Reorientational Dynamics of Water Confined in Zeolites

We present a detailed molecular‐dynamics study of water reorientation and hydrogen‐bond dynamics in a strong confinement situation, within the narrow pores of an all‐silica Linde type A (LTA) zeolite. Two water loadings of the zeolite are compared with the bulk case. Water dynamics are retarded in this extreme hydrophobic confinement and the slowdown is more pronounced at higher water loading. We show that water reorientation proceeds mainly by large‐amplitude angular jumps, whose mechanism is similar to that determined in the bulk. The slowdown upon hydrophobic confinement arises predominantly from an excluded‐volume effect on the large fraction of water molecules lying at the interface with the zeolite matrix, with an additional minor contribution coming from a structuring effect induced by the confinement.     

Droplet Growth Dynamics in a Water/Oil/Surfactant System

We have studied the droplet growth dynamics in a water-oil-surfactant system, using the cell dynamics system simulations based on the time-dependent Ginzburg-Landau model with two order parameters. Our simulations are carried out in a two-dimensional system of uneven composition of water and oil. For various average surfactant concentrations, the spatial patterns and their time evolution are obtained. The Ostwald ripening behaviors in the sparse regime of the droplet distributions are obtained. Numerical simulations are also extended to the dense regime so that the interactions between the droplet domains cannot be neglected. In such a system, the dynamics of pattern formation become significantly slow as the average surfactant concentration increases and we cannot apply the familiar scaling law in this case. Copyright 2001 Academic Press.     

反胶束体系制备负载型TiO2纳米光催化剂

在AOT/异辛烷反胶束体系中制备了粒径为2～5nm的单分散球形TiO₂纳米粒子,用TEM,DSC和XRD等手段对其进行了分析;用浸渍法以小孔分子筛HZSM-5为载体制备了负载型TiO₂纳米粒子,用FTIR,Langmuir及BET等手段进行了表征;用以上2种TiO₂粒子作光催化剂进行了简单模拟废水处理研究,用UV-Vis光谱分析其催化效果表明,负载型TiO₂纳米粒子比纯TiO₂纳米粒子的光催化活性更高.     

高分子在受限稀溶液中的结构和动力学性质

利用平衡态及非平衡态耗散粒子动力学模拟方法, 分别研究了平衡态和流场作用下受限高分子在稀溶液中的链结构和动力学. 采用没有滑移和密度涨落的边界条件模拟纳米管道环境, 进而研究了高分子回转半径和扩散系数对受限强度及高分子与溶剂间相互作用的依赖关系. 在非平衡态模拟中, 分别考虑了Poiseuille和Couette两种流场. 研究发现, 在这两种流场作用下, 高分子都随着溶剂与高分子排斥作用的降低而向管道中心迁移. 在强流场下, 在Poiseuille流场中高分子密度呈现出双峰分布, 而在Couette流场中则呈现为单峰分布.     

Influence of Confined Water on the Photophysics of Dissolved Solutes in Reverse Micelles

The photophysical parameters of two probes with largely different hydrophobic character, namely, coumarin 1 and coumarin 343, are investigated in sodium bis‐(2‐ethylhexyl)sulfosuccinate (AOT)/hexane/water reverse micelles at various water/AOT molar ratio w₀. Correlation of photophysical parameters such as fluorescence quantum yield, fluorescence lifetime, and emission maxima with w₀ indicate distinctly different trends below and above w₀≈7 for both probes. The variation of the average rotational correlation times obtained from fluorescence anisotropy decays for both probes in reverse micelles further corroborate the above observation. Similar studies were also performed in nonaqueous reverse micelles with acetonitrile as polar solvent. Similar to aqueous reverse micelles, breaks in the photophysical parameters with increasing acetonitrile/AOT molar ratios w′₀ were also observed in these cases, although at a much lower w′₀ value of 3. The present results indicate that around w₀≈7 for aqueous reverse micelles (and around w′₀≈3 for nonaqueous reverse micelles) a distinct change occurs in the probe microenvironment, which is rationalized on the basis of the relative populations of interfacial and core water. We propose that until the ionic head groups and counterions are fully solvated by polar solvents, that is, up to w₀≈7 (or w′₀≈3), the interfacial water population dominates. Above these molar ratios coalescence of excess water molecules with each other to form truncated H‐bonded water clusters leads to a sizable population of core water. This is further substantiated by changes in the IR absorption spectra for the O? D stretching mode of diluted D₂O in reverse micelles with varying w₀. Critical comparison of the present results with relevant literature reports provide clear support for the proposals made on water structure in reverse micelles. The role of relative size of the probe and the reverse micelles for differences in polar solvent to AOT ratios (w₀=7 and w′₀=3) in the observed breaks in the two types of reverse micelles is also discussed.     

Unique Dynamics of Water Confined on the Surface of Metal Oxide Clusters

Water confined on metal oxide surface plays significant roles in heterogeneous catalysis. Heteropolyacid, a 1.2 nm-metal oxide cluster with well-defined structure, is applied as a model to understand the dynamics of water on its surface. The surface water strongly associates with heteropolyacid cluster and form the so-called ‘pseudoliquid phase’ where catalytic reactions are conducted. Broadband dielectric spectroscopy and differential scanning calorimetry have been applied to probe the dynamics of water in this pseudoliquid phase. A supercooling phase transition of water below its normal melting temperature and a dipolar glassy relaxation behaviour due to the hindered dynamics of water have been observed. The rich dynamic behavior on the surface of such well-defined metal clusters provide new perspectives to understand the properties of surface water and their relation to catalytic performance of heteropolyacid.     

Properties of Water Confined in Periodic Mesoporous Organosilicas: Nanoimprinting the Local Structure

The properties of materials confined in porous media are important in scientific and technological aspects. Topology, size, and surface polarity of the pores play a critical role in the confinement effects, however, knowledge regarding the guest–pore interface structure is still lacking. Herein, we show that the molecular mobility of water confined in periodic mesoporous organosilicas (PMOs) is influenced by the polarity of the organic moiety. Multidimensional solid‐state NMR spectroscopy directly probes the spatial arrangement of water inside the pores, showing that water interacts either with only the silicate layer or with both silicate and organic layers depending on the alternating surface polarity. A modulated and a uniform pore filling mode are proposed for different types of PMOs.     

Structure and Excitation Dynamics of β-Carotene Aggregates in Cetyltrimethylammonium Bromide Micelle

The β-carotene(β-Car) aggregate was prepared by self-assembly in cetyltrimethylammonium bromide (CTAB) micelle. The ground state absorption measurement showed that the aggregate has J-type characteristics and resonance Raman spectra gave the intrinsic explanation of molecular interaction in aggregate. Upon excitation at the optical allowed S₂ state of aggregate, direct generation of triplet state via singlet fission(SF) mechanism was observed. Excitation dynamics was elucidated by fs-transient absorption spectroscopy and ns-flash photolysis, respectively. The triplet state life time of aggregate was found to be independent of the ambient oxygen molecules.     

两性/阴离子表面活性剂形成具有耐盐性能的蠕虫状胶束

利用流变学方法研究了两性表面活性剂十四烷基磺基甜菜碱(TDAPS)和阴离子表面活性剂十二烷基硫酸钠(SDS)混合体系中蠕虫状胶束的耐盐性能, 分析了二价金属离子对蠕虫状胶束微观结构的影响. 结果表明, 在加入MgCl₂和CaCl₂使Mg^2＋和Ca^2＋总浓度达到0～1900 mg/L的情况下, TDAPS/SDS体系中形成的蠕虫状胶束的粘弹性能和耐剪切能力不仅没有损失而且增强. 对静态流变和动态流变结果进一步分析表明体系中同时存在两种可区分尺寸的蠕虫状胶束. 加入二价金属离子, 体系的微观结构发生了由小尺寸蠕虫状胶束向大尺寸蠕虫状胶束转变, 同时, 大尺寸蠕虫状胶束线性增长并发生枝化. 两性表面活性剂头基上的正电荷中心减小了蠕虫状胶束的反离子结合程度, 抑制了线性生长到枝化生长的过程, 使体系表现出优异的耐盐性能.     

水为洗脱液在表面活性剂胶束涂层固定相上分离手性药物

讨论了手性固定相稳定的条件，以表面活性剂胶束涂层为固定相，纯水作流动相，对氨氯地平，麻黄碱，伪麻黄碱，芬必得，美西律平和扑尔敏等外消旋药物进行了手性拆分，探索了手性药物氨地平及麻黄碱，伪麻黄碱的分离条件，当流动相的PH值为5．5时分离效果最佳，在流动相中加入2.5-5mmol/L硼酸时分离因子较大。     

阴离子表面活性剂在水/正烷烃界面的分子动力学模拟(英文)

利用分子动力学模拟方法研究了阴离子表面活性剂在水/正烷烃(壬烷,癸烷和十一碳烷)界面的结构和动力学特点.十六烷基苯磺酸钠作为研究对象,其中苯磺酸基团在十六碳烷的第4号碳原子上,记作4-C16.分析了不同油相和特定盐度条件下正烷烃-表面活性剂-水体系的界面特点(如密度剖面图、界面张力和径向分布函数).模拟结果表明平衡模型体系展现了一个很好的水/正烷烃界面.当加氯化钠到水溶液中,正烷烃-表面活性剂-水体系的界面张力有微小的变化,有趣的是表面活性剂二面角的反式结构分数的变化联系着界面张力的微小变化.可见,表面活性剂在界面处的结构对降低界面张力起到重要的作用.此外,还发现表面活性剂的极性头与钠离子和水分子存在较强的相互作用.     

石墨烯狭缝受限孔道中水分子的分子动力学模拟

石墨烯是一种具有广泛应用前景的纳米材料,特别是由石墨烯片层自组装形成的二维纳米通道能够应用于物质的过滤分离.本文采用分子动力学模拟方法研究了原态石墨烯/羟基改性石墨烯狭缝孔道中水分子的微观行为,模拟计算了水的界面结构性质和扩散动力学性质,所研究的石墨烯孔宽为0.6-1.5 nm.模拟结果表明,在石墨烯狭缝孔道中,水分子受限结构呈现层状分布,在超微石墨烯孔道(0.6-0.8 nm)中水分子可形成特殊的环状有序结构,石墨烯表面可诱导产生特殊的水分子界面取向.在石墨烯孔道中,水分子的扩散运动低于主体相水分子的扩散运动,羟基化石墨烯孔道可以促使水分子的扩散能力降低.对于改性石墨烯狭缝孔道,由于羟基的作用,水分子可以自发渗入0.6 nm的石墨烯孔道内.模拟所得到的受限水分子的动力学性质与水分子在石墨烯孔道内的有序结构有关.本文研究结果将有助于分析理解水分子通过石墨烯纳米通道的渗透机理,为设计基于石墨烯的纳米膜提供理论指导.     

反胶束法合成氧化锌微晶及其荧光特性

0引言材料的结构(微结构)、尺寸和形貌等因素对其特性及其实际应用具有重要的影响。对无机材料特别是氧化物半导体进行结构控制的研究近年来引起了人们极大的关注。氧化锌作为一种宽带隙(3.2eV)半导体材料,可广泛应用于压电材料、气体传感器、橡胶添加剂和光学器件等领域,而且还因其在室温下可产生激射现象使其成为纳米光学材料研究领域中的一大热点[1￣6]。目前,除了传统的固相-气相(V S)反应外,用于氧化锌微晶的制备方法主要有共沉淀法[7]、多羟基化合物水解法[8]、有机金属气相沉积法[9￣12]和水热法[13]等。通过选择不同的制备方法和…     

反胶束体系中有机染料PDS对TiO_2纳米粒子的表面修饰

反胶束法制备纳米粒子是 2 0世纪 80年代兴起的研究领域[1] .反胶束是指表面活性剂在非极性溶剂中定向排列而自发形成的聚集体 [2 ] ,反胶束的“水池”是一种特殊的纳米空间 ,以此作为微反应器 ,通过控制含水量 W0 ( W0 =[H2 O]/[Surft.],即水与表面活性剂的摩尔比 )和选择不同的表面活性剂种类及浓度可以获得单分散的粒径小于 1 0 nm的微粒 [3～ 5] .Ti O2 作为一种典型的光催化剂 ,由于其化学性质稳定、氧化还原性强 ,且具有抗光阴极腐蚀性、难溶、无毒、成本低等特点 ,在有机污染物的去除 ,废水处理等方面具有广阔的应用前景[6 ] .而…     

Molecular Dynamics Simulations of Sulfobetaine-Type Zwitterionic Surfactant at the Decane/Water Interface

Automated Topology Builder (ATB) and GAMESS (US) were used to build the model of a new sulfobetaine-type zwitterionic surfactant. And a serious of molecular dynamics simulations of the new sulfobetaine-type zwitterionic surfactant were performed at the decane/water interface by GROMACS, the influence of surfactant structure to the interfacial properties was investigated. The results show that the surfactant molecules can adsorb at the decane/water interface closely and reduce the interfacial tension significantly between decane and water. In another word, the model of the sulfobetaine-type zwitterionic surfactant is correct. The minimum interfacial tension could reach up to 1.6 mN · m^?1 when the number of surfactants was up to 134, which corresponds to the critical micelle concentration and consistent with the experimental values of the system.     

阴离子表面活性剂在油水界面聚集的分子动力学模拟

用分子动力学方法模拟了油、水和阴离子表面活性剂组成的混合溶液从初始“均相”到“油水两相”分离的动力学过程, 研究了十二烷基苯磺酸钠(SDBS)在界面分离过程中的作用. 模拟发现, 油水两相能够在短时间内分离达到平衡, 形成一个明显的油水界面; 在SDBS存在情况下, 油水界面的分离时间随着SDBS浓度的增加逐渐增加, 达到平衡时SDBS会在界面处形成一个明显的界面膜, 并对油水界面处的水分子有限制作用. 模拟表明, 分子动力学方法可以作为实验的一种补充, 为实验提供必要的微观分子结构信息.     

Effect of the Head Group of Surfactant on the Miscibility of Sodium Chloride and Surfactant in an Adsorbed Film and Micelle

The thermodynamic treatment of a surfactant mixture was applied to the mixture of sodium chloride, NaCl, with octyl methyl sulfoxide (OMS) and that with decyldimethylphosphine oxide (DePO). The surface tension of aqueous solutions of the mixtures was measured as a function of the total concentration and the composition of the mixtures at 298.15 K. The total surface densities of the mixtures and the composition of the adsorbed films and micelles were evaluated by applying thermodynamic equations to the expeimental results. It was found that the adsorbed film and micelle are almost composed of the surfactant and there is slight attractive interaction between the ions of NaCl and the head groups of OMS and DePO molecules in the adsorbed films and micelles. A difference in the miscibility of NaCl and surfactant was observed between the OMS and DePO systems and attributed to the difference in the hydration of the head group between OMS and DePO molecules. The comparison of these results with those of the mixtures of NaCl with tetraethylene glycol monooctyl ether (C(8)E(4)) and dodecylammonium chloride (DAC) indicated that the small difference in the miscibility in an adsorbed film and micelle among these nonionic surfactant systems arises from the difference in hydration and structure of the head groups and the large one between the nonionic surfactant and DAC systems results from electrostatic interactions between dodecylammonium and sodium ions. Copyright 2001 Academic Press.     

PEO-PPO嵌段共聚物反胶束的形成及其热力学行为

水增溶;临界胶束浓度;PEO-PPO嵌段共聚物反胶束的形成及其热力学行为     

高岭石-水体系中水分子结构的分子动力学模拟

以Hendricks模型为初始结构, 利用CLAYFF力场对高岭石-水体系进行无晶体学限制的分子动力学模拟. 结果表明, 层间水有三种类型: I型类似于Costanzo提出的“洞水”分子, 其HH矢量(水分子中从一个氢原子位置指向另一个氢原子位置的方向矢量)平行于(001)平面, 而C2轴稍微倾斜于(001)面法线; II型类似于“连接水”, 一个氢氧键指向临近的层间四面体氧形成氢键, 另一个氢氧键与(001)面近似平行; III型水分子在层间近似保持为竖直状, 一个氢与层间四面体氧形成氢键, 而另一个氢与对面层的羟基氧形成氢键. 高岭石羟基氢沿(001)晶面法线的浓度曲线显示一部分羟基指向变为近似平行于(001)面, 羟基氧因此能够暴露出来与层间水分子氢形成氢键. 此外, 模拟中还观察到部分II型水分子氧偏离于层间的平均位置而更靠近四面体层, 这和Costanzo的实验结果一致, 可能是X射线谱图中(002)弱衍射峰出现的原因.     

阳离子Gemini表面活性剂3,5-双(亚甲基十八烷基二甲基溴化铵)-1,2,4-三氮唑胶束对酯碱性水解的影响

在25℃条件下,研究了乙酸乙酯和乙酸戊酯在阳离子Gemini表面活性剂3,5—双(亚甲基十八烷基二甲基溴化铵)—1,2,4—三氮唑(简称18—triazole—18)胶束中的碱性水解反应。实验结果表明．在一定的表面活性剂浓度范围内,乙酸乙酯和乙酸戊酯在Gemini表面活性剂18—triazole—18胶束溶液中的碱性水解反应速率随表面活性剂浓度的增加呈上升趋势,达到一最大值后,随着浓度的增加呈下降趋势。实验结果还表明,18—triazole—18对乙酸乙酯碱性水解的影响较对乙酸戊酯碱性水解的影响大。随着底物疏水性的增加,乙酸乙酯和乙酸戊酯的碱性水解速率在18—triazole—18胶束中表观反应速率常数最大值分别为无表面活性剂时的5．5倍和1．1倍。