氨基酸功能化的果胶/姜黄素胶体粒子的合成与性质

通过酯化反应合成了新型的氨基酸功能化的果胶衍生物, 通过红外光谱(FTIR)和元素分析确认了果胶衍生物的化学组成及结构, 用动态光散射(DLS)和透射电子显微镜(TEM)表征了果胶衍生物胶体的形貌和尺寸. 结果表明, 果胶衍生物胶体呈现不规则的球状结构, 粒度分布较均一, 平均粒径200 nm. 用紫外-可见(UV-Vis)光谱测试了果胶衍生物胶体对姜黄素的包裹和控制释放, 结果表明, 姜黄素能够有效被果胶衍生物胶束包裹. 体外细胞毒理实验结果表明, 果胶衍生物胶体载体能显著提高姜黄素对HepG2细胞生长的抑制作用.     

丁二烯聚合铁系胶体催化剂的相态研究

通过Tyndall效应、电子显微镜观察、超过滤实验和非水体系电导率测定证明 ,Fe(naph) 2 Al(i Bu) 3 CH2 CHCH2 Cl 催化剂在溶有丁二烯的加氢汽油介质中为胶体分散系 ,活性位位于胶粒表面 ,因此是胶体催化剂 .Al(i Bu) 3 以缔合状态存在并解离成离子对 ;它同Fe (naph ) 2 的反应是形成胶核的主要反应 ;与CH2 CHCH2 Cl 反应生成的氯化异丁基铝在胶核表面形成活性位 ;适当过量Al(i Bu) 3 形成双电层 ,使胶粒相对稳定 .催化剂颗粒是无定型的 .催化剂各组分的配比影响胶粒的形态 ,其中以较佳配比所得到的催化剂胶粒较小 ,分布均匀 ,催化活性高 .因是聚结不稳定胶体体系 ,陈化时胶粒迅速聚结长大 ,因而催化活性显著降低     

胶体分形聚集体分维数与随时间变化的SERS强度关系研究

由于胶体聚集的动力学过程可用分形理论描述,从而对胶体动力学生长机制有了新的理解。Lin等研究了金胶、硅胶及聚乙烯乳胶的直接光散射后认为,胶体的两种生长机制DLCA和RLCA聚集体具有不依赖于胶体个性的普适分数维。对这一结果用不同方法对不同胶体进行验证十分必要。我们曾研究了吡啶吸附于AgBr胶体随时间变化的SERS规律,本文进一     

胶体分散体系与有序分子组合体的小角X射线散射研究

小角X射线散射(SAXS)是当前化学、物理、生物等学科前沿交叉领域--软凝聚态物质的一个强有力研究工具.本文评述了SAXS方法自身的优势及其在胶体分散体系与有序分子组合体研究中的广泛应用,重点论述了对粒子尺寸或孔径大小分布、胶体体系分散状态、长程有序结构以及混合体系之间相互作用的测量与表征等.     

木质素基偶氮聚合物胶体球的制备

利用造纸废液中的碱木素(AL)合成了木质素基偶氮聚合物(AL-azo-COOEt), 并研究其自组装胶体化过程. 木质素偶氮聚合物的成功合成通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱和元素分析等表征方法得到证实. 激光光散射(LLS)监测了AL-azo-COOEt的胶体化过程, 自组装形成的胶体球利用透射电镜(TEM)、扫描电镜(SEM)、X射线光电子能谱仪(XPS)和元素分析等进行表征. 结果表明,木质素偶氮聚合物通过疏水聚集作用可以形成规整的实心胶体球, 且为内部较疏水外部较亲水性质的结构. 木质素偶氮聚合物胶体球可以包载疏水性药物阿霉素(DOX), 且其缓释性能可以通过缓冲溶液的pH值来调控.     

黄豆蛋白胶体的制备和聚沉

物理化学中胶体化学部分原有实验是氢氧化铁胶体制备和电泳速率测定,属于验证性实验,对胶体特征的表征局限于电学性质,缺少对粒径、光学性质的表征探究及创新训练。本文通过黄豆蛋白胶体的制备、表征和聚沉,将原先的验证性实验改进为具有综合性和探究性的实验。通过物理分散法获得黄豆蛋白胶体,对其粒径、光学性质、电学性质进行了表征,并对聚沉条件进行探究,最终获得豆腐产品。结果表明,黄豆蛋白胶体粒径范围为20–120 nm、最可几分布为51 nm,胶粒平均带电-41.8 mV。通过丁达尔效应,在与入射光垂直方向观察到散射的蓝光,并观察到透过的光呈橙红色。通过探究反离子种类、温度、pH等条件的影响,加深了对植物蛋白胶体聚沉过程的理解。该实验引入了现代Zeta电位及粒度分析仪,加入了蛋白质聚沉的特殊情况,强化对书本知识的延伸应用。产品豆腐与生活密切联系,有利于思政教育,彰显化学魅力。     

可控纳米银胶体的稳定性

纳米银胶体(AgNPs)长期储存不稳定性问题是本研究的中心,着重考察了不同前驱体对纳米银胶体的稳定性影响。分别以银氨([Ag(NH3)2]OH)溶液和Ag NO3溶液为前驱体制备了多份纳米银胶体样品并通过UV-Vis、FE-SEM、EDS、ZETA电位仪等现代分析测试手段研究了纳米银胶的形貌、粒径大小以及稳定性。对比分析发现,以[Ag(NH3)2]OH溶液为前驱体,制备的纳米银胶体具有粒径可控,尺寸均一,分散性良好等特点;而且经过一个月的常温储存,表现出比用Ag NO3溶液为前驱体制备的纳米银胶体具有更高的储存稳定性。     

氢氧化铁胶体电泳实验的改进

人民教育出版社全日制普通高级中学教科书(必修加选修)化学第三册第19页讲胶体性质中Fe(OH)3胶体电泳是高中化学中关于胶体性质的一个重要实验.因课本中Fe(OH)3胶体电泳实验是采用把电极直接插入胶体内使溶胶被破坏而凝聚析出胶粒.聚集成的颗粒使电极附近的溶胶变成红褐色沉淀,即形成电泳,但现象不明显,笔者通过反复实验,改进实验装置和实验方法后实验效果较明显.     

光敏性无规共聚物P(FA_2C-co-AA)的自组装及乳化性能

光敏性单体ε-己内酯改性丙烯酸酯肉桂酸酯(FA2C)与丙烯酸(AA)在偶氮二异丁腈(AIBN)的引发作用下,于N,N-二甲基甲酰胺(DMF)中发生自由基共聚反应,制备了具有光敏性的双亲无规共聚物P(FA2C-co-AA)。以红外光谱、凝胶渗透色谱、差示扫描量热和紫外光谱等分析测试手段对共聚产物进行了表征。P(FA2C-co-AA)在选择性溶剂DMF水溶液中自组装得到纳米粒径的胶体粒子。用紫外光引发胶体粒子内双键发生光交联反应,得到稳定的胶体粒子,并用动态激光光散射(DLS)表征了胶体粒子交联前后的粒径变化。结果表明:该胶体粒子具有良好的乳化性能。     

胶体铜催化丙烯腈水合的高选择性及其活性中心结构的研究

研究了胶体铜催化丙烯腈水合制丙烯酰胺的高选择性与活性中心结构的关系. 在聚乙烯吡咯烷酮(PVP)保护下, 用肼和氢氧化钠混合液还原CuCl2制得胶体铜, 用其催化丙烯腈水合反应, 选择性达到100％, 产生高选择性的原因如下: (1) 胶体铜的活性中心不是胶粒表面的点缺陷, 而是胶体铜颗粒表面的位错端点. (2) 由于胶体铜具有高硬度和高强度的力学特性, 保证了活性中心结构的稳定性; 胶体铜颗粒的平均粒径(45 nm)超过晶粒的特征长度, 进一步保证了活性中心的稳定性.     

Characterization of polymer-silica nanocomposite particles with core-shell morphologies using Monte Carlo simulations and small angle X-ray scattering

A two-population model based on standard small-angle X-ray scattering (SAXS) equations is verified for the analysis of core-shell structures comprising spherical colloidal particles with particulate shells. First, Monte Carlo simulations of core-shell structures are performed to demonstrate the applicability of the model. Three possible shell packings are considered: ordered silica shells due to either charge-dependent repulsive or size-dependent Lennard-Jones interactions or randomly arranged silica particles. In most cases, the two-population model produces an excellent fit to calculated SAXS patterns for the simulated core-shell structures, together with a good correlation between the fitting parameters and structural parameters used for the simulation. The limits of application are discussed, and then, this two-population model is applied to the analysis of well-defined core-shell vinyl polymer/silica nanocomposite particles, where the shell comprises a monolayer of spherical silica nanoparticles. Comprehensive SAXS analysis of a series of poly(styrene-co-n-butyl acrylate)/silica colloidal nanocomposite particles (prepared by the in situ emulsion copolymerization of styrene and n-butyl acrylate in the presence of a glycerol-functionalized silica sol) allows the overall core-shell particle diameter, the copolymer latex core diameter and polydispersity, the mean silica shell thickness, the mean silica diameter and polydispersity, the volume fractions of the two components, the silica packing density, and the silica shell structure to be obtained. These experimental SAXS results are consistent with electron microscopy, dynamic light scattering, thermogravimetry, helium pycnometry, and BET surface area studies. The high electron density contrast between the (co)polymer and the silica components, together with the relatively low polydispersity of these core-shell nanocomposite particles, makes SAXS ideally suited for the characterization of this system. Moreover, these results can be generalized for other types of core-shell colloidal particles.     

Modified reverse microemulsion synthesis for iron oxide/silica core–shell colloidal particles

Iron oxide/silica core–shell colloidal particles were prepared by basic reverse microemulsion (RM) method and two modified RM methods. By basic RM method, maximum particle size obtained was mere 40 nm. For building photonic crystals working in the visible range, the colloidal particles must be larger than 100 nm. Thus two modified RM methods were used. By alcohol modified RM method, short chain alcohols were used as co-surfactant. The particle size rose to near 100 nm, but the core–shell structure was comparatively poor. By emulsifier pair modified RM method, the particle size leapt to over 200 nm and a narrow growth window was found favorable to enhance the stability and rigidity of the surfactants layers. The core–shell mechanism was also discussed and a new four-step mechanism was proposed.     

Influence of surfactant structure on reverse micelle size and charge for nonpolar electrophoretic inks

Electrophoretic inks, which are suspensions of colorant particles that are controllably concentrated and dispersed by applied electric fields, are the leading commercial technology for high-quality reflective displays. Extending the state of the art for high-fidelity color in these displays requires improved understanding and control of the colloidal systems. In these inks, reverse micelles in nonpolar media play key roles in media and particle charging. Here we investigate the effect of surfactant structure on reverse micelle size and charging properties by synthesizing different surfactants with variations in polyamine polar head groups. Small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) were used to determine the micelle core plus shell size and micelle hydrodynamic radius, respectively. The results from SAXS agreed with DLS and showed that increasing polyamines in the surfactant head increased the micelle size. The hydrodynamic radius was also calculated on the basis of transient current measurements and agreed well with the DLS results. The transient current technique further determined that increasing polyamines increased the charge stabilization capability of the micelles and that an analogous commercial surfactant OLOA 11000 made for a lower concentration of charge-generating ions in solution. Formulating magenta inks with the various surfactants showed that the absence of amine in the surfactant head was detrimental to particle stabilization and device performance.     

Synthesis and characterization of nanogels of poly(N-isopropylacrylamide) by a combination of light and small-angle X-ray scattering

Thermo-responsive crosslinked nanogels of N-isopropylacrylamide (NIPAM) were synthesized by emulsion polymerization and the size was varied using different concentrations of surfactant (sodium dodecyl sulfate, SDS) in the polymerization process. The collapse behavior of the nanogels at the lower critical solution temperature at around 32 °C was investigated by dynamic light scattering, and by combined static light scattering (SLS) and small-angle X-ray scattering (SAXS). The combined data from SLS and SAXS were analyzed by a model for the nanogels which at intermediate temperatures included a central core and a more diffuse outer layer describing pending polymer chains with a low degree of cross linking. In the expanded state, the particles were modeled with a single component with a broad graded surface. In the collapsed state the nanogels were modeled as homogeneous and relatively compact particles. The amount of surfactant used had a profound effect on the final size of the nanogels owing to the phenomenon of colloidal stabilization of the emulsion droplets during polymerization. The combination of SLS and SAXS as applied to the nanogels is an attractive method for particle characterization as it spans a very large range of scattering vector from q = 0.0004 to 0.22 ?(-1).     

Time-resolved small-angle X-ray scattering studies of polymer-silica nanocomposite particles: initial formation and subsequent silica redistribution

Small angle X-ray scattering (SAXS) is a powerful characterization technique for the analysis of polymer-silica nanocomposite particles due to their relatively narrow particle size distributions and high electron density contrast between the polymer core and the silica shell. Time-resolved SAXS is used to follow the kinetics of both nanocomposite particle formation (via silica nanoparticle adsorption onto sterically stabilized poly(2-vinylpyridine) (P2VP) latex in dilute aqueous solution) and also the spontaneous redistribution of silica that occurs when such P2VP-silica nanocomposite particles are challenged by the addition of sterically stabilized P2VP latex. Silica adsorption is complete within a few seconds at 20 °C and the rate of adsorption strongly dependent on the extent of silica surface coverage. Similar very short time scales for silica redistribution are consistent with facile silica exchange occurring as a result of rapid interparticle collisions due to Brownian motion; this interpretation is consistent with a zeroth-order Smoluchowski-type calculation.     

Correcting for a density distribution: particle size analysis of core-shell nanocomposite particles using disk centrifuge photosedimentometry

Many types of colloidal particles possess a core-shell morphology. In this Article, we show that, if the core and shell densities differ, this morphology leads to an inherent density distribution for particles of finite polydispersity. If the shell is denser than the core, this density distribution implies an artificial narrowing of the particle size distribution as determined by disk centrifuge photosedimentometry (DCP). In the specific case of polystyrene/silica nanocomposite particles, which consist of a polystyrene core coated with a monolayer shell of silica nanoparticles, we demonstrate that the particle density distribution can be determined by analytical ultracentrifugation and introduce a mathematical method to account for this density distribution by reanalyzing the raw DCP data. Using the mean silica packing density calculated from small-angle X-ray scattering, the real particle density can be calculated for each data point. The corrected DCP particle size distribution is both broader and more consistent with particle size distributions reported for the same polystyrene/silica nanocomposite sample using other sizing techniques, such as electron microscopy, laser light diffraction, and dynamic light scattering. Artifactual narrowing of the size distribution is also likely to occur for many other polymer/inorganic nanocomposite particles comprising a low-density core of variable dimensions coated with a high-density shell of constant thickness, or for core-shell latexes where the shell is continuous rather than particulate in nature.     

Scattering curves of ordered mesoscopic materials

Analytical expressions for the scattering functions of ordered mesoscopic materials are derived and compared to experimentally determined scattering curves. Ordered structures comprising spheres (fcc, bcc, hcp, sc), cylinders (hex, sq), and lamellar structures are considered. The expressions take into account particle size distributions and lattice point deviations, domain size, core/shell structures, as well as peak shapes varying analytically between Lorentzian and Gaussian functions. The expressions allow one to quantitatively describe high-resolution synchrotron small-angle X-ray (SAXS) and neutron scattering (SANS) curves from lipid and block copolymer lyotropic phases, core/shell nanoparticle superstructures, ordered nanocomposites, and ordered mesoporous materials. In addition, the diffuse out-of-plane scattering of grazing incidence GISAXS and GISANS experiments of laterally ordered thin films can be quantitatively analyzed.     

In situ small-angle X-ray scattering studies during the formation of polymer/silica nanocomposite particles in aqueous solution

This study is focused on the formation of polymer/silica nanocomposite particles prepared by the surfactant-free aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) in the presence of 19 nm glycerol-functionalized aqueous silica nanoparticles using a cationic azo initiator at 60 °C. The TFEMA polymerization kinetics are monitored using ¹H NMR spectroscopy, while postmortem TEM analysis confirms that the final nanocomposite particles possess a well-defined core–shell morphology. Time-resolved small-angle X-ray scattering (SAXS) is used in conjunction with a stirrable reaction cell to monitor the evolution of the nanocomposite particle diameter, mean silica shell thickness, mean number of silica nanoparticles within the shell, silica aggregation efficiency and packing density during the TFEMA polymerization. Nucleation occurs after 10–15 min and the nascent particles quickly become swollen with TFEMA monomer, which leads to a relatively fast rate of polymerization. Additional surface area is created as these initial particles grow and anionic silica nanoparticles adsorb at the particle surface to maintain a relatively high surface coverage and hence ensure colloidal stability. At high TFEMA conversion, a contiguous silica shell is formed and essentially no further adsorption of silica nanoparticles occurs. A population balance model is introduced into the SAXS model to account for the gradual incorporation of the silica nanoparticles within the nanocomposite particles. The final PTFEMA/silica nanocomposite particles are obtained at 96% TFEMA conversion after 140 min, have a volume-average diameter of 216 ± 9 nm and contain approximately 274 silica nanoparticles within their outer shells; a silica aggregation efficiency of 75% can be achieved for such formulations.

SAXS is used to study the formation of polymer/silica nanocomposite particles prepared by surfactant-free aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate in the presence of silica nanoparticles using a azo initiator at 60 °C.     

Seeded growth of titania colloids with refractive index tunability and fluorophore-free luminescence

Titania is an important material in modern materials science, chemistry, and physics because of its special catalytic, electric, and optical properties. Here, we describe a novel method to synthesize colloidal particles with a crystalline titania, anatase core and an amorphous titania-shell structure. We demonstrate seeded growth of titania onto titania particles with accurate particle size tunability. The monodispersity is improved to such an extent so that colloidal crystallization of the grown microspheres becomes feasible. Furthermore, seeded growth provides separate manipulation of the core and shell. We tuned the refractive index of the amorphous shell between 1.55 and 2.3. In addition, the particles show luminescence when trace amounts of aminopropyl-triethoxysilane are incorporated into the titania matrix and are calcined at 450 °C. Our novel colloids may be useful for optical materials and technologies such as photonic crystals and optical trapping.     

Synthesis of SiO2@SiO2 core-shell microspheres using urea-formaldehyde polymers as the templates for fast separation of small solutes and proteins

The monodisperse superficially porous core-shell silica microspheres (CSSMs) with controllable shell thickness and pore size were synthesized by an improved polymerization-induced colloid aggregation (PICA) approach for fast separation of small solutes and proteins.