4种典型纳米材料对小鼠胚胎成纤维细胞毒性的初步研究

为探讨不同种类纳米材料对原代培养小鼠胚胎成纤维细胞(Mouse embryo fibroblasts,MEF)的毒性效应及作用机制,选择4种典型的纳米材料(纳米碳、单壁碳纳米管、纳米氧化锌、纳米二氧化硅)制备颗粒悬液,设立5个剂量组(5、10、20、50、100μg·mL-1)对BALB/c小鼠MEF细胞进行24、48、72h染毒培养,利用细胞形态学观察和噻唑蓝实验(MTT比色法)检测上述4种纳米材料对MEF细胞活性的影响,同时,测定染毒24h后细胞培养液上清中乳酸脱氢酶(LDH)活性以探讨纳米颗粒对细胞膜完整性的影响.结果显示:1)4种纳米材料均能明显影响MEF细胞的生长形态.染毒24h后,MEF细胞发生不同程度的回缩变形,细胞间隙增大,排列稀疏,胞内颗粒物增多,细胞透明度下降.2)纳米碳、纳米氧化锌、纳米二氧化硅对MEF细胞增殖的抑制作用和对细胞膜完整性的损伤作用均随染毒剂量的升高而增强,具有明显的剂量-效应关系,其半数致死浓度(24h-IC50)分别为21.85、21.94、461.10μg·mL-1;碳纳米管组的剂量-效应之间不呈对数线性关系,未能得出其24h-IC50.3)在不同染毒剂量水平上,4种纳米材料的毒性对比差异显著:低剂量水平上纳米碳与碳纳米管的毒性强于纳米氧化锌和纳米二氧化硅,随着剂量的升高纳米氧化锌的细胞毒性升高最为显著.结果提示,纳米材料能够对MEF细胞造成毒性损伤,破坏细胞膜的完整性可能只是作用途径之一;纳米材料的毒性可能受粒径、形状、化学组成等许多因素的影响.     

Preconcentration of cadmium and copper ions on magnetic core–shell nanoparticles for determination by flame atomic absorption

Magnetic core–shell nanoparticles modified by (3-aminopropyl) trimethoxy silane were prepared and used as adsorbent for the extraction and preconcentration of cadmium and copper ions. The ions were desorbed with nitric acid followed by determination with flame atomic absorption spectrometry. The extraction conditions were investigated systematically. The method was applied for the determination of Cd(II) and Cu(II) ions in different water samples. The accuracy was also evaluated through analysis of certified reference material.     

Effect of two TiO2 nanoparticles on the growth of unicellular green algae using the OECD 201 test guideline: influence of the exposure system

This work aimed at assessing the influence of different exposure systems to perform the commonly used OECD 201 freshwater algal growth inhibition test in the context of nanoparticles hazard assessment. Two distinct TiO₂ nanoparticles were considered and three different exposure systems were investigated: Erlenmeyers flasks and 24-well microplates (both using an orbital shake system), and an alternative system using cylindrical vials and magnetic stirring. All three systems are in accordance with the OECD 201 test guideline recommendations. We concluded that the exposure systems applied to achieve the test can substantially affect the ecotoxicological results and the subsequent calculated ECx. The selected systems influenced both the interaction between algal cells and TiO₂ nanoparticles as well as the growth inhibition recorded. Disparities in ecotoxicity relative to the TiO₂ nanoparticles tested were also observed and are finally discussed.     

不同老化时间的TiO_2纳米颗粒对玉米生长的影响

为探讨老化时间对TiO_2纳米颗粒(nanoparticles,NPs)生物有效性的影响,研究了不同老化时间的Ti O_2NPs(0~120 d)对玉米幼苗生长的影响、在玉米体内的吸收及其在植株不同部位的存在位点等。研究发现,不同浓度的TiO_2NPs(1 000 mg·kg~(-1)和2 000 mg·kg~(-1))加入到土壤中,对玉米幼苗干鲜重没有明显的影响,但老化时间小于60 d时,对玉米幼苗株高有一定的抑制效应,老化60 d之后,随着老化时间的继续延长,毒性逐渐降低,最后趋于稳定。老化60 d时,TiO_2NPs处理的玉米幼苗根冠增大,玉米幼苗体内产生H2O_2的累积。在Ti O_2老化土壤中生长的玉米幼苗根系和地上部均有Ti的累积,1 000 mg·kg~(-1)的TiO_2NPs在玉米幼苗根部的生物累积系数达到35.4%,在地上部为13.6%,在玉米植株体内的转运系数为0.38;通过TEM观察,TiO_2NPs可以进入到玉米幼苗体内,并存在于根细胞的细胞质和叶绿体膜上,在叶片细胞的液泡和细胞核中也发现有TiO_2NPs的存在。上述研究结果为客观评价TiO_2NPs的生态风险提供了有用信息。     

Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption

In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds (vinyl polychlorides including trichloroethylene (TCE), tetrachloroethylene (PCE), and alkyl polychlorides including 1,1,1-trichloroethane (1,1,1-TCA), and 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA)) to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, k_SA, showed a systematic dependence on the electronic structure (the density of states at the Fermi level) of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first (weakest) dissociated C-Cl bond, suggesting that C-Cl bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydrodechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular (non-dissociative) adsorption on the noble metals rather than with the first C-Cl bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.     

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.