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Perovskite light-emitting diodes (PeLEDs) have drawn tremendous research attention recently. However, they are mainly prepared via solution processes, while the devices fabricated using the all-vacuum deposition procedure still remain largely unexplored. In this work, we prepared a cesium-lead-bromide perovskite film using the vacuum deposition method, and realized a more balanced stoichiometry by replacing some CsBr with NaBr. It was discovered that the introduction of an appropriate amount of NaBr not only reduced the insulating Cs4PbBr6 phase in the active layer, but also passivated the trap states effectively, which resulted in a 2-fold increase of the peak external quantum efficiency (EQE) of the PeLEDs to 2% with the maximum luminance reaching close to 40 000 cd m−2 and significantly improved device operational stability compared to the undoped counterparts. Furthermore, we fabricated the first top-emissive silicon-based PeLED using the all-vacuum deposition method based on the NaBr doped perovskite films, and achieved a peak EQE of 0.33%, which has provided a promising alternative way for the design and preparation of high-performance silicon-based display devices in the future.

Tris(2-chloroethyl)phosphate (TCEP) is a widely used environmental organic pollutant. Studies have revealed the presence of both TCEP and its metabolites in environmental media. The neurotoxicity of TCEP has been investigated in vitro but rarely in mammals. This study aimed to determine the neurotoxic effects of TCEP on rats and to explore the possible intrinsic relationships between neurochemical alterations and the neurotoxic effects. For this, 6-week-old female SD rats were administered 50, 100, or 250 mg/kg/d TCEP daily by oral gavage for 60 days. TCEP exposure produced neurotoxicity in the female SD rats. The Morris water maze results revealed a dose-dependent decline in spatial learning and memory functions of exposed rats. In addition, pathological examination of the brain showed apoptotic and necrotic lesions in the CA1 field pyramidal cells of the hippocampus; further, rats treated with the highest TCEP dose showed inflammatory cells and calcified/ossified foci in the cortex areas. Furthermore, 1H-nuclear magnetic resonance metabolomics results revealed that TCEP exposure interfered with normal biological processes, including amino acid and neurotransmitter metabolism, energy metabolism, and cell membrane function integrity by changing the concentrations of glutamate, γ-aminobutyric acid, N-acetyl-d-aspartate, creatine, and lactic acid metabolites in the brain of treated rats. However, the changes in the concentrations of taurine, myo-inositol, creatine, and choline metabolites, which are associated with antioxidant physiological processes, might be a neuroprotective mechanism to prevent the neurotoxicity induced by TCEP. Thus, metabolomics combined with neuropathology and neurobehavioral analyses provided critical insights to investigate the TCEP-induced neurotoxic effects and mechanisms.

As a commonly used organophosphorus flame retardant (OPFR), tris (1,3-dichloro-2-propyl) phosphate (TDCIPP) has become an environmental pollutant. Studies have shown that TDCIPP exposure has many toxic effects, such as neurotoxicity, reproductive development toxicity and endocrine disturbance. CircRNAs are circular noncoding RNAs that have been found to play important roles in the occurrence of a variety of diseases. However, it is unclear whether circRNAs play a role in the cytotoxicity induced by TDCIPP exposure. In this study, we analysed the circRNA microarray results of a control group and a TDCIPP exposure group of PC12 cells and detected 3432 differentially expressed circRNAs (P 0.05), of which 1682 were upregulated and 1750 were downregulated in the TDCIPP-exposure group. The expression levels of 2 upregulated and 3 downregulated circRNAs were verified by real-time quantitative PCR, and the results were consistent with the microarray results. Then, ceRNA analysis was performed on several kinds of circRNAs to predict the possible binding miRNAs and binding sites. The target genes were analysed by Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis. Through predictive analysis, it was found that rno_circRNA_013845, rno-miR-361-3p, and rno-miR-702-3p may be involved in the regulation of Traf2 expression, thereby affecting the expression of the downstream NF-κB signalling pathway and causing apoptosis.

Microplastics are abundant in oceans, lakes, soils and even air, and can pose potential threats to human health through food or respiratory intake. Moreover, microplastics have synergistic toxicity to the body after absorbing organic pollutants. In this study, laser scanning confocal microscope and flow cytometry were used to observe the intake of colonic cancer Caco-2 cells to polystyrene plastic with five different particlesizes (300 nm, 500 nm, 1 μm, 3 μm, 6 μm). The uptake rates of microplastics with different particle sizes were 73%, 71%, 49%, 43%, and 30%, respectively. Then, High Performance Liquid Chromatography (HPLC) was used to analyze the adsorption differences of polystyrene plastic with different particle sizes to bisphenol A (BPA). Finally, the proliferation toxicity of polystyrene microplastics with different particle sizeson Caco-2 cells before and after adsorption of BPA was compared. MTT experiments confirmed that microplastics caused an increase in cytotoxicity. This result may be related to increased cellular oxidative stress and mitochondrial depolarization. This hypothesis has been confirmed in reactive oxygen species (ROS) and mitochondrial membrane potential (MMP) assays because nanoscale microplastics cause a large amount of ROS on Caco-2 cells after microplastic exposure, and micron-scale microplastics cause a significant decrease in MMP. At the same time, nanoscale microplastics can cause further depolarization of mitochondria due to their large specific surface area adsorption of BPA, which leads to enhanced cytotoxicity of microplastics after BPA adsorption. The results of this study are of great significance in the evaluation of the safety of microplastics in the human body.

Inorganic metal oxide electron-transport layers (ETLs) have the potential to yield perovskite solar cells with improved stability, but generally need high temperature to form conductive and defect-less forms, which is not compatible with the fabrication of flexible and tandem solar cells. Here, we demonstrate a facile strategy for developing efficient inorganic ETLs by doping SnO2 nanocrystals (NCs) with a small amount of Sb using a low-temperature solution-processed method. The electrical conductivity was remarkably enhanced by Sb-doping, which increased the carrier concentration in Sb:SnO2 NCs. Moreover, the upward shift of the Fermi level owing to doping results in improved energy level alignment, which led to reduced charge recombination, and thus longer electron recombination lifetime and improved open-circuit voltage (VOC ). Therefore, Sb-doping of SnO2 significantly enhanced the photovoltaic performance of planar perovskite devices by increasing the fill factor and VOC , and reducing photocurrent hysteresis, extending the potential application of low-temperature-processed ETLs in future flexible and tandem solar cells.

The large mobilities and carrier lifetimes of hybrid perovskite single crystals and the high atomic numbers of Pb, I and Br make them ideal for X-ray and gamma-ray detection. Here, we report a sensitive X-ray detector made of methylammonium lead bromide perovskite single crystals. A record-high mobility-lifetime product of 1.2 x 10(-2) cm(2) V-1 and an extremely small surface charge recombination velocity of 64 cm s(-1) are realized by reducing the bulk defects and passivating surface traps. Single-crystal devices with a thickness of 2-3 mm show 16.4% detection efficiency at near zero bias under irradiation with continuum X-ray energy up to 50 keV. The lowest detectable X-ray dose rate is 0.5 mu Gy(air) s(-1) with a sensitivity of 80 mu C Gy(air)(-1) cm(-2), which is four times higher than the sensitivity achieved with alpha-Se X-ray detectors. This allows the radiation dose applied to a human body to be reduced for many medical and security check applications.

The health risks of exposure to plasticizers have received widespread attention, however, little is known about the effects of fast food packaging plasticizers on steroid hormone synthesis. In the present study, the types and migration of plasticizers in some commonly used fast-food packaging materials were detected by GC–MS, and the interference effects of these plasticizers and their metabolites on steroid hormone synthesis in the human body were evaluated by the H295R steroidogenesis assay. The GC–MS results showed that the main plasticizer compounds that migrated from fast food packaging into food were di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP) and bis(2-ethylhexyl) adipate (DEHA). Exposure to these chemicals (100–1000 μM) can significantly reduce the viability of H295R cells in a dose-response manner, and these plasticizers and their metabolites that migrated into oily foods at high temperatures (0.25–25 μM) could significantly increase the E2 level and reduce the T level in H295R cells. According to the qRT-PCR data, 0.25 to 25 μM mono(2-ethylhexyl) phthalate (MEHP) significantly upregulated the expression levels of 17β-HSD1 and CYP19A1, and downregulated those of CYP17A1, CYP11A1 and StAR. The Western blot results were consistent with those of qRT-PCR. In summary, these results indicated that even exposure to low concentrations (≤1 mg/l or 2.5 μM) of these chemicals and their metabolites can cause significant endocrine-disrupting effects.

Previous studies demonstrated that tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) caused adverse effects on thyroid hormone (TH) imbalance in aquatic and avian organisms. This study focused on the effects of TDCIPP on thyroid function and hormone homeostasis in mammals. Pubertal female Sprague-Dawley rats were orally administered 50, 100, or 250 mg per kg per d of TDCIPP from postnatal day (PND) 22 to PND42 for 21 days. The serum triiodothyronine (T3) levels increased significantly at 250 mg per kg per d of TDCIPP. There were no significant differences in the body weight, serum thyroxine (T4) and free thyroxine (FT4) levels between the control and TDCIPP treated groups. There were significant dose-dependent increases in the mRNA and protein expression levels of genes related to drug metabolism (cytochrome-p450-3A1, CYP3A1) and TH clearance (udp-glucuronosyltransferase-1A6, UGT1A6) in the liver. Treatment with TDCIPP increased hepatic type 1 deiodinase (DIO1) mRNA at 250 mg per kg per d but down-regulated hepatic TH receptor beta (TRβ) mRNA expression. In addition, TDCIPP exposure induced slight thyroid follicular hyperplasia, and several genes involved in TH biosynthesis (NIS, TPO, Tg) were altered at 100 and 250 mg per kg per d of TDCIPP. Nevertheless, serum thyroid stimulating hormone (TSH) levels and the receptor (TSHr) mRNA significantly decreased at only the low dose group. Based on these results, we certified that TDCIPP disturbs the normal bioprocess on TH synthesis, biotransformation or clearance, and hepatic detoxification of pubertal female SD rats, causing thyroid function disorder.

The family of polyoxometalate (POM) intercalated layered double hydroxide (LDH) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12 O40 ](3-) (PW12 ) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such an intercalated compound of Mg0.73 Al0.22 (OH)2 [PW12 O40 ]0.04 ⋅0.98 H2 O (Mg3 Al-PW12 ) has been successfully obtained by applying a spontaneous flocculation method. The Mg3 Al-PW12 has been fully characterized by using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3 Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3 Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z-CH2 -Z' type substrates (ethyl cyanoacetate and malononitrile) at 60 °C in mixed solvents (V2-propanol :Vwater =2:1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3 Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3 Al-PW12 -catalyzed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47 980 reported so far for this reaction.

Balanced carrier diffusion in perovskites The efficient operation of solar cells based on inorganic-organic perovskites requires balanced transport of positive and negative charge carriers over long distances. Dong et al. used a top-seeded solution growth method to obtain millimeter-scale single crystals of the organolead trihalide perovskite CH 3 NH 3 PbI 3 . Under low light illumination, the electron and hole diffusion lengths exceeded 3 mm, and under full sunlight illumination, they exceeded 175 µm. Science , this issue p. 967

The ionic defects at the surfaces and grain boundaries of organic–inorganic halide perovskite films are detrimental to both the efficiency and stability of perovskite solar cells. Here, we show that quaternary ammonium halides can effectively passivate ionic defects in several different types of hybrid perovskite with their negative- and positive-charged components. The efficient defect passivation reduces the charge trap density and elongates the carrier recombination lifetime, which is supported by density-function-theory calculation. The defect passivation reduces the open-circuit-voltage deficit of the p–i–n-structured device to 0.39 V, and boosts the efficiency to a certified value of 20.59 ± 0.45%. Moreover, the defect healing also significantly enhances the stability of films in ambient conditions. Our findings provide an avenue for defect passivation to further improve both the efficiency and stability of solar cells. Losses in solar cells can be caused by material defects in the bulk or at interfaces. Here, Zheng et al. use quaternary ammonium halides to passivate various perovskite absorbers and prepare solar cells with certified efficiency above 20%, suggesting that both anionic and cation defects are affected.

The efficiency of perovskite solar cells has surged in the past few years, while the bandgaps of current perovskite materials for record efficiencies are much larger than the optimal value, which makes the efficiency far lower than the Shockley–Queisser efficiency limit. Here we show that utilizing the below-bandgap absorption of perovskite single crystals can narrow down their effective optical bandgap without changing the composition. Thin methylammonium lead triiodide single crystals with tuned thickness of tens of micrometers are directly grown on hole-transport-layer covered substrates by a hydrophobic interface confined lateral crystal growth method. The spectral response of the methylammonium lead triiodide single crystal solar cells is extended to 820 nm, 20 nm broader than the corresponding polycrystalline thin-film solar cells. The open-circuit voltage and fill factor are not sacrificed, resulting in an efficiency of 17.8% for single crystal perovskite solar cells., Thin films of halide perovskites are promising for solar cell technology but they do not perform well at the band edge due to the low optical absorption. Herein, Chen et al. fabricate a high efficiency single crystal perovskite solar cell with thicker single crystals to harvest the below-bandgap photons.

Tris (1,3-dichloro-2-propyl) phosphate (TDCIPP), one of the most universally used organophosphate flame retardants (OPFRs), is an environmental pollutant. However, limited information is available regarding its toxicity and environmental health risk. In the present study, PC12 cells provided a useful model for the evaluation of the toxic effects of TDCIPP. Exposure to 7.5, 15, 30, or 60 μM TDCIPP for 72 h inhibited cell viability, and enhanced cellular apoptosis and oxidative stress. To further explore the underlying mechanisms, digital gene expression (DGE) technology was used to identify early transcriptional changes following TDCIPP exposure. Expression of the transcripts of 161 genes was significantly altered upon treatment with TDCIPP. Functional and pathway analysis of the transcriptional profile demonstrated that genes showing significant TDCIPP-associated changes in expression were involved in the phosphatidylinositol 3-kinase (PI3K)/protein kinase B (Akt) signaling pathway, extracellular matrix–receptor interactions, protein digestion and absorption, and microRNAs in cancer. Using quantitative real-time PCR, we validated the differential expression of selected genes. These results showed that the expression profiles of cells exposed to 60 μM TDCIPP were consistent with the DGE data. Furthermore, western blotting showed that treatment with TDCIPP reduced the Bcl-2/Bax ratio and attenuated PI3K/Akt/Myc signaling. Taken together, these data suggest that TDCIPP exposure can reduce cell viability and induce apoptosis in PC12 cells by inhibiting activation of the PI3K/Akt/Myc signaling pathway. These observations provide valuable preliminary information regarding the mechanisms of TDCIPP-induced toxicity in PC12 cells and indicate that further study of the toxicity of other environmental OPFRs is warranted.

Currently, photovoltaic/electroluminescent (PV/EL) perovskite bifunctional devices (PBDs) exhibit poor performance due to defects and interfacial misalignment of the energy band. Interfacial energy-band engineering between the perovskite and hole-transport layer (HTL) is introduced to reduce energy loss, through adding corrosion-free 3,3'-(2,7-dibromo-9H-fluorene-9,9-diyl) bis(n,n-dimethylpropan-1-amine) (FN-Br) into a HTL free of lithium salt. This strategy can turn the n-type surface of perovskite into p-type and thus correct the misalignment to form a well-defined N-I-P heterojunction. The tailored PBD achieves a high PV efficiency of up to 21.54% (certified 20.24%) and 4.3% EL external quantum efficiency. Free of destructive additives, the unencapsulated devices maintain >92% of their initial PV performance for 500 h at maximum power point under standard air mass 1.5G illumination. This strategy can serve as a general guideline to enhance PV and EL performance of perovskite devices while ensuring excellent stability.

In this paper, we report the supercapacitor electrodes with excellent cycle stability, which are made of silicon carbide nanowires (SiC NWs) grown on flexible carbon fabric. A high areal capacitance of 23 mF cm−2 is achieved at a scan rate of 50 mV s−1 at room temperature and capacitances increase with the rise of the working temperature. Owing to the excellent thermal stability of SiC NWs and carbon fabric, no observable decrease of capacitance occurs at room temperature (20 °C) after 105 cycles, which satisfies the demands of the commercial applications. Further increasing the measurement temperature to 60 °C, 90% of the initial capacitance is still retained after 105 cycles. This study shows that silicon carbide nanowires on carbon fabric are a promising electrode material for high temperature and stable micro-supercapacitors.

Silver, zinc oxide, and titanium dioxide nanoparticles are used as sterilisation materials to enhance the performance of disinfectants. We investigated the respiratory tract immune toxicity ("immunotoxicity") of these nanoparticles in vivo and in vitro, and we explored the relationships between particle size, particle shape, chemical composition, chemical stability and the toxicological effects of these typical nanoparticles in rats. In vivo, the rats were exposed to nanoparticles by intratracheal instillation. Exposure to nanoparticles caused an increase in oxidative injury to the lungs and disorders in regulating the cytokine network, which were detected in the bronchoalveolar lavage fluid, suggesting that oxidative stress might be important for inducing the respiratory immunotoxicity of nanoparticles. In vitro, the phagocytic function of alveolar macrophages (AMs) was dose-dependently reduced by nanoparticles, and ZnO nanoparticles induced greater cytotoxicity than the silver and titanium-dioxide nanoparticles, which were coincident with the results of multiple measurements, such as a cell viability assay by WST-8 and LDH measurements. Comparative analyses demonstrated that particle composition and chemical stability most likely had a primary role in the biological effects of different nanoparticles.

This study investigated the correlation between differentially expressed proteins in amniotic fluid (AF) and cleft palate induced by all-trans retinoic acid (atRA), and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in mice. Seven proteins were differentially expressed at embryonic day (E) 16.5 in atRA and control groups as revealed by label-based mouse antibody array. Enzyme-linked immunosorbent assay was further used to detect the expression levels of these proteins in AF from E13.5 to E16.5 in atRA, TCDD, and control groups. The cleft palate groups showed lower concentrations of receptor for advanced glycation end products (RAGE) and epiregulin at E16.5. RAGE immunostaining obviously decreased in palatal tissue sections obtained from E14.5 to E16.5 in the cleft palate groups as revealed by immunohistochemistry. These findings indicate that reduced levels of RAGE and epiregulin in AF are correlated to chemically induced cleft palate in mice.

Tris (1,3-dichloro-2-propyl) phosphate (TDCIPP) is one of the widely used organophosphorus flame retardants (OPFRs), which are regarded as suitable substitutes for brominated flame retardants (BFRs). Previously, we have validated the toxicity of TDCIPP in PC12 cells owing to the induced alterations in GAP43, NF-H, CaMK2a/2b, and tubulin α/β proteins; however, limited information is currently available on the toxicity and mechanism of TDCIPP. In the present study, cytotoxicity effects were evaluated by exposing PC12 cells to different concentrations of TDCIPP (0-50 μM) for 4 days. To explore the possible mechanisms through which cytotoxicity is induced, changes in intracellular [Ca2+ ]i levels and the activation of calmodulin dependent protein kinase 2 (CaMK2), c-Jun N-terminal kinase (JNK), extracellular regulated protein kinases (ERK1/2), and p38 mitogen-activated protein kinases (MAPK) pathways were evaluated. Furthermore, PC12 cells were pretreated with CaMK2 inhibitor KN93 to investigate the relationship between TDCIPP-induced phosphorylation of CaMK2 and activation of JNK, ERK1/2, and p38 MAPK pathways. Our results indicate that TDCIPP-induced toxicity might be associated with the overload of [Ca2+ ]i levels, increased phosphorylation of CaMK2, and activation of the JNK, ERK1/2, and p38 MAPK pathways, the lattermost of which was further demonstrated to be partially elicited by the CaMK2 phosphorylation.

We report on the feasible control of the threshold voltage (V th) in ultra-thin ZnO nanobelt FETs by using substoichiometric molybdenum trioxide (MoO x , x < 3) either as a modification layer on the surface of ZnO nanobelts or as electrodes instead of the widely used Ti/Au. ZnO nanobelt FETs using Ti/Au as the electrodes usually exhibit a negative threshold voltage, indicating n-channel depletion mode behavior, whereas ZnO FETs with MoO x /Au electrodes instead of Ti/Au show a positive shift of threshold voltage, exhibiting an n-channel type enhancement mode, which can be explained by a high Schottky barrier created at the interface of MoO x and the ZnO channel. In contrast, the decoration on the surface of ZnO channel by MoO x significantly increases the zero-bias conductivity and electron carrier concentration, and then negatively shifts the threshold voltage. We propose that MoO x thin film may play a passivation effect role, much more so than the doping effect role, due to the large amount of adsorbed species on as-grown ZnO nanobelts, especially oxygen species.

A simple and cost-effective chemical method was introduced to assemble gold (Au) nanoparticles on smooth silver (Ag) spheres for realizing surface-enhanced Raman scattering (SERS) enhancement by the replacement reaction between chloroauric acid and Ag spheres. In addition, the Ag-Au core-shell spheres were fabricated when a certain amount of chloroauric acid was used in the reaction solution. We found that the Ag particles decorated with small Au nanoparticles demonstrated the strongest SERS enhancement, while Ag-Au core-shell spheres showed the weakest enhancement.

Uniform and high-electronic-quality perovskite thin films are essential for high-performance perovskite devices. Here, it is shown that the 3-(decyldimethylammonio)-propane-sulfonate inner salt (DPSI), which is a sulfonic zwitterion, plays dual roles in tuning the crystallization behavior and passivating the defects of perovskites. The synergistic effect of crystallization control and defect passivation remarkably suppresses pinhole formation, reduces the charge trap density, and lengthens the carrier recombination lifetime, and thereafter boosts the small-area (0.08 cm2 ) planar perovskite device efficiency to 21.1% and enables a high efficiency of 18.3% for blade-coating large-area (1 cm2 ) devices. The device also shows good light stability, which remains at 88% of the initial efficiency under continuous unfiltered AM 1.5G light illumination for 480 h. These findings provide an avenue for simultaneous crystallization control and defect passivation to further improve the performance of perovskite devices.

Si nanowires (SiNWs) have been synthesized facilely from products in the thermal decomposition of copper oxalate in a chemical vapor deposition (CVD) system by the vapor–solid–solid (VSS) mechanism. Raman investigations showed that the phonon confinement appeared in the grown SiNWs. We found the mechanism of catalyst formation to be that the initial copper oxalate micro balls were thermally decomposed to fabricate Cu and Cu2O nanoparticles, which reacted with silane sequentially to form Cu3Si, serving as the nuclei for the sequential VSS growth of SiNWs.

Novel and extended ZnO/Zn5(OH)8Ac2·2H2O architectures are desirable for many applications. Here we report on the design and growth of the novel ZnO/Zn5(OH)8Ac2·2H2O architectures by a hydrothermal synthesis approach. ZnO microrods and/or columnar film are grown in the aqueous solution containing Zn(Ac)2·2H2O and hexamethylenetetramine, while Zn5(OH)8Ac2·2H2O microspheres and/or porous film are formed when enough citrate anions are added into the solution. The citrate anions not only modify the morphology but also decide the phase of the grown zinc compounds. The ZnO thin layer coated on glass substrate is used to control the nucleation event and finally modifies the morphology of the grown ZnO. Our work provides an effective and facile approach to design and selectively grow the novel ZnO/Zn5(OH)8Ac2·2H2O architectures at a low temperature of 95 °C.

A novel flow injection chemiluminescence (CL) sensor for the determination of maleic hydrazide (MH) using molecularly imprinted polymer (MIP) as recognition element is reported. The MH-MIP was synthesized by thermal initiated polymerization in methanol, using methacrylic acid (MAA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker in the maleic hydrazide template molecule. Molecular modeling was employed to simulate the possible recognition process of the MIP, and to achieve high selectivity. Then the synthesized MH-MIP was employed as recognition element by packing into flow cell to establish a novel flow injection CL sensor. The CL intensity responded linearly to the concentration of MH in the range 3.5 × 10−4–5.0 × 10−2 mg/mL with a detection limit of 6.0 × 10−5 mg/mL (3σ), which is lower than that of conventional methods. The relative standard deviation (RSD) for the determination of 1.0 μg/mL of MH was 2.7% (n = 11). The sensor is reusable and has a great improvement in sensitivity and selectivity for CL analysis. As a result, the new MIP–CL sensor had been successfully applied to the determination of MH in vegetable samples.

To obtain the desired specific adsorbents for carbaryl to enrichment, separation, and analysis of trace pesticide residues in environmental water, molecularly imprinted polymer (MIP) microspheres were prepared by precipitation polymerization using carbaryl, methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), azobisisobutyronitrile (AIBN), and acetonitrile as template, functional monomer, cross-linker, initiator, and porogen, respectively. Molecular modeling software was used to compute rational interaction between the template molecule and function monomer. The adsorption properties of carbaryl in acetonitrile for imprinted microspheres were evaluated by equilibrium rebinding experiments. Scatchard plot analysis revealed that there was one class of binding sites populated in the imprinted polymer microspheres with dissociation constants of 3.3 × 10−2 mol/l and an apparent maximum number of 1.95 µmol/g. The specificity of the imprinted microspheres was investigated by binding analysis using carbaryl and structurally related carbamate pesticides. The results indicated that the obtained imprinted microspheres showed a good selectivity for carbaryl. Copyright © 2007 John Wiley & Sons, Ltd.

Molecular imprinting technology was employed to produce one kind of malachite green (MG) molecularly imprinted polymers by precipitation polymerization using MG, methacrylic acid, ethylene glycol dimethacrylate, azobisisobutyronitrile, and acetonitrile as template, functional monomer, cross-linker, initiator and porogen, respectively. The binding properties of MG on imprinted polymers were evaluated in acetonitrile by equilibrium rebinding experiments. Scatchard plot's analysis revealed that there was one class of binding sites populated in the imprinted polymers with an apparent maximum number of MG (2.33 μmol/g). The specificity and selectivity of the imprinted polymers were investigated by binding analysis using MG and structurally related compounds. The results indicated that the imprinted polymers showed a good selectivity and specificity for MG. So the polymers can be used to separate MG from seafood, water and other matrices.

To obtain the desired specific adsorbents for monocrotophos (MCP) to enrichment, separation, and analysis of trace pesticides residue in soils and foods, molecularly imprinted polymer microspheres were prepared by precipitation polymerization using MCP, methacylic acid (MAA), ethylene glycol dimethacrylate, azobisisobutyronitrile, and toluene as template, functional monomer, crosslinker, initiator, and porogen, respectively. Computer simulation was employed to demonstrate the mechanism of the interaction between MCP and MAA in toluene. It was found that one MCP was entrapped by two MAAs in toluene through hydrogen bond. The binding properties of MCP in toluene for imprinted microspheres were evaluated by equilibrium rebinding experiments. Scatchard plot analysis revealed that there were two classes of binding sites populated in the imprinted polymer microspheres with dissociation constants of 0.0019 and 0.12 mmol/L, respectively. The specificity of the imprinted microspheres was investigated by binding analysis using MCP and structurally related organophosphorous pesticides. The results indicated that the obtained imprinted microspheres showed a good selectivity for MCP. POLYM. ENG. SCI., 47:1302–1308, 2007. © 2007 Society of Plastics Engineers

A new test strip method for field screening of nitrite in aqueous samples based on the diazo‐coupling reaction between the nitrite and the Griess reagents has been developed. The test strip has a circular sensing zone that contains two layers: the Griess reagents act as the sensing reagent and is immobilized in the bottom layer; the top layer is a cellulose acetate membrane that can be used as a dialysis membrane to remove the matrix from the sample, which can enhance the selectivity of this method. When the test strip was directly dipped into the samples, a color change of the test strip was observed, and the intensity of color that appears on the test strip is proportional to the concentration of nitrite in the range from 0.50 to 25 µg mL−1 in food samples. Under the experimental conditions, as low as 0.20 µg mL−1 nitrite can be observed; most of anionic and cationic species as well as other sample matrixes basically do not interfere with the nitrite measurement.

Because of their high sensitivity, piezoelectric sensor techniques are extremely useful for environmental or clinical analysis. We developed a piezoelectric crystal DNA biosensor for the detection of the hybridization reaction based on the self-assembled monolayer technology and biotin–avidin system. 3,3′-Dithiopropionic acid was applied to form a self-assembled monolayer (SAM) on the gold surface of the quartz crystal. Avidin was coated on the gold electrode conjugated with 1-ethyl-3-[3-(dimethylamino)propyl]-carbodiimide (EDC) and N-hydroxysuccinimide (NHS), and then biotinylated nucleotide acids were immobilized on the gold electrode surface through the specific interaction of biotin and avidin. Our results indicated that, using this immobilization method, the piezoelectric DNA sensor shows a higher sensitivity and specificity in detecting the hybridization reaction. The sensor can be used repeatedly by electrode regeneration.

A meso-tetra-[4-( p-toluene-sulfonyloxy) phenyl] porphyrin (H 2 TTSOPP) was synthesized under the condition of phase-transfer catalyst. The complexes of cobalt(II) and manganese(II) were also synthesized. All of the synthesized products were characterized by elemental analysis, electronic absorption spectrum, IR spectrum and proton magnetic resonance spectrum. The oxidation of aromatic aldehydes with O 2 was likewise investigated in the presence of porphyrin complexes, which were used as photocatalysts under illuminated with 450 W high-pressure mercury lamp (HPML). The oxygen uptaking volume was measured during the reaction process. It was observed that the complex could catalyze the oxidation of aromatic aldehydes. The photocatalytic oxidation kinetics of p-chlorobenzaldehyde was also investigated. It was found that apart from the first sampling time - which was included in the induction period - the disappearance of p-chorobenzaldehyde thoroughly conformed with first-order kinetics, and the kinetics decay constant was 0.00561 min -1 , while the lifetime was 134.3 min.

An automatic direct spectrophotometric method for the simultaneous determination of nitrite and nitrate by flow-injection analysis has been developed. The method is based on the reaction of nitrite and nitrate with the spectrophotometric reagent N-phenylanthranilic acid in sulfuric acid medium (pH=0.4∼0.6) to form the same color products while the absorbance is measured at 410 nm. This method has the advantage of direct determination of nitrite and nitrate and without reducing nitrate to nitrite as other reported methods. Various analytical parameters, such as flow rate, sample size, effect of acidity(pH), reagent concentration and interfering species were studied. The detection limit is 2.5 ng ml−1 for nitrite and 12 ng ml−1 for nitrate. Up to 35 samples per hour can be analyzed with a relative precision of ca. 0.1–2%.

Illuminated with 450 W high pressure mercury lamp (HPML), the oxidation of aromatic aldehydes was investigated with molecular oxygen in the presence of Co(II)[meso-tetra(benzoyloxy-phenyl) porphyrin] (CoTBCOPP). The oxygen uptake was measured during the reaction process. Under the mild condition (30°C, 1 atm O 2 ), the oxidation reactions occurred without consumption of reducing agent. It was observed that CoTBCOPP could catalyze the oxidation of aromatic aldehydes by reversibly binding molecular oxygen. The effects of the concentrations of catalyst and substrate in the oxidation reaction system were studied, meanwhile the factor of solvents was discussed in detail. The induction period was greatly shortened by raising the temperature of oxidation system or adding hydrogen dioxide. However, low dioxygen absorbed and the long induction period were obtained when imidazole was added as the fifth ligand.

A flow-injection catalytic spectrophotometric method is proposed for the determination of nitrite based on its catalytic effect on potassium bromate oxidation of acridine orange in phosphoric acid medium. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of acridine orange at 491.5 nm coupling with the stopped-flow technique. The calibration curve was linear between 3.4 and 65 ng/mL, and the detection limit was 2.2 ng/mL. Up to 30 samples can be analyzed per hour with a relative precision of ca. 1.9%. The proposed method was successfully applied to the determination of nitrite in waters and food samples with satisfactory results.

This paper describes a reversed flow injection spectrophotometric method for determination of manganese(II) at low levels. A new chromogenic system TCMOPPH2-Cd(II)-imidazole has been set up using a novel synthetic chromogenic reagent meso-tetra[4-(carboxymethylenoxy)phenyl]porphyrin [TCMOPPH2] by a substitution reaction of Mn(II) and Cd(II)-TCMOPP complex. The linear range extends from 0.01 to 1.75mg.L−1 with a sampling frequency of 90 h−1. Co(II), Cu(II), Cr(III) and Fe(II) exert no interference until their concentrations are up to 30, 32, 15 and 23 times of that of Mn(II), respectively. The proposed method is proved to be simple, sensitive and suitable for on-line determination of Mn(II), and it has been used in analysis of Mn(II) in water samples of Liaohe Oil Field water treat plant during the on spot purification. The detection limit was 2.8μg.L−1.

An on-line determination of chlorine dioxide (ClO2) in potable water using chlorophenol red (CPR) by gas diffusion flow-injection analysis (FIA) was investigated in the presence of various chlorinated species that can occur under normal water-treatment conditions. A gas diffusion membrane is used to separate the donor (sample) stream from the acceptor (detecting) stream (the donor stream transports the sample stream to the membrane separate device, and the acceptor stream collects all of the penetrated analytes and transports quantitatively to the detector) and makes it possible for this method to eliminate interference from metal ions, as well as other oxychlorinated compounds such as chlorite and chlorate. The system is more selective for chlorine dioxide than chlorine. The linear range of ClO2 concentration is 0–0.5 mg·mL−1 with a detection limit of 0.02 μg·mL−1 (S/N = 3) and a sampling frequency of 50 h−1. © 1999 John Wiley & Sons, Inc. Lab Robotics and Automation 11: 157–161, 1999

TDCPP and TCEP are two major types of organophosphorus flame retardants (OPFRs) that are bioaccumulative and persistent in the environment. The toxicity effects of TDCPP and TCEP on PC12 cell are not well understood. In the present study, we investigated morphology, viability and apoptosis in cultured PC12 cells in response to TDCPP and TCEP. The mRNA and protein expression levels of CAMKII, GAP43, tubulin and NF-H were quantified in PC12 cells treated with varying concentrations of the two agents. Results indicate that, upon treatment with the two OPFRs, cell growth decreased, apoptosis increased, morphology was altered and significant changes were found in the gene and protein levels. Treatment with TDCPP caused a reduction in the levels of each of the six proteins studied and in the gene levels of GAP43, NF-H and the two tubulins, but it resulted in an increase in CAMKII gene levels. Treatment with TCEP resulted in similar changes in gene levels to TDCPP and led to decreases in the protein levels of GAP43 and the tubulins while increasing the CAMKII and NF-H protein levels. These results suggest that changes in the gene and protein levels of the regulatory proteins (CAMKII, GAP43) and the structural proteins (tubulin, NF-H) are due to different mechanisms of the toxins, and these proteins may be useful biomarkers for the cytotoxicity and neurotoxicity.

In order to investigate the interrelationship between particulate matter (PM) size and in vitro toxicological effects of mainstream cigarette smoke, PM sized between 10 nm and 10 μm in mainstream cigarette smoke was sampled and divided into six stages. The in vitro cytotoxicity, genotoxicity and cell inhibition effects of PM were assessed by the neutral red cytotoxicity assay, Salmonella mutagenicity assay, micronucleus test and flow cytometry analysis, respectively. The results showed that all test samples were cytotoxic in the neutral red cytotoxicity assay. The IC50 values in the small-sized groups were significantly lower than those in the large-sized groups. Most test samples were mutagenic in the Salmonella mutagenicity assay (TA98 with S9 and TA100 with S9) and increased the frequency of micronucleated cells. Most PM disturbed the normal progression of the cell cycle, resulting in the accumulation of cells in the G0/G1 phase and the induction of apoptosis. In these tests, PM of a large size induced less toxicity compared with PM of a small size. These findings suggest that most PM samples induced toxicity in vitro, and PM of a small size was more toxic than PM of a large size.

Pentachlorophenol (PCP) is a ubiquitous contaminant that has been shown to lead to hepatoxicity and is implicated in the incidence of liver tumors in human. A number of previous studies have described the toxic effects of PCP based on conventional toxicological indices. However, little evidence on protein levels is available at present. For further understanding of mechanisms of action and identifying the potential protein biomarkers for PCP exposure, two-dimensional electrophoresis coupled with mass spectrometry has been used to identify proteins differentially expressed in the livers of rare minnow (Gobiocypris rarus) following PCP exposure of 0.5, 5, 50 μg/L. After comparison of the protein profiles from treated and control groups, 39 protein spots were found altered in abundance (>2-fold) from male and female PCP-treated groups. Matrix-assisted laser desorption/ionization (MALDI) tandem time-of-flight mass spectrometry (TOF/MS) analysis allowed the unambiguous identification, and 18 protein spots were identified successfully, 12 proteins in females and 6 proteins in males, respectively. These proteins were involved in transport, metabolism, response to oxidative stress and other biological processes. Of these proteins, four differentially expressed mRNA encoding proteins underwent quantitative analysis by quantitative real-time PCR (QRT-PCR). The consistent and discrepant results between mRNA and protein levels suggested that complicated regulatory mechanisms of gene expression were implicated in the response to PCP exposure. In addition, marked gender differences in response to PCP have been described from the comparison of the male and female liver protein profiles.

The high toxicity of pesticides and their wide use in modern agriculture has increased public concern. People are also worried about health threats caused by deleterious materials added to food. Current detection methods for these materials have their shortcomings. Microarray technology provides a highly sensitive and precise technique for obtaining information from biological samples, with the added advantage that it can handle a large number of samples simultaneously for rapid analysis. A direct competitive immunoassay for the screening of poisonous chemical haptens is proposed. Complete antigens of atrazine and papaverine were labeled with fluorescence. The fluorescence intensity linearly increased with decreasing concentration of analytes. The detection limits of atrazine and papaverine were 0.001 /spl mu/g/ml and 0.01 /spl mu/g/ml respectively.

As the daminozide (DM) and its metabolite have been identified to be potentially carcinogenic, rapid detection method for them is necessary for food safety. A type of piezoelectric crystal sensor has been prepared by using a molecularly imprinted polymer (MIP) as recognition element. The molecularly imprinted polymer was prepared by hot-induced precipitation polymerization, and then the polymer particles were fixed on the surface of the electrode. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to evaluate the obtained imprinted polymer particles and the MIP sensitive film coated on the electrode. The results showed that a typical time-response curve of the MIP-coated crystal to the DM solution had been given, frequency shifts versus logarithm changes of DM showed good linear correlation within the concentration range of 1.0x10(-9) to 10(-6) mg/mL (y=11.38 lg x+115.45, r=0.9872) and 1.0x10(-6) to 10(-1) mg/mL (y=25.22lgx+209.44, r=0.9938), respectively. The detection limit was 5.0x10(-8) mg/mL (S/N=3), which is lower than that of conventional methods. Further, computer simulation technology was employed to investigate the interaction between methacrylic acid and DM for elucidating the recognition mechanism. The influencing factor pH has also been investigated. The injection experiments of DM structurally related compounds indicated that the obtained sensor has high sensitivity, excellent selectivity, low cost, good reproducibility, and reusable property by combining with piezoelectric crystal and molecularly imprinted polymer.

The toxicological effects of single-walled carbon nanotubes (SWCNTs) were investigated after intratracheal instillation in male Wistar rats over a 15-day period using metabonomic analysis of 1H (nuclear magnetic resonance) NMR spectra of blood plasma and liver tissue extracts. Concurrent liver histopathology examinations and plasma clinical chemistry analyses were also performed. Significant changes were observed in clinical chemistry features, including alkaline phosphatase, total protein, and total cholesterol, and in liver pathology, suggesting that SWCNTs clearly have hepatotoxicity in the rat. 1H NMR spectra and pattern recognition analyses from nanomaterial-treated rats showed remarkable differences in the excretion of lactate, trimethylamine oxide, bilineurin, phosphocholine, amylaceum, and glycogen. Indications of amino acid metabolism impairment were supported by increased lactate concentrations and decreased alanine concentrations in plasma. The rise in plasma and liver tissue extract concentrations of choline and phosphocholine, together with decreased lipids and lipoproteins, after SWCNTs treatment indicated a disruption of membrane fluidity caused by lipid peroxidation. Energy, amino acid, and fat metabolism appeared to be affected by SWCNTs exposure. Clinical chemistry and metabonomic approaches clearly indicated liver injury, which might have been associated with an indirect mechanism involving nanomaterial-induced oxidative stress.