Single-Mg-Atom Catalyst with a Dual Active Center as an Emerging Promising Sensing Platform.

Bisphenol compounds [bisphenol A (BPA), etc.] are one class of the most important and widespread pollutants in food and environment, which pose severe endocrine disrupting effect, reproductive toxicity, immunotoxicity, and metabolic toxicity on humans and animals. Simultaneous rapid determination of BPA and its analogues (bisphenol S, bisphenol AF, etc.) with extraordinary potential resolution and sensitivity is of great significance but still extremely challenging. Herein, a series of single-atom catalysts (SACs) were synthesized by anchoring different metal atoms (Mg, Co, Ni, and Cu) on N-doped carbon materials and used as sensing materials for simultaneous detection of bisphenols with similar chemical structures. The Mg-based SAC enables the potential discrimination and simultaneous rapid detection of multiple bisphenols, showing outstanding analytical performances, outperforming all other SACs and traditional electrode materials. Our experiments and density functional theory calculations show that pyrrolic N serves as the adsorption site for the adsorption of bisphenols and the Mg atom serves as the active site for the electrocatalytic oxidation of bisphenols, which play a synergistic role as dual active centers in improving the sensing performance. The results of this work may pave the way for the rational design of SACs as advanced sensing and catalytic materials.

Ultrasensitive rapid detection of antibiotic resistance genes by electrochemical ratiometric genosensor based on 2D monolayer Ti3C2@AuNPs.

As an important emerging pollutant, antibiotic resistance genes (ARGs) monitoring is crucial to protect the ecological environment and public health, but its rapid and accurate detection is still a major challenge. In this study, a new single-labeled dual-signal output ratiometric electrochemical genosensor (E-DNA) was developed for the rapid and highly sensitive detection of ARGs using a synergistic signal amplification strategy of T3C2@Au nanoparticles (T3C2@AuNPs) and isothermal strand displacement polymerase reaction (ISDPR). Specially, two-dimensional monolayer T3C2 nanosheets loaded with uniformly gold nanoparticles were prepared and used as the sensing platform of the E-DNA sensor. Benefiting from excellent conductivity and large specific surface area of Ti3C2@AuNPs, the probe immobilization capacity of the E-DNA sensor is doubled, and electrochemical response signals of the E-DNA sensor were significantly improved. The proposed single-labeled dual-signal output ratiometric sensing strategy exhibits three to six times higher sensitivity for the sul2 gene than the single-signal sensing strategy, which significantly reduces cost meanwhile retaining the advantages of high sensitivity and reliability offered by conventional dual-labeled ratiometric sensors. Coupled with ISDPR amplification technology, the E-DNA sensor has a wider linear range from 10 fM to 10 nM and a limit of detection as low as 2.04 fM (S/N=3). More importantly, the E-DNA sensor demonstrates excellent specificity, good stability and reproducibility for target ARGs detection in real water samples. The proposed new sensing strategy provides a highly sensitive and versatile tool for the rapid and accurate quantitative analysis of various ARGs in environmental water samples.

An electrochemical sensor based on synergistic enhancement effects between nitrogen-doped carbon nanotubes and copper ions for ultrasensitive determination of anti-diabetic metformin.

Metformin (MET) is the primary medicine for type II diabetes, which produces carcinogenic byproducts during chlorine disinfection, so the detection of MET in aqueous environment is crucial. In this work, an electrochemical sensor based on nitrogen-doped carbon nanotubes (NCNT) has been constructed for ultrasensitive determination of MET in the presence of Cu(II) ions. The excellent conductivity and rich π-conjugated structure of NCNT facilitate the electron transfer rate of fabricated sensor and benefit the adsorption of cation ions. Cu(II) ions can chelate with MET to form MET-Cu(II) complex, which are easily accumulated on the surface of NCNT through cation-π interaction. Attributing to the synergistic enhancement effects of NCNT and Cu(II) ions, the fabricated sensor exhibits excellent analytical performances with a low detection limit of 9.6 nmol L-1, high sensitivity of 64.97 A mol-1 cm-2 and wide linear range of 0.3-10 µmol L-1. The sensing system has been successfully applied for rapid (20 s) and selective determination of MET in real water samples with satisfactory recoveries (90.2 %-108.8 %). This study provides a robust strategy for MET detection in aqueous environment and holds great promise for rapid risk assessment and early warning of MET.

Dense Conductive Metal-Organic Frameworks as Robust Electrocatalysts for Biosensing.

Due to the fascinating properties such as high porosity, large surface areas, and tunable chemical components, metal-organic frameworks (MOFs) have emerged in many fields including catalysis, energy storage, and gas separation. However, the intrinsic electrical insulation of MOFs severely restricts their application in electrochemistry. Here, we synthesize a series of 2D conductive MOFs (cMOFs) through tuning the structure with atomic precision using simple hydrothermal methods. Various electroactive probes are used to reveal the structure-property relationships in 2D cMOFs. Then, we demonstrate the first exploration and implementation of 2D cMOFs toward the construction of electrochemical biosensors. In particular, the biosensor based on Cu3(tetrahydroxy-1,4-quinone)2 [Cu3(THQ)2] displays a remarkably improved electrocatalytic performance at a much lower potential. The mechanism study reveals the essential role of charge-transfer interactions between the dense catalytic sites of Cu3(THQ)2 and analytes. Furthermore, the Cu3(THQ)2-based biosensor demonstrates robust anti-interference capability, good stability, fast response speed, and an ultralow detection limit for paraoxon. These promising results indicate the great potential of cMOFs in biomedical, food safety, and environmental sensing applications.

2D Conductive Covalent Organic Frameworks with Abundant Carbonyl Groups for Electrochemical Sensing.

Due to their permanent porosity, robust chemical stability, and tunable structure, covalent organic frameworks (COFs) are very attractive in the application of energy storage, catalysis, sorption, and sensing. However, the very low conductivity of COFs severely restricts their application in electrochemical sensing. Here, an aza-fused π-conjugated COFs with abundant carbonyl groups (COF1) was synthesized and deployed as electrode materials in electrochemical sensing for the first time. The current response of the acetylcholinesterase biosensor based on COF1 increases three times when compared to the electrode without COF1. The effects of carbonyl groups on signal enhancement were proved in depth by a series of characterization and comparison experiments with the prepared COF2 without carbonyl groups. The results demonstrated that exposed carbonyl active sites of COF1 can promote the effective immobilization and bioactivity preserving of enzyme molecules and contribute to the enrichment of analytes. Together with the good conductivity of COF1 derived from a fully extended 2D aromatized π-conjugated system, all of which improve the biosensor performance. The COF1-based biosensor exhibited fast response speed, high sensitivity, good selectivity and practicability, and robust stability for organophosphorus pesticide detection and proved to be a promising tool for the rapid and onsite detection of organophosphorus pesticides in the environment.

[Screening of risky substances in sea cucumbers based on gas chromatography-orbitrap high-resolution mass spectrometry].

A new method for sample pretreatment using improved QuEChERs was established, and 289 organic pollutants with health risks could be identified and quantified through gas chromatography-orbitrap high-resolution mass spectrometry (GC-Orbitrap HRMS). A high-resolution database of 289 environmental pollutants belonging to ten categories, including organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), phthalates (PAEs), polychlorinated biphenyls (PCBs), and other agricultural chemicals (ACs), was established for the non-targeted screening and quantitative analysis. A simple method for biological sample preparation using improved QuEChERs was proposed by combining a conventional QuEChERs method and a column purification method. After purification using a Florisil column, the lipid content was reduced by 99.9%, which significantly reduced the interference of the matrix effect observed during the analysis. Furthermore, simultaneous high-accuracy qualitative screening and quantitative analysis of the target compounds were performed through high-resolution mass spectrometry (60000 resolution) conducted in the full scan mode. The limits of quantification were 0.56-57.8 pg/g, presenting a large linear range (~106), and the recovery range was 40%-120%. Due to the high-resolution and sensitivity of Q Exactive GC-Orbitrap HRMS, the limits of quantification of the target compounds were significantly lower than those achieved through methods based on conventional chromatography and mass spectrometry. Moreover, ultratrace organic contaminants that cannot be detected by conventional methods can be accurately quantified by the proposed method. Sea cucumber samples collected at the breeding site were analyzed using the proposed high-coverage multi-objective analytical method, and more than 100 types of organic pollutants were detected; the mean contents of PAHs, ACs, PAEs, and OCPs were 157.8, 153.2, 64.4, and 46.4 ng/g dw, respectively, which were higher than those of other pollutants. Some new contaminants, such as 9-chlorofluorene, 5-chloroacenaphthene, and 3-methylcholanthrene, were detected at very low contents for the first time in the sea cucumber samples. The proposed method is simple and efficient, allows the detection of pollutants at very low contents, and provides accurate and reliable results. Thus, this high-coverage multi-objective analytical method can be widely used for broad-spectrum screening and accurate quantification of contaminants in various aquatic products, providing technical support for food safety control.

Sensitive Electrochemical Biosensor for Rapid Screening of Tumor Biomarker TP53 Gene Mutation Hotspot.

Rapid and sensitive detection of cancer biomarkers is crucial for cancer screening, early detection, and improving patient survival rate. The present study proposes an electrochemical gene-sensor capable of detecting tumor related TP53 gene mutation hotspots by self-assembly of sulfhydryl ended hairpin DNA probes tagged with methylene blue (MB) onto a gold electrode. By performing a hybridization reaction with the target DNA sequence, the gene-sensor can rearrange the probe's structure, resulting in significant electrochemical signal differences by differential pulse voltammetry. When the DNA biosensor is hybridized with 1 µM target DNA, the peak current response signal can decrease more than 60%, displaying high sensitivity and specificity for the TP53 gene. The biosensor achieved rapid and sensitive detection of the TP53 gene with a detection limit of 10 nmol L-1, and showed good specific recognition ability for single nucleotide polymorphism (SNP) and base sequence mismatches in the TP53 gene affecting residue 248 of the P53 protein. Moreover, the biosensor demonstrated good reproducibility, repeatability, operational stability, and anti-interference ability for target DNA molecule in the complex system of 50% fetal bovine serum. The proposed biosensor provides a powerful tool for the sensitive and specific detection of TP53 gene mutation hotspot sequences and could be used in clinical samples for early diagnosis and detection of cancer.

Ultrathin graphdiyne nanosheets confining Cu quantum dots as robust electrocatalyst for biosensing featuring remarkably enhanced activity and stability.

There is an urgent need for developing electrochemical biosensor based on the acetylcholinesterase (AChE) inhibition to real-time analysis of organophosphorus pesticides (OPs), but it is suffered from the sluggish electrode kinetics and high oxidation potential toward signal species. Herein, a nanocomposite of ultrafine Cu quantum dots (QD) uniformly loaded on three-dimensional ultrathin graphdiyne (GDY) nanosheets (denoted as Cu@GDY) was synthesized via a one-step strategy, which showing high-density of active sites with persistent stability. Then an AChE biosensor based on Cu@GDY was fabricated to detect OPs, and the results revealed that the Cu@GDY nanocomposite can significantly amplifies electrochemical signal and reduces the oxidation potential for OPs. The strong interaction between active site of Cu@GDY and thiocholine signal species caused rapid analyte aggregation and decreased the reaction activation energy of thiocholine electro-oxidation. Benefiting from the excellent catalytic activity of Cu@GDY nanocomposite and reasonable regulation of enzyme inhibition kinetics, the biosensor achieved rapid and sensitive detection of OPs with a detection limit of 1 µg L-1 for paraoxon. Furthermore, the biosensor demonstrated great reproducibility, good stability and high recovery rate for OPs detection in real samples. Cu@GDY based sensor also displayed high catalytic activities and good selectivity to the non-enzymatic detection of glucose in alkaline medium. Cu@GDY offers a versatile and promising platform for sensors and biosensors featuring remarkably enhanced activity and stability, and can be applied to many other fields as desirable electrocatalyst.

[Accumulation Characteristics and Dietary Exposure Estimation of Heavy Metals in Vegetables from the Eastern Coastal Region of China].

The levels of six toxic metals and five essential metals in five groups of vegetables marketed in the eastern coastal region of China were analyzed using inductively coupled plasma mass spectrometry. The results showed that the concentrations of six toxic heavy metals in all the vegetables did not exceed the maximum residue limits. The health risk assessment indicated that consumption of vegetables may not pose a potential noncarcinogenic risk to consumers, while there is a carcinogenic risk level of 10-5 level from inorganic arsenic exposure through vegetable consumption. Additionally, a similar trend was observed for the accumulation of toxic and essential metals. Furthermore, compared with other vegetable groups, edible fungi have a high potential to accumulate toxic and essential metals, which indicates that pollution monitoring of edible fungi should be strengthened.

Nitrogen-Doped Graphdiyne as a Robust Electrochemical Biosensing Platform for Ultrasensitive Detection of Environmental Pollutants.

Owing to its unique chemical structure, natural pores, high structure defects, good surface hydrophilicity and biocompatibility, and favorable electrical conductivity, nitrogen-doped graphdiyne (NGDY) has been attracting attention in the application of electrochemical sensing. Taking advantage of these fascinating electrochemical properties, for the first time, two types of electrochemical enzymatic biosensors were fabricated for the respective detection of organophosphorus pesticides (OPs) and phenols based on the immobilization of acetylcholinesterase or tyrosinase with NGDY. Results revealed that the sensitivities of the NGDY-based enzymatic biosensors were almost twice higher than that of the matching biosensor in the absence of NGDY, proving that NGDY plays a vital role in immobilizing the enzymes and improving the performance of the fabricated biosensors. The effects of nitrogen doping on improving the biosensing performance were studied in depth. Graphitic N atoms can enhance the electrical conductivity, while imine N and pyridinic N can help to adsorb and accumulate the substance molecules to the electrode surface, all of which contribute to the significantly improved performance. Furthermore, these two types of biosensors also demonstrated excellent reproducibility, high stability, and good recovery rate in real environmental samples, which showed a valuable way for the rapid detection of OPs and phenols in the environment. With these excellent performances, it is strongly anticipated that NGDY has tremendous potential to be applied to many other biomedical and environmental fields.

Accumulation characteristics and estimated dietary intakes of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in plant-origin foodstuffs from Chinese markets.

The levels and accumulation characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were investigated in nine pools of representative plant-origin foodstuffs randomly collected from markets located in five regions of the Chinese mainland during 2018-2019. The collected foodstuffs consisted of cereals, beans, potatoes, leafy vegetables, root and stem vegetables, melon vegetables, legume vegetables, edible fungi, and mixed vegetable oil. In the fresh plant food pools, the concentrations of toxic equivalency (WHO-TEQ) were in the ranges of 0.9-14.5 pg/kg in upperbound (UB) scenario and 0.002-7.3 pg/kg in lowerbound (LB) scenario on a fresh weight basis; and TriCDFs and TeCBs were the predominant PCDD/F and PCB homologues, respectively. In the mixed vegetable oil, the WHO-TEQ concentrations were 129.4 pg/kg and 103.6 pg/kg on a lipid weight basis in UB and LB scenarios, respectively; and high-chlorinated PCDD/F and PCB homologues were much more abundant. The estimated plant food-borne dietary intakes of WHO-TEQ by a standard adult in the five surveyed regions were in the ranges of 3.39-4.20 and 1.57-2.13 pg WHO-TEQ/kg body weight/month in UB and LB scenarios, respectively. Among all surveyed regions, consumption of cereals and vegetable oil made up the primary contributions to the estimated dietary intakes of WHO-TEQ. TriCDFs accounted for 41.1-83.9% of the PCDD/Fs dietary intakes via consumption of plant foods, and TeCBs made up 61.2-73.0% of the PCBs dietary intakes via consumption of plant foods, suggesting that the potential toxic effects of TriCDFs and TeCBs on human health should be concerned.

Tyrosinase nanocapsule based nano-biosensor for ultrasensitive and rapid detection of bisphenol A with excellent stability in different application scenarios.

Bisphenol A (BPA), one of the most important endocrine disrupting chemicals, is a threat to human and wildlife health. Electrochemical enzyme biosensor has been regarded as ideal alternative analytical technique for ultrasensitive and rapid detection of BPA, while the unstable and easily deactivated nature of enzyme limits its development. In order to improve the stability of enzyme, tyrosinase was chosen as a model enzyme, and tyrosinase nanocapsules (nTyr) were prepared by encapsulating a single tyrosinase molecule into a thin network polymer shell through in-situ polymerization method in aqueous solution. The characterization of particle size distribution, TEM and FTIR indicated the successful formation of single tyrosinase molecule nanocapsule. And the porous network polymer shell of nTyr ensured the maintenance of tyrosinase activity and fast substrate transportation. The obtained nTyr was used to construct an electrochemical biosensor for BPA detection, exhibiting a low detection limit of 12 nmol L-1 and a wide linear range from 5 × 10-8 to 2 × 10-6 mol L-1. Compared with native tyrosinase, the nTyr based biosensor displayed dramatically enhanced stability including thermal stability, organic solvent tolerance and acid/base tolerance. The excellent performance of nTyr based biosensor was not only attributed to the protection of biocompatible rigid polymer shells, but also the multipoint covalent attachments between tyrosinase cores and polymer shells. The robust biosensor was further used for rapid detection of BPA leached from plastic products with satisfactory results. The nTyr based nano-biosensor provides a prospective solution to resolve the stability problem of enzyme biosensors in different application scenarios.

Robust Single-Molecule Enzyme Nanocapsules for Biosensing with Significantly Improved Biosensor Stability.

The present study demonstrates the use of highly stable single-molecule enzyme nanocapsules (SMENs) instead of traditional native enzyme as biorecognition element in enzyme-based biosensors. The main purpose of this study is to resolve the major obstacle and challenge in the biosensor field, i.e., the poor stability of enzyme-based biosensors, including thermal stability, organic solvent tolerance, long-term operational stability, etc. Highly active and robust SMENs of glucose oxidase (GOx, as a model enzyme) were synthesized (nGOx) using an in situ polymerization strategy in an aqueous environment. The particle-size distribution, transmission electron microscopic (TEM) images, and UV-vis spectral characterization revealed the formation of a thin polymer layer around each enzyme molecule. The polymer shell effectively stabilized the GOx enzyme core while enabling rapid substrate transportation, resulting in a new class of biocatalytic nanocapsules. Multiple covalent attachments between a thin polymer layer and an enzyme molecule strengthened the encapsulated GOx molecule. Encapsulation created a favorable microenvironment to avoid any structural dissociation at high temperature and helped to retain essential water during the organic solvent operation. The present work reports a study implementing nGOx SMENs as highly stable nano(bio)sensors for point-of-care diagnostic applications. Prepared nGOx SMENs manifested significantly improved thermal stability (even at 65 °C) and organic solvent tolerance without any compromise in biocatalytic activity. For example, the native GOx-based biosensor lost its catalytic activity for glucose after 4 h of incubation at high temperature (65 °C), while the nGOx/N-CNTs-Chi/GCE nano(bio)sensor maintained ∼56% of its original catalytic activity for glucose oxidation. The proposed SMENs-based nano(bio)sensors with robust stability in variable working environment could promote the development and applications of biosensors in point-of care diagnostics, biomedical detection, wearable devices, implantable equipment, and biofuel cells.

[Simultaneous determination of polycyclic aromatic hydrocarbons and phthalate esters in surface water by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by high performance liquid chromatography].

Polycyclic aromatic hydrocarbons (PAHs) and phthalate esters (PAEs) are internationally recognized as priority pollutants; hence, it is important to monitor their concentrations in the environment. However, the low concentrations of PAHs and PAEs in surface water make the direct and sensitive determination of these compounds by instrumental methods difficult. Therefore, the development of an accurate and rapid sample pretreating method for the determination of PAHs and PAEs in water has always been the goal of environmental scientists. Dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) is a simple, rapid, low-cost, sensitive, and environmentally friendly method. Methods based on DLLME-SFO for the simultaneous determination of PAHs and PAEs in surface water have rarely been reported. In this study, a novel DLLME-SFO method was developed for the simultaneous determination of 16 PAHs and 6 PAEs in surface water samples. To optimize the extraction efficiency for the target compounds, various parameters, including the types and volumes of extractants and dispersants, ionic strength, and extraction time, were investigated. First, 1-undecanol (melting point:19℃) and 1-dodecanol (melting point:24℃) were selected as extractive solvents, and their extraction efficiency was investigated. The results showed that 1-dodecanol had better extraction efficiency. The melting point of 1-undecanol was relatively low, and the droplets that solidified during the experiment were easy to melt and break, which led to the low recovery rate of extraction. Then, the effect of the volume (10, 20, 30, 40, 50 µL) of 1-dodecanol was investigated, and the extraction efficiency of the target compounds was found to decrease with increasing volume of 1-dodecanol. Second, the effect of four dispersive solvents (methanol, ethanol, acetonitrile, and acetone) on the extraction efficiencies was studied. The extraction efficiencies of the target compounds were the highest when methanol was used as the dispersant; hence, the effect of different volumes of methanol on the extraction efficiency was further examined. When the volume of methanol was less than 500 µL, the contact area between the extraction solvent and the water phase increased with increasing methanol volume, and the extraction efficiency increased. However, when the volume of methanol was more than 500 µL, the excessive dispersant increased the solubility of the target compound in the water phase, which led to a decrease in the extraction efficiency. Finally, the effects of salt addition and vortex oscillation time on the extraction efficiency were probed. The experimental results indicated that the extraction efficiency increased with an increase in the quantity of NaCl. When the NaCl quantity was greater than 0.2 g, there was no notable change in the extraction efficiency. Vortex oscillation could accelerate the establishment of the extraction equilibrium, and the extraction efficiency reached a stable state when the vortex oscillation time was more than 2 min. According to the abovementioned results, the optimized DLLME-SFO conditions were established as follows:for 5.0 mL water samples, 10 µL of 1-dodecanol was chosen as the extraction solvent, 500 µL of methanol was used as the dispersive solvent, the vortex oscillation extraction time was 2 min, and the NaCl quantity was 0.2 g. The target compounds were analyzed by high-performance liquid chromatography. Separation of the PAHs and PAEs was achieved on a SUPELCOSILTM LC-PAH column (150 mm×4.6 mm, 5 µm) with acetonitrile-water as the mobile phase using a gradient elution program. Fifteen PAHs were detected using a fluorescence detector, and six PAEs and acenaphthylene were detected by an ultraviolet detector. Quantitative determination was achieved by the external standard method. This method was successfully validated for the analyses of the 16 PAHs and 6 PAEs in two types of water samples (tap water and river water). The average recoveries of the target compounds were 60.2%-113.5%, and the corresponding relative standard deviations (RSDs, n=3) were 1.9%-14.3%. The limits of detection (LODs, S/N=3) ranged from 0.002 µg/L to 0.07 µg/L for the PAHs and from 0.2 µg/L to 2.2 µg/L for the PAEs. The limits of quantification (LOQs, S/N=10) ranged from 0.006 µg/L to 0.23 µg/L for the PAHs and from 0.8 µg/L to 7.4 µg/L for PAEs. The proposed method is simple, fast, low-cost, and environmentally friendly, and it is suitable for the rapid determination of trace PAHs and PAEs in surface water samples.

Levels and patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans and polychlorinated biphenyls in foodstuffs of animal origin from Chinese markets and implications of dietary exposure.

The concentrations and distribution profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were measured in representative animal origin foodstuffs randomly collected from markets located in five regions of the Chinese mainland during 2018-2019. The collected foodstuffs were classified into 11 pools consisting of pork, beef, mutton, poultry meat, chicken eggs, pure milk, mixed animal fat, fish, shrimp, shellfish, and cephalopods. The levels of tri-to octa-CDD/Fs (∑PCDD/Fs), tri-to deca-CBs (∑PCBs), and WHO-TEQ in the collected animal foods were found to be in the ranges of 0.4-14.3 pg/g, 0.04-2.8 ng/g, and 0.013-0.75 pg/g on a fresh weight basis, respectively. The concentrations of PCDD/Fs and PCBs in most of the animal food groups from coastal regions were obviously higher than those from inland regions. Remarkable differences in the homologue and congener distribution of PCDD/Fs and PCBs were observed between terrestrial and aquatic animal foods. The dietary intakes of WHO-TEQ via consumption of animal foods by a standard adult in the five regions were estimated to be in the range of 3.57-19.63 pg WHO-TEQ/kg body weight/month. Consumption of the aquatic animal food and pork categories contributed most of the estimated dietary intakes of WHO-TEQ in the coastal regions, whereas consumption of beef, mutton, and milk made up the primary contributions in Northwest region.

Quantification of Cl-PAHs and their parent compounds in fish by improved ASE method and stable isotope dilution GC-MS.

This study aimed at developing a simple and accurate method for determination of emerging chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) in fish by stable isotope dilution gas chromatography tandem mass spectrometry. Fish samples were extracted by improved accelerated solvent extraction (ASE) method. Matrix effects were observed, and matrix-matched calibration was verified with good intra-day and inter day precisions (lower than 16.1% and 15.1% respectively). Method detection limits were 0.10-5.62 ng g-1 (dry weight) with satisfactory linearity, and recoveries ranged from 50% to 150%, with relative standard deviation values less than 18.5% at different concentration levels. This improved ASE method was proved to be suitable for analyzing Cl-PAHs in fish samples, with good analytical selectivity, linearity, recovery and precision. Furthermore, the composition analysis revealed that chlorinated compounds of phenanthrene, pyrene and acenaphthene were dominated in Cl-PAHs contaminants. The correlationship between the pollution of Cl-PAHs and their corresponding parent structures in fish samples was also analyzed in detail.

Co3O4 nanoparticles supported mesoporous carbon framework interface for glucose biosensing.

The present work reports the preparation of advanced functional nanostructures based on cobalt oxide supported mesoporous carbon framework (Co3O4@MCF) for electrochemical biosensing. Co3O4@MCF was synthesized by simple hythrothermal & pyrolysis method and further characterized by various microscopic and spectroscopic techniques. The transmission electron microscopic (TEM) images show the lattice fringes of crystalline Co3O4 with interlayer spacing of 0.24 nm. The characteristic 311 plane in X-ray diffraction (XRD) studies further confirmed the presence of crystalline Co3O4 on carbon frameworks. Reflection of prominent A1g peak along with D and G band in raman spectra confirmed the successful fabrication of Co3O4@MCF nanocomposite. Prepared Co3O4@MCF manifested great porosity, good biocompatibility and large surface area which allowed effective immobilization of glucose oxidase (GOx) onto its surface using chitosan (Chi) as a binder. Thus, a nanocomposite (Co3O4@MCF-Chi-GOx) modified glassy carbon electrode (GCE) was fabricated for highly selective detection of glucose using amperometry and cyclic voltammetry. The Co3O4@MCF-Chi-GOx/GCE electrode exhibited excellent biosensing performance for glucose monitoring with detection limit of (LOD) of 107.70 µM and reproducibility of 4.7% RSD. Moreover, the biosensor holds great promise for its effective implications in point-of-care diagnostics of small biomolecules.

Bioaccumulation and human health implications of essential and toxic metals in freshwater products of Northeast China.

Bioaccumulation and human health risks of essential and toxic metals in ten species of freshwater products from Northeast China were investigated in this study. The concentrations (mg/kg wet weight) of target metals in aquatic products were: Fe (4.6-165.4), Zn (4.1-33.4), Mn (0.28-80.0), Cu (0.24-15.8), Cr (0.074-0.80), As (0.0068-0.72), Hg (0.016-0.58), Ni (0.019-0.58), Pb (0.017-0.27) and Cd (0.0004-0.058). There was no significant regional difference of target metal levels in fish samples between Liaoning province and Inner Mongolia Autonomous Region according to matched sample t-test. Every daily intakes (EDI) of target metals from freshwater products were far below their corresponding limits. However, health risk assessment of individual metal in freshwater products showed methyl mercury (MeHg) and Mn could pose potential noncarcinogenic risk to human, and inorganic arsenic (iAs) would cause potential carcinogenic risk to consumers at the level of 1 in 100,000. Furthermore, freshwater product species-specific bioaccumulation characteristics for different metals are quite different. The total hazard quotients of target metals in different aquatic product species demonstrated that co-exposure of target metals by consumption of these six species (C. auratus, E. sinensis, C. erythropterus, C. carpio, M. anguillicaudatus and O. cantor) from Northeast China could cause potential noncarcinogenic risk to human, and the pollution of toxic metals in E. sinensis and C. auratus were most serious among all investigated aquatic species.

Ion-Selective Polyamide Acid Nanofiber Separators for High-Rate and Stable Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have attracted great attention because of their high energy density and high theoretical capacity. However, the "shuttle effect" caused by the dissolution of polysulfides in liquid electrolytes severely hinders their practical applications. Herein, we originally propose a carboxyl functional polyamide acid (PAA) nanofiber separator with dual functions for inhibiting polysulfide transfer and promoting Li+ migration via a one-step electrospinning synthesis method. Especially, the functional groups of -COOH in PAA separators provide an electronegative environment, which promotes the transport of Li+ but suppresses the migration of negative polysulfide anions. Therefore, the PAA nanofiber separator can act as an efficient electrostatic shield to restrict the polysulfide on the cathode side, while efficiently promoting Li+ transfer across the separator. As a result, an ultralow decay rate of only 0.12% per cycle is achieved for the PAA nanofiber separator after 200 cycles at 0.2 C, which is less than half that (0.26% per cycle) of the commercial Celgard separator.

Bioaccumulation and human health risks of OCPs and PCBs in freshwater products of Northeast China.

The levels and spatial distribution of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in freshwater products from Northeast China were investigated by gas chromatography coupled to isotope dilution high-resolution mass spectrometry. All samples were on-spot sampled from main production regions of freshwater products in Northeast China, and these samples were used to systematically assess the potential health risks of OCPs and PCBs associated with consumption of these fishery products. Dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexane (HCHs), hexachlorobenzene (HCB) and PCBs were the major pollutants with 100% detection rates, and their levels ranged from 0.086 to 58, 0.038-3.3, 0.093-4.5 and 0.032-1.4 ng g-1 wet weight, respectively. The estimated dietary intakes of these contaminants were all below their corresponding acceptable daily intakes. Significant regional differences in the levels of OCPs and PCBs (P ≦ 0.001) were found in samples from Liaoning and Inner Mongolia. The results showed that the concentrations of targeted contaminants in aquatic products had species-specific characteristics, and the levels of targeted pollutants in Oncorhynchus mykiss and Eriocheir sienesis were significantly higher than those in other aquatic product species. Advisories on ten species of aquatic products suggested that consumption of Eriocheir sinensis, Oncorhynchus mykiss and Cyprinus carpio at a rate exceeding 15 meals per month would pose a cancer risk. A health risk assessment indicated that exposure to these pollutants through freshwater products consumption would cause a non-ignorable potential carcinogenic risk to humans.