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A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation method coupled with gas chromatography–tandem mass spectrometry has been developed for the simultaneous analysis of amide/dinitroaniline/substituted urea herbicides in bivalve shellfish samples. A molecularly imprinted polymer (MIP) synthesized through bulk polymerization exhibited strong group–selective interactions with pigments, including β-carotene, chlorophyll A, and fucoxanthin, in bivalve shellfish extracts. Afterward, a modified QuEChERS method based on MIPs and primary and secondary amines was established to effectively remove matrix components in bivalve shellfish samples. Under the optimal conditions, good linearities were obtained in all of the analytes with R2 larger than 0.9995. Limits of quantification were in the range of 0.03–8.88 μg kg−1, respectively. The recoveries of all of the herbicides spiked at three concentrations of 10, 25, and 50 μg kg−1 in blank bivalve shellfish samples ranged from 81 to 109% with intra-day and inter-day relative standard deviations less than 8%, respectively. Results demonstrated that the proposed QuEChERS method coupled with GC–MS/MS was applied successfully to simultaneously determine 26 amide/dinitroaniline/substituted urea herbicides in bivalve shellfish.

In this study, marine mussels (Mytilus coruscus) were exposed to three typical PAEs (dimethyl phthalate [DMP], dibutyl phthalate [DBP] and di(2-ethylhexyl) phthalate [DEHP]) at a range of doses for different times to investigate the ecotoxicological effects. The accumulation of the three PAE congeners in M. coruscus exhibited the following trend: DEHP > DBP > DMP. The antioxidant response of mussel gonadal tissue was enhanced with increasing concentrations of PAEs. For the DBP and DEHP treatment groups, glutathione (GSH) worked in concert with antioxidant enzymes to protect cells against reactive oxygen species (ROS), while GSH played a prominent antioxidant role in the DMP-treated group. The metabolomics results revealed that PAE exposure disrupted the metabolic balance of mussels. Overall, PAEs affect the amino acid metabolism, lipid metabolism, energy metabolism, osmoregulation and nerve activities of mussels. Our results provide further insight into the toxicological effects of PAEs on marine organisms.

Atrazine (ATR) is one of the most commonly used herbicides that could directly impair the growth and health of organisms in mariculture areas and adversely affect human health through the food chain. This study investigated the contaminant occurrence, migration, and transformation of ATR and three of its chlorinated metabolites, namely deethylatrazine (DEA), deisopropylatrazine (DIA), and didealkylatrazine (DDA), in surface seawater, sediment, and aquatic organisms from the Xiangshan Harbor. ATR was detected in all samples, while DIA and DDA were only respectively detected in aquatic and seawater samples. The distribution of ATR and its metabolites presented different patterns depending on the geographic location and showed a higher level in the aquaculture area than that in the non-aquaculture area. The bioaccumulation of ATR in aquaculture organisms showed that benthic organisms, such as Ditrema, and Sinonovacula constricta (Sin), had increased levels. The ecological risks indicated that ATR posed medium or high risks to algae in the water phase of the study area. The microcosm experiment showed that the main fate of ATR in the simulated microenvironment was sedimentation, which followed the first-order kinetic equation. The ATR in the sediment could be enriched 3-5 times in Sin, and its major metabolites were DEA and DIA.

A highly selective and sensitive molecularly imprinted electrochemiluminescence (MIECL) sensor was developed based on the multiwall carbon nanotube (MWCNT)-enhanced molecularly imprinted quantum dots (MIP-QDs) for the rapid determination of cyfluthrin (CYF). The MIP-QDs fabricated by surface grafting technique exhibited excellent selective recognition to CYF, resulting in a specific decrease of ECL signal at the MWCNT/MIP-QD modified electrode. Under optimal conditions, the MIECL signal was proportional to the logarithm of the CYF concentration in the range of 0.2 &micro, g/L to 1.0 &times, 103 &micro, g/L with a determination coefficient of 0.9983. The detection limit of CYF was 0.05 &micro, g/L, and good recoveries ranging from 86.0% to 98.6% were obtained in practical samples. The proposed MIECL sensor provides a novel, rapid, high sensitivity detection strategy for successfully analyzing CYF in fish and seawater samples.

The spatial distribution, chemical composition and ecological risk of 16 phthalate esters (PAEs) were investigated in the sea-surface microlayer (SML), seawater and sediment samples of the Bohai Sea (BS) and the Yellow Sea (YS). The concentration levels of the ΣPAEs spanned a range of 449–13441 ng L−1 in the SML, 453–5108 ng L−1 in seawater, and 1.24–15.8 mg kg−1 in the sediment samples, respectively, with diisobutyl phthalate (DiBP), di-n-butyl phthalate (DBP) and di-ethylhexyl phthalate (DEHP) as the dominant PAEs in both the water and sediment samples. The concentrations of ΣPAEs in the BS were higher than those in the YS. The vertical distribution of ΣPAEs in the water column showed that the concentrations were higher in the surface waters, but decreased slightly with depth, and started to increase at the bottom. Additionally, PAEs were significantly enriched in the SML, with an average enrichment factor of 1.46. The ecological risk of the PAEs was evaluated by the risk quotient (RQ) method, which indicated that DEHP posed a high risk to aquatic organisms in the whole water-phase, while the RQ values of DBP and DiBP reached a high risk levels in sedimentary environment.

Spatiotemporal variability in seawater, spatial variation in sediment, pollution characteristics, and risks related to 16 phthalate esters (PAEs) were investigated in the Yangtze River estuary and its adjacent East China Sea. The total concentrations of ΣPAEs in surface water were 0.588–17.7 μg L−1 in summer, 2.63–22.9 μg L−1 in winter, and 1.93–20.7 μg L−1 in spring, with average values of 2.05, 10.2, and 4.89 μg L−1, respectively. PAE concentrations exhibited notable seasonal variations with the highest value in winter and the lowest value in summer. The seasonal variation in PAE concentrations may be influenced by runoff and diluted water from the Yangtze River. The chemical composition of PAEs showed that di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP) had significantly higher (p

A series of remarkable crystalline compounds were obtained from the simple one-step solvothermal reaction of zinc nitrate or copper nitrate, benzentricarboxylate (BTC) and certain macrocyclic metal complexes. In these compounds, the macrocyclic metal complexes were alternately arrayed as noncoordinating guests in the cages of a Zn-BTC or Cu-BTC-based metal organic framework host matrix. Powder X-ray diffraction analysis, ICPAES, EDS, H2 adsorption studies demonstrated the validity of encapsulation of macrocyclic metal complexes and the enhancement of hydrogen capacities. It is the first time that the construction of metal-organic frameworks (MOFs) is based on macrocyclic metal complexes as templates. Actually, it is worth to be noted that the introduction of macrocylic metal complexes contributes to increasing the active sites or the adsorption sites interacting to hydrogen gas.

The high-density polyethylene (HDPE) and the polystyrene (PS), which are typical microplastic contaminants, are frequently detected in the environment and have potential hazard to environmental health. In this study, the accumulation, elimination, tissue distribution and potential effects of the HDPE and the PS in the mussels (Mytilus galloprovincialis) were evaluated. The HDPE and the PS were found in various tissues (digestive gland > gill > gonad ≈ muscle) with no difference in distribution patterns. The accumulation of the HDPE and the PS rapidly increased in the first 48 h exposure, and the accumulation of HDPE was higher than that of PS. After 144 h of elimination, most of the HDPE and the PS were cleared by mussels. In addition, the activities of superoxide dismutase (SOD), catalase (CAT) and the content of oxidized glutathione considerably increased, indicating that the HDPE and the PS induced oxidative stress and prevented oxidative damage in elimination. The metabolomic analysis suggested that exposure to HDPE and PS induced alterations in the metabolic profiles of mussel. Differential metabolites were involved in energy metabolism, lipid metabolism, tricarboxylic acid cycle and neurotoxic response., and Meanwhile, the PS had a lower effect on mussel metabolism during elimination, but the effect of HDPE was increased. Overall, this study elucidated that the HDPE and the PS caused adverse effects on the mussels and provided insights toward understanding the hazard of different microplastics on aquatic organisms.

The pollution characteristics, spatiotemporal variation, sediment–water partitioning, and potential ecological risk assessment of phthalate esters (PAEs) in the sediment–seawater system of the Hangzhou Bay (HZB) in summer and autumn were researched. The sum of the concentrations of the 10 PAEs in seawater ranges from 7305 ng/L to 22,861 ng/L in summer and from 8100 ng/L to 33,329 ng/L in autumn, with mean values of 15,567 ± 4390 and 17,884 ± 6850 ng/L, respectively. The Σ16PAEs in the sediments are between 118 and 5888 μg/kg and 145 and 4746 μg/kg in summer and autumn, respectively. The level of PAEs in seawater varies with the seasons, but it is relatively stable in the sediments. Di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), and diisobutyl phthalate (DiBP) are the predominant PAE congeners in the HZB. The DnBP and DiBP concentrations in seawater are greater than the DEHP concentration, which is the opposite in the sediments. The sediment–seawater equilibrium distribution study indicates that the PAEs with medium molecular weights, such as DiBP, butyl benzyl phthalate, and DnBP, are near dynamic equilibrium in the sediment–seawater system; PAEs with high molecular weights (e.g., di-n-octyl phthalate and DEHP) tend to transfer from water to the sediments; and PAEs with low molecular weights (e.g., dimethyl phthalate, diethyl phthalate, and diamyl phthalate) tend to spread to seawater. The risk assessment results in seawater indicate that DEHP and DiBP might pose high potential risks to sensitive organisms, and DnBP might exhibit medium ecological risks. In the sediment, DiBP might display a high potential risk to fish, and the potential risk of DEHP is high in several sites.

Phthalic acid esters (PAEs), as the most important plasticizers, are widely used in the production of plastic products. The accurate analysis of PAEs in seawater and sediment would be of great significance in studying the transformation of PAEs and their ecological effects in marine environment. In this study, the method of gas chromatography-mass spectrum detector coupled with solid-phase microextraction was established to analyze the concentration of PAEs in seawater and sediment, and the experimental conditions, such as extraction time and extraction temperature, were optimized. Under the optimum conditions, the precision of this method was less than 10.0%, and the limits of detection were 0.04–0.32 ng L −1 and 0.12–1.6 μg kg −1 . Except dimethyl phthalate, the recovery of PAEs in seawater and sediment ranged from 68.0% to 114.0% and 76.4% to 105.0%, respectively. Moreover, the concentrations of PAEs measured by the method were 0.270–1.39 μg L −1 and 0.79–34.8 μg kg −1 in seawater and sediment samples of Changjiang River Estuary and its adjacent area, respectively. In conclusion, the analytical method is easy to operate and reduces the extraction volume of seawater. Thus, this method meets the requirements of the analysis of PAEs in coastal seawater and sediment.

A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure combined with GC-MS/MS detection approach using a dynamic multiple reaction monitoring (DMRM) mode was successfully applied for the simultaneous analysis of 84 polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in shellfish samples. The novel molecular imprinted polymers (MIPs) were synthesized by precipitation polymerization and characterized by Scanning electron microscopy, Brunauer-Emmett-Teller, Fourier transform infrared spectra and adsorption experiment. The MIPs exhibited good adsorption capability to pigment coextractives in shellfish samples without the loss of analytes compared with other sorbents. Under optimal conditions, spiked experiments in sinonovacula, mussel, and clam at 10.0-100.0 μg/kg concentrations showed excellent recoveries ranging from 70% to 120% for all analytes with the relative standard deviations of10%. The developed method showed good linearity with the correlation coefficient above 0.9980, and the limits of quantification were in the range of 0.01-9.02 μg/kg. The developed QuEChERS procedure combined with GC-MS/MS was successfully applied to 84 PCBs and OCPs residues detection in shellfish samples.

The spatial and temporal distribution, congener profiles and ecological risk of phthalic acid esters (PAEs) were investigated in the seawater and sediment samples from the East China Sea in spring and autumn. The average concentrations of ΣPAEs in water samples were 3.16 ± 2.16 μg L−1 in autumn and 1.63 ± 1.20 μg L−1 in spring. The ΣPAEs in sediment was much higher than that in seawater, with an average value of 7.36 ± 6.70 mg kg−1 (dw). PAEs levels in the sea-surface microlayer (SML) in spring were 3.61 ± 3.36 μg L−1, indicating that the PAEs were noticeably concentrated in the SML, with an average enrichment factor of 2.10. Among the 16 PAE congeners, di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP) were the preponderant PAEs in both sediment and seawater samples. Additionally, PAE concentrations in autumn were higher than those in spring, and this difference resulted mainly from the terrigenous input and marine transportation. The horizontal distributions of PAEs showed an opposite distribution pattern to salinity and temperature, a pattern which might be influenced by the inputs of fresh water. The vertical distributions of ΣPAEs were characterized by high concentrations in the surface waters, with a slight decrease with depth, and then an increase close to the seabed. The results of ecological risk in the water-phase showed that the level of potential risk followed the order of DEHP > DiBP and DnBP > DMP and DEP, which posed a high (DEHP), medium (DiBP and DnBP) and low (DMP and DEP) risk to the sensitive organisms, respectively. For the sediment-phase, DiBP and DnBP represented a high risk to the sensitive organisms, whereas DMP, DEP and DEHP had only a low risk.

A highly selective molecularly imprinted electrochemiluminescence (MIECL) sensor based on molecularly imprinted Fe3O4 nanocrystals (MIP-Fe3O4/NCs) and luminol was developed for bisphenol A (BPA) determination. MIP-Fe3O4-NCs were synthesized and immobilized on the glassy carbon electrode (GCE) surface to fabricate the electrogenerated chemiluminescence (ECL) system. The GCE modified with MIP-Fe3O4-NCs could greatly promote the cathodic ECL of luminol. After incubation with the BPA solution, the imprinting sites on the surface of MIP-Fe3O4-NCs could specifically rebind BPA, resulting in selective and sensitive ECL quenching by hindering electron transfer capability. Under optimal conditions, the relative ECL intensities were proportional to the logarithm of BPA concentration ranging from 0.002 μg/L to 5.0 × 103 μg/L at a limit of detection of 2.0 × 10−4 μg/L. Satisfactory recoveries of 93.5 %–98.3 % were obtained in fish and seawater samples at a relative standard deviation of

Molecularly imprinted polymers (MIPs) are attracting substantial interest as artificial plastic antibodies because of their biometric capability for targeting small molecules. In this study, molecularly imprinted silica material-coated quantum dots (MIS-QDs) with selective recognition capability to okadaic acid (OA) were developed and characterized. The synthesized MIS-QDs with specific imprinting cavities exhibited excellent recognition capability similar to those of biological antibodies and high fluorescence (FL) quenching selectivity for OA. Furthermore, the MIS-QDs with unsaturated bonds were immobilized onto the surface of 96-well microplates by cold plasma-induced grafting. A novel direct competitive microplate assay strategy was then proposed. The FL quenching properties of the developed microplate assay showed an excellent linear relationship with OA in the range of 10.0-100.0 μg/kg with a correlation coefficient of 0.9961. The limit of detection for OA was 0.25 μg/kg in the shellfish samples. The mean quantitative recoveries were 92.5%-101.0% and 92.9%-101.3%, with relative standard deviations of7.7% and 7.6% for pure solvents and purified shellfish samples, respectively. The established microplate assay strategy can be used as a rapid and high-throughput method for analyzing OA marine toxins in biological samples.

Perfluoroalkyl acids (PFAAs) are ubiquitous pollutants present in various environmental media, including marine sediments. A method was proposed for the determination of 17 target PFAA analytes in marine sediment samples (n = 49) collected from the Yangtze Estuary and East China Sea. The proposed method involves the use of an optimized pretreatment procedure and ultrahigh-performance liquid chromatography electrospray ionization–tandem mass spectrometry in dynamic multiple reaction monitoring mode. The method relied on extraction cycles using methanol followed by concentration, filtration, and small volume injection to UHPLC-MS/MS. The recovery, time efficiency, and detection limit of the proposed method are improved relative to those of traditional methods. Limits of detection varied from 0.003 to 0.045 ng/g, and spike recoveries to sediment ranged from 90% to 110% with suitable precisions (1.7%–14.6%). PFAAs were widely present in the samples, and ΣPFAAs ranged from 0.67 ng/g dw to 36.75 ng/g dw. Results indicated that terrigenous input strongly influences PFAA distribution in sediments from the study areas. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) were identified as the dominant perfluorocarboxylic acid (PFCA) and perfluoroalkylsulfonate (PFSA) in sediment samples from the Yangtze Estuary and the East China Sea. Preliminary environmental risk assessment indicated that PFOS may pose a higher environmental risk than PFOA. Furthermore, risk quotient values indicated that PFOS poses a significant risk to the aquatic ecosystem of the study areas.

A total of 133 seawater samples and 17 sediment samples were collected from 81 sampling sites in the Changjiang River Estuary and its adjacent area and were analyzed for 16 phthalate esters (PAEs). The Σ16 PAE concentrations in the seawater and sediment samples ranged from 180.3ng·L-1 to 3421ng·L-1 and from 0.48μg·g-1 to 29.94μg·g-1dry weight (dw), respectively, with mean values of 943.6ng·L-1 and 12.88μg·g-1. The distribution of ∑16PAE concentrations in the water column showed that PAE concentrations in the bottom samples were higher than those in the surface samples (except the transect C located inside the Changjiang River Estuary), with the maxima appearing in the bottom layer at the offshore stations. Among the 16 PAEs, di (2-ethylhexyl) phthalate (DEHP), diisobutyl phthalate (DiBP), and dibutyl phthalate (DnBP) dominated the PAEs, with 25.1%, 21.1%, and 18.9% of the Σ16PAEs in seawater, respectively. The comparison of ∑16PAEs and salinities in transects C and A6 suggested that the Changjiang River runoff was an important driving factor influencing the distribution of PAEs. DEHP concentrations in water samples and DEHP and DnBP concentrations in sediment samples exceeded the environmental risk levels (ERL), indicating their potential hazard to the ocean environment.

The occurrence of 17 target PFAA analytes was determined in surface sediments (n = 37) of the East China Sea and potential influencing factors were examined. ΣPFAAs ranged from 0.41 ng/g dw to 3.06 ng/g dw, with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) as the most abundant perfluorocarboxylic acid and perfluoroalkyl sulfonate, respectively. PFAAs in the sediments were strongly influenced by terrigenous input. Analysis of the relationship between dynamic influence factors and PFAA concentrations showed that the characteristics of PFAA distribution were rather complex. ΣPFAA concentrations and TOC were positively correlated (p 0.0001). Circumfluence also influenced the whole PFAA distribution and seasonal variation. In addition, correlation analysis suggested that log K

During the course of searching for antiviral agents from Chinese medicinal herbs, we found that the supercritical fluid extract (SFE) of Centipeda minima possessed good in vitro antiviral activity against influenza virus A/Puerto Rico/8/34 H1N1 (PR8). Bioassay-guided isolation and identification led to the isolation from this extract of seven pseudoguaianolides (1-7). These, as well as nine other sesquiterpene lactones (8-16) previously isolated from this herb were all tested for their anti-PR8 activity using both the cytopathogenic effect (CPE) reduction and cell counting kit 8 (CCK8) assays. As a result, eight pseudoguaianolides (1-8) possessing an α,β-unsaturated cyclopentenone moiety showed antiviral activity against PR8 to different extents. Of the active compounds, brevilin A (4) exhibited the strongest anti-PR8 activity, with an IC50 value much lower than that of the positive control ribavirin. Mechanistic study revealed that brevilin A affected the intracellular replication of PR8 via downregulating the expression of viral M2 protein. All these results suggest the potential application of the pseudoguaianolides containing an α,β-unsaturated cyclopentenone moiety (e.g. brevilin A) in the treatment of influenza virus infection.