Quantitative characterization of Cu binding potential of dissolved organic matter （DOM） in sediment from Taihu Lake using multiple techniques

Dissolved organic matter （DOM） plays an important role in heavy metal speciation and distribution in the aquatic environment especially for eutrophic lakes which have higher DOM concentration. Taihu Lake is the third largest freshwater and a high eutrophic lake in the downstream of the Yangtze River, China. In the lake, frequent breakout of algae blooms greatly increased the concentration of different organic matters in the lake sediment. In this study, sediment samples were collected from various part of Taihu Lake to explore the spatial difference in the binding potential of DOM with Cu. The titration experiment was adopted to quantitatively characterize the interaction between Cu（II） and DOM extracted from Taihu Lake sediments using ion selective electrode （ISE） and fluorescence quenching technology. The ISE results showed that the exogenous DOM had higher binding ability than endogenous DOM, and DOM derived from aquatic macrophytes had a higher binding ability than that derived from algae. The fluorescence quenching results indicated that humic substances played a key role in the complexation between DOM and Cu（II） in the lake. However, because of the frequent breakout of algae blooms, protein-like matters are also main component like hnmic matters in Taihu Lake. Therefore, the metals bound by protein-like substances should be caused concern as protein-like substances in DOM were unstable and they will release bound metal when decomposed.     

ATR-FTIR and XPS study on the structure of complexes formed upon the adsorption of simple organic acids on aluminum hydroxide

Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.     

三维荧光光谱法研究四环素与活性污泥EPS的相互作用

用三维荧光光谱仪研究了活性污泥EPS(Extracellular polymeric substances)和四环素的相互作用。活性污泥EPS中发现2种类蛋白荧光峰A(Ex/Em=225/340)和B(Ex/Em=280/338),其荧光强度随着盐酸四环素的加入而显著降低,峰A和盐酸四环素结合生成了不发荧光的物质,而峰B和盐酸四环素结合生成的物质在Ex/Em=295/416 nm处发荧光。峰A和峰B与盐酸四环素的相互作用适合用修正后的Stern-Volmer和Hill模型拟合,盐酸四环素和峰A的结合点位数、结合常数分别为1.33、7.02,大于和峰B的结合点位数和结合常数,说明盐酸四环素和荧光峰A的结合比较稳定。猝灭速率常数kq远远大于最大扩散碰撞猝灭速率常数(2.0×1010L(/mol.s)),表明峰A和峰B和盐酸四环素相互作用的荧光猝灭主要是静态猝灭过程。因此土壤和水环境中大量存在EPS会影响盐酸四环素在环境中的迁移转化。     

磁性共价有机框架的制备方法研究

磁性共价有机框架（magnetic covalent organic framework,MCOFs）是一种新型多孔结晶有机框架材料,由于其结合了磁性纳米颗粒和共价有机框架（covalent organic frameworks,COFs）的优点,具有比表面积大、热稳定性和化学稳定性良好、饱和磁化强度高等特点,能够快速实现污染物与溶液的分离,弥补了COFs难以分离和回收的缺点,因此在磁性固相萃取、生物检测、传感等方面具有巨大的潜在应用.然而关于MCOFs制备方法的文章鲜见报道,其制备方法根据磁性纳米颗粒与COFs不同的连接形式而不尽相同,根据2011—2019年关于MCOFs的重要文献,综述了目前MCOFs的制备方法,包括包覆法、单体聚合法及原位合成法等,指出了不同制备方法的优缺点,同时探讨了MCOFs今后的发展方向和潜在应用,希望能够为MCOFs研究提供理论依据.包覆法制备条件较温和,保存了磁性纳米颗粒的完整性,是最为广泛应用的一种策略方法;单体聚合法操作简单,但制备条件苛刻,可控性不强;原位合成法制备MCOFs更多依赖于单体聚合法制备的共价三嗪骨架,需要不断开发基于其他类型COFs的MCOFs制备条件.今后MCOFs的制备方法应从材料设计多样性、应用广泛性等方面进行考虑,并向有望实现大规模工业应用方面发展.      

共价三嗪骨架活化过一硫酸盐降解磺胺甲恶唑

通过微波合成技术制备磁性共价三嗪骨架材料（MCTF）.利用SEM、TEM和FTIR对其形貌特征和表面基团进行表征分析;测定分析其微观介孔结构与饱和磁化强度;并将合成的MCTF用于活化过一硫酸盐（PMS）降解磺胺甲恶唑（SMX）.研究了MCTF/PMS体系降解SMX的主要影响因素,包括MCTF投加量、PMS浓度、pH值、无机离子.研究表明：在MCTF投加量0.3g/L,PMS浓度1.50mmol/L,SMX初始浓度0.05mmol/L的室温条件下,30min内SMX的降解率可达100%.随pH值升高,SMX的降解率随之降低.SO₄^2-与HCO₃^-对SMX的降解具有抑制作用,Cl^-则具有双重作用.循环试验证明MCTF具有良好的重复利用性能.MCTF/PMS体系中降解SMX的活性物质为硫酸根自由基（SO₄^-·）和羟基自由基（·OH）,并主要在催化剂表面生成反应;通过UHPLC-MS/MS对SMX的降解途径与产物进行推测分析.     

PCDFs的Ah受体结合能力的定量结构效应关系

应用单苯环氯取代方法取G₁～G₁₀10个分子结构描述符,通过正向逐步线性回归方法构建对于Ah受体结合能力的定量结构-性质相关(QSAR)模型.与有关文献相比,此模型能更好地预测多氯代二苯并呋喃(PCDFs)竞争结合Ah受体logEC₅₀值,各自变量间不存在共线性.模型可以较好地反映PCDFs分子Ah受体结合能力与其分子氯取代位点之间的关系.     

诺氟沙星对海月水母螅状体Hsp70基因、GTP结合蛋白基因和氧化应激蛋白基因表达的影响

诺氟沙星(norfloxacin,NFLX)广泛应用于水产养殖中的鱼类细菌性疾病治疗。为探讨诺氟沙星对海洋生物的毒性作用,选择海月水母螅状体为受试生物,考察了不同浓度诺氟沙星和不同暴露时间对GTP结合蛋白(GTP binding protein)、氧化应激蛋白(oxidative stress protein)和热休克70 k Da蛋白(heat shock 70 k Da protein,Hsp70)表达量的影响。结果表明,NFLX对海月水母螅状体的48 h的半致死浓度(48 h-LC_(50))是415.1 mg·L~(-1),NFLX对海月水母螅状体的毒性属于低毒。随着NFLX浓度的升高和培养时间的延长,Hsp70基因在第7天浓度300 mg·L~(-1)时表达量受到显著性诱导(P0.05),较对照组升高9.1倍;GTP结合蛋白基因和氧化应激蛋白基因的表达量都呈现先急剧升高后降低的趋势。2个基因均在第1天受到显著性诱导(P0.05),分别在NFLX浓度100 mg·L~(-1)和300 mg·L~(-1)时表达量达到最大值,较对照组升高10.15倍和50.5倍。Hsp70基因、GTP结合蛋白基因和氧化应激蛋白基因在实验期间都对NFLX表现出较好的响应。     

石墨烯与抑癌基因p53 DNA片段相互作用的分子模拟与光谱学验证

石墨烯(graphene,G)及其衍生物由于具有独特的理化性质,被广泛应用于能源、生物医学等领域,但尚缺乏其对生物体和环境潜在危害的研究。采用分子动力学模拟并结合光谱学方法(紫外可见吸收光谱、紫外变温实验及荧光光谱),分析了石墨烯与抑癌基因p53启动子区DNA片段(p53-DNA)间的相互作用,并探讨了相关作用机制。石墨烯的部分芳香环与p53-DNA碱基的芳香环之间存在π-π堆积作用,两者可以通过嵌插作用进行结合,同时还通过沟槽作用进一步结合。光谱实验进一步证实,在石墨烯作用下,p53-DNA的熔点(Tm)值升高,EB-DNA体系发生静态荧光淬灭,说明石墨烯能与p53-DNA结合;同时,p53-DNA与石墨烯结合后在260 nm处的吸光度升高,说明石墨烯对p53-DNA的双螺旋结构具有一定的破坏作用。上述研究结果从分子水平上分析了石墨烯与p53-DNA间的相互作用机制,有助于进一步阐明石墨烯的毒性作用机理。