复合CaCO3法制备医用多孔明胶微球

采用W/O型乳化-固化法制备了明胶CaCO3复合微球,将此复合微球用盐酸处理除去表面CaCO3,得到多孔的明胶微球.以差示扫描量热法、热重分析、红外光谱、扫描电子显微镜等方法对复合微球和多孔明胶微球的物理性质进行了表征,同时探讨了多孔明胶微球的合成机理.结果表明,两种微球中均含有CaCO3;扫描电镜显示,微球表面呈多孔结构,粒径在20～40μm之间.     

原位聚合制备PLLA/Fe3O4磁性复合微球及其表征

介绍了一种新的PLLA/Fe3O4磁性复合微球的制备方法——表面引发开环聚合法,先利用硅烷偶联剂Z-6040对Fe3O4进行改性,在其表面引入羟基,再通过羟基引发丙交酯在磁粒子表面开环聚合制备PLLA/Fe3O4磁性复合微球。探讨了复合微球的形成机理,对磁粒子改性效果和微球形貌、粒径、结构、磁含量及磁性能等进行了表征,并详细研究了磁性复合微球性能的影响因素。     

磁性高分子复合微球的研究进展

综合介绍了磁性复合微球的研究进展及目前常用的制备磁性复合微球的方法,总结了各种制备方法的优缺点和适用范围,并着重介绍了单体聚合法,最后展望了磁性复合微球的发展趋势.     

磁性高分子复合微球的制备

通过选用含有乙烯基的有机硅烷偶联剂对自制的纳米Fe3O4进行表面修饰后,采用悬浮聚合法成功制备了单分散磁性高分子复合微球,并重点研究了分散剂浓度、搅拌速度、磁含量等因素对制备的磁性高分子复合微球的影响.结果表明,合适的分散剂浓度和搅拌速度可以获得球径分布良好的磁性高分子复合微球,微球的磁感应强度可以通过改变Fe3O4磁性粒子的含量进行调节.     

层层自组装法制备碳包覆的Fe_3O_4碳量子点磁性荧光双功能材料

通过化学共沉淀法制备Fe_3O_4磁性纳米颗粒,在其表面包覆碳层,形成Fe_3O_4@C磁性微球,采用层层自组装法将聚二烯丙基二甲基氯化铵(PDDA)修饰到微球表面。将该微球与表面富含羧基的碳量子点(CQDS)连接,得到碳包覆的Fe_3O_4@CQDS(Fe_3O_4@C@CQDS)磁性荧光双功能复合微球。通过X射线衍射(XRD)、振动样品磁强计(VSM)、扫描电子显微镜(SEM)、荧光分光光度计和荧光显微镜等表征手段对该复合微球进行结构表征以及性能测试。结果表明:复合微球粒径约为50nm,饱和磁强度为23.39emu/g,这种性能优异的磁性荧光双功能复合微球有望在生命科学领域得到广泛应用。     

多孔聚合物微球成孔技术的最新研究进展

综述了多孔聚合物微球的制备方法及成孔机理。种子溶胀法和微膜乳化法用于制备具有微孔、中孔结构的单分散聚合物微球;而大孔聚合物微球的制备通常采用传统的悬浮聚合,并通过后交联法改善其孔性能,提高其比表面积。     

Ni/PS核壳结构纳米复合微球的制备及磁性能

采用乳液聚合法制备了纳米级聚苯乙烯微球,利用化学沉积法在微球表面镀镍,制备出了具有磁性的金属/高分子(Ni/PS)纳米复合微球。利用透射电子显微镜(TEM)、X射线衍射仪(XRD)和能量色散谱仪(EDS)分别对镀镍前后纳米微球的形貌结构、相组成、化学成分进行表征分析,用振动样品磁强计(VSM)测试了不同制备工艺条件下复合微球的磁学性能。结果表明,活化工艺、还原剂浓度、镀液pH值和温度对镀后复合微球的磁性能有显著影响。根据磁性能结果,优化工艺参数,制备了具有规则球形、单分散性好、粒径约为100nm、镀层完整、均匀的磁性Ni/PS核壳结构纳米复合微球,并获得最大的饱和磁化强度Ms=8.8764emu/g。     

以丝素蛋白微球为模板制备介孔SiO_2空心微球

以自组装方法制备的丝素蛋白(SF)微球为模板,采用溶胶-凝胶法直接在SF微球表面涂覆硅层,随后高温锻烧制备介孔二氧化硅(SiO_2)空心微球并研究了氨水用量对SF微球表面沉积SiO_2胶粒的影响。通过SEM表征显示,随着氨水用量的增加,SiO_2胶粒在SF微球表面的沉积量增大;SF/SiO_2复合微球锻烧后经TEM和比表面积测试表明,SiO_2微球具有良好的空腔结构,比表面积为92.127m~2/g,孔体积为0.477cm~3/g,孔径为4.56nm。研究证明,在没有添加任何表面活性剂或偶联剂条件下,SF能够诱导SiO_2胶粒沉积,为制备介孔SiO_2空心微球提供了一条简单有效的新途径。     

模板法制备SiO2/Au复合微球及其催化性能评价

采用脲醛树脂为模板,金胶体为前体的新方法,制备了具有较大比表面积的SiO2/Au复合微球。该方法通过将金胶体与硅溶胶混合,加入尿素、甲醛溶液并在酸性条件下引发聚合反应,得到脲醛树脂(UF)/SiO2/Au复合微球;经高温煅烧除去UF模板,得到中孔SiO2/Au复合微球。采用紫外可见吸收光谱、高分辨透射电镜、原子吸收分光光度计和氮气吸附-脱附等手段对金纳米粒子在载体中的分散性、金负载量及材料比表面积和孔径分布进行了表征。该复合微球在硼氢化钠还原对硝基苯胺的反应中显示了良好的催化活性。     

埃洛石纳米管热敏复合微球的制备及吸附性能

通过种子乳液聚合法在埃洛石纳米管(HNTs)表面包覆聚N-异丙基丙烯酰胺(PNIPAM),制备了HNTs/PNIPAM热敏复合微球。利用红外光谱仪(FT-IR)、粒度仪、比表面积测试仪(BET)对复合微球的结构和形貌进行了分析,通过分光光度法研究了复合微球对亚甲基蓝的吸附性能。结果表明,复合微球粒径约为1.8μm,比表面积约为18.2m2/g;其体积相转变温度约为33.6℃,具有热敏性。实验条件下,复合微球对溶液中亚甲基蓝(MB)的吸附率为99.4%,吸附MB后的复合微球在室温下再生60min后,MB解吸附趋于平衡,进一步在40℃进行解吸附时,微球中MB可以进一步释放。     

溶胶凝胶法制备具有介孔结构的聚酰亚胺/SiO_2多孔复合微球

采用反相乳液法,以水溶性聚酰胺酸三乙胺盐(PAAS)、正硅酸乙酯(TEOS)为前驱体,通过溶胶凝胶法制备了具有介孔结构的聚酰亚胺(PI)/SiO_2多孔复合微球。将PAAS水溶液和TEOS水解液的混合溶液在液体石蜡中形成反相乳液,TEOS经水解缩合形成无机三维骨架,通过化学酰亚胺化使复合体系中的PAAS转变为PI,成功制备了含有介孔结构的PI/SiO_2多孔复合微球。研究发现,随着SiO_2含量的增加,复合微球的规整性不断提高,其比表面积由20.5 m~2/g增加至521.8 m~2/g。同时发现,调节TEOS水解液的pH值,微球的比表面积也会发生相应的变化。此外,热重分析结果显示该复合微球的热分解温度超过500℃,表明其具有优异的热稳定性。     

Preparation and application of novel magnetically separable γ-Fe2O3/activated carbon sphere adsorbent

Magnetic γ-Fe₂O₃/activated carbon microspheres have been synthesized by an activation process of carbon microspheres containing iron oxides, which were prepared by hydrothermal method. The structure and morphology of the magnetic porous carbon microspheres were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), thermogravimetry and differential thermal analysis (TG-DTA) and N₂ adsorption-desorption technique. The results showed that the as-prepared activated carbon spheres were the composite of single-phase γ-Fe₂O₃ and activated carbon material, and the content of carbon was about 3.87%. Using methyl orange as model pollutant, the magnetic porous carbon microspheres showed good adsorption capacities of 44.65 mg/g. The isotherm evaluations revealed that the Langmuir model attained better fits to the experimental equilibrium data than the Freundlich model. These magnetic porous carbon microspheres could potentially be applied in separation processes.     

Preparation of open porous polycaprolactone microspheres and their applications as effective cell carriers in hydrogel system

Common hydrogel, composed of synthetic polymers or natural polysaccharides could not support the adhesion of anchorage-dependent cells due to the lack of cell affinitive interface and high cell constraint. The use of porous polyester microspheres as cell-carriers and introduction of cell-loaded microspheres into the hydrogel system might overcome the problem. However, the preparation of the open porous microsphere especially using polycaprolactone (PCL) has been rarely reported. Here, the open porous PCL microspheres were fabricated via the combined emulsion/solvent evaporation and particle leaching method. The microspheres exhibited porous surface and inter-connective pore structure. Additionally, the pore structure could be easily controlled by adjusting the processing parameters. The surface pore size could be altered from 20 μm to 80 μm and the internal porosities were varied from 30% to 70%. The obtained microspheres were evaluated to delivery mesenchymal stem cells (MSCs) and showed the improved cell adhesion and growth when compared with the non-porous microspheres. Then, the MSCs loaded microspheres were introduced into agarose hydrogel. MSCs remained alive and sustained proliferation in microsphere/agarose composite in 5-day incubation while a decrement of MSCs viabilities was found in agarose hydrogel without microspheres. The results indicated that the microsphere/hydrogel composite had a great potential in cell therapy and injectable system for tissue regeneration.     

基于凝固浴剪切法制备多孔实心聚(乳酸-羟基乙酸)共聚物载药微球

以聚(乳酸-羟基乙酸)为基质材料,采用一种新颖的流动凝固浴剪切法制备包载盐酸万古霉素的载药微球,并研究微球的形貌结构、粒径、包封率、载药率、体外释放性能及其影响因素。结果表明,所制备的载药微球平均粒径在15~29μm范围,微球呈现内部实心表面多孔的复合结构;微球的包封率及载药可分别在15%~75%和1.5%~9.3%范围内调控。微球制备过程中的工艺条件对微球结构形貌、包封率、载药率及释放性能有重要影响,通过调整微球的粒径,可有效减缓释药过程中的突释现象。     

Synthesis of aligned porous poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite microspheres

We synthesized poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite microspheres with an aligned porous structure and evaluated their potential applications in bone tissue engineering. A range of HA particles (0, 5, 10 and 20 wt.% in relation to the PCL polymer) were added to a PCL solution in order to improve the biocompatibility of the porous PCL/HA composite microspheres. All the synthesized microspheres showed that the HA particles were distributed well in the PCL matrix, while preserving their aligned porous structure. The average size of the PCL/HA composite microspheres increased from 62 ± 7 to 179 ± 95 μm with increasing HA content from 0 to 20 wt.%. The incorporation of the HA particles to the PCL polymer led to a considerable improvement in in vitro bioactivity, which was assessed by immersing the PCL/HA composite microspheres in simulated body fluid (SBF). A number of apatite crystals could be precipitated on the surface of the aligned porous PCL/HA composite microspheres after soaking in the SBF for 7 days.     

Selective Capture and Quick Detection of Targeting Cells with SERS‐Coding Microsphere Suspension Chip

Circulating tumor cells (CTCs) captured from blood fluid represent recurrent cancers and metastatic lesions to monitor the situation of cancers. We develop surface‐enhanced Raman scattering (SERS)‐coding microsphere suspension chip as a new strategy for fast and efficient capture, recovery, and detection of targeting cancer cells. Using HeLa cells as model CTCs, we first utilize folate as a recognition molecule to be immobilized in magnetic composite microspheres for capturing HeLa cells and attaining high capturing efficacy (up to 95%). After capturing cells, the composite microsphere, which utilizes a disulfide bond as crosslinker in the polymer shell and as a spacer for linking folate, can recycle 90% cells within 20 min eluted by glutathion solution. Taking advantage of the SERS with fingerprint features, we characterize captured/recovered cells with the unique signal of report‐molecule 4‐aminothiophenol through introducing the SERS‐coding microsphere suspension chip to CTCs. Finally, the exploratory experiment of sieving cells shows that the magnetic composite microspheres can selectively capture the HeLa cells from samples of mixed cells, indicating that these magnetic composite microspheres have potential in real blood samples for capturing CTCs.     

Fabrication and characterization of hydroxyapatite microspheres obtained by ultrasonic atomization method

Two kinds of hydroxyapatite microspheres were prepared using an ultrasonic atomization method. The surface morphology, phase composition, size distribution and specific surface area were determined by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffractometry and laser diffraction particle size analysis, respectively. The results indicate that the hydroxyapatite microspheres are composed of nanosized crystals and have porous surface morphology. The specific surface areas are different before sintering, and have a slight difference after sintering. The size distribution of the microspheres added with Lopon 885 is narrow and the average size is smaller than those fabricated without the addition of Lopon 885. Besides, the impurity phase, tetracalcium phosphate, appeared during ultrasonic atomizing procedure, and can be completely removed after sintering at 650°C for 1 h.     

表面可修饰的荧光复合微球的制备及表征

采用反相悬浮乳液法合成了丙烯酸(AA)含量不同的N-异丙基丙烯酰胺(NIPAM)共聚丙烯酸(AA)的聚合物模板P(NIPAM-co-AA), 以此作为微反应器, 分别用两种不同的方法制备了P(NIPAM-co-AA)-co-Alq3 (八羟基喹啉铝)荧光复合微球, 再用四乙氧基硅烷(TEOS)对其表面进行修饰, 获得了表面功能化的P(NIPAM-co-AA)-Alq3-SiO₂荧光复合微球。用SEM、 IR、 FM和XRD等手段对其结构和性能进行表征。结果表明: 所制备的荧光复合微球单分散性好、 荧光发光效率较高且性能稳定, 同时具有较大的比表面积; 功能化的荧光复合微球可用于高通量药物筛选和识别生物大分子等生物医学领域。      

核-壳结构磁性复合微球的制备与表征

通过分散共聚制得了聚(丙烯酸-丙烯腈-苯乙烯)(PAAS)三元共聚物微球,调整聚合反应介质乙醇与水的体积比及分散剂的用量,可将PAAS微球的粒径控制在230～680nm的范围内;扫描电子显微镜观察发现,所得微球粒径具有较好的单分散性.以该PAAS共聚物微球为载体,在二价和三价铁盐存在的条件下控制体系的pH,经共沉淀将Fe_3O_4纳米颗粒有效沉积在微球表面,得到了以PAAS为核,Fe_3O_4为壳的核-壳结构磁性复合微球;热重分析结果表明,复合微球上Fe_3O_4的含量达41%,对磁场具有明显的响应性.