Application of Cellulose Microfibrils in Polymer Nanocomposites

Cellulose microfibrils obtained by the acid hydrolysis of cellulose fibers were added at low concentrations (2–10% w/w) to polymer gels and films as reinforcing agents. Significant changes in mechanical properties, especially maximum load and tensile strength, were obtained for fibrils derived from several cellulosic sources, including cotton, softwood, and bacterial cellulose. For extruded starch plastics, the addition of cotton-derived microfibrils at 10.3% (w/w) concentration increased Young’s modulus by 5-fold relative to a control sample with no cellulose reinforcement. Preliminary data suggests that shear alignment significantly improves tensile strength. Addition of microfibrils does not always change mechanical properties in a predictable direction. Whereas tensile strength and modulus were shown to increase during addition of microfibrils to an extruded starch thermoplastic and a cast latex film, these parameters decreased when microfibrils were added to a starch–pectin blend, implying that complex interactions are involved in the application of these reinforcing agents.     

Ecotoxic Effect of Photocatalytic Active Nanoparticles (TiO2) on Algae and Daphnids (8 pp)

Background, Aim and Scope Due to their large potential for manifold applications, the use of nanoparticles is of increasing importance. As large amounts of nanoparticles may reach the environment voluntarily or by accident, attention should be paid on the potential impacts on the environment. First studies on potential environmental effects of photocatalytic TiO2 nanoparticles have been performed on the basis of widely accepted, standardized test systems which originally had been developed for the characterization of chemicals. The methods were adapted to the special requirements of testing photocatalytic nanoparticles. Materials and Methods: Suspensions of two different nanoparticles were illuminated to induce their photocatalytic activity. For testing, the growth inhibition test with the green alga Desmodesmus subspicatus and the immobilization test with the daphnid Daphnia magna were selected and performed following the relevant guidelines (algae: ISO 8692, OECD 201, DIN 38412-33; daphnids: ISO 6341, OECD 202, DIN 38412-30). The guidelines were adapted to meet the special requirements for testing photocatalytic nanoparticles. Results: The results indicate that it is principally possible to determine the ecotoxicity of nanoparticles. It was shown that nanoparticles may have ecotoxicological effects which depend on the nature of the particles. Both products tested differ in their toxicity. Product 1 shows a clear concentration-effect curve in the test with algae (EC50: 44 mg/L). It could be proven that the observed toxicity was not caused by accompanying contaminants, since the toxic effect was comparable for the cleaned and the commercially available product. For product 2, no toxic effects were determined (maximum concentration: 50 mg/L). In the tests with daphnids, toxicity was observed for both products, although the concentration effect-curves were less pronounced. The two products differed in their toxicity; moreover, there was a difference in the toxicity of illuminated and non-illuminated products. Discussion: Both products differ in size and crystalline form, so that these parameters are assumed to contribute to the different toxicities. The concentration-effect curves for daphnids, which are less-pronounced than the curves obtained for algae, may be due to the different test organisms and/or the differing test designs. The increased toxicity of pre-illuminated particles in the tests with daphnids demonstrates that the photocatalytic activity of nanoparticles lasts for a period of time. Conclusions: The following conclusions can be drawn from the test results: (I) It is principally possible to determine the ecotoxicity of (photocatalytic) nanoparticles. Therefore, they can be assessed using methods comparable to the procedures applied for assessing soluble chemicals. - (II) Nanoparticles may exert ecotoxicological effects, which depend on the specific nanoparticle. - (III) Comparable to traditional chemicals, the ecotoxicity depends on the test organisms and their physiology. - (IV) The photocatalytic activity of nanoparticles lasts for a relevant period of time. Therefore, pre-illumination may be sufficient to detect a photocatalytic activity even by using test organisms which are not suitable for application in the pre-illumination-phase. Recommendations and Perspectives: First results are presented which indicate that the topic 'ecotoxicity and environmental effects of nanoparticles' should not be neglected. In testing photocatalytic nanoparticles, there are still many topics that need clarification or improvement, such as the cause for an observed toxicity, the improvement of the test design, the elaboration of a test battery and an assessment strategy. On the basis of optimized test systems, it will be possible to test nanoparticles systematically. If a potential risk by specific photocatalytic particles is known, a risk-benefit analysis can be performed and, if required, risk reducing measures can be taken.     

凝胶模板燃烧法制备纳米ZnO及其光催化性能

以硝酸锌为原料,明胶为模板分散剂,采用凝胶模板燃烧法制备纳米ZnO.利用TG-DTA,FT-IR,XRD,TEM和HPLC等手段对制备过程、样品的结构和性能进行了研究,探讨燃料及氧化剂的比例以及热处理温度的变化对产物粒径和光催化活性的影响.结果表明:产物粒子形状为球形,属六方晶系结构且无杂相.以染料罗丹明B溶液为目标降解物,1h的降解率为99.9%,最佳光催化剂的合成条件为:燃料与氧化剂的比例为0.84,400℃热处理3h.     

海洋酸化与重金属、有机污染物和人工纳米颗粒的联合毒性效应研究进展

由于大量人类活动的影响,大气CO_2浓度持续增加,其中约1/3被海洋吸收,导致表层海水pH值降低和碳酸盐平衡体系波动,即"海洋酸化"现象。污染物的海洋环境效应一直是全球环境科学领域研究的热点。在实际环境中,海洋酸化往往与污染物共同存在并作用于海洋生态系统,且海洋酸化极有可能改变污染物的海洋环境行为从而影响其毒性效应。但现有研究大多针对海洋酸化或者污染物单独作用下的毒性效应展开,对海洋酸化与污染物的联合毒性效应的研究不足、亟待加强。为此,综述了近年来海洋酸化与典型污染物(重金属、有机污染物)及新型污染物(人工纳米颗粒)的相关文献,重点阐述了海洋酸化对污染物环境行为的影响和海洋酸化与污染物对海洋生物的联合毒性效应,指出当前的研究不足,并对未来的研究方向进行了展望。     

H2O2 formation from photocatalytic processes at the ZnO/water interface

The paper focuses on the production of H2O2 by photocatalysis over ZnO in an aerated aqueous phase. The presence of different reductants that increase the H2O2 production in the aqueous phase is analysed; particular attention is paid to nitrite, which has been shown to be the reductant that produces the most significant increments in the H2O2 production. The photocatalytic anodic decomposition of ZnO in the presence of the different reductants is also investigated. From the results obtained, the relevance of the ZnO photocatalysis in the formation of environmental hydrogen peroxide is estimated.     

Cu/ZnO-RGO的抗菌性能及应用

采用溶胶-凝胶法制备铜锌复合氧化物（Cu/ZnO）,并将Cu/ZnO纳米粒子负载到还原氧化石墨烯（RGO）表面制备Cu/ZnO-RGO复合材料.对Cu/ZnO-RGO复合材料进行表征分析及抗菌性能考察,结果表明,Cu/ZnO纳米粒子成功负载在RGO表面,负载前后Cu/ZnO纳米粒子形态不发生改变,复合材料纯度较高.Cu/ZnO-RGO复合材料对大肠杆菌与金黄色葡萄球菌均有着优异的抗菌性能,可以破坏细菌细胞膜,导致细菌内容物流出,延长细菌进入对数生长期所需的时间.当RGO质量分数为15%?Cu/ZnO-RGO复合材料使用量为120μg/mL时,在循环冷却水系统中作用2h即可拥有96.76%的抗菌率.     

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.     

二氧化钛纳米颗粒对湖滨沼泽土壤氮矿化的影响

二氧化钛纳米颗粒（TiO₂NPs）的广泛应用使其环境释放量不断增加,从而影响到土壤氮的转化过程.然而,目前关于TiO₂NPs对湖滨沼泽土壤氮矿化的影响机制尚不明确.因此,本研究以典型沼泽土壤为研究对象,通过室内培养实验研究不同剂量TiO₂NPs处理（0 mg·kg^-1（CK）、10 mg·kg^-1（A10）、100 mg·kg^-1（A100）、250 mg·kg^-1（A250）、1000 mg·kg^-1（A1000））对土壤理化性质、酶活性和氮矿化过程的影响,探讨TiO₂NPs输入对土壤氮矿化过程影响的内在机制.结果表明：①不同剂量TiO₂NPs处理显著降低了土壤pH和总有机碳（TOC）含量（p<0.05）,A100、A250和A1000处理显著降低了硝态氮（NO₃^--N）含量（p<0.05）.②A250和A1000处理显著抑制了过氧化氢酶活性（p<0.05）;培养7 d,不同剂量TiO₂NPs处理均显著促进了脲酶活性（p<0.05）,抑制了脱氢酶活性（p<0.05）;随着培养时间延长,TiO₂NPs处理对脲酶和脱氢酶活性的抑制作用逐渐减弱,表明TiO₂NPs的负面作用会随时间减弱.③不同剂量TiO₂NPs处理对氨化速率没有显著影响（p>0.05）,A250、A1000处理对硝化和矿化速率有显著抑制作用（p<0.01）.④土壤氮矿化速率与土壤pH、总磷（TP）、NO₃^--N含量呈显著正相关,与脲酶、过氧化氢酶活性呈显著负相关.TiO₂NPs主要通过改变沼泽土壤NO₃^--N含量影响氮矿化过程.本研究可为湖滨湿地保护和TiO₂NPs环境风险评估提供理论依据.     

Comparative toxicity of silver nanoparticles and silver ions to Escherichia coli

With the increase in silver(Ag)-based products in our lives, it is essential to test the potential toxicity of silver nanoparticles(Ag NPs) and silver ions(Ag ions) on living organisms under various conditions. Here, we investigated the toxicity of Ag NPs with Ag ions to Escherichia coli K-12 strain under various conditions. We observed that both Ag NPs and Ag ions display antibacterial activities, and that Ag ions had higher toxicity to E. coli K-12 strain than Ag NPs under the same concentrations. To understand the toxicity of Ag NPs at a cellular level, reactive oxygen species(ROS) enzymes were detected for use as antioxidant enzymatic biomarkers. We have also studied the toxicity of Ag NPs and Ag ions under various coexistence conditions including: fixed total concentration, with a varied the ratio of Ag NPs to Ag ions; fixed the Ag NPs concentration and then increased the Ag ions concentration; fixed Ag ions concentration and then increasing the Ag NPs concentration.Exposure to Ag NPs and Ag ions clearly had synergistic toxicity; however, decreased toxicity(for a fixed Ag NPs concentration of 5 mg/L, after increasing the Ag ions concentration) to E. coli K-12 strain. Ag NPs and Ag ions in the presence of L-cysteine accelerated the bacterial cell growth rate, thereby reducing the bioavailability of Ag ions released from Ag NPs under the single and coexistence conditions. Further works are needed to consider this potential for Ag NPs and Ag ions toxicity across a range of environmental conditions.Environmental Significance Statement: As silver nanoparticles(Ag NPs)-based products are being broadly used in commercial industries, an ecotoxicological understanding of the Ag NPs being released into the environment should be further considered. Here, we investigate the comparative toxicity of Ag NPs and silver ions(Ag ions) to Escherichia coli K-12 strain, a representative ecotoxicological bioreporter. This study showed that toxicities of Ag NPs and Ag ions to E. coli K-12 strain display different relationships when existing individually or when coexisting, and in the presence of L-cysteine materials. These findings suggest that the toxicology research of nanomaterials should consider conditions when NPs coexist with and without their bioavailable ions.     

Application of nanoparticle tracking analysis for characterising the fate of engineered nanoparticles in sediment-water systems

Novel applications of nanotechnology may lead to the release of engineered nanoparticles (ENPs), which result in concerns over their potential environmental hazardous impact. It is essential for the research workers to be able to quantitatively characterise ENPs in the environment and subsequently to assist the risk assessment of the ENPs. This study hence explored the application of nanoparticle tracking system (NTA) to quantitatively describe the behaviour of the ENPs in natural sediment-water systems. The NTA allows the measurement of both particle number concentration (PNC) and particle size distribution (PSD) of the ENPs. The developed NTA method was applied to a range of gold and magnetite ENPs with a selection of surface properties. The results showed that the positively-charged ENPs interacted more strongly with the sediment than neutral and negatively-charged ENPs. It was also found that the citrate coated Au ENPs had a higher distribution percentage (53%) than 11-mercaptoundecanoic acid coated Au ENPs (20%) and citrate coated magnetite ENPs (21%). The principles of the electrostatic interactions between hard (and soft) acids and bases (HSAB) are used to explain such behaviours; the hard base coating (i.e. citrate ions) will interact more strongly with hard acid (i.e. magnetite) than soft acid (i.e. gold). The results indicate that NTA is a complementary method to existing approaches to characterise the fate and behaviour of ENPs in natural sediment.