Preparation of three-dimensional ordered macroporous SiCN ceramic using sacrificing template method

Three-dimensional (3D) long range well ordered macroporous SiCN ceramics were prepared by infiltrating sacrificial colloidal silica templates with the low molecular weight preceramic polymer, polysilazane. This was followed by a thermal curing step, pyrolysis at 1250 °C in a N₂ atmosphere, and finally the removal of the templates by etching with dilute HF. The produced macroporous SiCN ceramics showed high BET surface areas (pore volume) in the range 455 m²/g (0.31 cm³/g)–250 m²/g (0.16 cm³/g) with the pore sizes of 98–578 nm, which could be tailored by controlling the sizes of the sacrificial silica spheres in the range 112–650 nm. The sphere-inversed macropores were interconnected by 50 ± 30 nm windows and 3–5 nm mesopores embedded in the porous SiCN ceramic frameworks, which resulted in a trimodal pore size distribution. The surface of the achieved porous SiCN ceramic was then modified by Pt–Ru nanoparticle depositing under mild chemical conditions.     

Production and evaluation of vildagliptin-loaded poly(dl-lactide) and poly(dl-lactide-glycolide) micro-/nanoparticles: Response surface methodology approach

A laboratory scale spray dryer was used to encapsulate vildagliptin (VLG), an antihyperglycemic drug, into different polymers such as poly(dl-lactide) (PDLA), poly(dl-lactide-glycolide)-50:50 (PLGA 50:50), and poly(dl-lactide-glycolide)-75:25 (PLGA 75:25). Response surface methodology (RSM) was employed to evaluate the effects of process and formulation factors on the encapsulation efficiency (EE). The physicochemical properties of the drug-loaded micro-/nanoparticles, mainly the drug loading (DL), particle size distribution, surface morphology, drug–polymer compatibility, and release rate were investigated. % EE of drug-loaded micro-/nanoparticles were in the range of 57.10% to 76.44%. PLGA50:50 micro-/nanoparticles showed highest EE as compared to PDLA and PLGA75:25 micro-/nanoparticles. The mean particle size of the micro-/nanoparticles containing PLGA 50:50, PLGA 75:25, and PDLA polymers were 428?nm, 640?nm, and 1.22 µm, respectively. Surface morphology study revealed smooth, spherical and nonporous surface structures of the micro-/nanoparticles. Fourier transform infrared spectroscopy studies confirmed the drug–polymer compatibility. Powder X-ray diffraction analysis of micro-/nanoparticles revealed that VLG was present in the amorphous form within the micro-/nanoparticles formulations. In vitro release study demonstrated that VLG is slowly released from micro-/nanoparticles for 12?h and the drug release rate was influenced by type and viscosity of polymers used. This work suggests that PDLA, PLGA 50:50, and PLGA75:25 polymers are able to sustain the VLG release rates from micro-/nanoparticles.     

Characterization of poly(vinylidenefluoride-co-hexafluoropropylene)-based polymer electrolyte filled with TiO2 nanoparticles

Nanoscale TiO₂ particle filled poly(vinylidenefluoride-co-hexafluoropropylene) film is characterized by investigating some properties such as surface morphology, thermal and crystalline properties, swelling behavior after absorbing electrolyte solution, chemical and electrochemical stabilities, ionic conductivity, and compatibility with lithium electrode. Decent self-supporting polymer electrolyte film can be obtained at the range of <50 wt% TiO₂. Different optimal TiO₂ contents showing maximum liquid uptake may exist by adopting other electrolyte solution. Room temperature ionic conductivity of the polymer electrolyte placed surely on the region of >10⁻³ S/cm, and thus the film is very applicable to rechargeable lithium batteries. An emphasis is also be paid on that much lower interfacial resistance between the polymer electrolyte and lithium metal electrode can be obtained by the solid-solvent role of nanoscale TiO₂ filler.     

Effects of the reinforcement and toughening of acrylate resin/CaCO3 nanoparticles on rigid poly(vinyl chloride)

Novel composite particles based on nanoscale calcium carbonate (nano‐CaCO₃) as the core and polyacrylates as the shell were first synthesized by in situ encapsulating emulsion polymerization in the presence of the fresh slush pulp of calcium carbonate (CaCO₃) nanoparticles. Subsequently, these modified nanoparticles were compounded with rigid poly(vinyl chloride) (RPVC) to prepare RPVC/CaCO₃ nanocomposites. At the same time, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were investigated, and the synergistic effect of modified nanoparticles with chlorinated polyethylene (CPE) was also studied. The results showed that in the presence of nano‐CaCO₃ particles, the in situ emulsion polymerization of acrylates was carried out smoothly, and polyacrylates successfully encapsulated on the surface of nano‐CaCO₃ to prepare the modified nanoparticles, breaking down nano‐CaCO₃ particle agglomerates, improving their dispersion in the matrix, and also increasing the particle–matrix interfacial adhesion. Thus, the effects of the reinforcement and toughening of these modified nanoparticles on RPVC were very significant, and the cooperative effect of the nanoparticles with CPE occurred in the united modification system. Scanning electron microscopy analyses indicated that large‐fiber drawing and network morphologies coexisted in the system of joint modification of nanoparticles with CPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3940–3949, 2007     

From Molecular Clusters to Metal Nanoparticles

Different methods to prepare supported metal nanoparticles of uniform size are discussed. (i) Supported ruthenium particles were generated from Ru and Ru-Fe bimetallic molecular metal carbonyl cluster precursors (MCC). (ii) Gold nanoparticle formation in the supercage of Y zeolite was studied on Au/NaY, Au/HY and Au-Fe/HY system. (iii) Palladium nanoparticles were grown in liquid phase then deposited on an SiO₂ support or they were grown on the support surface in a solid-liquid interfacial layer. The particle size control was more efficient in the latter two cases than in the preparation starting from MCC.     

Synthesis and physicochemical characterization of amphiphilic block copolymer self‐aggregates formed by poly(ethylene glycol)‐block‐poly(ϵ‐caprolactone)

Diblock copolymers with different poly(ε‐caprolactone) (PCL) block lengths were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG‐OH, MW 2000) as initiator. The self‐aggregation behaviors and microscopic characteristics of the diblock copolymer self‐aggregates, prepared by the diafiltration method, were investigated by using ¹H NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG–PCL block copolymers formed the self‐aggregate in an aqueous environment by intra‐ and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations of the block copolymer self‐aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The partition equilibrium constants (K_v) of pyrene, measured by fluorescence spectroscopy, revealed that the inner core hydrophobicity of the nanoparticles increased with increasing PCL chain length. The aggregation number of PCL chain per one hydrophobic microdomain, investigated by the fluorescence quenching method using cetylpyridinium chloride as a quencher, revealed that 4–20 block copolymer chains were needed to form a hydrophobic microdomain, depending on PCL block length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3520–3527, 2006     

表面巯基化修饰的磁性Fe_3O_4纳米粒子合成与表征

通过化学共沉淀法制备了粒径约30nm的磁性四氧化三铁(Fe3O4)纳米粒子,并采用3-巯丙基三乙氧基硅烷(MPTES)将Fe3O4纳米粒子表面修饰上巯基(-SH)官能团,获得了表面巯基化的磁性Fe3O4纳米粒子。利用X-射线粉末衍射仪(XRD),透射电子显微镜(TEM),带有能谱仪(EDS)的扫描电子显微镜(SEM),光电子能谱仪(XPS),以及磁学测量系统(MPMS)对粒子的结构和性能进行了表征和分析。结果表明:表面巯基化后的磁性粒子粒径略有增加,室温下磁化强度由原来的64emu/g变为62emu/g,较好地保留了原始磁性特征。研究结果对巯基化磁性纳米粒子实现生物分子结合、固定负载乃至生物传感的应用具有重要意义。     

Effects of fullerenes and single-wall carbon nanotubes on murine and human macrophages

The discovery in 1985 of C-fullerenes, a novel carbon allotrope with a polygonal structure made up solely by 60 carbon atoms, and in 1991 of C-nanotubes, thin carbon filaments (1-3 μm in length and 0.001 μm in diameter) with extraordinary mechanical properties, opened a wide field of activity in carbon research. While toxicity and biocompatibility of C-fullerenes have been widely investigated, literature data concerning the biological properties and biotoxicity of C-nanotubes are poor and contradictory. Here we test the ability of highly purified C-Single-Walled-Nanotubes (SWNTs) and C-fullerenes to elicit an inflammatory response by murine and human macrophage cells in vitro. In order to determine the potential of these C-derivatives as biological inducers of inflammatory reactions we evaluate the ability of C-single-walled nanotubes and C-fullerenes to induce the release of NO by murine macrophages cells, to stimulate the phagocytic activity of human macrophage cells and to be cytotoxic against these cells. We show that SWNTs-C-nanotubes, when highly purified, as well as C-fullerenes, do not stimulate the release of NO by murine macrophage cells in culture, their uptake by human macrophage cells is very low, and they possess a very low toxicity against human macrophage cells.     

Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006     

超分散稳定纳米ZnS的非水原位构筑及摩擦学性能

设计并合成了油溶性环烷酸锌和异氰酸酯类超分散稳定剂,采用原位构筑方法获得了非水纳米ZnS分散系,用冷冻蚀刻电镜对其进行了表征,用离心实验对其分散稳定性进行了考察.对纳米粒子的形成过程、分散稳定机理进行了阐述.用环块和四球摩擦试验机对纳米ZnS分散系的摩擦学性能进行了研究.结果表明:ZnS为40 nm的粒状颗粒,大小均匀,在介质中呈单粒子分散;纳米分散系经72 h普通离心和56 h非连续超离心均未发生沉降,表现出理想的分散稳定性;试验显示超分散稳定纳米ZnS的存在,能明显改善油样的抗磨减摩性能和承载能力.在试验范围内,添加的纳米ZnS的量越大,其抗磨减摩性能也越好,但当n-ZnS的质量分数大于0.25%时,其承载能力趋于稳定.