磷酸钙料浆性质对雾化干燥羟基磷灰石微球的影响

以甲烷火焰为干燥介质,将3种不同性质的磷酸钙料浆利用火焰-雾化干燥法制备出不同形态和性能的羟基磷灰石(HA)微球。对比分析了料浆成分、温度、结晶程度等参数对所得HA微球形貌、相组成、结晶度、比表面积以及孔隙分布等的影响。结果表明,料浆中的氨水在雾化干燥过程中会聚集突释,得到具有“爆破状”开口的形态的HA微球。低温并且结晶程度较低的磷酸钙料浆经过火焰-雾化快速干燥后,得到结构松散、结晶度较低、比表面积及孔体积较大的HA微球,说明料浆的性质将会直接影响火焰-雾化干燥后HA微球的特性。     

超声悬浮共聚法制备聚合物微球及其形态

采用超声粉碎和悬浮聚合法,以甲基丙烯酸甲酯、苯乙烯为主单体,过氧化苯甲酰为引发剂,颜料黄74为着色剂,合成了彩色聚合物微球。光学显微镜以及扫描电镜的观察和分析表明：利用超声粉碎法可使聚合物微球的粒径从几百微米降低到几微米;热熔融后,聚合物微球内包覆了细小的颜料颗粒。     

Synthesis of hydrophilic microspheres with LCST close to body temperature for controlled dual‐sensitive drug release

Novel stimuli‐responsive hydrophilic microspheres were prepared by free radical polymerization of hydroxyethyl methacrylate (HEMA) and methacrylic acid (MA), as hydrophilic monomers, and N‐isopropylacrylamide (NIPAAm) and N,N′‐ethylenebisacrylamide (EBA), as thermo‐sensitive monomer and crosslinker, respectively. Hydrophilic comonomers were introduced in the macromolecular network to synthesize materials with tunable thermal behavior. In addition, by introducing in the polymerization feed both a hydrophilic and a pH‐sensitive monomer, such as MA, dual stimuli‐responsive (pH and temperature) hydrogels were synthesized. The incorporation of monomers in the network was confirmed by infrared spectroscopy, while the network density and the shape of hydrogels was found to strictly depend on the concentration of monomers in the polymerization feed. Thermal analyses showed negative thermo‐responsive behavior with pronounced water affinity of microspheres at a temperature lower than lower critical solution temperature (LCST). In our experiment, the LCST values of the hydrogels were in the range 34.6–37.5°C, close to the body temperature, and the amount of hydrophilic moieties in the polymeric network allows to collect shrinking/swelling transition temperatures higher than the LCST of NIPAAm homopolymers. In order to test the preformed materials as drug carriers, diclofenac diethylammonium salt (DDA) was chosen and drug entrapment percent was determined. Drug release profiles, in media at different temperature and pH, depend on hydrogels crosslinking degree and drug–bead interactions. By using semi‐empirical equations, the release mechanism was extensively studied and the diffusional contribute was evaluated. Copyright © 2010 John Wiley & Sons, Ltd.     

The selective cleanup of complex matrices and simultaneous separation of benzo[a]pyrene by solid-phase extraction with MgO microspheres as sorbents

A new method for the selective cleanup of complex matrices and simultaneous separation of benzo[a]pyrene (BaP) was developed in this study. This method was based on solid-phase extraction (SPE) using magnesium oxide microspheres as sorbents, and it eliminated interferences from various impurities, such as lipids, sulphur, pigments, halobenzenes, polychlorodibenzo-p-dioxins and polychlorodibenzofurans. Several parameters, including the volume of rinsing and eluting solvents, the type of loading solvents and SPE sorbents, were optimized systematically. The capability for impurity removal was verified by gel permeation chromatography, gas chromatography, and liquid chromatography. Compared to commercial sorbents (silica gel, florisil and alumina), MgO microspheres exhibited excellent performance in the selective isolation of BaP and removal of impurities. The proposed method was applied to detect BaP in complex samples (sediments, soils, fish, and porcine liver). The limit of quantification (LOQ) was 1.04 ngL(-1), and the resulting regression coefficient (r(2)) was greater than 0.999 over a broad concentration range (9.5-7600 ngL(-1)). In contrast to traditional methods, the proposed method can give rise to higher recovery (85.1-100.8%) and better selectivity with simpler operation and less consumption of organic solvents (20-40 mL).     

塑料微球表面制备聚乙烯醇涂层研究进展

在聚苯乙烯（PS）-聚乙烯醇（PVA）-碳氢聚合物（CH）三层球的设计中制备PVA涂层的方法主要包括乳液微封装法、炉内成球涂层法、浸(旋)涂法、界面缩聚法及喷涂法等,前三种方法目前最为常用。总结了前三种制备PVA涂层方法的优缺点及目前的研究和制备现状。乳液微封装法适合于500 m以下小尺寸双层球的制备,具有微球成活率高、产品质量较好等优点,但制备过程受人为因素影响较大,且不易制备大直径双层球。炉内成球涂层法也适用于小尺寸双层球的制备,其制备周期短,但液滴发生器的设计苛刻,PVA层的均匀性差,且不易制得较大尺寸的双层球。浸（旋）涂法可制备1000 m以上的大直径双层球,但该方法中影响PVA涂层铺展的因素较多,得到的PVA涂层均匀性较差,且涂层很薄。     

基于动态溶胀法制备中空聚合物微球

以表面带正电荷的m级聚苯乙烯微球为种子,经过甲苯、二乙烯基苯溶胀,聚合与包覆等过程制备了直径约5 m的中空聚合物微球。研究了溶剂类型、溶剂用量对动态溶胀法制备的中空聚合物微球粒径、分布和结构的影响,讨论了中空聚合物微球的形成机理。结果表明：添加一定量甲苯、二甲苯等挥发性溶剂是动态溶胀法形成中空聚合物微球的前提;甲苯用量越多,溶胀后形成的中空结构越明显,孔径越大;选择低溶解性的二甲苯溶剂更有利于中空结构的形成。     

中空Ag纳米球壳的制备及性能表征

以改性聚苯乙烯微球为模板,采用化学镀法在聚苯乙烯微球表面包覆一层银,在四氢呋喃溶液中将聚苯乙烯微球溶解,得到中空Ag纳米球壳。采用扫描电镜、透射电镜和X射线衍射仪对样品进行了表征及分析,并用紫外可见分光光度计研究了粒子的光学性质。实验结果表明：运用此法成功地制备出中空Ag纳米球壳的内径为250 nm,壁厚约为15 nm,并且成功地使纳米粒子的紫外吸收光谱由600 nm红移至900 nm左右,实现了在可见光至近红外光区调节Ag纳米结构的吸收峰。     

PS-RF双层空心微球的制备

采用聚苯乙烯(PS)空心微球为模板,间苯二酚-甲醛(RF)为前驱体溶液,邻苯二甲酸二丁酯为分散剂,以界面聚合反应为基础初步总结出一条PS-RF双层聚合物空心微球的制备工艺,并就制备过程中RF溶液与分散剂油相的选择、预聚时间、搅拌速率、固化温度等影响因素进行了讨论。当RF溶液质量分数为25%,间苯二酚与碳酸钠的物质的量之比为100,预聚24 h,搅拌速率120～200 r/min,固化温度35 ℃时,制得了球形度和同心度达到95%以上,表面粗糙度小于10 nm的PS-RF双层空心微球。     

Development of Novel Polypropylene Syntactic Foams Containing Paraffin Microcapsules for Thermal Energy Storage Applications

polypropylene (PP) syntactic foams (SFs) containing hollow glass microspheres (HGMs) possess low density and elevated mechanical properties, which can be tuned according to the specific application. A possible way to improve their multifunctionality could be the incorporation of organic Phase Change Materials (PCMs), widely used for thermal energy storage (TES) applications. In the present work, a PCM constituted by encapsulated paraffin, having a melting temperature of 57 °C, was embedded in a compatibilized polypropylene SF by melt compounding and hot pressing at different relative amounts. The rheological, morphological, thermal, and mechanical properties of the prepared materials were systematically investigated. Rheological properties in the molten state were strongly affected by the introduction of both PCMs and HGMs. As expected, the introduction of HGMs reduced both the foam density and thermal conductivity, while the enthalpy of fusion (representing the TES capability) was proportional to the PCM concentration. The mechanical properties of these foams were improved by the incorporation of HGMs, while they were reduced by addition of PCMs. Therefore, the combination of PCMs and HGMs in a PP matrix generated multifunctional materials with tunable thermo-mechanical properties, with a wide range of applications in the automotive, oil, textile, electronics, and aerospace fields.     

Radiochemical Feasibility of Mixing of 99mTc-MAA and 90Y-Microspheres with Omnipaque Contrast

Yttrium-90 (⁹⁰Y) microspheres are widely used for the treatment of liver-dominant malignant tumors. They are infused via catheter into the hepatic artery branches supplying the tumor under fluoroscopic guidance based on pre-therapy angiography and Technetium-99m macroaggregated albumin (^99mTc-MAA) planning. However, at present, these microspheres are suspended in radiolucent media such as dextrose 5% (D5) solution. In order to monitor the real-time implantation of the microspheres into the tumor, the ⁹⁰Y microspheres could be suspended in omnipaque contrast for allowing visualization of the correct distribution of the microspheres into the tumor. The radiochemical purity of mixing ⁹⁰Y-microspheres in various concentrations of omnipaque was investigated. The radiochemical purity and feasibility of mixing ^99mTc-MAA with various concentrations of a standard contrast agent were also investigated. Results showed the radiochemical feasibility of mixing ⁹⁰Y-microspheres with omnipaque is radiochemically acceptable for allowing real-time visualization of radioembolization under fluoroscopy.