Inhibition of thrombin by functionalized C60 nanoparticles revealed via in vitro assays and in silico studies

The studies on the human toxicity of nanoparticles (NPs) are far behind the rapid development of engineered functionalized NPs. Fullerene has been widely used as drug carrier skeleton due to its reported low risk. However, different from other kinds of NPs, fullerene-based NPs (C₆₀ NPs) have been found to have an anticoagulation effect, although the potential target is still unknown. In the study, both experimental and computational methods were adopted to gain mechanistic insight into the modulation of thrombin activity by nine kinds of C₆₀ NPs with diverse surface chemistry properties. In vitro enzyme activity assays showed that all tested surface-modified C₆₀ NPs exhibited thrombin inhibition ability. Kinetic studies coupled with competitive testing using 3 known inhibitors indicated that six of the C₆₀ NPs, of greater hydrophobicity and hydrogen bond (HB) donor acidity or acceptor basicity, acted as competitive inhibitors of thrombin by directly interacting with the active site of thrombin. A simple quantitative nanostructure-activity relationship model relating the surface substituent properties to the inhibition potential was then established for the six competitive inhibitors. Molecular docking analysis revealed that the intermolecular HB interactions were important for the specific binding of C₆₀ NPs to the active site canyon, while the additional stability provided by the surface groups through van der Waals interaction also play a key role in the thrombin binding affinity of the NPs. Our results suggest that thrombin is a possible target of the surface-functionalized C₆₀ NPs relevant to their anticoagulation effect.     

珠江广州河段及其邻近河流表层沉积物中烷基酚的污染状况

为确定珠江广州河段及其邻近河流水体沉积物中烷基酚的时空分布状况,对该河段表层沉积物采样并应用气相色谱-质谱单离子扫描模式进行了烷基酚(APs)含量分析。结果表明壬基酚(NP)和辛基酚(OP)在样品中均有检出,其含量(以干质量计)范围分别在36.04～24694.10ng·g-1之间(中值为3717.52ng·g-1)和0.36～498.54ng·g-1之间(中值为21.10ng·g-1);珠江广州河段整体含量明显高于其邻近支流各采样点。所研究的表层沉积物样品中烷基酚含量普遍高于世界上其它都市和工业中心附近地区的污染水平,其中壬基酚含量均低于对摇蚊属昆虫(Chironomus riparius)的10d半致死浓度(LC50),但两个含量最高值均已与壬基酚对小虾(shrimp)的亚急性毒性最低效应浓度(LOEC)相接近,且大部分样品中的辛基酚含量都超过了对淡水螺(Potamopyrgus antipodarum)的8周最低效应浓度值(LOEC)标准。因此,烷基酚对该区生物造成的生态风险是一个必须加以认真对待的问题。     

黄河(兰州段)水环境中壬基酚及壬基酚聚氧乙烯醚污染的初步研究

对黄河(兰州段)4个排污点的水样和6个断面各个介质(包括水体、悬浮颗粒物和沉积物)中壬基酚(NP)及壬基酚聚氧乙烯醚(NPnEO)的污染调查结果表明,4个排污点水样中分别含有浓度不等的NP,NPnEO(n=1—11);6个断面采样点中,大分子的NPnEO(n>2)在各个介质中均未检出,水样中NP在0.24—2.10μg·l-1之间,NP1EO在0.060-0.35μg·l-1之间,NP2EO在0.039—0.26μg·l-1之间,说明NPnEO在黄河水体发生了有效降解,但是NPnEO小分子降解产物,特别是NP,持久性加强,在不同断面检测到不同程度的污染;在悬浮颗粒物和沉积物中也检测到了相应的NP,NP1lEO和NP2EO,其浓度均大于水体,而悬浮颗粒物对NP,NP1EO和NP2EO的富集大于沉积物对它们的富集.     

异养硝化细菌Acinetobacter junii NP1的同步脱氮除磷特性及动力学分析

针对传统生物脱氮除磷过程存在工艺流程复杂、抗冲击负荷能力差、基建与运行费用高等问题,以具有高效脱氮除磷功能的异养硝化细菌Acinetobacter junii NP1为研究对象,开展其同步脱氮除磷性能、影响因子及动力学分析.结果表明,菌株NP1具有高效的异养硝化能力,氨氮最大去除率达99. 12%,反应过程只有少量的硝化中间产物积累,并且能够耐受较高的氨氮负荷.菌株NP1同时具有良好的好氧反硝化特性,能够利用亚硝酸盐和硝酸盐进行生长代谢,最大去除率分别为91. 40%和95. 10%.此外,菌株NP1异养硝化过程还伴随着同步的聚磷作用,适当的氮磷比有利于氮磷的同步去除,当氮磷比为5∶1时,最大氨氮和磷酸盐去除率分别为99. 21%和88. 35%.菌株NP1生长特性符合Logistic模型(R~2 0. 99),氮素和磷酸盐降解过程则与修饰的Compertz模型相匹配(R~2 0. 99),拟合所得氮和磷酸盐最大转化速率R_m为:氨氮硝氮亚硝氮,迟滞时间t_0为:硝氮亚硝氮氨氮.通过基质降解动力学以及氮磷去除率分析,最佳条件是碳源为琥珀酸钠、C/N=10、T=30℃以及r=160 r·min~(-1).     

藻类有机质的组成结构对菲和壬基酚生物吸附的影响

对不同来源藻及其有机级分进行元素分析,利用高级核磁共振技术(multi/CP13C NMR)来准确地定量其有机官能团,并研究它们对菲和壬基酚的生物吸附行为和机理。结果表明游离脂和非水解有机碳级分对菲和壬基酚有最高的吸附能力,其吸附容量与脂肪结构呈极显著的正相关,而与极性官能团呈极显著的负相关;而且对壬基酚的吸附容量都大于对菲的吸附容量,可以用专性作用(如π-π键作用和氢键作用)来解释。     

1-硝基芘和多环芳烃联合致突变性的研究

测定了１－硝基芘（１－ＮＰ）和其它（硝基一）多环芳烃对Ａ试验的６个菌株（ＴＡ９８，ＴＡ１００，ＹＧ１０２１，ＹＧ１０２４，ＹＧ１０２６，ＹＧ１０２９）的单一和联合致突变性，１，６－二硝基芘（１．６ＤＮＰ）、１－硝基芘（１－ＮＰ）和２－硝基坊（２－ＮＦ）所单一致突变性都为ＹＧ１０２４，ＹＧ１０２１，ＴＡ９８，ＹＧ１０２６，ＹＧ１０２９，ＴＡ１００，地２－ＮＦ的敏感性稍有差别，联合致突变性实验结果表明     

Pollution of NPEOs in four municipal sewage treatment plants in the north of China

The concentration and distribution of nonylphenol polyethoxylates (NPEOs represents the mixture, and NPnEO represents the monomer) and its metabolites in the influent and effluent of four municipal sewage treatment plants (STPs) in the north of China were measured. Moreover, the concentration and distribution of the above chemicals in the sludge of two STPs were also determined, and the transfer and fate of NPEOs in the sewage treatment process were discussed primarily by analyzing the distribution of the products in the effluent and the sludge. The results showed that NPEOs and its metabolites existed in all the samples of the influent, effluent, and sludge. NPEOs were degraded in the sewage treatment process with the removal efficiency in the range of 23.38%–77.11%, or an average of 52.86%. However, the large analogs of NPnEO were only degraded to small ones, whose degradation rate was rather slow, and consequently the degradation was not complete. Hence, the concentrations of some small metabolites, such as nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) were elevated in the effluent. These small metabolites are more toxic than the large NPnEO analogs, and some of them were reported to exhibit environmental endocrine disrupting activity. From this point of view, the process of sewage treatment does not reduce but elevate the risk of NPEOs, which becomes the main source of these small NPnEO in the environment. The sludge exhibited good adsorption ability for NPEOs, especially for the small analogs, which led to the high level of NPEOs in the sludge. Hence, reasonable disposal of the surplus sludge to avoid re-pollution is very important. Translated from Research of Environmental Sciences, 2006, 19(3): 61–66 [译自: 环境科学研究]     

纳米CuO在水体环境中的转化行为及其对大型溞的毒性效应

为探究纳米CuO颗粒（CuO NP）在水体中的环境暴露风险,考察了腐殖酸（SRHA）和酸根离子对CuO NP转化行为的影响,探讨了CuO NP在不同条件下转化对大型溞的毒性效应差异.结果表明,与单独水体中CuO NP的转化行为相比,H₂PO₄^-显著促进了CuO NP释放Cu²⁺,Cl^-、NO₃^-、SO₄^2-对CuO NP的转化行为没有显著影响,而CO₃^2-、HCO₃^-、PO₄^3-、HPO₄^2-抑制了CuO NP中Cu²⁺的释放;SRHA显著促进了CuO NP释放Cu²⁺,但HCO₃^-、PO₄^3-的存在可以明显抑制SRHA促进CuO NP中Cu²⁺释放的进程.CuO NP在单独水体中,以及在Cl^-、PO₄^3-和SRHA+PO₄^3-存在的水体中转化后对大型溞的致死中浓度为16~32 mg·L^-1,而在SRHA与SRHA+Cl^-存在的水体中转化后对大型溞的致死中浓度分别降到0.8和2.5 mg·L^-1,说明SRHA促进了CuO NP释放Cu²⁺,提高了CuO NP颗粒分散性,使其易于被大型溞体内细胞组织摄取,增加了CuO NP对大型溞的毒性效应,因此,环境转化对CuO NP的环境暴露风险有重要影响.     

Organic Contaminants from Sewage Sludge Applied to Agricultural Soils. False Alarm Regarding Possible Problems for Food Safety? (8 pp)

Goal, Scope and Background Sewage sludge produced in wastewater treatment contains large amounts of organic matter and nutrients and could, therefore, be suitable as fertiliser. However, with the sludge, besides heavy metals and pathogenic bacteria, a variety of organic contaminants can be added to agricultural fields. Whether the organic contaminants from the sludge can have adverse effects on human health and wildlife if these compounds enter the food chain or groundwater still remains a point of controversial discussion. Main Features This paper presents an overview on the present situation in Europe and a summary of some recent results on the possible uptake of organic contaminants by crops after addition to agricultural fields by sewage sludge. Results Greenhouse experiments and field trials were performed to study the degradation and uptake of organic micro-contaminants in sludge-amended agricultural soil in crops, such as barley and carrots grown in agricultural soil amended with anaerobically-treated sewage sludge from a wastewater treatment plant, but studies hitherto have revealed no immediate risks. Common sludge contaminants such as linear alkylbenzene sulphonates (LAS), nonylphenol ethoxylates (NPE), polycyclic aromatic hydrocarbons (PAH), bis(diethylhexyl) phthalate (DEHP), showed neither accumulation in soil nor uptake in plants. Discussion It is assumed that the annual amount of sewage sludge produced in Europe will increase in the future, mainly due to larger amounts of high quality drinking water needed by an increasing population and due to increasing demands for cleaner sewage water. Application of sewage sludge to agricultural soils is sustainable and economical due to nutrient cycling and disposal of sewage sludge. However, this solution also involves risks with respect to the occurrence of organic contaminants and other potentially harmful contents such as pathogens and heavy metals present in the sludge. There have been concerns that organic contaminants may accumulate in the soil, be taken up by plants and thereby transferred to humans via the food chain. Results obtained so far revealed, however, no immediate risk of accumulation of common organic sludge contaminants in soil or uptake in plants when applying sewage sludge to agricultural soil. With very high dosages of sewage sludge, there may be a risk for accumulation of very apolar contaminants, such as DEHP, to the soil. Conclusions Any conclusions on the safe use of sewage sludge in agriculture have to be drawn carefully, as the studies performed until now have been limited. Further studies are required, and before final statements can be drawn, it is imminent to study a larger variety of common crops and the effect sewage sludge application may have on a possible accumulation of organic contaminants in the crops. Furthermore, a larger variety of organic contaminants need to be studied and special focus should be given to contaminants newly introduced into the environment. Besides investigating possible plant uptake of organic contaminants, the fate of these compounds in soil after sludge application need to be monitored too. Here, special attention has to begiven to studies on degradation and the formation of degradation products, to weathering and to leaching effects on groundwater, to the application of different crops on the same field (crop rotation), to the use of full-width tillage and strip tillage, and to long term application of sewage sludge on the soil. Recommendations and Perspectives There are environmental, political as well as economical incentives to increase the agricultural application of sludge. However, such usage should be performed with care as there are also ways in which sludge fertilisation could harm the environment and human health. Recently, a new European COST Action (859) has been established covering the field of food safety and improved food quality. Part of the Action is dealing with the application of sewage sludge in agriculture. Before any political and economical measures can be taken, the pros and cons have to be sufficiently investigated on a scientific level first. ESS-Submission Editor: Prof. Elena Maestri (elena.maestri@unipr.it)     

壬基酚对胶州湾典型微藻的毒性效应

以胶州湾常见优势藻种中肋骨条藻(Skeletonema costatum)和旋链角毛藻(Chaetoceros curvisetus)为受试生物,考察了壬基酚(NP)对两种海洋微藻的急性毒性效应,同时以超氧化歧化酶(SOD)活性和丙二醛(MDA)含量为指标,研究了两种海洋微藻细胞内抗氧化系统对NP氧化胁迫的响应。结果表明,NP对中肋骨条藻和旋链角毛藻生长抑制的96 h-EC50分别为0.13 mg/L和0.22 mg/L,中肋骨条藻对NP的毒性更为敏感。当中肋骨条藻培养体系中NP浓度在0.04～0.16 mg/L和旋链角毛藻培养体系中NP浓度在0.05～0.20 mg/L时,两种海洋微藻体内SOD活性均呈现出先诱导上升后抑制降低的变化趋势,MDA含量则随NP浓度的增大而增大;而在低浓度NP(<0.05 mg/L)胁迫下,96 h实验周期内,两种微藻细胞内SOD活性和MDA含量与不添加NP的对照组相比无显著差异(P>0.05),表明低浓度的NP胁迫下微藻体内诱导产生的抗氧化酶能够及时清除活性氧自由基,防止细胞受到损伤。暴露实验72 h后,两种微藻细胞内的SOD活性和MDA含量与NP作用浓度呈现显著的浓度-效应关系,这表明微藻细胞内SOD活性和MDA含量可以作为生物标志物用于近海水体中NP生态风险评价。