电化学微传感器检测水中痕量铜离子

为改善微电极在阳极溶出伏安法检测重金属离子过程中低电流响应和低电催化能力的缺点,提出了一种在碳纤维微电极表面合成还原氧化石墨烯/纳米金材料制得还原氧化石墨烯纳米金修饰碳纤维微电极（rGO/AuNPs CFMEs）的方法.通过SEM表征,所制备的rGO/AuNPs CFMEs具有比表面积高、吸附能力强和催化活性好的特点,因此改性微电极适合作为方波阳极溶出伏安法（SWASV）测定水中铜离子（Cu²⁺）的工作电极.在构建微传感器测试水中痕量铜离子系统后,对pH值、电导率、富集时间和富集电位等检测条件进行了优化.在pH值为4,电导率为36.1S/m,富集时间为360s,富集电位为-1.2V的最佳条件下,铜的线性范围和检出限分别0~1.0μmol/L和2.4nmol/L.此外,微传感器的可重复性、长期稳定性以及选择性也得到了验证.     

巯基化合物在万寿菊镉解毒中的作用

采用水培实验方法研究了万寿菊体内镉积累和解毒与巯基化合物含量的关系。万寿菊植株分别在镉浓度为0、0.1、0.5、2和8 mg/L的营养液中暴露7 d,测定了根、茎、叶中镉、非蛋白巯基(NPT)、半胱氨酸(Cys)、γ-谷氨酰半胱氨酸(γ-EC)、谷胱甘肽(GSH)和植物络合素(PCs)的含量。植物根、茎、叶中镉含量都随着镉暴露浓度的增加而增加。当溶液中镉浓度较低(0.1～2 mg/L)时,茎叶中NPT、PCs、Cys和γ-EC含量随着镉浓度增加而增大;当镉浓度较高(8 mg/L)时,茎叶中PCs含量迅速降低,GSH含量大幅度增高。在根部,这些巯基化合物的含量几乎不受镉处理影响,且含量较低。以上研究结果表明:PCs在万寿菊镉的解毒机制中发挥一定的作用,暴露于高浓度的镉,GSH比PCs起着更为重要的解毒作用。     

Enzyme-electrolytic degradation of dichloromethane: Efficiency, kinetics and mechanism

Enzymatic electrolysis cell(EEC) has advantages over microbial electrolysis cell(MEC) due to the needless of microbe inoculation and high-efficiency of enzymatic reaction. In this study, an EEC was first applied to achieve the effective degradation of halogenated organic pollutants and dichloromethane(CH_2Cl_2) was utilized as a model pollutant. The results indicate that the degradation efficiency of CH_2Cl_2 after 2 hr reaction in the EEC was almost100%, which was significantly higher than that with enzyme(51.1%) or current(19.0%). The current induced the continuous regeneration of reduced glutathione(GSH), thus CH_2Cl_2 was degraded under the catalysis of GSH-dependent dehalogenase through stepwise dechlorination, and successively formed monochloromethane(CH_3Cl) and methane(CH_4). The kinetic result shows that with a current of 15 mA, the maximum specific degradation rate of CH_2Cl_2(3.77 × 10~(-3) hr~(-1)) was increased by 5.7 times. The optimum condition for CH_2Cl_2 dechlorination was also obtained with pH, current and temperature of 7.0, 15 mA and 35°C,respectively. Importantly, this study helps to understand the behavior of enzymes and the fate of halogenated organic pollutants with EEC, providing a possible treatment technology for halogenated organic pollutants.     

Reduced-glutathione concentrations in Boleophthalmus pectinirostris tissues exposed to benzo(a)pyrene

ＩｎｔｒｏｄｕｃｔｉｏｎＢｅｉｎｇａｔｙｐｉｃａｌｐｏｌｙｃｙｃｌｉｃａｒｏｍａｔｉｃｈｙｄｒｏｃａｒｂｏｎｓ(ＰＡＨｓ) ,ｂｅｎｚｏ[ａ]ｐｙｒｅｎｅ(ＢａＰ)ｄｅｓｅｒｖｅｓｓｅｒｉｏｕｓｓｔｕｄｙｂｅｃａｕｓｅＰＡＨｓａｒｅｎｏｗｒｅｃｏｇｎｉｚｅｄａｓｍａｊｏｒｅｎｖｉｒｏｎｍｅｎｔａｌｐｏｌｌｕｔａｎｔｓ .ＥｘｐｏｓｕｒｅｔｏＰａＨｓｉｓｖｉｒｔｕａｌｌｙｕｎａｖｏｉｄａｂｌｅａｎｄｉｓｓｔｒｏｎｇｌｙｓｕｓｐｅｎｄｅｄｏｆｂｅｉｎｇａｃａｕｓａｔｉｖｅｆａｃｔｏｒｉｎｃｅｒｔａｉｎｔｕｍｏ…     

沙尘暴细颗粒物对大鼠肺泡巨噬细胞钙水平和脂质过氧化的影响

2004年3月采集甘肃省武威市和内蒙古包头市正常良好天气、局地扬沙天气和沙尘暴天气的大气细颗粒物(PM2．5)样品,以不同浓度的细颗粒物悬液体外处理大鼠肺泡巨噬细胞后测定细胞内丙二醛(MDA)、谷胱甘肽(IgSH)及胞质游离Ca^2 含量,并观察不同处理时间的细胞存活率．研究结果表明：(1)沙尘暴与非沙尘暴PM2．5均使细胞内MDA和Ca^2 含量升高、GSH含量下降,且对细胞毒性存在时间．效应和剂量．效应关系,(2)PM2．5对各指标的影响仅与处理剂量有关,而与样品种类无关．沙尘暴期间大气PM2．5浓度很高,因而沙尘暴PM2.5的危害作用不可忽视。     

纳米二氧化锰/还原态氧化石墨烯复合材料催化臭氧降解苯酚的研究

制备以还原态氧化石墨烯为载体的纳米二氧化锰催化剂,并以苯酚为目标降解物,研究了其催化臭氧化性能,对影响催化臭氧化效果因素及降解机理进行了初步探讨。使用SEM、TEM和XPS对材料进行表征;纳米二氧化锰/还原态氧化石墨烯催化臭氧降解苯酚反应为准一级反应;催化剂的最佳使用量为0.2 g/L;当p H=3时,苯酚催化臭氧化去除率相对于单独臭氧提高了119.0%;催化剂连续使用4次性能良好。     

Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Biochemical biomarkers and overall health status of mussels Mytilus galloprovincialis exposed to nickel and chromium

This study examined the effects of nickel and chromium exposure on two biochemical biomarkers, glutathione peroxidase (GPX) and acetylcholinesterase (ACHE), in parallel with an indicator of overall health, Scope for Growth (SFG), in the mussel Mytilus galloprovincialis to evaluate their ecological relevance and to assess their potential use as biomarkers of Ni and Cr pollution. SFG integrates major physiological responses into an index that represents the energy status of the animals and is considered an ecologically relevant biomarker. Following exposure to a range of Ni and Cr concentrations effects of Ni and Cr were evident on GPX and SFG but not on ACHE. Accumulation in the mussels’ tissues increased according to exposure concentrations. Adverse effects on the energy status and induction of GPX were found at the higher exposure concentrations while possible hormetic effects on the energy status and moderate GPX suppression were associated with lower exposure concentrations. Nevertheless GPX was negatively correlated with SFG suggesting that GPX responses reflect the overall health of the organisms and thus show potential as an early warning signal of population level effects of Ni and Cr. On the other hand, our results indicate that ACHE is not a suitable biomarker for Ni and Cr pollution.     

Levels of plasma B-esterases and glutathione-S-transferase activities in three South American toad species

We determined the normal levels of butyrylcholinesterase (BChE), carboxylesterase (CbE), and glutathione S-transferases (GST) activities in three South American toad species in order to establish reference values for field pesticide monitoring purposes. Interspecies variations in B-esterase and GST activities were examined according to body mass. In addition, comparative inhibition of BChE and CbE activities using malaoxon, and chemical reactivation of malaoxon-inhibited BChE activity using pyridine-2-aldoxime methochloride (2-PAM) were investigated. Bufo fernandezae had average activity values for BChE: 17.31 mmol min^?1 ml^?1; CbE: 621.49 nmol min^?1 ml^?1 and GST: 1.94 mmol min^?1 ml^?1 while B. arenarum enzymatic average activities were BChE: 9.51 mmol min^?1 ml^?1; CbE: 270.07 nmol min^?1 ml^?1, and GST: 1.59 mmol min^?1 ml^?1; finally Bufo schneideri had enzymatic mean values of BChE: 2.08 mmol min^?1 ml^?1; CbE: 301.95 nmol min^?1 ml^?1, and GST: 1.60 mmol min^?1 ml^?1. Moreover, we found an allometric relationship between plasma BChE and CbE activities and body size for the three toad species. We suggest that B. fernandezae would be the species with a higher tolerance capacity to organophosphorous insecticides compared to the other toad species, while B. schneideri may be the most vulnerable toad species to field pesticide exposure, although some other factors (e.g., brain AChE sensitivity or pesticide metabolism by phosphotriesterases) should be also taken into account. The malaoxon-inhibited BChE activity of the three toad species was reactivated in the presence of 2-PAM, and it is recommended as a specific and sensitive methodology in the assessment of field exposure to OP insecticides together to compare BChE activity levels between OP-exposed and nonexposed individuals.     

Protective role of epigallocatechin 3-gallate against lead-induced toxicity in human neuroblastoma cells

Lead (Pb) is a heavy metal, known to induce oxidative stress and produce damage to the antioxidant defence system ultimately leading to cell death. Antioxidants such as epigallocatechin 3-gallate (EGCG), a green tea polyphenol, was shown to play a protective role during Pb-exposure. In this study, human SH-SY5Y neuroblastoma cells were exposed to different concentrations (0.01–10?µM) of Pb for 48?h to determine effects on the viability of cells. It was observed that IC₅₀ was at 5?µM and at this concentration the cells exhibited a significant increase in caspase-3 activity, an indicator of apoptosis at least by 10-fold and the decrease of 59.4% in glutathione (GSH) content. The total cellular prostaglandin-E₂ (PGE₂) level was found to be elevated at least 10-fold upon Pb exposure. However, the effects of Pb on cells pre-incubated with 50?µM EGCG followed by 5?µM Pb showed 40% inhibition in cell viability, 17.3% decrease in caspase-3 activity, 23% increase in GSH content, and 11.4% fall in PGE₂ levels when compared with cells exposed to Pb only. Data suggest that EGCG exerted a significant protection to cell viability in preventing cell death and elevation in levels of GSH in cells exposed to Pb. However, EGCG did not elicit any significant effect on release of PGE₂ indicating the nature of EGCG as an effective anti-apoptotic, antioxidant, and anti-inflammatory agent.