Self-assembly of Carboxyl Functionalized Polystyrene Nanospheres into Close-packed Monolayers via Chemical Adsorption

The polyacrylic acid functionalized polystyrene nanospheres were synthesized and self-assembled into irregular, densely packed monolayers in non-aqueous media. The polymer nanoparticles were chemically adhered to substrates. The morphologies of the resulting films were investigated. The impact of the volume fraction of alcohol in the mixed solvents on the particle adsorption and fabrication of nanosphere assembled films was examined.     

Toughening of epoxies via craze-like damage

The fracture behavior of a core-shell rubber (CSR) modified epoxy is investigated using both fracture mechanics and microscopy tools. The CSR-modified epoxy is found to be toughened via numerous line-array cavitations of the CSR particles, followed by plastic flow of the epoxy matrix. The toughening effect via the above craze-like damage process is found to be as effective as that of the well-known widespread rubber cavitation/matrix shear yielding mechanisms. The conditions for triggering the craze-like damage appear to be both stress state and rubber concentration dependent. The type of rubber tougheners utilized also plays a critical role in triggering this rather unusual craze-like damage in epoxy systems. © 1993 John Wiley & Sons, Inc.     

Facile syntheses of surface-functionalized micelles and shell cross-linked nanoparticles

Block copolymer micelles and shell cross-linked nanoparticles (SCKs) presenting Click-reactive functional groups on their surfaces were prepared using two separate synthetic strategies, each employing functionalized initiators for the controlled radical polymerization of acrylate and styrenic monomers to afford amphiphilic block copolymers bearing an alkynyl or azido group at the α-terminus. The first route for the synthesis of the azide-functionalized nanostructures was achieved via sequential nitroxide-mediated radical polymerization (NMP) of tert-butyl acrylate and styrene, originating from a benzylic chloride-functionalized initiator, followed by deprotection of the acrylic acids, supramolecular assembly of the block copolymer in water and conversion of the benzylic chloride to a benzylic azide. In contrast, the second strategy utilized an alkynyl-functionalized reversible addition fragmentation transfer (RAFT) agent directly for the RAFT-based sequential polymerization of tetrahydropyran acrylate and styrene, followed by selective cleavage of the tetrahydropyran esters to give the α-alkynyl-functionalized block copolymers. These Click-functionalized polymers, with the functionality located at the hydrophilic polymer termini, were then self-assembled using a mixed-micelle methodology to afford surface-functionalized “Clickable” micelles in aqueous solutions. The optimum degree of incorporation of the Click-functionalized polymers was investigated and determined to be ca. 25%, which allowed for the synthesis of well-defined surface-functionalized nanoparticles after cross-linking selectively throughout the shell layer using established amidation chemistry. Functionalization of the chain ends was shown to be an efficient process under standard Click conditions and the resulting functional groups revealed a more “solution-like” environment when compared to the functional group randomly inserted into the hydrophilic shell layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5203–5217, 2006     

Ag核Au壳双金属复合纳米线的制备及其表面增强拉曼光谱研究

采用氧化铝模板结合交流电沉积技术制备纯银纳米线, 然后通过化学还原方法, 并控制加入的金盐的量, 在已制备好的银线表面包裹不同厚度的金壳层, 得到具有核壳结构的Ag_核Au_壳复合纳米线. 采用电子显微镜(SEM, TEM)和表面增强拉曼光谱对该复合结构纳米线进行相关表征, 纳米线的表面形貌与加入的金盐的量有关. 以苯硫酚(TP)和对巯基苯胺(PATP)为探针分子, 研究了此类复合纳米线的表面增强拉曼散射效应. 并以PATP在金银纳米线表面吸附的表面增强拉曼光谱的差别为探针, 表征了复合纳米线表面金的包裹程度, 结果表明一定厚度的包裹程度可制备无针孔效应的核壳结构金银复合纳米线.     

Generalization of in-situ polymerization method for preparing core-shell polymeric nanospheres and hollow spheres

According to the new method of preparing core-shell nanospheres developed by our group, by using two monomers, 2-hydroxypropyl methacrylate(HPMA) and vinyl acetate(VAc), two kinds of core-shell nanospheres with poly(ɛ-caprolactone) (PCL) as the core and crosslinked poly(2-hydroxypropyl methacrylate) (PHPMA) or poly(vinyl acetate) (PVAc) as the shell were successfully prepared under similar conditions. After degrading the PCL cores of the two kinds of nanospheres by lipase, the corresponding crosslinked poly(methyl acrylic acid) hollow spheres and crosslinked poly(vinyl alcohol) hollow spheres were obtained. Results indicate that the new method we proposed for preparing core-shell polymeric nanospheres via in-situ polymerization can be generalized to a certain extent, and it is suitable for many systems provided the monomer used is soluble in water, while its corresponding polymer is insoluble in water. Translated from Chemical Journal of Chinese University, 2006, 27(9): 1762–1766 [译自: 高等学校化学学报]     

壳聚糖作用下一步法合成具有高电活性的AgCl@聚苯胺核壳结构

在壳聚糖的作用下，采用简单的一步法合成了具有星状结构的氯化银/聚苯胺核壳型复合材料。当壳聚糖的浓度为1%时，所制备的氯化银/聚苯胺复合材料具有高度的分散性，壳层厚度为30～80 nm、核的直径在25～60 nm范围内。通过透射电镜、红外光谱和X-射线衍射对样品的形态和组成进行了表征。循环伏安实验结果表明这种复合材料在中性条件下具有很好的电化学活性。     

Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.     

Fracture mechanisms in rigid core-shell particle modified high performance epoxies

The fracture mechanisms of a high performance epoxy system modified with two types of preformed rigid core-shell particles (RCSP) were investigated. The use of the preformed RCSP anables the control of the dispersion of the toughener phase in the epoxy, which, in turn, allows the mechanical properties of the modified epoxy to be optimized. The toughening effect via the RCSP modification is found to be as good as that via the core-shell rubber modification. The moduli andT _g of these RCSP-modified epoxies are virtually unaltered via the RCSP modification, when compared with the neat epoxy resin equivalent. The toughening mechanisms in these toughened systems appear to be predominantly crack deflection, crack bifurcation, and microcracking. Approaches for effective toughening of high performance polymers via rigid polymers are discussed.     

Synthesis of spherical microcapsules by photopolymerization in aerosols

 The preparation of polymer microcapsules of well defined size in the range of 10–50 μm with different shell thickness to core diameter ratios is described. An aerosol of monodisperse droplets of a homogeneous ternary liquid system which contained a hydrophobic component and a hydrophilic component dissolved in a high-volatile mutual solvent, was produced by dispersing with a vibrating-orifice aerosol generator. After the evaporation of the solvent in a nitrogen atmosphere the particles demix and form a two-phase droplet of core-shell type. These droplets were illuminated with UV light and polymerized to highly monodisperse microcapsules with a solid polymer shell and a liquid core. The properties of the resulting particles (size, size distribution, shell thickness, shape and surface characteristics) were investigated by scanning electron microscopy, Raman spectroscopy on single optically levitated particles, and confocal Raman micro spectroscopy. The microcapsules were highly monodisperse and have spherical shape. Received: 24 July 1996 Accepted: 29 August 1996     

Preparation of PdCo Bimetallic Hollow Nanospheres and its Electrocatalytic Activity for Oxidation of Formic Acid

The performance of the direct formic acid fuel cell (DFAFC) is considerably higher than the direct methanol fuel cell (DMFC) because of some characteristics of formic acid1. For example, formic acid is non-toxic. Formic acid has two orders of magnitude smaller crossover flux through a Nafion membrane than methanol2. In DFAFC, the concentration of formic acid can be as high as 20 mol/L, while the best concentration of methanol in DMFC is only about 2 mol/L3. Thus, the power density of …