Optimizing synthesis conditions of nanoscale zero-valent iron (nZVI) through aqueous reactivity assessment

Nanoscale iron particles (nZVI) is one of the most important engineered nanomaterials applied to environmental pollution control and abatement. Although a multitude of synthesis approaches have been proposed, a facile method to screen the reactivity of candidate nZVI materials produced using different methods or under varying synthesis conditions has yet been established. In this study, four reaction parameters were adjusted in the preparation of borohydride-reduced nZVI. The reductive properties of the resultant nanoparticles were assayed independently using two model aqueous contaminants, Cu(II) and nitrate. The results confirm that the reductive reactivity of nZVI is most sensitive to the initial concentration of iron precursor, borohydride feed rate, and the loading ratio of borohydride to ferric ion during particle synthesis. Solution mixing speed, in contrast, carries a relative small weight on the reactivity of nZVI. The two probing reactions (i.e., Cu(II) and nitrate reduction) are able to generate consistent and quantitative inference about the mass-normalized surface activity of nZVI. However, the nitrate assay is valid in dilute aqueous solutions only (50 mg·L⁻¹ or lower) due to accelerated deactivation of iron surface at elevated nitrate concentrations. Additional insights including the structural and chemical makeup of nZVI can be garnered from Cu(II) reduction assessments. The reactivity assays investigated in this study can facilitate screening of candidate materials or optimization of nZVI production parameters, which complement some of the more sophisticated but less chemically specific material characterization methods used in the nZVI research.     

Effects of molecular weight and concentration of carboxymethyl cellulose on morphology of hydroxyapatite nanoparticles as prepared with one-step wet chemical method

Nano-sized apatite particles (nAP) synthesized with carboxymethyl cellulose (CMC) have shown great application potentials in in situ heavy metal remediation. However, differences in CMC’s properties effects on the size of nAP produced are not well understood. In this paper, two types of CMC, with respective molecular weights (MW) of ～120000 and ～240000 Dalton or respective polymerization degrees of 500 (CMC-500) and 1050 (CMC-1050), were studied in a concentration range of 0.05%–0.5% (w/w) for nAP synthesis. Morphology of the particles was characterized with transmission electron microscopy (TEM). Results showed that 0.05% CMC-500 solution gave an average particle size of 148.7±134.9 nm, 0.25% CMC-500 solution produced particles of 21.8±20.4 nm, and, 0.5% CMC-500 solution contained particles of 15.8±7.7 nm. In comparison, 0.05% CMC-1050 solution produced nanoparticles of 6.8±3.2 nm, 0.25% CMC-1050 produced smaller nAP of 4.3±3.2 nm, and 0.5% CMC-1050 synthesized the smallest nanoparticles in this study, with an average diameter of 3.0±2.1 nm. Chemical composition of the products was identified with X-ray diffraction (XRD) as pure hydroxyapatite. Interactions between nAP and CMC were discussed with help of attenuated total reflection Fourier transform infrared (ATRFTIR) spectroscopic data. This study showed that CMC at higher concentration as well as higher MW facilitated to produce finer nanoparticles, showing that nAP size could be manipulated by selecting appropriate CMC MW and/or applying appropriate CMC concentration.     

亲水荷电超滤膜的制备及对腐殖酸的分离性能

为改善聚醚砜(PES)超滤膜的抗污染性能和提高对腐殖酸(HA)的截留率,以介孔二氧化硅(MS)为添加剂,采用相转化法制备了亲水性PES/MS复合超滤膜,并对膜表面进行荷电改性.研究了MS对膜的断面结构、表面化学性质和过滤性能的影响,考察了荷电改性PES/MS超滤膜对水中HA的分离性能以及溶液pH值、离子强度和钙离子浓度等因素对荷电膜超滤过程的影响.SEM表征结果显示,MS颗粒在PES/MS复合膜的表面分散均匀,膜孔的连通性改善.亲水荷电改性后,膜表面接触角由68°降至57°,zeta电位由-6.31mV降至-11.45mV,膜对HA的去除率由72%提高到95%,通量衰减率由29.8%减小到4.9%.结果表明,对PES超滤膜进行亲水荷电改性可有效提高对HA的截留率,同时减轻膜污染;另外,溶液的pH值、离子强度和钙离子浓度对荷电超滤膜的过滤性能有较大影响,调节合适的溶液环境可在提高截留率的同时,减轻膜污染.     

Determination of F2-isoprostanes in cultured human lung epithelial cells after exposure to metal oxide and silica nanoparticles by high-performance liquid chromatography/tandem mass spectrometry

The environmental impact of nanotechnology has caused a great concern. Many in vitro studies showed that many types of nanoparticles were cytotoxic. However, whether these nanoparticles caused cell membrane damage was not well studied. F₂-isoprostanes are specific products of arachidonic acid peroxidation by nonenzymatic reactive oxygen species and are considered as reliable biomarkers of oxidative stress and lipid peroxidation. In this article, we investigated the cytotoxicity of different nanoparticles and the degree of cellular membrane damage by using F₂-isoprostanes as biomarkers after exposure to nanoparticles. The human lung epithelial cell line A549 was exposed to four silica and metal oxide nanoparticles: SiO₂ (15 nm), CeO₂ (20 nm), Fe₂O₃ (30 nm), and ZnO (70 nm). The levels of F₂-isoprostanes were determined by using high-performance liquid chromatography/mass spectrometry. The F₂-isoprostanes’ peak was identified by retention time and molecular ion m/z at 353. Oasis HLB cartridge was used to extract F₂-isoprostanes from cell medium. The results showed that SiO₂, CeO₂, and ZnO nanoparticles increased F₂-isoprostanes levels significantly in A549 cells. Fe₂O₃ nanoparticle also increased F₂-isoprostanes level, but was not significant. This implied that SiO₂, CeO₂, ZnO, and Fe₂O₃ nanoparticles can cause cell membrane damage due to the lipid peroxidation. To the best of our knowledge, this is the first report on the investigation of effects of cellular exposure to metal oxide and silica nanoparticles on the cellular F₂-isoprostanes levels.     

A nanosilver-based spectrophotometric method for sensitive determination of methyl violet in river water

A method is reported for the determination of methyl violet in the range of 10–120 nmol L^?1. The method is based on the catalytic effect of silver nanoparticles (AgNPs) on the oxidation reaction of methyl violet by potassium bromate in acid medium. The reaction is followed spectrophotometrically by measuring the change in absorbance () at 620 nm using a fixed time method. The reaction variables were optimized in order to achieve highest sensitivity. The 3б criterion detection limit was 5 nmol L^?1, and the relative standard deviation for ten replicate determinations at a concentration of methyl violet of 15 nmol L^?1 was 0.97% (n = 10). The method was successfully applied to the determination of methyl violet in river water samples.     

Structural effect on photocatalytic degradation of metallised azo dyes in aqueous TiO2 suspension

Three metallised azo dyes were investigated under TiO₂‐photocatalytic and photosensitised conditions in aqueous buffering solutions. The degradation follows apparent first‐order kinetics. The size and strength of intramolecular conjugation determine the light‐fastness of the investigated dyes. Compared with ¹O₂ produced in photosensitised process, the more powerful *OH radicals in TiCO₂ photocatalytic process are highly reactive towards the investigated azo dyes. And as a result, the TiO₂‐photocatalysis makes little less distinction in the degradation kinetic data of the azo dyes compared with the photosensitised degradation of them.     

纳米金颗粒进入梨形四膜虫体内的方式及其分布

以梨形四膜虫为模式动物,研究水体中的纳米金颗粒进入生物体的方式、分布及其生物学效应.实验中所采用的纳米金颗粒平均粒径为13 nm,分散均匀.透射电镜结果表明,纳米金颗粒可以通过口沟（进食）和细胞膜（内吞）两种方式进入梨形四膜虫体内;纳米金颗粒进入梨形四膜虫体内后,主要分布在食物泡中,另外细胞质和细胞核（大核）中也含有少量的纳米金颗粒.同时,研究表明在实验所用的浓度范围内,纳米金颗粒对梨形四膜虫无明显毒性.     

纳米Fe3O4对小鼠肺细胞的氧化损伤

纳米Fe3O4作为一种功能材料,在生物医药、生物靶向材料、微波吸收材料和高梯度磁分离器等方面应用前景广阔,其潜在的生物毒性也备受关注。为研究纳米Fe3O4对生物体可能造成的氧化损伤,以昆明小鼠为受试体,设置5、10、20和40mg·kg-14个染毒组,腹腔注射染毒7d后,测定小鼠肺组织中活性氧(reactive oxygen species,ROS)、还原型谷胱甘肽(glutathione,GSH)和丙二醛(malondialdehyde,MDA)的含量。结果显示,随着纳米Fe3O4染毒剂量的升高,肺组织ROS和MDA含量逐渐上升,GSH含量逐渐降低,各指标均呈一定的剂量-效应关系。剂量≥10mg·kg-1,肺组织ROS含量与对照组相比有显著差异(p<0.05);剂量≥20mg·kg-1,肺组织MDA含量与对照组相比有显著差异(p<0.05);剂量≥40mg·kg-1,肺组织GSH含量与对照组相比有显著差异(p<0.05)。研究表明,较高剂量(≥20mg·kg-1)的纳米Fe3O4颗粒材料会引起小鼠肺细胞的氧化损伤。     

高分子树脂与介孔分子筛吸附-脱附VOCs性能对比

采用溶剂热法制备介孔聚二乙烯基苯(PDVB)树脂,并以介孔分子筛MCM-41、SBA-15为参照,从吸附-脱附甲苯、邻二甲苯、均三甲苯性能和高湿度下的疏水性能方面对其进行对比研究.结果表明,PDVB具有最大的比表面积1219.1m2/g,其对低浓度甲苯吸附量约为介孔分子筛的2倍,同时吸附性能几乎不受水汽影响.随着VOCs分子尺寸增加,3种吸附剂对VOCs的饱和吸附量均有所增加,但PDVB的穿透吸附量明显高于分子筛.热重分析表明,在200℃以下3种吸附剂上吸附的有机分子均能脱附完全,具有优良的脱附再生性能.     

Dissolution of zinc oxide nanoparticles in exposure media of algae,daphnia, and fish embryos for nanotoxicological testing

Zinc oxide nanoparticles (ZnO NPs) are being widely investigated in a bioassay due to potential negative effects to biological receptor. The dissolution of metal nanoparticles such as ZnO NPs is crucial to interpret nanotoxicity results because ZnO NPs can release toxic-free ions in exposure media. In the present study, dissolution of ZnO NPs was evaluated in three selected synthetic media for aquatic toxicological testing: Elendt M4 daphnia medium, OECD algal medium, and fish embryo rearing solution. Both media are currently recommended for OECD testing for daphnia and algae. Time-dependent dissolution of ZnO NPs has been investigated in terms of sonication time to be used for the preparation of aqueous NPs suspension, and dissolution time corresponding to exposure period in toxicity testing. Since sonication is widely applied for NPs dispersion in the most of nanotoxicological testing, the emphasis of this study was on the dissolution of NPs as a function of sonication time. We also investigated the concentration-dependent dissolution of ZnO NPs. Our results demonstrated that dissolution of ZnO NPs was significantly affected by sonication and dissolution time, as well as NPs concentration. This study showed that parameters affecting dissolution of ZnO NPs should be considered in nanotoxicological testing.