Transport of citrate and polymer coated gold nanoparticles (AuNPs) in porous media: Effect of surface property and Darcy velocity

With the release of nanoparticles(NPs) into the subsurface,it is imperative to better understand the fate and transport of NPs in porous media.Three types of stable AuNPs were used as model NPs to investigate the impact of surface coatings(type and coverage) and water velocity on the NP transport in a porous media(column studies).The NPs were electrostatic stabilized citrate AuNPs and sterically stabilized AuNPs with amphiphilic block co-polymer(PVA-COOH) in two particle/polymer ratios(weak vs.strong stabilization).The citrate AuNPs transport was sensitive to ionic changes in the mixing front of the plume,where destabilization occurred,and will therefore depend on the size/type of release.Blocking of deposition sites by aggregates was seen to facilitate transport,whereby a higher flow velocity(larger shadow zone) also resulted in better transport.The polymeric surface coating had great impact with steric repulsion as a main force contributing to the transport of NPs in the porous media.Sufficient polymer coating was crucial to obtain highly unfavorable attachment conditions(very low α) where the enhanced NP mobility was independent of the water velocity(comparable to solute tracer).Without sufficient steric stabilization,the transport and recovery was significantly reduced compared to the solute tracer,but increased with increasing water velocity.This highlights the importance of sufficient surface coating to achieve enhanced mobility,but also the increased risk of spreading to down-gradient receptors.For the(weakly) sterically stabilized NPs,the loss of polymer through ligand exchange with the porous media negates transport.     

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.      

小麦对纳米银的吸收及毒性响应

以纳米银（AgNPs）为研究对象,Ag⁺（AgNO₃）为对照,通过添加半胱氨酸（L-cysteine）探讨小麦对AgNPs的吸收累积和毒性响应.小麦幼苗于不同浓度的AgNPs悬浮液中培养4h后,根系出现氧化应激反应和细胞膜损伤,丙二醛（MDA）和过氧化氢酶（CAT）含量分别由对照组的（2.9±0.5）nmol/L/mgprot和（8.6±1.2）U/mgprot增加至（4.9±1.5）nmol/L/mgprot和（12.4±1.2）U/mgprot.半胱氨酸缓解了AgNO₃对小麦的毒性并使小麦对AgNO₃的吸收速率常数从（275.4±12.3）L/（kg×h）降低到（210.8±11.2）L/（kg×h）.然而,半胱氨酸并没有缓解AgNPs对小麦的毒性,且AgNPs的吸收速率常数没有显著性变化[（12.6±0.8）和（11.2±0.6）L/（kg×h）].这说明AgNPs对小麦的有效性和毒性不仅来源于其释放的Ag⁺,还来源于纳米颗粒本身.通过进一步计算AgNPs暴露液中不同形态Ag的吸收速率常数,发现Ag⁺吸收速率常数最高[（275.4±12.3）L/（kg×h）],Ag-cysteine络合物吸收速率常数次之[（210.8±11.2）L/（kg×h）],纳米颗粒吸收速率常数最低[1.6L/（kg×h）].实验中建立了吸收速率常数预测方程,该方程预测结果与实验观测结果一致,说明该方程能够较好地描述小麦吸收AgNPs的具体过程.     

纳米银与银离子对土壤微生物及酶活性的影响

为研究纳米银和银离子对土壤微生物的影响,采用土壤培养方式,对不同剂量纳米银(10、50、100 mg·kg~(-1))和银离子(1、5、10 mg·kg~(-1))暴露下黄褐土、砖红壤中可培养微生物数量及土壤酶活性(脲酶、荧光素二乙酸酯水解酶、蔗糖酶、过氧化氢酶)进行研究,并采用纯培养方法对纳米银和银离子暴露下的大肠杆菌(Escherichia coli)、金黄色葡萄球菌(Staphylococcus aureus)凋亡情况进行检测,对纳米银释放的银离子毒性进行评估。结果表明,随着纳米银剂量的增加,土壤可培养微生物数量显著减少,脲酶和过氧化氢酶活性降低,蔗糖酶、荧光素二乙酸酯水解酶(FDA酶)活性没有显著变化;银离子处理中微生物数量明显减少,但土壤酶活性被激活。10 mg·L~(-1)纳米银暴露1 h后大肠杆菌、金黄色葡萄球菌凋亡率、死亡率增高;随着培养时间的延长,纳米银缓慢释放银离子,并促进大肠杆菌的凋亡。综上分析,纳米银能够抑制土壤可培养微生物生长和酶活性,其中脲酶、过氧化氢酶对纳米银较为敏感,蔗糖酶、FDA酶受纳米银的影响较小;纳米银的毒性一方面是其本身的特异抗菌性,也有部分来自缓慢释放的银离子。     

Characterization of colloidal arsenic at two abandoned gold mine sites in Nova Scotia, Canada, using asymmetric flow-field flow fractionation-inductively coupled plasma mass spectrometry

Asymmetric flow-field flow fractionation-inductively-coupled plasma-mass spectrometry was used to determine whether colloidal arsenic(As) exists in soil pore water and soil extract samples at two arsenic-contaminated abandoned gold mines(Montague and Goldenville, Nova Scotia). Colloidal arsenic was found in 12 out of the 80 collected samples(= 15%), and was primarily associated with iron(Fe) in the encountered colloids. The molar Fe/As ratios indicate that the colloids in some samples appeared to be discrete iron–arsenic minerals, whereas in other samples, they were more consistent with As-rich iron(oxy)hydroxides. Up to three discrete size fractions of colloidal As were encountered in the samples, with mean colloid diameters between 6 and 14 nm. The pore water samples only contained one size fraction of As-bearing colloids(around 6 nm diameter), while larger As-bearing colloids were only encountered in soil extracts.     

Assessing the effect of different natural dissolved organic matters on the cytotoxicity of titanium dioxide nanoparticles with bacteria

Titanium dioxide nanoparticles(TiO_2 NPs) are among the most widely manufactured nanomaterials on a global scale. However, prudent and vigilant surveillance, incumbent upon the scientific community with the advent of new technologies, has revealed potentially undesirable effects of TiO_2 NPs on biological systems and the natural environment during their application and discharge. Such effects are likely best evaluated by first assessing the fate of the TiO_2 NPs in natural environments. In this study, the effects of terrestrial humic acid(HA) and tannic acid(TA), two major members of the collective:dissolved organic matter(DOM), on the cytotoxicity of TiO_2 NPs to Escherichia coli were investigated in the presence and absence of natural sunlight. Qualitative(transmission electron microscopy(TEM)) and quantitative(LC50) analyses were employed in this study. In addition, the production of reactive oxygen species(ROS) in the form of UOH was further assessed—as HA or TA increased the production of ROS decreased. The inhibition of bacterial viability in the light treatment groups, with respective treatment organics at concentrations of 10 ppm, was less in TA than in terrestrial HA. SAS was used to analyze the treatment effect of individual factors of light irradiation, DOM, and concentration of TiO_2 NPs.     

纳米氧化锌对EBPR系统的长期作用机制研究:从宏观到微观

研究了纳米氧化锌(ZnO NPs)对强化生物除磷(EBPR)系统的长期作用机制,系统分析了EBPR系统在ZnO NPs长期抑制下宏观运行性能与微观结构的变化.结果发现,当进水开始添加ZnO NPs后,系统沉降性能随之降低.厌氧释磷速率与好氧吸磷速率均出现显著降低并降至0 mg·g~(-1)·h~(-1)(以每g MLSS释(吸)P量(mg)计,下同),从而使得系统丧失除磷效果.同时,厌氧段COD开始积累.ZnO NPs浓度增加至10 mg·L~(-1)时,多糖与蛋白质含量在抑制条件下均开始减少.通过高通量技术对微观层面进行分析发现,ZnO NPs将会严重抑制聚磷菌的正常生长.ZnO NPs对系统内不同细菌有截然不同的作用,Proteobacteria门在试验过程中比例减小,而Bacteroidetes门却受到促进作用.恢复阶段,较低浓度(2 mg·L~(-1))抑制条件下,EBPR系统恢复速度与程度均优于高浓度(6、10 mg·L~(-1))抑制条件.然而,即使系统得到一定程度恢复也难以恢复到初始水平.     

Cu_xO(CuO-Cu_2O)纳米球催化剂制备及对CO_2电化学还原性能影响的研究

通过水热合成法制备Cu_xO(CuO-Cu2_O)纳米球催化剂,控制水热温度为180℃,合成时间为2h时,制备的催化活性最佳,CO_2还原的起峰电位可达-0.55V(vs.SHE),在-1.25V(vs.SHE)电位下的最大电流密度可达-20.5mA/cm~2。测试电容能达到800μF/cm~2,是同样的测试条件下的气体扩散电极(GDL)电容的4.7倍左右。SEM分析结果表明,其具有特殊的三维纳米球结构。BET分析结果表明,其比表面积达到约63.50m~2/g。Cu_xO180~(-2)/GDL电极的交换电流密度约为1.6×10~(-5)A/cm~2,高出同类研究的i0值(-10~(-10)A/cm~2)约5个数量级。     

Molecular toxicity and defense mechanisms induced by silver nanoparticles in Drosophila melanogaster

The widely use of silver nanoparticles (AgNPs) as antimicrobial agents gives rise to potential environmental risks. AgNPs exposure have been reported to cause toxicity in animals. Nevertheless, the known mechanisms of AgNPs toxicity are still limited. In this study, we systematically investigated the toxicity of AgNPs exposure using Drosophila melanogaster. We show here that AgNPs significantly decreased Drosophila fecundity, the third-instar larvae weight and rates of pupation and eclosion in a dose-dependent manner. AgNPs reduced fat body cell viability in MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assays. AgNPs caused DNA damage in hemocytes and S2 cells. Interestingly, the mRNA levels of the entire metallothionein gene family were increased under AgNPs exposure as determined by RNA-seq analysis and validated by qRT-PCR, indicating that Drosophila responded to the metal toxicity of AgNPs by producing metallothioneins for detoxification. These findings provide a better understanding of the mechanisms of AgNPs toxicity and may provide clues to effect on other organisms, including humans.     

Dispersive solid phase extraction of chlorophenols using carbon-coated magnetic nanoparticles

Abstract

Carbon-coated magnetic nanoparticles were modified with cationic surfactant and used for the dispersive solid phase extraction of chlorophenols from aqueous samples. Surfactant adsorbed on the surface of the nanoparticles resulted in mixed hemimicelles for high extraction efficiency of chlorophenols. Under optimized conditions, calibration curves were linear from 0.5–20?mg L^?1 for analytes with limit of detection between 0.2 and 0.4?mg L^?1. The method was applied to extraction of chlorophenols from tap water, well water and industrial effluent. Recoveries were in the range of 94.0–99.4%, suggesting that sample matrix had little effect on the yields of extraction.