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.     

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.     

依据材料与构件的受弯性能综合评价ECC的控裂性

为了研究国产的工程水泥基复合材料(Engineered Cementitious Composites,ECC)和普通聚乙烯醇(Polyvi-nyl Alcohol,PVA)纤维混凝土对结构增韧和控裂的效果,分别采用材料试验和构件试验进行研究。通过四点弯曲试验,发现ECC的峰值荷载和峰值荷载对应的拉应变要远远大于普通混凝土、PVA纤维混凝土,而且ECC起裂以后,裂缝宽度较小,且发展较慢,控制较好;采用不同高度的ECC、PVA纤维混凝土作为钢筋混凝土梁底保护层,发现1/4h ECC对钢筋混凝土增韧的效果最好,且裂缝宽度为0.2mm时,1/4h ECC的承载能力比普通钢筋混凝土提高1.6倍,峰值荷载比普通钢筋混凝土提高约12%;同时发现,在相同荷载作用下,采用ECC作为梁底保护层时,裂缝宽度比钢筋混凝土小,且可以有效地控制裂缝宽度的快速增长,间接提高结构的耐久性。     

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。     

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.     

Entomotoxic effect of silicon dioxide nanoparticles on Plutella xylostella (L.) (Lepidoptera: Plutellidae) under laboratory conditions

The use of higher dosage and repeated applications of conventional pesticides have led to the rapid development of insect resistance to pesticide and adverse effects on human health and environment. Accordingly, researchers are prompted to identify an alternative entomotoxic agent for crop protection. Nanocides are being considered as alternatives to conventional insecticides because they are expected to lessen the application rate and reduce the chances of resistance development in pests. In this study, we evaluated the entomotoxic effects of nanosilica on larvae of Plutella xylostella, in a laboratory by using dust spray, larva dipping, leaf dipping, and solution spray methods. Dust treatment showed a more highly significant effect than the other three treatments. The mortality percentage increased up to 58% and 85% at 24 and 72 h after treatment, respectively, when nanosilica was applied at a rate of 1 mg cm^?2. In all four bioassays, mortality rate increased with both increased time after nanosilica exposure and increased concentration. Light microscopy and scanning electron microscopy images showed that larval death was due to desiccation, body wall abrasion, and spiracle blockage. These results suggested that nanosilica can be an alternative to conventional pesticides if dust formulation would be properly used.