HDTMA改性蒙脱土的稳定性

利用十六烷基三甲基溴化铵(HDTMA)改性天然蒙脱土,观察其在不同环境条件下的稳定性.试验结果表明:随着阳离子交换量(CEC)的增加改性蒙脱土在蒸馏水中的稳定性逐渐降低,1.0CEC改性蒙脱土中HDTMA发生解吸.改性蒙脱土在水体中的稳定性随着振荡强度的加强而降低.从室温到70℃对改性蒙脱土的稳定性几乎无影响.超声波处理使改性蒙脱土的稳定性有所降低.NaCl能提高水体中改性蒙脱土的稳定性,而CaCl₂却使其稳定性有所下降.同酸性条件相比,在碱性条件下改性蒙脱土的稳定性更好.因此,废水的温度、pH和无机盐对低改性蒙脱土稳定性的影响都比较小,这为改性蒙脱土处理废水和它的再生提供了可能.同时在较低振荡强度下,改性蒙脱土也许还能成为废水生物处理的载体.     

水中C60纳米颗粒的稳定性研究

以两种C60纳米颗粒悬浮液为对象,研究贮存时间、pH、电解质和有机物等因素对其稳定性的影响.结果表明,溶剂替换法制备的C60纳米颗粒(C60/son)稳定性优于延时搅拌法(C60/aq),可长时间保持稳定;pH升高可使C60纳米颗粒稳定性增强;电解质投加可使C60纳米颗粒的|ζ|减小、粒径增大,促进凝聚的发生;水中C60纳米颗粒凝聚过程可分为慢速凝聚和快速凝聚两个阶段,符合经典胶体稳定性(DLVO)理论.C60/son的临界凝聚浓度:NaCl 321 mmol·L-1、KCl 316 mmol·L-1、MgCl29.6 mmol·L-1和CaCl26.7 mmol·L-1,C60/aq的临界凝聚浓度:NaCl 295 mmol·L-1、KCl 278 mmol·L-1、MgCl27.8 mmol·L-1和CaCl25.9 mmol·L-1,均远高于其在天然水体中的浓度;腐殖酸存在可通过空间位阻效应显著增强水中C60纳米颗粒的稳定性,这表明C60纳米颗粒可稳定存在于典型的水环境中.     

蒙脱土、高岭土和针铁矿对DNA吸附与解吸特征

采用平衡法研究了蒙脱土、高岭土和针铁矿在不同pH值和不同电解质溶液下的DNA吸附解吸特征.结果表明,在4种电解质体系中,尤其在溶液pH值>5.0时,3种矿物在吸附过DNA后,pH有不同程度上升,但CaCl2电解质体系中含针铁矿溶液的pH开始下降.针铁矿对DNA的吸附率大约为75%～91%,高岭土对DNA的吸附率从pH为3.5时的90%开始下降,至pH 6.0～7.0时的下降至大约18%～50%.在一价电解质体系,当溶液pH值为2.2～5.0时蒙脱土对DNA的吸附率大约为90%开始下降至25%～40%,但在二价电解质体系蒙脱土对DNA的吸附率大约为92%.Freundlich等温吸附方程能更好的拟合针铁矿、蒙脱土和高岭土对DNA的吸附.蒙脱土对DNA相对吸附容量在pH 3.5时大于针铁矿,而pH 5.0时小于针铁矿.以NaOAc为解吸剂,针铁矿、蒙脱土和高岭土上吸附DNA在不同pH时解吸率分别为0.1%～0.4%、63.7%～90.2%和29.7%～87.5%.以NaH2PO4为解吸剂时,这些矿物吸附DNA的解吸率分别为69.6%～78.7%、0.8%～7.0%和0.4%～2.2%.这表明针铁矿吸附DNA时键合作用较大,蒙脱土和高岭土静电引力较大,这是DNA在不同电荷类型矿物表面的吸附差异.     

吸附在改性蒙脱土上有机物的稳定性

利用十六烷基三甲基溴化铵(HDTMA)改性的蒙脱土来吸附含油废水中的有机物,并在不同环境条件下观察被吸附有机物的稳定性.结果表明,改性蒙脱土对含油废水中的有机物有很强的吸附能力,吸附在改性蒙脱土上的有机物在超声波作用下能发生一定数量的解吸,提高温度略微降低被吸附有机物稳定性,而无机盐对其的解吸影响很小.在碱性(pH12.0)条件下,吸附在改性蒙脱土上的有机物能发生大量的解吸,因此其稳定性差,可以通过加碱的方式对改性蒙脱土进行再生,这为改性蒙脱土的循环使用提供了可能.     

水中富勒烯(C_(60))纳米颗粒凝聚动力学研究

采用动态光散射技术研究了电解质和天然有机物对水中C60纳米颗粒凝聚动力学的影响。结果表明,电解质存在可使水中C60纳米颗粒的|ζ|减小、粒径增大,促进凝聚的发生。C60纳米颗粒凝聚过程分为反应控制和扩散控制2个阶段,符合经典的胶体稳定性(DLVO)理论。Na+、K+、Ca2+和Mg2+的临界凝聚浓度分别为321、295、9.6和6.7 mmol/L,远高于其在水环境中的浓度水平;腐殖酸存在可通过空间位阻效应显著增强水中C60纳米颗粒的分散性;表明C60纳米颗粒可稳定存在于典型的水环境中。     

改性蒙脱土颗粒吸附直接染料的分形特征

研究了改性蒙脱土颗粒(050823和MMT35)吸附2种直接染料(直接耐晒黑G和直接大红4BE)的吸附特性,并从类分形动力学规律、颗粒吸附染料前后的表面分形特征变化等方面对上述吸附过程进行了探讨.结果表明,颗粒对染料的吸附可分为快速的边缘覆盖和缓慢的晶层吸附2个过程.整个吸附过程符合准-二级反应动力学方程,并且染料进入晶层的吸附阶段具有类分形特征.除MMT35-直接大红4BE染料吸附体系外,Freundlich、Langmuir吸附等温模型的非线性方程、不同形式的线性方程及分形Langmuir模型对其余3个吸附体系(050823-直接耐晒黑G、050823-直接大红4BE、MMT35-直接耐晒黑G)等温线数据的模拟均取得了较好的效果,其中,非线性方程是获得统一模型参数较好的方法.此外,染料分子主要通过静电引力/斥力和范德华引力的综合作用吸附在颗粒上,并通过晶层膨胀和开孔作用,使颗粒表面粗糙度增加,相应的表面分形维数Ds升高.     

超临界干燥制备TiO_2/蒙脱土光催化剂及性能研究

文章采用溶胶凝胶法结合超临界流体干燥法制备了纳米级TiO2/蒙脱土光催化剂,以苯酚光催化降解为反应模型,探讨了煅烧温度、不同用量的蒙脱土对光催化活性的影响。研究结果表明,煅烧温度为600℃,蒙脱土为44.1%时制的TiO2/蒙脱土光催化剂的光催化性能最好。并用XRD、TEM等手段进行了表征。TiO2以锐钛矿型形式存在。由超临界干燥法制备的光催化剂具有粒径小,比表面积大,光催化活性高等特点。     

有机改性蒙脱土对萘的吸附机制和影响因子

我国场地土壤中多环芳烃（PAHs）污染或PAHs-重金属复合污染是常见的污染类型,对公众健康与环境构成巨大威胁.本研究利用耗散型石英晶体微天平（QCM-D）技术和批量吸附实验,探究实验室制备的2种有机改性黏土对萘的吸附机制,以及萘与Cu²⁺共存时黏土颗粒吸附情况.结果表明,25℃时,十六烷基三甲基溴化铵改性蒙脱土（CTAB-SMF）的吸附等温线符合Freundlich模型（R²>0.92,n>1）,说明其对萘的吸附位点具有多样性,在较高萘平衡浓度（c_e=1 mmol ·L^-1）下吸附分配系数K_d为SMF的13.4倍;3-巯基丙基三甲氧基硅烷改性蒙脱土（TMSP-SMF）的吸附等温线符合Langmuir模型（R²>0.96）,在较高萘平衡浓度（c_e=1 mmol ·L^-1）下吸附分配系数K_d为SMF的1.14倍.说明2种有机改性黏土对萘的吸附效果优于SMF颗粒.3种黏土颗粒对萘的吸附焓在-30~-10 kJ ·mol^-1之间,均为自发物理吸附.溶液离子强度升高抑制了SMF吸附萘,但对改性黏土吸附萘无显著影响.萘平衡浓度较低（c_e=0.1 mmol ·L^-1）时,Cu²⁺的存在使TMSP-SMF对萘的吸附效果增加了3倍;同时萘能促进2种改性黏土对Cu²⁺的吸附.本研究通过原位在线QCM-D检测了黏土对萘的吸附机制,结果与批量吸附实验结果一致：CTAB-SMF对萘的吸附位点主要为黏土层间的改性剂基团,TMSP-SMF则位于黏土颗粒表面的改性剂基团.本项研究结果显示,QCM-D技术是一种有效的原位在线表征黏土膜吸附有机污染物的方法,2种有机改性的黏土颗粒可作为应用于PAHs或PAHs-重金属复合污染场地的修复材料.     

蒙脱土负载硫化纳米零价铁降解有机污染物

通过一步法合成了蒙脱土负载硫化纳米零价铁(CSZVI),使用TEM、BET、XRD、XPS、接触角测量仪对CSZVI的表面物化性质和材料结构进行表征,重点探究了n(S)/n(Fe)对CSZVI去除有机污染物的影响。结果表明：蒙脱土负载有效抑制了硫化纳米零价铁(SnZVI)的团聚并降低了其粒径;在m(蒙脱土)/m(铁)=5时,CSZVI表现出最高的反应活性,在15 min内对氟苯尼考(FF)的降解效率达到100%;n(S)/n(Fe)为0.112时,CSZVI对2,4-二硝基甲苯(DNT)、对硝基苯酚(PNP)、FF、氯霉素(CAP)均表现出最高的反应活性,随着n(S)/n(Fe)增加,反应活性均表现出下降趋势;与纯水相相比,在V(水)/V(乙醇)=7∶3的共溶剂体系中,随着n(S)/n(Fe)增加其对相对亲水的PNP产生的抑制作用增大,而对相对疏水的FF所产生的抑制作用减小。研究结果证明,n(S)/n(Fe)增加会增强CSZVI的表面疏水性,从而提升对疏水污染物降解效率,降低对亲水污染物降解效率。     

蒙脱土/聚丙烯酰胺杂化絮凝剂制备及絮凝性能研究

利用十六烷基三甲基溴化铵(CTAB)与钠基蒙脱土(Na-MMT)的阳离子交换反应制得有机化蒙脱土(O-MMT),通过硝酸铈铵引发丙烯酰胺单体在有机化蒙脱土片层间原位插层聚合制得蒙脱土/聚丙烯酰胺(MMT/PAM)杂化物. 同时,研究了引发剂用量、聚合反应时间和蒙脱土含量对杂化物特性粘数的影响,并用XRD、FTIR、TEM对Na-MMT、O-MMT和MMT/PAM杂化物进行结构表征. 最后实验对比了MMT/PAM杂化物与PAM对三氧化二铬悬浮液的絮凝效果. XRD、TEM结果显示,纳米尺寸大小的蒙脱土均匀地分散在PAM基体中. 絮凝实验结果显示,添加质量分数0.5％~5.0％MMT的MMT/PAM杂化物的絮凝效果优于纯PAM.     

天然有机物和电解质对水中 C60凝聚行为的影响

以富勒烯(C60)纳米颗粒稳定悬浮液为对象,采用动态光散射技术研究了天然有机物和电解质对其在水中凝聚行为的影响.结果表明,采用甲苯溶剂替换法制备的稳定悬浮液中C60浓度为20 mg·L-1左右,表面呈较高的电负性,粒径在120 nm左右,具有较强的稳定性.投加简单电解质可通过压缩双电层机制使其发生凝聚,并符合经典的胶体稳定性(DLVO)理论.Mg Cl2和Ca Cl2的临界凝聚浓度分别为9.6 mmol·L-1和6.7 mmol·L-1.腐殖酸(humic acid,HA)存在时,投加Na Cl和Mg Cl2可使C60颗粒间有效碰撞概率及凝聚反应速度降低,临界凝聚浓度提高;HA可通过增大C60颗粒间的空间位阻效应,抑制凝聚反应发生,提高其在水中的稳定性.但Ca2+可与HA间发生络合反应,并对C60纳米颗粒产生吸附架桥作用,导致凝聚速度大幅提高,强化凝聚反应发生.水中C60纳米颗粒的凝聚和分散行为将受到有机物性质和电解质种类等复杂因素的影响.     

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.     

载铜蒙脱石对大肠杆菌K88吸附性能的研究

以蒙脱石(MMT)和硫酸铜为主要原料,制备了载铜蒙脱石(MMT-Cu),并对MMT-Cu吸附大肠杆菌K88的能力进行比较研究.结果表明:MMT和MMT-Cu对大肠杆菌K88均有较强的吸附作用,但载铜后蒙脱石吸附大肠杆菌的能力明显增强.细菌与吸附材料作用90min后可达到吸附平衡.介质pH值、离子强度和吸附温度对MMT和MMT-Cu吸附细菌的能力均有不同程度的影响.     

Removal of Cs from water and soil by ammonium-pillared montmorillonite/Fe3O4 composite

To remove cesium ions from water and soil, a novel adsorbent was synthesized by following a one-step co-precipitation method and using non-toxic raw materials. By combining ammonium-pillared montmorillonite (MMT) and magnetic nanoparticles (Fe₃O₄), an MMT/Fe₃O₄ composite was prepared and characterized. The adsorbent exhibited high selectivity of Cs⁺ and could be rapidly separated from the mixed solution under an external magnetic field. Above all, the adsorbent had high removal efficiency in cesium-contaminated samples (water and soil) and also showed good recycling performance, indicating that the MMT/Fe₃O₄ composite could be widely applied to the remediation of cesium-contaminated environments. It was observed that the pH, solid/liquid ratio and initial concentration affected adsorption capacity. In the presence of coexisting ions, the adsorption capacity decreased in the order of Ca^2 + > Mg^2 + > K⁺ > Na⁺, which is consistent with our theoretical prediction. The adsorption behavior of this new adsorbent could be expressed by the pseudo-second-order model and Freundlich isotherm. In addition, the adsorption mechanism of Cs⁺ was NH₄⁺ ion exchange and surface hydroxyl group coordination, with the former being more predominant.     

海洋多孔介质中微塑料和富勒烯的共迁移

采用海水和天然海砂,模拟构建了一维柱状的海洋多孔介质体系,研究了粒径1μm的聚苯乙烯微塑料（PS）与富勒烯（C₆₀）在海水饱和砂柱中的共迁移行为.结果发现：单体系下,15mg/L PS的穿透率（M_eff）和最大穿透浓度（MEC）可分别达到36.8%和0.42;而15mg/L的C₆₀团聚明显,其M_eff和MEC值仅分别为16.8%和0.22.当15mg/L PS与15mg/L C₆₀ 1：1共存时,PS能与部分C₆₀形成稳定共团聚体,促进C₆₀迁移;但反之C₆₀却抑制了PS迁移.如果将双体系下PS的浓度由15mg/L增至45mg/L,PS对C₆₀的迁移促进则转变为迁移抑制,这主要源于PS-C₆₀共团聚体体积的增大和数量的增加.     

Heterogeneous reaction of NO2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO₂ on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO₂ on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.     

人工纳米材料富勒烯（C60）低剂量长期暴露对鲫鱼的氧化伤害

为更好地判断人工纳米材料(富勒烯,C60)对水生生物的潜在健康危害,以鲫鱼(Carassius auratus)幼鱼为受试生物,研究了低剂量C60(0.04～1.0 mg·L-1)长期(32 d)暴露对鲫鱼的氧化伤害.结果表明,各实验组中鲫鱼幼鱼脑、肝脏、鳃组织中的还原型谷胱甘肽(GSH)含量都发生显著降低(p＜0.05),其中1 mg·L-1 nC60,aq的暴露对鳃组织GSH含量的抑制率为14.3%,高于对鱼脑、肝脏组织中的抑制率;肝脏组织中过氧化氢酶(CAT)和超氧化物歧化酶(SOD)活性,以及鳃组织中Na -K -ATP酶活性均被显著激活,其最大活性分别是对照的121.34%(0.04 mg·L-1暴露组)、114.80%(0.04 mg·L-1暴露组)和348.59%(0.20mg·L-1暴露组).实验结果揭示,长期暴露引起机体组织的氧化应激可能是水环境中C60的致毒机制之一.     

Effects of stable aqueous fullerene nanocrystal (nC60) on Daphnia magna: Evaluation of hop frequency and accumulations under different conditions

We investigated the effects of environmental factors and properties of water-stable crystal fullerene (nC60) on the uptake of nC60 by Daphnia magna based on known accumulation in our laboratory. This study was performed for seven days using different environmental factors including temperature, pH, water hardness, concentration (density of particle), and particle size. Results demonstrated that body burden of C60 increased with time in all experiments. Body burden of C60 increased with increasing concentration and particle size, and uptake of particles >100 nm reached their maximums more quickly than those <100 nm. Under high hardness in aqueous systems with lower pH and high temperature, uptake was higher than those under opposite conditions. Uptake in all batch tests reached balance within five days. Both nC60 properties and environmental factors influenced uptake of nC60 by D. magna in an aqueous system. Additionally, environmental factors may have affected accumulation by changing nC60 properties, which are critical to understand the accumulation of fullerenes in aqueous systems.     

Effects of stable aqueous fullerene nanocrystal （nC60） on Daphnia magna： Evaluation of hop frequency and accumulations under different conditions

We investigated the e ects of environmental factors and properties of water-stable crystal fullerene (nC60) on the uptake of nC60 by Daphnia magna based on known accumulation in our laboratory. This study was performed for seven days using di erent environmental factors including temperature, pH, water hardness, concentration (density of particle), and particle size. Results demonstrated that body burden of C60 increased with time in all experiments. Body burden of C60 increased with increasing concentration and particle size, and uptake of particles >100 nm reached their maximums more quickly than those <100 nm. Under high hardness in aqueous systems with lower pH and high temperature, uptake was higher than those under opposite conditions. Uptake in all batch tests reached balance within five days. Both nC60 properties and environmental factors influenced uptake of nC60 by D. magna in an aqueous system. Additionally, environmental factors may have a ected accumulation by changing nC60 properties, which are critical to understand the accumulation of fullerenes in aqueous systems.