Enhanced visual detection of pesticides using gold nanoparticles

The presence of parts per billion (ppb) levels of chlorpyrifos (O,O-Diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate) and malathion (S-1,2-bis(ethoxycarbonyl) ethyl O,O-dimethyl phosphorodithioate), two common pesticides found in the surface waters of developing countries, have been visually detected using gold nanoparticles. Visual detection of the presence of pesticide is possible when the color change occurring by the adsorption of pesticides on gold nanoparticles is enhanced by sodium sulfate. The method presented here is simple and there is no need of sample preparation or preconcentration. The response occurs within seconds and the color change is very clear. The detection is possible if chlorpyrifos and malathion are present up to a concentration of 20 and 100 ppb, respectively. The method shows great potential for on-site pesticide monitoring. The method is also applicable as a qualitative technique for the performance evaluation of various household water filters, which claim pesticide removal.     

In vivo genotoxicity assessment of titanium,zirconium and aluminium nanoparticles,and their microparticulated forms,in Drosophila

As in vivo system, we propose Drosophila melanogaster as a useful model for study the genotoxic risks associated with nanoparticle exposure. In this study we have carried out a genotoxic evaluation of titanium dioxide (TiO₂), zirconium oxide (ZrO₂) and aluminium oxide (Al₂O₃) nanoparticles and their microparticulated forms in D. melanogaster by using the wing somatic mutation and recombination assay. This assay is based on the principle that loss of heterozygosis and the corresponding expression of the suitable recessive markers, multiple wing hairs and flare-3, can lead to the formation of mutant clones in treated larvae, which are expressed as mutant spots on the wings of adult flies. Third instar larvae were feed with TiO₂, ZrO₂ and Al₂O₃ nanoparticles, and their microparticulated forms, at concentrations ranging from 0.1 to 10 mM. Although a certain level of aggregation/agglomeration was observed in solution, it must be noted than the constant digging activity of larvae ensures that treated medium pass constantly through the digestive tract ensuring exposure. The results showed that no significant increases in the frequency of all spots (e.g. small single, large single, twin, total mwh and total spots) were observed, indicating that these nanoparticles were not able to induce genotoxic activity in the wing spot assay of D. melanogaster. Negative data were also obtained with the microparticulated forms. This indicates that the nanoparticulated form of the selected nanomaterials does not modify the potential genotoxicity of their microparticulated versions. These in vivo results contribute to increase the genotoxicity database on the TiO₂, ZrO₂ and Al₂O₃ nanoparticles.     

Relevance study of bare and coated zero valent iron nanoparticles for lindane degradation from its by-product monitorization

Zero-valent iron nanoparticles (NZVI) as well as polymer–stabilized nanoparticles were synthesized and used for lindane (γ-hexachlorocyclohexane) degradation in aqueous solution. To study the effectiveness of the different coated nanoparticles, simple and rapid analytical methods have been developed to measure and to detect lindane and its by-products. For the monitorization of lindane degradation solid-phase extraction (SPE) was used, while volatile by-products formation measurement was carried out by headspace-solid phase microextraction (HS–SPME) followed by GC/MS. The SPE–GC/MS method provides low detection limits (0.2 μg L⁻¹), high recovery (above 95%) and it is a valuable tool for kinetic studies of the degradation process for each polymer used, while HS–SPME–GC/MS has proved to be an effective tool for the extraction and evaluation of volatile degradation by-products.     

不同培养介质中纳米氧化铜对小麦毒性的影响

采用琼脂培养和水培方法比较了纳米氧化铜(CuONPs)在不同暴露介质中的环境化学行为及其对小麦根生长的影响,并探讨了不同培养介质对CuONPs植物毒性的影响机制.结果表明,琼脂介质相对水相(营养液)环境可以减少CuONPs的团聚,增强其分散性.在琼脂和水相中Cu离子溶出随CuONPs浓度变化规律存在明显差异,在50～1000mg CuONPs·L-(1以Cu计)范围内,CuONPs在琼脂中无论是Cu2+的溶出浓度还是溶出比率均低于其在水相中的值.CuONPs在不同介质中表现出显著的小麦毒性差异.琼脂培养下小麦根生长半抑制效应浓度EC50(以CuONPs浓度表示)为108mg·L-1,而在水培方式下为9.0mg·L-1,说明琼脂介质极大缓解了CuONPs引起的植物毒性.分析表明,Cu2+溶出浓度较CuONPs投放量与小麦根生长抑制效应之间存在更好的指数相关关系,这说明该研究体系下CuONPs小麦毒性主要是由纳米颗粒释放Cu2+引起的.此结论较好地解释了当培养介质从水相变成琼脂时,Cu2+溶出减少,纳米毒性降低的现象.该研究结果认为,当前国内外使用水培法获得的纳米材料植物毒性研究结果在外推至实际土壤状况时将高估其环境安全性风险,推荐使用琼脂作为纳米材料土壤环境风险评价的模拟介质.     

Rapid method for on-site determination of phenolic contaminants in water using a disposable biosensor

A disposable biosensor was fabricated using single-walled carbon nanotubes, gold nanoparticles and tyrosinase (SWCNTs-AuNPs-Tyr) modified screen-printed electrodes. The prepared biosensor was applied to the rapid determination of phenolic contaminants within 15 minutes. The SWCNTs-AuNPs-Tyr bionanocomposite sensing layer was characterized with scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry methods. The characterization results revealed that SWCNTs could lead to a high loading of tyrosinase (Tyr) with the large surface area and the porous morphology, while AuNPs could retain the bioactivity of Tyr and enhance the sensitivity. The detection conditions, including working potential, pH of supporting electrolyte and the amount of Tyr were optimumed. As an example, the biosensor for catechol determination displayed a linear range of 8.0 × 10^-8 to 2.0 × 10^-5 mol·L^-1 with a detection limit of 4.5 × 10^-8 mol·L^-1 (S/N = 3). This method has a rapid response time within 10 s, and shows excellent repeatability and stability. Moreover, the resulting biosensor could be disposable, low-cost, reliable and easy to carry. This kind of new Tyr biosensor provides great potential for rapid, on-site and cost-effective analysis of phenolic contaminants in environmental water samples.     

纳米四氧化三铁同步去除水中的Pb（Ⅱ）和Cr（Ⅲ）离子

采用共沉淀方法制备纳米四氧化三铁颗粒（MNPs）,通过扫描电镜（SEM）、X射线衍射（XRD）和光电子能谱分析（XPS）等表征手段对材料进行分析。同时考察了不同MNPs投加量、pH值、温度和初始浓度条件下对纳米四氧化三铁同步去除水中Pb（Ⅱ）和Cr（Ⅲ）离子的影响。结果表明,在pH为6.0、温度为25℃、纳米四氧化三铁的投加量为4.0 g/L下,吸附3 h后,Pb（Ⅱ）-Cr（Ⅲ）复合溶液中Pb的去除率为70.5%,Cr的去除率可达77.4%。pH和温度对去除过程影响较大。SEM和XRD分析证实成功制备了纳米级四氧化三铁,XPS结果表明,复合溶液中Pb（Ⅱ）和Cr（Ⅲ）离子的去除过程为同步吸附。吸附等温线研究说明,Pb（Ⅱ）的吸附是放热过程且为单相吸附;相反Cr（Ⅲ）的吸附是吸热过程且为多相吸附。重复利用实验表明,MNPs利用3次后对Pb和Cr的去除率几乎未受影响。因此,MNPs可用于实际工程中多种重金属离子共存废水的原位处理。     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Preliminary investigation on cytotoxicity of fluorinated polymer nanoparticles

As well-known persistent organic pollutants(POPs), organofluorine pollutants such as perfluorooctane sulfonate(PFOS) have been proven to be bioaccumulated and harmful to health. However, toxicological assessment of organofluorinated nanoparticles, which have emerged as a novel tool for biomedical and industrial applications, is lacking, to the best of our knowledge. To assess the biological effects and health risk of fluorinated nanoparticles,trifluoroethyl aryl ether-based fluorinated poly(methyl methacrylate) nanoparticles(PTFEPMMA NPs) were synthesized with various fluorine contents(PTFE-PMMA-1 NPs 12.0 wt.%,PTFE-PMMA-2 NPs 6.1 wt.% and PTFE-PMMA-3 NPs 5.0 wt.%), and their cytotoxicity was investigated in this study. The in vitro experimental results indicated that the cytotoxicity of PTFE-PMMA NPs was mild, and was closely related to their fluorine(F) contents and Fcontaining side chains. Specifically, the cytotoxicity of PTFE-PMMA NPs decreased with increasing F content and F-containing side chains. After exposure to PTFE-PMMA NPs at a sublethal dose(50 μg/m L) for 24 hr, the phospholipid bilayer was damaged, accompanied by increasing permeability of the cell membrane. Meanwhile, the intracellular accumulation of reactive oxygen species(ROS) occurred, resulting in the increase of DNA damage, cell cycle arrest and cell death. Overall, the PTFE-PMMA NPs were found to be relatively safe compared with typical engineered nanomaterials(ENMs), such as silver nanoparticles and graphene oxide, for biomedical and industrial applications.     

污水处理厂不同单元工艺水中重金属及其纳米颗粒的分布

以成都双流国际机场污水处理厂中连续处理废水工艺中的9个不同处理单元工艺为研究对象,通过电感耦合等离子体质谱法（ICP-MS）和单颗粒电感耦合等离子体质谱法（SP-ICP-MS）分别对污水处理厂中不同处理单元工艺中的重金属总质量浓度以及重金属纳米颗粒的数量浓度和粒径分布进行了分析,并研究了不同处理单元工艺对重金属元素及重金属纳米颗粒的去除效果.结果表明,不同处理单元工艺对不同重金属元素的去除效果存在差异,对Fe元素的影响最为显著,主要在二沉池中被去除,去除率达98.53%;不同处理单元工艺对不同重金属纳米颗粒的去除效果存在显著差异,对Ni、Pd和Fe纳米颗粒的影响最为显著,不同重金属纳米颗粒在不同处理单元工艺（曝气沉砂池、二沉池和高效沉淀池）中被去除;重金属纳米颗粒在不同处理单元工艺中的粒径分布为23.28~147.83 nm,不同处理单元工艺不会对各重金属纳米颗粒的粒径造成显著影响;pH与Fe元素和Fe纳米颗粒呈显著负相关关系,除Fe元素和Fe纳米颗粒外,其他重金属元素与其纳米颗粒之间均属于不显著相关,不同处理单元工艺对重金属元素和重金属纳米颗粒的去除机制存在差异.     

两种纳米颗粒对沸石吸附环丙沙星的影响

为了探明纳米颗粒（NPs）共存对抗生素在黏土矿物上的吸附的影响,以沸石为供试黏土矿物,环丙沙星（CIP）为目标污染物,研究了不同温度、 pH值和离子强度条件下,纳米氧化锌（ZnO NPs）和纳米二氧化钛（TiO₂ NPs）这2种NPs对沸石吸附CIP的影响,并结合沸石的表面特征探讨不同类型NPs对CIP吸附的影响机制.结果表明,除5 mg·L^-1ZnO NPs共存时,轻微促进了CIP的吸附,其他NPs浓度均对CIP产生不同程度的抑制,抑制程度表现出TiO₂ NPs>ZnO NPs的顺序;随温度升高,NPs的存在增强了沸石对CIP吸附的增温正效应;当离子强度由0.001mol·L^-1增加到0.01mol·L^-1时,CIP的吸附量下降,但2种NPs的存在均减弱了离子强度的负效应;溶液pH会影响CIP的存在形态和NPs的性质,进而影响CIP的吸附.沸石对单一CIP的吸附存在静电引力、氢键和孔径填充作用,ZnO NPs主要通过静电引力竞争吸附位点对CIP吸附产生影响,而TiO