有序介孔碳载金/L-赖氨酸/纳米金修饰电极的制备及其对邻苯二酚、对苯二酚的检测响应研究

通过化学还原的方法合成有序介孔碳负载纳米金粒子,并构筑有序介孔碳载金/L-赖氨酸/纳米金复合膜修饰玻碳电极;利用扫描电镜观察介孔碳和介孔碳复合膜的微观结构,并用循环伏安法、电化学阻抗谱表征自组装电极的过程.在此基础上用差分脉冲伏安法研究对苯二酚和邻苯二酚混合物在该电极上的电催化氧化,研制了一种基于有序介孔碳载金/L-赖氨酸/纳米金复合膜修饰电极分别检测对苯二酚和邻苯二酚的传感器.在最优的实验条件下,该传感器在对苯二酚和邻苯二酚浓度为1×10-6～8×10-4mol·L-1的范围内具有良好的线性关系,检出限分别为3×10-7mol·L-1、7×10-7mol·L-1.     

Photocatalytic activity of TiO2 containing anatase nanoparticles and rutile nanoflower structure consisting of nanorods

A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.     

名山河流域黄壤无机纳米微粒对钙的吸附解吸特征

以名山河流域老冲积黄壤无机纳米微粒为对象,从纳米尺度分析钙的吸附解吸机制对土壤养分状况的影响,并采用等温吸附法和静态解吸法,比较不同土地利用方式下钙的吸附解吸特征差异.结果表明:1)不同土地利用方式土壤无机纳米微粒对钙的吸附解吸量均随钙质量浓度增加而增加,在低质量浓度范围内吸附量增加较快,在高质量浓度范围内增加趋缓,不同土地利用方式下钙的吸附能力从高到低为水田(2 580.69 mg/kg)、茶园(2 452.30 mg/kg)、旱地(1 935.10mg/ks)、林地(1 867.36mg/kg)、果园(1 520.65 mg/kg),土壤无机纳米微粒对钙的解吸率从大到小为果园、林地、旱地、茶园、水田,且解吸率随外加钙质量浓度增加而增大;2)去除土壤组分(有机质、游离氧化铁)后,无机纳米微粒对钙的吸附量及解吸量均有所增加,5种土地利用方式吸附增加量从大到小为水田、旱地、茶园、林地、果园;3)去除土壤组分前后,无机纳米微粒对钙的等温吸附均以Freundlich方程拟合效果最佳,相关系数在0.954 5～0.989 0,达到极显著水平,Langmuir方程与Temkin方程拟合效果不佳.研究表明,钙离子以非专性吸附为主,专性吸附为辅,有机质和游离氧化铁的存在会阻碍土壤对钙的吸附及解吸.     

Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching

Acid mine water from in situ chemical leaching of uranium (Straz pod Ralskem, Czech Republic) was treated in laboratory scale experiments by zero-valent iron nanoparticles (nZVI). For the first time, nZVI were applied for the treatment of the real acid water system containing the miscellaneous mixture of pollutants, where the various removal mechanisms occur simultaneously. Toxicity of the treated saline acid water is caused by major contaminants represented by aluminum and sulphates in a high concentration, as well as by microcontaminants like As, Be, Cd, Cr, Cu, Ni, U, V, and Zn. Laboratory batch experiments proved a significant decrease in concentrations of all the monitored pollutants due to an increase in pH and a decrease in oxidation-reduction potential related to an application of nZVI. The assumed mechanisms of contaminants removal include precipitation of cations in a lower oxidation state, precipitation caused by a simple pH increase and co-precipitation with the formed iron oxyhydroxides. The possibility to control the reaction kinetics through the nature of the surface stabilizing shell (polymer vs. FeO nanolayer) is discussed as an important practical aspect.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Transport of copper as affected by titania nanoparticles in soil columns

The effects of TiO₂ nanoparticles on the transport of Cu through four different soil columns were studied. For two soils (HB and DX), TiO₂ nanoparticles acted as a Cu carrier and facilitated the transport of Cu. For a third soil (BJ) TiO₂ nanoparticles also facilitated Cu transport but to a much lesser degree, but for a fourth soil (HLJ) TiO₂ nanoparticles retarded the transport of Cu. Linear correlation analysis indicated that soil properties rather than sorption capacities for Cu primary governed whether TiO₂ nanoparticles-facilitated Cu transport. The TiO₂-associated Cu of outflow in the Cu-contaminated soil columns was significantly positively correlated with soil pH and negatively correlated with CEC and DOC. During passage through the soil columns 46.6-99.9% of Cu initially adsorbed onto TiO₂ could be “stripped” from nanoparticles depending on soil, where Cu desorption from TiO₂ nanoparticles increased with decreasing flow velocity and soil pH.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.     

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.     

金属离子诱导Trichoderma sp.WL-Go合成纳米金特性研究

生物法合成纳米金是一种环境友好且经济高效的合成途径,受到广泛关注.普遍认为微生物合成纳米金是通过胞外分泌生物大分子而实现的一种自发脱毒过程.同时,相关研究表明低浓度的重金属离子对菌株胞外酶的活性会产生一定的影响,进而会对菌株合成纳米金的能力产生影响.基于此,本研究选择一株前期筛选得到的真菌Trichoderma sp. WL-Go,探究不同金属离子诱导菌株对其合成的纳米金特性的影响.结果表明,经Co~(2+)、Al~(3+)、Zn~(2+)、Sn~(2+)、Ni~(2+)等金属离子诱导后,菌株WL-Go合成纳米金的能力均有所提升,而Pb~(2+)、Cu~(2+)、Fe~(3+)与对照组相比,其合成的纳米金浓度及转化率都无明显变化.此外,Co~(2+)诱导菌株合成的纳米金呈现肉眼可见的团簇状,发生明显的团聚现象.本实验还考察了生物合成纳米金对4-硝基苯酚还原的催化特性,结果表明,Sn~(2+)和Pb~(2+)的诱导使菌株WL-Go合成的纳米金催化速率得到明显提升,而其他金属离子均有所抑制.最后选取革兰氏阳性菌Arthrobacter sp. W1和革兰氏阴性菌Escherichia coli BL21 (DE3)验证了不同金属离子诱导后合成的纳米金均具有良好的生物相容性.综上,本研究为对于拓宽纳米金的工业化应用前景有着重要意义.     

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.