currently, information regarding enantiomer-specific exposure to PFOS in humans through transplacental transfer is lacking. This study examined 32 matched maternal serum, cord serum and placenta samples collected from mother-infant pairs in Wuhan, China. The enantiomer fraction (EF) value of perfluoro-1-methylhptanesulfonate (1m-PFOS) was lower in cord sera (0.362 ± 0.062, n = 23) compared to maternal sera (0.422 ± 0.048, n = 21) and placenta (0.410 ± 0.060, n = 16). Evaluations of the difference between EF1m-PFOS suggested enantioselective transplacental transfer of 1m-PFOS. In silico evaluation of the binding affinity of 1m-PFOS to human serum albumin (HSA) showed that the two 1m-PFOS enantiomers enantioselectively interacted with the HSA. This result hints the enantioselective carrier protein affinity may be a key factor for stereoselective 1m-PFOS transplacental transfer. The percentage of branched PFOS (%br-PFOS) and EF1m-PFOS was correlated in maternal sera, but not in cord sera and placentas. These data indicated that %br-PFOS and EF1m-PFOS may be less reliable in identifying PreFOS exposure when it comes to complex biological processes, such as transplacental transport. This study could expand our understanding of stereoselective placental contaminant transfer in humans.

A new perspective on volatile halogenated hydrocarbons in Chinese agricultural soils.

Soil contamination by volatile organic compounds has been greatly studied. However, there is still limited information regarding the occurrence, distribution and health effects of typical volatile halogenated hydrocarbons (VHCs) in soils on a national scale. In this study, headspace-based extraction with gas chromatography/mass spectrometry (HS-GC/MS) detection was optimized for the simultaneous analysis of 18 VHCs (haloalkanes, haloalkenes and halogenated aromatics) in 112 surface agricultural soil samples across China in 2016. The results show that 100% of the soil samples were contaminated by VHCs, and 13 of the 18 VHCs investigated were detected. The haloalkanes were the dominant group. Five VHC components had detection rates greater than 35%, including dichloromethane (DCM), chloroform (CF), 1,2-dichloroethane (1,2-DCA), chlorobenzene (CB) and 1,4-dichlorobenzene (1,4-DCB). For total VHCs, North and Southwest China were the hotspots for contamination. The highest concentrations were found in Shanxi Province and Chongqing municipality, which could be the result of long-term aerial deposition and wet deposition from various accidental industrial leakages or natural sources. In addition, the applications of sewage sludge and pesticides in agricultural activities may also contribute to soil VHC pollution. By using the health risk-assessing models recommended by the U.S. Environment Protection Agency (U.S. EPA), the estimated hazard indices (HIs) of all VHCs were below 1, and the carcinogenic risk (CR) values were all at acceptable levels (<1 × 10-6). These findings indicated that the agricultural soils may not trigger serious long-term health impacts on public health nationwide. The results from this study can initially grasp the agricultural soil VHC pollution level and provide an understanding to avoid potential ecological and human health risks.

A strategy to reduce the dose of multichiral agricultural chemicals: The herbicidal activity of metolachlor against Echinochloa crusgalli.

Agricultural chemicals are normally used as mixtures of several isomers, e.g., enantiomers. In theory, in order to minimize the pesticides dose, it is desirable to use the most target-active isomer. Metolachlor is a typical multichiral herbicide belonging to amide herbicides. An asymmetric carbon atom and a chiral axis yield four stereoisomers. In this study, a novel laboratory method was developed to prepare the S-metolachlor and the four stereoisomers using high performance liquid chromatography. The separated isomers had a purity of >99%, with their absolute configurations assigned by electronic circular dichroism. The enantioseparation by ultra performance convergence chromatography tandem mass spectrometry was also performed for the rapid and sensitive detection of metolachlor stereoisomers. The enantioselective herbicidal activity toward the target weed (Echinochloa crusgalli) was systematically assessed for the first time by measuring the morphology of the weed after treatment with rac-, S-metolachlor and the four stereoisomers, respectively. Among the commercial pesticides, S-metolachlor was more effective in weed inhibition than rac-metolachlor, and to the four stereoisomers, the herbicidal activities were ranked as: SS > SR ≫ RS > RR, and the RR-isomer even had some stimulative effect to the weed growth at lower concentration (1 ppm). Thus, we concluded that in these cases, the chiral carbon feature played a major role in herbicidal activity rather than the chiral axis feature, and the higher bioactivity of the S-isomers was confirmed by more effective uptake and stronger interaction with target enzymes that were involved in the gibberellic acid biosynthesis. Although the SS-isomer shows the highest herbicidal activity, controlling the major chiral feature is still much easier and more economical than controlling two chiral features.

Enantioselectivity and allelopathy both have effects on the inhibition of napropamide on Echinochloa crus-galli.

Napropamide is a chiral acetamide herbicide commonly applied to control Echinochloa crus-galli in maize. The inhibition effect may be enantioselective for Echinochloa crus-galli and maize. It may also be affected by the potential allelopathy at field condition. To investigate this, we have examined the inhibition effect of napropamide on Echinochloa crus-galli mono-cultured or co-cultured with maize at field conditions. Our results on morphology, physiology, chlorophyll content and chlorophyll fluorescence suggest that R-napropamide has stronger inhibitory effect than Rac-napropamide and S-napropamide on Echinochloa crus-galli, while none of them affects maize. We found that both glutathione-S-transferase (GST) genes and oxidative enzymes (superoxide dismutase, malondialdehyde) played roles in the inhibition. Accumulations of napropamide in Echinochloa crus-galli were more prominent in roots than in shoots, and no enantioselectivity was found in medium dissipation. We have observed relative allelopathy when applying napropamide to Echinochloa crus-galli co-cultured with maize. The results warrant further field studies on the enantioselectivity and allelopathy of herbicides.

[Salt stress tolerance of cucumber-grafted rootstocks].

Taking 4 different Cucurbita maxima x C. moschata rootstocks for cucumber (Cucumis sativus) as test materials, a solution culture experiment was conducted to study their growth and antioxidative enzyme activities under the stresses of Ca(NO3)2 and NaCl, with the salt stress tolerance of the rootstocks evaluated by subordinate function. At 30 mmol x L(-1) of Ca (NO3)2 or 45 mmol x L(-1) of NaCl, the growth of the rootstock seedlings was improved; but at 60 and 120 mmol x L(-1) of Ca(NO3)2 or 90 and 180 mmol x L(-1) of NaCl, the growth and the antioxidative systems of the seedlings were inhibited, and the salt injury index of 'Qingzhen No. 1' was the smallest, with the decrement of biomass and SOD, POD and CAT activities and the increment of relative conductance being significantly lower than those of the others. Under the stress of high concentration Ca(NO3)2, the SOD, POD and CAT activities of test rootstocks were higher, and the salt injury index and relative conductance were lower, as compared with those under high concentration NaCl, suggesting that the damage of Ca(NO3)2 stress to cucumber-grafted rootstock were smaller than that of NaCl stress. Among the 4 rootstocks, 'Qingzhen No. 1' had the strongest salt stress tolerance, followed by 'Zuomu Nangua', 'Fengyuan Tiejia', and 'Chaoba Nangua'.

[Study on the immune response of the therapeutic multi-epitope gene vaccine of hepatitis B virus in mice].

AIM: To study the immunogenicity of the therapeutic multi-epitope gene vaccine of Hepatitis B virus. METHODS: Multi-epitope gene of Hepatitis B virus was cloned into prokaryon expression vector pBAD/gIIIA to express a non-fusional antigen B-BPT and BALB/c mice were immunized with the antigen. Cytotoxic T-lymphocyte(CTL) was determined with CytoTox96 kit which quantitatively measures the lactate dehydrogenase(LDH) that is released on cell lysis. CD4(+);, CD8(+); T lymphocytes subsets in immunized mice was detected by using flow cytometry (FCM). Lymphocyte proliferation response was completed by MTT colorimetry. RESULTS: Injection of B-BPT elicited high-level of CTL response and also stimulus spleen lymphocytes to proliferate effectively. CONCLUSION: B-BPT can induce specific cellular immune responses and may be a good candidate for therapeutic vaccine.