Residue dissipation dynamics and dietary risk assessment of emamectin benzoate, chlorantraniliprole, chlorfenapyr, and lufenuron in cabbage.

Emamectin benzoate (EB), chlorantraniliprole (CTP), chlorfenapyr (CFP), and lufenuron (LFR) are widely used to control Spodoptera exigua on cabbage. This study is aimed at establishing a universal, sensitive, accurate, and efficient method for the determination of these pesticide residues in cabbage using QuEChERS pretreatment combined with ultra-performance liquid chromatography or gas chromatography-tandem mass spectrometry (UPLC‒MS/MS or GC‒MS/MS). The recoveries of these pesticides (containing metabolites) in cabbage detected by the optimized method ranged between 80.9% and 99.9%, with relative standard deviations (RSDs) of 0.164-12.5%. The limit of quantification (LOQ) of the four pesticides was determined to be 0.01 mg/kg. The standard curve, accuracy, precision, and LOQ of the analysis method all met the requirements of pesticide residue detection. The optimized method was used to detect the dissipation dynamics and terminal residues in 12 regions. The dissipation half-lives of CTP, CFP, and LFR were 3.35-7.01 d, 2.29-4.75 d, and 3.24-6.80 d, respectively. The terminal residues of all these pesticides were below the maximum residue limits (MRLs). The dietary risk assessment indicated that the dietary risk probabilities for EB, CTP, CFP, and LFR were all less than 1 and were within the acceptable range. This study provides a comprehensive assessment of the residues and dietary risks of EB, CTP, CFP, and LFR for the scientific use of pesticides.

Distribution and pollution assessment of heavy metals in surface sediments along the Weihai coast, China.

In this study, 78 surface sediment samples were collected from the Weihai coastal area and analyzed for heavy metals. Their concentrations and pollution status were evaluated. The distribution of heavy metals was mainly dominated by sediment grain size, and the sediments in the Weihai, Sanggou, and Rushan Bays, which have finer grain sizes, had higher concentrations. The mean geoaccumulation index values for all heavy metals were <0. Expect for Hg, the mean enrichment factor values of the other metals were <1.5, indicating that they are natural sourced. Overall, the environmental quality of the Weihai costal area was relatively good and should be maintained and protected. The heavy metals that had potential impacts on the ecological environment were Cd and Hg, which were mainly distributed west of Weihai Bay and inside Rushan Bay. They are affected by human activities and must be controlled.

Modification of sedimentation and bioaccumulation behavior as an efficient strategy to modulate the toxicity of pyraclostrobin to zebrafish (Danio rerio).

The behavior of pesticide particles or droplets might significantly influence their environmental risks. However, studies on the risk of different pesticide formulations in aqueous environments have rarely been reported. In this study, we prepared three types of pyraclostrobin formulations to evaluate their behavior in the aqueous environment and toxicological risks to zebrafish. The results showed that pyraclostrobin emulsifiable concentrate (EC) sank faster in water with increasing hydrophilicity and density of the solvent. The particles also sank faster with increasing particle size and particle density for suspension concentrate (SC) and microcapsules (MCs). Diverse behavior in water results in different temporal and spatial distributions of the active ingredient. EC-EGDA, SC-5 µm, CS-Large and EC-MO sink or float over time, therefore reducing the effective dose suspended in water. Lower toxicological risks of the pesticides were also observed by reducing the enrichment of pyraclostrobin in zebrafish. In addition to the direct toxicity of the active ingredient, the type of pesticide formulations and their specific compositions might also influence the integrated toxicity. The environmental behavior of pesticide formulations should also be considered for their systematic assessment of environmental risks to ensure the scientific application of pesticides in different scenarios.

Ecotoxicological risk assessment of 14 pesticides and corresponding metabolites to groundwater and soil organisms using China-PEARL model and RQ approach.

Global use of pesticides brings uncertain risks to human and nontarget species via environmental matrix. Currently, various models for exposure risk assessment are developed and widely used to forecast the impact of pesticides on environmental organisms. In this study, five commonly used insecticides, seven herbicides and three fungicides were chosen to analyze the subsequent risks in groundwater in simulated scenarios using China-PEARL (Pesticide Emission Assessment at Regional and Local Scales) model. In addition, their exposure risks to soil organisms were characterized based on risk quotient (RQ) approach. The results indicated that 23.3% of the total 528 predicted environmental concentrations (PECs) of pesticides and respective metabolites in groundwater from six Chinese simulated locations with ten crops were above 10 µg L-1. Furthermore, acceptable human risks of pesticides in groundwater were observed for all simulation scenarios (RQ < 1). Based on the derived PECs in soil short-term and long-term exposure simulation scenarios, all compounds were evaluated to be with acceptable risks to soil organisms, except that imidacloprid was estimated to be with unacceptable chronic risk (RQ = 27.5) to earthworms. Overall, the present findings provide an opportunity for a more-comprehensive understanding of exposure toxicity risks of pesticides leaching into groundwater and soil.

Visible-light-driven photocatalytic degradation of dye and antibiotics by activated biochar composited with K+ doped g-C3N4: Effects, mechanisms, actual wastewater treatment and disinfection.

To improve the performance of graphitic carbon nitride (g-C3N4), a hotly researched metal-free photocatalyst, for better application in the efficient removal of organic pollutants, adsorption synergistically enhanced photocatalysis mechanism was thoroughly explored. Based on KOH pore-forming activated biochar (ACB) and K+ doped g-C3N4 (K-gC3N4), the novel activated biochar-based K-gC3N4 composite (ACB-K-gC3N4) was synthesized via the innovative ultrasonic-milling method. Rhodamine B (RhB), tetracycline (TC), norfloxacin (NOR), and chloramphenicol (CAP) were selected as target pollutants, and the effects of environmental factors, recycling and actual wastewater tests, disinfection effects, and various enhancement strategies were investigated. The results showed that K-gC3N4 was successfully composited with ACB by various characterizations, where the loading mass ratio of 1:2 exhibited the best performance. ACB-K-gC3N4 possessed a larger specific surface area, richer functional groups, suitable band gap (2.29 eV), and broader visible light absorption (~716 nm) than K-gC3N4. ACB-K-gC3N4 presented effective removal efficiency over K-gC3N4 for four pollutants, in which the removal efficiency of RhB reached 93.26%, and the degradation rate constant of 0.0119 min-1 was four times higher than K-gC3N4 (0.0029 min-1). Moreover, ACB-K-gC3N4 was superior to K-gC3N4 in disinfecting S. aureus and E. coli, with a sterilization rate of exceeding 90% for 12 h. The photodegradation activity was dominated by ·O2-, h+, and ·OH, and the mechanisms involved in the three stages. This was attributed to the unique structure and surface properties (defects and persistent free radicals) of ACB, as evidenced by improved adsorption stage and transfer of degradation intermediates, facilitated the generation of active species, accelerated migration of photogenerated electrons, and inhibited photogenerated carriers recombination by the heterojunction. The good reusability and stability, enhancement strategies (blowing air and heating), and satisfactory feasibility for actual wastewater allow ACB-K-gC3N4 possible to promote high-concentration wastewater treatment and disinfection.

Transcriptome analysis of Plantago major as a phytoremediator to identify some genes related to cypermethrin detoxification.

Cypermethrin (CYP) is a toxic manmade chemical compound belonging to pyrethroid insecticides contaminating the environment. Plantago major (PM) has numerous excellent advantages like high biomass yield and great stress tolerance, which make it able to increase the efficacy of phytoremediation. So far, no study has directly or indirectly made a transcriptome analysis (RNA-seq) of PM under CYP stress. The aim of this study is to identify the genes in PM related to CYP detoxification (10 µg mL-1) and compared with control. In this study, BGISEQ-500 high-throughput sequencing technology independently developed by BGI was used to sequence the transcriptome of P. major. Six libraries were constructed including (CK_1, CK_2, and CK_3) and (CYP_1, CYP_2, and CYP_3) were sequenced for transcripts involved in CYP detoxification. Our data showed that de novo assembly generated 138,806 unigenes with an average length of 1129 bp. Analyzing the annotation results of the KEGG database between the samples revealed 37,177 differentially expressed genes (DEGs), 18,062 down- and 19,115 upregulated under CYP treatment compared with control. A set of 107 genes of cytochrome P450 (Cyt P450), 43 genes of glutathione S-transferases (GST), 25 genes of glycosyltransferases (GTs), 113 genes from ABC transporters, 21 genes from multidrug and toxin efflux (MATE), 11 genes from oligopeptide transporter (OPT), and 3 genes of metallothioneins (MT) were upregulated notably. By using quantitative real-time PCR (qRT-PCR), the results of gene expression for 12 randomly selected DEGs were confirmed, showing the different patterns of response to CYP in PM tissues. Furthermore, the enzyme activity of Cyt P450 and GST in PM under CYP stress was significantly increased in roots and leaves than in control. This study introduces a clue to understand the metabolic pathways of plants used in phytoremediation by identifying the highly expressed genes related to phytoremediation which would be utilized to enhance pesticide detoxification and reduce pollution problem.

Comparative ecotoxicity of neonicotinoid insecticides to three species of Trichogramma parasitoid wasps (Hymenoptera: Trichogrammatidae).

Compatibility of neonicotinoid insecticides with the natural enemies has been concerned for decades. This study aims to evaluate and compare the acute and sublethal toxicity effects of neonicotinoid insecticides on three species of Trichogramma parasitoid wasps (i.e. Trichogramma dendrolimi, T. ostriniae and T. confusum) with broad distribution and great relevance to integrated pest management (IPM) strategies. A residual contact bioassay demonstrated that nitenpyram had the greatest intrinsic toxicity to T. dendrolimi and T. ostriniae with LC50 values of 0.060 (0.056-0.065) and 0.066 (0.050-0.087) mg a.i. L-1, respectively. But for T. confusum, the most toxic neonicotinoid insecticide is dinotefuran with a LC50 value of 0.065 (0.055-0.078) mg a.i. L-1. Furthermore, based on the risk quotient estimation, acetamiprid was considered to be the only safe neonicotinoid insecticide (Class 1, RQ＜50). A dipped egg contact bioassay showed that neonicotinoid insecticides induced significant toxic effects on the parasitism of three Trichogramma spp. at low-lethal concentrations. Additionally, emergence probability of the unexposed offspring was also significantly reduced by neonicotinoids. According to the estimated EC50 values, acetamiprid possessed the least toxicity to the parasitism and emergence of T. dendrolimi and T. ostriniae, and for T. confusum, the least toxic neonicotinoid insecticide was thiacloprid. Overall, among the test neonicotinoid insecticides, acetamiprid and thiacloprid may exhibit the less ecotoxicity to the test Trichogramma species.

Elevated expression of transient receptor potential vanilloid type 1 in dorsal root ganglia of rats with endometriosis.

Pain is the most pronounced complaint of women with endometriosis, however the underlying mechanism is still poorly understood. In the present study, the authors evaluate the effect of transient receptor potential vanilloid type 1 (TRPV1) of dorsal root ganglia (DRG) on endometriosis-associated pain. A total of 36 SD rats were randomly divided into a sham group (n=9) and a Model group (n=27), accepted auto­transplanted pieces of fat or uterus to the pelvic cavity. At 4 weeks, the Model group was randomly subdivided into the following groups: ENDO group (no treatment, n=9), BCTC group (Model + BCTC, an antagonist of TRPV1, n=9), Vehicle group (Model + cyclodextrin, the vehicle of BCTC, n=9). Tail­flick test was performed prior to surgery, 1 h prior to and following treatment of BCTC or cyclodextrin. The expression of TRPV1, substance P (SP), calcitonin gene­related peptide (CGRP) in L1­L6 DRG was measured via immunohistochemistry, western blotting and RT­qPCR. The results indicated that the Model group exhibited a significant decrease in tail flick latency compared to pre­surgical baseline, and the expression of TRPV1, SP, CGRP protein and mRNA in L1­L6 DRG significantly increased compared to the sham group. BCTC significantly improved tail flick latency, and downregulated the expression of TRPV1, SP and CGRP protein and mRNA levels in L1­L6 DRG compared to ENDO group. However, there were no significant differences of those in Vehicle group compared with the ENDO group. Taken together, the current study provides evidence that TRPV1 expressed in DRG may serve an important role in endometriosis-associated pain.

Vitamin K3 inhibits mouse uterine contraction in vitro via interference with the calcium transfer and the potassium channels.

Previous studies have demonstrated vitamin K3 had a great relief to smooth muscle spastic disorders, but no researches have yet pinpointed its possible anti-contractile activity in the uterus. Here, we evaluated the effect of vitamin K3 on myometrial contractility and explored the possible mechanisms of vitamin K3 action. Myograph apparatus were used to record the changes in contractility of isolated mouse uterine strips in a tissue bath. Uterine strips were exposed to vitamin K3 or vehicle. Vitamin K3 suppressed spontaneous contractions in a concentration dependent manner. It significantly decreased the contractile frequency induced by PGF2ɑ but not their amplitude (expect 58.0 µM). Prior incubation with vitamin K3 reduced the effectiveness of PGF2ɑ-induced contraction. The antispasmodic effect of vitamin K3 was also sensitive to potassium channel blockers, such as tetraethylammonium, 4-aminopyridine, iberiotoxin) but not to the nitric oxide related pathway blockers. High concentrations (29.0, 58.0 µM) of vitamin K3 weakened the Ca(2+) dose response and inhibited phase 1 contraction (intracellular stored calcium release). These dates suggest that vitamin K3 specifically suppresses myometrial contractility by affecting calcium and potassium channels; thus, this approach has potential therapy for uterine contractile activity related disorders.

Vascular endothelial growth factor receptor-2 inhibitor cediranib causes regression of endometriotic lesions in a rat model.

Vascular endothelial growth factor (VEGF) receptor-2 plays an essential role in angiogenesis, and it also expressed in the glandular epithelium and stromal cells of ectopic endometrium. Cediranib is a protein tyrosine kinase inhibitor that potently inhibits VEGF receptor-2, but there is no study about its effects on the endometriosis. We induced endometriosis on both sides of the abdominal wall in 20 female Sprague-Dawley rats and randomly divided them into 2 groups. They were administered: cediranib 4 mg/kg/day (group 1), equal saline (group 2) for 12 days. Then, the lesion volumes were calculated, and Masson trichrome was used to detect fibrosis. Angiogenesis was evaluated by CD-31 immunohistochemistry and serum VEGF levels. Proliferation was indicated by proliferating cell nuclear antigen immunohistochemistry. Apoptosis was measured by a TUNEL assay and cleaved caspase-3 immunohistochemistry. In the treatment group, the lesion volumes were smaller (P < 0.05), and the degree of fibrosis was greater. The microvessel density was lower (P < 0.05) than control, however, serum VEGF was up-regulated by a negative feedback mechanism (P < 0.01). In addition, proliferation was significantly suppressed (P < 0.01), and apoptosis in the lesions was more obvious in the treatment group. These data indicated that cediranib can inhibit development of endometriotic lesions in rats.

Protein-inorganic hybrid nanoflowers as ultrasensitive electrochemical cytosensing interfaces for evaluation of cell surface sialic acid.

The identification of biocompatible nanomaterials with high conductivities as sensing interfaces is important in developing novel electrochemical cytosensors. We prepared a novel protein-inorganic nanomaterial-bovine serum albumin (BSA) incorporated Ag nanoflowers with three-dimensional porous architectures, using a simple biomimetic method. The BSA-incorporated Ag nanoflowers were modified on a glassy carbon electrode (GCE) surface and conjugated with a targeting lectin molecule, i.e., Sambucus nigra agglutinin (SNA), for sensing DLD-1 human colon cancer cells. The BSA-incorporated Ag nanoflowers were a suitable platform, and showed improved cell-immobilization capacity, and good biocompatibility, with retention of activity of the immobilized cells. These properties are attributed to the large surface area of the porous structure and the natural BSA layer acting as a biocompatible support. The attachment of DLD-1 cells to the GCE increased the electron-transfer resistance, with a good correlation with the logarithm of the concentration from 1.35×10(2) to 1.35×10(7) cells mL(-1), with a low detection limit of 40 cells mL(-1). Based on the affinity between SNA and sialic acid (SA), the UV-vis absorption spectrum of the one-step reaction between SA and acidic ninhydrin indicated that the average number of SA molecules on a single living DLD-1 cell surface was approximately 2.16×10(12). This proposed cytosensing strategy had good reproducibility, acceptable precision, and high specificity for SA-over-expressed cells, indicating that it has potential applications for the early monitoring of tumor cells and convenient evaluation of SA on living cells.

Visual and highly sensitive detection of cancer cells by a colorimetric aptasensor based on cell-triggered cyclic enzymatic signal amplification.

Rapid and efficient detection of cancer cells at their earliest stages is one of the central challenges in cancer diagnostics. We developed a simple, cost-effective, and highly sensitive colorimetric method for visually detecting rare cancer cells based on cell-triggered cyclic enzymatic signal amplification (CTCESA). In the absence of target cells, hairpin aptamer probes (HAPs) and linker DNAs stably coexist in solution, and the linker DNA assembles DNA-AuNPs, producing a purple solution. In the presence of target cells, the specific binding of HAPs to the target cells triggers a conformational switch that results in linker DNA hybridization and cleavage by nicking endonuclease-strand scission cycles. Consequently, the cleaved fragments of linker DNA can no longer assemble into DNA-AuNPs, resulting in a red color. UV-vis spectrometry and photograph analyses demonstrated that this CTCESA-based method exhibited selective and sensitive colorimetric responses to the presence of target CCRF-CEM cells, which could be detected by the naked eye. The linear response for CCRF-CEM cells in a concentration range from 10(2) to 10(4) cells was obtained with a detection limit of 40 cells, which is approximately 20 times lower than the detection limit of normal AuNP-based methods without amplification. Given the high specificity and sensitivity of CTCESA, this colorimetric method provides a sensitive, label-free, and cost-effective approach for early cancer diagnosis and point-to-care applications.

Multifunctional phenylboronic acid-tagged fluorescent silica nanoparticles via thiol-ene click reaction for imaging sialic acid expressed on living cells.

Multifunctional fluorescent silica nanoparticles with phenylboronic acid tags were developed for labeling sialic acid on the surface of living cancer cells. In this paper, fluorescent silica nanoparticles (FSNPs) with strong and stable emission at 515 nm were firstly prepared through a reverse microemulsion process, and then modified with highly selective phenylboronic acid (PBA) tags on their surface via an aqueous 'thiol-ene' click reaction. These nanoparticles had a hydrodynamic diameter of 92.6 ± 9.1 nm, and a bright fluorescence signal, which is 366 times higher than that of a single dye molecule. Meanwhile, these PBA-tagged FSNPs were found very stable in aqueous solution as well as in cell culture medium, verified by transmission electron microscopy, X-ray photoelectron spectroscopy and zeta potential analysis. The over-expressed sialic acid (SA) on the membrane of living HeLa cells was visualized in situ by a confocal laser scanning microscopy, ascribed to the specific interaction between PBA and SA. Thus, the PBA-FSBPs showed a great potential in probing SA expressed on living cells with high selectivity and sensitivity.

One-pot synthesis of Gd3+-functionalized gold nanoclusters for dual model (fluorescence/magnetic resonance) imaging.

Multimodal imaging that aims to advance imaging by strategically combining existing technologies with uniquely designed probes has attracted great interest in recent years. Here, Gd3+-functionalized gold nanoclusters (Gd-AuNCs) were synthesized for dual model (fluorescence/magnetic resonance) imaging. We designed a cyclodecapeptide that contained one tyrosine and two cysteines for the synthesis, and it biomineralized gold nanoclusters and chelated Gd3+ ions at the same time. The Gd-AuNC probes emit an intense red fluorescence under UV light, while exhibiting a high longitudinal relaxivity of 41.5 ± 2.5 mM-1 s-1 and a low r2/r1 ratio of 1.2 at 0.55 T. The versatility of the probes for dual model imaging has been demonstrated by means of cellular imaging and in vivo T1-weighted MRI. Thanks to the optimal size of the nanocluster, it can freely circulate in the blood pool without significant accumulation in the liver and spleen, but with a long circulation half-life (t1/2) of ∼128 min. Moreover, the nanoclusters can be noticeably excreted from the body within a period of 24 h through renal clearance, making it attractive for in vivo multimodal imaging.

SVR learning-based spatiotemporal fuzzy logic controller for nonlinear spatially distributed dynamic systems.

A data-driven 3-D fuzzy-logic controller (3-D FLC) design methodology based on support vector regression (SVR) learning is developed for nonlinear spatially distributed dynamic systems. Initially, the spatial information expression and processing as well as the fuzzy linguistic expression and rule inference of a 3-D FLC are integrated into spatial fuzzy basis functions (SFBFs), and then the 3-D FLC can be depicted by a three-layer network structure. By relating SFBFs of the 3-D FLC directly to spatial kernel functions of an SVR, an equivalence relationship of the 3-D FLC and the SVR is established, which means that the 3-D FLC can be designed with the help of the SVR learning. Subsequently, for an easy implementation, a systematic SVR learning-based 3-D FLC design scheme is formulated. In addition, the universal approximation capability of the proposed 3-D FLC is presented. Finally, the control of a nonlinear catalytic packed-bed reactor is considered as an application to demonstrate the effectiveness of the proposed 3-D FLC.

Visual and high-throughput detection of cancer cells using a graphene oxide-based FRET aptasensing microfluidic chip.

Rapid and efficient measurement of cancer cells is a major challenge in early cancer diagnosis. In the present study, a miniature multiplex chip was created for in situ detection of cancer cells by implementing a novel graphene oxide (GO)-based Förster resonance energy transfer (FRET) biosensor strategy, i.e. assaying the cell-induced fluorescence recovery from the dye-labeled aptamer/graphene oxide complex. Fluorescence intensity measurement and image analyses demonstrated that this microfluidic biosensing method exhibited rapid, selective and sensitive fluorescence responses to the quantities of the target cancer cells, CCRF-CEM cells. Seven different cancer cell samples can be measured at the same time in such a microfluidic chip. The linear response for target CCRF-CEM cells in a concentration range from 2.5 × 10(1) to 2.5 × 10(4) cells mL(-1) was obtained, with a detection limit about 25 cells mL(-1), which is about ten times lower than those of normal biosensors. The novel fluorescence biosensing microfluidic chip supplies a rapid, visible and high-throughput approach for early cancer diagnosis with high sensitivity and specificity.