Morphology and Pore Size Distribution of Biocompatible Interconnected Porous Poly(L-lactic acid) Foams with Nanofibrous Structure Prepared by Thermally Induced Liquid–Liquid Phase Separation

Biocompatible, highly interconnected microporous poly(L-lactic acid) (PLLA) foams with nanofibrous structure, containing pores with average diameter below 1 μm and fibers with diameters of 10² nm scale, were prepared through the thermally induced liquid–liquid phase separation (TIPS) method consisting of quenching of the PLLA solution, freeze extraction with ethanol, and vacuum drying. Diverse foam morphologies were obtained by systematically changing parameters involved in the TIPS process, such as polymer concentration, solvent composition, and quenching temperatures. The morphology of different foams was examined by scanning electron microscopy to characterize the pore size and the pore size distribution. The results showed that most porous foams had a nanofibrous structure with interconnected open pores. In the case of using tetrahydrofuran (THF) as solvent, the higher the PLLA concentration, the smaller the average pore diameter and the narrower the pore size distribution. In the case of using the mixed solvents of THF/DOX (1,4-dioxane) with higher than 6/4 volume ratio, there appeared a maximum value of average pore diameter and a widest pore size distribution at 0.09 g/mL PLLA concentration. The average pore diameter of the foams increased with increasing DOX content in the mixed solvent and ranged from 0.2 to 0.9 μm depending on the process parameters. When the DOX content reached 60% by volume, the morphology of the foams contained some large closed pores with diameter ranging from 1 to 10 μm. By decreasing the quenching temperature, the average pore diameter of foams decreased and the pore size distribution became narrower. All the pore size distribution fit F-distribution equations.     

非离子型表面活性剂Tween 20对大尺寸双层空心微球制备的影响

为了改善臭氧处理聚苯乙烯(PS)单层球与聚乙烯醇(PVA)溶液生成的双层乳粒在油相中的分散性,提高大尺寸双层球的成活率,在双层球制备过程中采用了非离子型表面活性剂Tween 20(T-20)来改性该种PS单层球。结果表明经表面活性剂T-20改性后显著降低了PS薄膜的亲水接触角,提高了PS与PVA间的相互作用,同时也大幅度提高了PS薄膜对PVA的吸附速率。红外光谱和紫外-可见分光光度计的测试结果证明:在PVA固化过程中,由于PVA与T-20的相比太大,PS表面吸附的表面活性剂T-20部分会被PVA置换、迁移至PVA溶液中。T-20的迁移提高了制备双层球过程中水相与外油相的粘度比且显著降低PVA溶液表面张力,从而有利于实现双重乳粒在油相中的单分散。因此,T-20是制备大尺寸PS-PVA双层空心微球有效的表面活性剂。     

Control of Size and Morphology of Gelatin Microspheres

Gelatin microspheres with different particle size and surface morphology were obtained through an emulsification-coacervation method in water-in-oil (W/O) emulsions. The effect of preparation parameters on the size and morphology of the gelatin microspheres was investigated, and the influence of post-treatment, including washing solvent and freeze-drying, on the surface morphology was also studied. The results showed that spherical microspheres, without aggregation phenomena and with a very smooth and uniform surface, are formed during the cross-linking process. The particle size of the gelatin microspheres increased with increasing concentration of the gelatin solution, emulsifying time, and W/O phase volume ratio; however, the particle size of the gelatin microspheres decreased with increasing concentration of the emulsifier and stirring rate. During the post-treatment process, the surface of the gelatin microspheres collapsed when dehydrated by acetone; the surface morphologies of microspheres were smoother when dehydrated by acetone/water solution with a volume ratio of 5:1 and acetone in sequence. When the obtained smooth gelatin microspheres were soaked in deionized water for 24 h and then treated by freeze-drying method for 12 h, microspheres with porous structure were obtained.     

搅拌法制备聚合物微球中油水相对壁厚的影响

为了研究乳液微封装技术中油水相对微球壁厚的影响,推导了在理想状态下微球壁厚、油相质量分数和油水相比这三者之间的函数关系。结果表明:当内相水滴半径和油相质量分数为常数时,微球壁厚是油水相比的单增函数;而当内相水滴半径和油水相比为常数时,微球壁厚是油相质量分数的单增函数。即提高油相质量分数或增大油水相比对增加壁厚而言具有等效性。根据此规律,在搅拌法制备小直径聚苯乙烯微球中,通过调整油水相的各参数,确定了制备小直径厚壁聚苯乙烯微球的关键工艺参数。实验表明:采用搅拌法制备10~25 m壁厚的小直径聚苯乙烯微球时,油相质量分数宜配制为5.3%~7.0%,油水相比宜控制在1.6~2.2之间,而外水相中聚乙烯醇质量分数宜控制在1%~3%之内。     

Influences of Process Variables on Size of Chitosan Microspheres

Chitosan microspheres, with a size range of 20–550 μm, were obtained by using an emulsification–coacervation method. The surface morphology and the structure of microspheres were characterized by scanning electron microscopy and X-ray diffraction. The effects of process variables, including stirring rate, chitosan concentration, emulsifier concentration, and cross-linker (glutaraldehyde) concentration, on the diameter of chitosan microspheres were investigated. The results showed that spherical microspheres, without aggregation phenomena and with a very smooth and uniform surface, were obtained when emulsifier concentration, chitosan concentration, stirring rate, and glutaraldehyde concentration were kept at 0.010–0.025 mL/mL, 0.05–0.20 g/mL, 800–2400 rpm, and 0.5–1.5% (v/v) respectively. The chitosan microsphere crystallinity degree decreased after cross-linking. The microsphere size increased with decreasing of stirring rate, emulsifier, and cross-linker concentration; however, the microsphere size increased with increase of chitosan concentration. This indicated that different diameters of chitosan microspheres can be achieved by controlling process variables.     

聚-α-甲基苯乙烯空心微球制备过程中的缺损研究

基于二次乳化技术产生W1/O/W2双重乳液,采用乳液微封装技术制备聚--甲基苯乙烯(PAMS)空心微球,研究了部分工艺参数对PAMS微球缺损形态和比例的影响。实验结果表明:薄壁微球的低强度导致了微球表面缺损。当微球壁厚一定时,有3个因素影响缺损微球比例:W2相中聚乙烯醇质量分数、CaCl2质量分数和O/W2的相比,当它们分别为1.0%,1.5%,0.01时,薄壁(2 m)微球的缺损比例低于40%,球壳内也无气泡存在。     

Fabrication of Poly(D,L-lactide-co-glycolide) Microspheres and Degradation Characteristics in vitro

Poly(D,L-lactide-co-glycolide) (PLGA, 75/25) microspheres were prepared by the emulsion solvent extraction/evaporation technique and their degradation behaviors in vitro at 37°C were investigated. PLGA microspheres with a smooth and nonporous surface were obtained, with a mean particle size of 114.15 μm. It was observed that mass loss and water uptake of PLGA increased with increasing degradation time; however, weight average molecular weight and the pH value of the phosphate buffered saline (PBS) solution decreased. The observed relative rates of mass loss vs. molecular weight decreases were consistent with the explanation that PLGA underwent bulk degradation rather than surface degradation. During the degradation time, the surface of the PLGA microspheres became coarse and there were many micropores that developed upon immersion in the PBS. The microspheres lost their spherical form with increasing degradation time.     

Gelation and Swelling Behavior of Semi-Interpenetrating Polymer Network Hydrogels Based on Polyacrylamide and Poly(vinyl alcohol)

Novel semi-Interpenetrating Polymer Network (semi-IPN) hydrogels based on partially Hydrolyzed Polyacrylamide (HPAM) and Poly(Vinyl Alcohol) (PVA) were prepared by solution crosslinking using chromium triacetate. Effects of PVA content on the gelation process and swelling behavior in tap water and different electrolyte solutions were investigated. Study of the gelation behavior using dynamic rheometery showed that the limiting storage modulus of the semi-IPN gels decreased with increasing PVA content. It was also found that increasing the PVA content increases the loss factor, indicating that the viscous properties of this gelling system increase more strongly than the elastic properties. The swelling ratio of the semi-IPN gels in tap water decreased as the concentration of the PVA increased. However, the semi-IPN gels showed lower salt sensitivity factor in synthetic oil reservoir water as compared with HPAM gels. Therefore, they are potentially good candidates for enhanced oil recovery applications.     

Study on the Electrospinnability of Polyvinyl Alcohol Solutions by Using Water/N,N-dimethylacetamide or Water/N,N-dimethylformamide as Solvents

The electrospinning of poly(vinyl alcohol) (PVA) (99% hydrolysis degree) aqueous solution with added organic solvents N, N-dimethylacetamide (DMAc) or N, N-Dimethylformamide (DMF) was investigated. After the addition of the organic solvents to the PVA aqueous solutions, the surface tension and conductivity decreased and the viscosity significantly increased, which caused an improved electrospinnability of the PVA solutions. The micro-structures of the three solutions were investigated by dynamic light scattering (DLS), differential scanning calorimetry (DSC) and dynamic viscoelastic measurements. The DLS data revealed that the swelling of the PVA coils was slightly increased but the overlaps of PVA coils decreased greatly after one of the organic solvents was added to the aqueous solution. The DSC data showed both the water-rich phase and PVA-rich phase were destroyed and the solution became more homogenous after the addition due to the interaction between the organic solvent and water. Viscoelastic data showed there was an obvious difference in the storage modulus behavior between the aqueous solutions and the water/solvents solutions. These changes in the micro-structure and properties were the reason for the improved electrospinnability of the PVA solution. According to scanning electron microscopy (SEM), the average diameter of the electrospun PVA nanofibers was about 308 nm for the DMF/water system, and 255 nm for the DMAC/water system, as compared with uneven diameter nanofibers for the water system.     

Preparation of nano-hydroxyapatite/poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) biocomposite microspheres

Nano-hydroxyapatite (HA)/poly(l-lactide) (PLLA) composite microspheres with relatively uniform size distribution were prepared by a solid-in-oil-in-water (s/o/w) emusion solvent evaporation method. The encapsulation of the HA nanopaticles in microshperes was significantly improved by grafting PLLA on the surface of the HA nanoparticles (p-HA) during emulsion process. This procedure gave a possibility to obtain p-HA/PLLA composite microspheres with uniform morphology and the encapsulated p-HA nanoparticle loading reached up to 40 wt% (33 wt% of pure HA) in the p-HA/PLLA composite microspheres. The microstructure of composite microspheres from core-shell to single phase changed with the variation of p-HA to PLLA ratios. p-HA/PLLA composite microspheres with the diameter range of 2–3 μm were obtained. The entrapment efficiency of p-HA in microspheres could high up to 90 wt% and that of HA was only 13 wt%. Surface and bulk characterizations of the composite microspheres were performed by measurements such as wide angle X-ray diffraction (WAXD), thermal gravimetric analysis (TGA), environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM).     

聚苯乙烯相对分子量对薄壁聚苯乙烯空心微球质量的影响北大核心CSCD

激光惯性约束聚变(ICF)作为探索受控核聚变的有效途径,有望获得清洁无污染的能源,而薄壁聚苯乙烯(PS)空心微球是ICF物理实验中亟需的一类微球。针对薄壁空心微球因径厚比(直径/壁厚)增大导致其在干燥、使用中易开裂的问题,研究了PS原料对薄壁微球质量的影响,探讨了其影响机制。结果表明:当油相PS质量分数为4%时,随着油相粘度增加,W1/O/W2复合乳粒稳定性逐渐提高;当油相质量分数不低于8%时,复合乳粒稳定性良好。PS原料对微球表面粗糙度影响较小,微球球形度和壁厚均匀性随初始油相粘度的增大而降低,在干燥过程中微球开裂率随原料力学性能提高而减小。在外水相中引入氟苯(FB)液滴,延缓固化速率,可减小油相粘度增加对微球球形度和壁厚均匀性的不利影响。     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

The Effect of Poly(Ethylene Succinate) on Mechanical Properties of PLLA/PES Blend Prepared by Melt-Blending

Fully biodegradable poly(L-lactide) and poly(ethylene succinate) (PLLA/PES) blends were prepared via melt-blending using PLLA and PES as reactants in a stainless steel chamber. The prepared PLLA/PES blend, as well as neat PLLA and PES, was characterized by Fourier transform infrared spectra (FTIR) and X-ray diffraction (XRD) to confirm the structure and the crystallization of PLLA in the blend. The mechanical properties of PLLA/PES blends were determined by bending and tensile tests and the effects of PES content on the mechanical properties of PLLA/PES blends were investigated. It was found that blending some amount of PES could significantly improve the elongation at break while still keeping considerably high strength and modulus. With increasing PES content, both strength and modulus gradually decreased; however the elongation at break significantly increased. SEM was used to examine the morphology of fracture surfaces of PLLA/PES blends.     

Immobilization of silver nanoparticles on silica microspheres

The silver nanoparticles (Ag NPs) have been immobilized onto silica microspheres through the adsorption and subsequent reduction of Ag⁺ ions on the surfaces of the silica microspheres. The neat silica microspheres that acted as the core materials were prepared through sol–gel processing; their surfaces were then functionalized using 3-mercaptopropyltrimethoxysilane (MPTMS). The major aims of this study were to immobilize differently sized Ag particles onto the silica microspheres and to understand the mechanism of formation of the Ag nano-coatings through the self-assembly/adsorption behavior of Ag NPs/Ag⁺ ions on the silica spheres. The obtained Ag NP/silica microsphere conglomerates were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy-dispersive spectroscopy (EDS). Their electromagnetic wave shielding effectiveness were also tested and studied. The average particle size of the obtained Ag NPs on the silica microsphere was found that could be controllable (from 2.9 to 51.5 nm) by adjusting the ratio of MPTMS/TEOS and the amount of AgNO₃.     

Optimization of Release Conditions of Alzheimer's Drug Donepezil Hydrochloride from Sodium Alginate/Sodium Carboxymethyl Cellulose Blend Microspheres

Microspheres of blends of sodium alginate (NaAlg) and sodium carboxymethyl cellulose (NaCMC) were prepared by a water-in-oil (w/o) emulsion crosslinking method and used for the release of donepezil hydrochloride (DP), which is an Alzheimer's drug. The microspheres were characterized with Fourier transform infrared spectroscopy (FTIR), differantial scanning calorimetry (DSC), and scanning electron microscopy (SEM). The microsphere characteristics, including DP entrapment efficiency, particle size, equilibrium swelling degree (ESD), and DP release kinetics, were determined. The effects of the preparation conditions, including the NaAlg/NaCMC (w/w) ratio, drug/polymer (w/w) ratio, cross-linker concentration and time of exposure to the cross-linker, on the release of DP were investigated for successive gastrointestinal tract pH values of 1.2, 6.8, and 7.4 at 37°C. The release of DP increased with the increase in NaAlg/NaCMC (w/w) ratio and drug/polymer (d/p) ratio, while it decreased with increasing extent of cross-linking. The optimum DP release was obtained as 99.13% for a NaAlg/NaCMC (w/w) ratio of 2/1, d/p ratio of 1/4, CaCl₂ concentration of 5% and crosslinking time of 30 min. It was also observed from release results that DP release from the microspheres through the external medium was higher at low pH (1.2) values than that at high pH (6.8 and 7.4) values. The DP release of the microspheres followed either Fickian transport below a value of n < 0.5 or anomalous transport (n = 0.5–1.0).     

一种高电导率PVA聚合物电解质的制备与表征

通过溶液浇注法制备了一种polymer in salt型PVA KOH H2O聚合物电解质.对该电解质进行了X射线衍射、热性质及电化学性质测试与分析.X射线衍射显示PVA和KOH在聚合物电解质中均以非晶态存在.随着KOH含量的增加,聚合物的玻璃转化点温度逐渐上升,而电解质电导率也随之增加.该电解质的电化学窗口可达1.4V,阻抗测试显示当电解质组成PVA/KOH为1/3(质量比)时,室温电导率可达0.15S/cm,电导率与温度关系符合Arrhenius方程.该电解质热力学稳定性好,机械强度高、电化学性质优越.     

Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

This Review examines recent developments in the morphological control of polymer microspheres fabricated via the phase separation of polymers as well as the alignment of functional nanoparticles inside microspheres prepared by so‐called bottom‐up synthesis techniques. Several methods for adjusting the internal and surface morphologies of polymer microspheres based on the phase separation of polymer blends and block copolymers are discussed, and the effects of microsphere size on phase separated structures and theoretical simulations of morphologies are also reviewed. The alignment of functional nanoparticles in phase separated polymer microspheres and applications of nanostructured and hybrid polymer microspheres are summarized.     

FTIR与XRD的均匀粒度分布Ce-Cu/TiO2空心微球制备机理研究

随着社会经济的发展,环境空气品质已经成为研究热点。TiO₂是一种化学稳定性高,耐腐蚀性强,对人体无毒无害的N型半导体材料。利用TiO₂的光催化性能提高室内环境空气品质已经成为研究焦点,但是由于TiO₂只能在紫外光源下才具有较高的光催化效率,而在可见光源下的光催化效率较低,从而极大的限制了TiO₂在室内环境领域的发展。因此,研发在可见光源下具有良好光催化性能的TiO₂复合材料势在必行。利用元素掺杂改性技术与提高比表面积方法可以改善光催化反应过程中量子效率和对光能的利用率,以加快电子和空穴向表面迁移的速率同时降低光生载流子的复合机率。以二氧化硅SiO₂为模板、聚乙烯吡咯烷酮为成膜剂、硝酸铈Ce(NO₃)₃·6H₂O和硝酸铜Cu(NO₃)₂·3H₂O为改性剂采用溶胶-凝胶法制备均匀粒度分布的Ce-Cu/TiO₂空心微球,并将制备过程分为四个阶段,即纳米SiO₂球模板的制备、Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备、Ce-Cu/TiO₂-SiO₂复合微球的制备和Ce-Cu/TiO₂空心微球的制备。利用傅里叶变换红外光谱仪（FTIR）与X射线衍射仪（XRD）对Ce-Cu/TiO₂空心微球的制备过程各阶段生成物进行测试与分析,即在纳米SiO₂球模板的制备阶段从微观角度研究纳米SiO₂球模板的搭建过程,在Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备阶段研究TiO₂附着于纳米SiO₂球模板的过程,在Ce-Cu/TiO₂-SiO₂复合微球的制备阶段研究煅烧工艺对Ce-Cu/TiO₂-SiO₂复合微球中晶相与结构的影响,在Ce-Cu/TiO₂空心微球的制备阶段研究氢氧化钠溶液对Ce-Cu/TiO₂-SiO₂复合微球中纳米SiO₂球模板洗涤效果的影响。利用紫外-可见分光光度计（UV-Vis）对Ce-Cu/TiO₂空心微球的光响应性能进行测试与分析,以研究Ce-Cu/TiO₂空心微球对可见光源的利用效率。利用激光粒度分析仪（LPSA）与扫描电子显微镜（SEM）对Ce-Cu/TiO₂空心微球的粒度分布与微观形貌进行测试与分析,以研究Ce-Cu/TiO₂空心微球的均匀粒度分布效果。结果表明：以Si-O-Si基团构建非晶体结构的无定形态纳米SiO₂球模板,有利于聚乙烯吡咯烷酮在纳米SiO₂球模板表面附着,从而控制Ce-Cu/TiO₂空心微球的空腔结构。Ce-Cu掺杂基本进入TiO₂晶体,极少进入纳米SiO₂球模板晶体,从而抑制了Ce-Cu/TiO₂-SiO₂复合微球中TiO₂由锐钛矿相向金红石相的转变。Ce-Cu掺杂TiO₂可以促使TiO₂内部形成新的能级,实现能量较小的光子捕获e-和h+,从而提高Ce-Cu/TiO₂空心微球对可见光源的利用效率。Ce-Cu/TiO₂空心微球的表面光滑且不存在明显的缺陷,其形貌呈现良好的球体且粒径分布均匀,即d₉₀为219.54 nm,d₅₀为151.60 nm、d₁₀为103.84 nm,以及d₉₀-d₁₀为115.70 nm。研究结果为进一步获得可见光源下具有良好光催化性能的均匀粒度分布Ce-Cu/TiO₂空心微球提供理论依据和研究基础。     

Isothermal Crystallization and Melting Behavior of Composites Composed of Poly(L-lactic Acid) and Poly(glycolic Acid) Fibers

Several composites of poly (L-lactic acid) (PLLA) with poly (glycolic acid) (PGA) fibers were prepared. The isothermal crystallization kinetics and melting behavior of PLLA and all of the composites were characterized by using differential scanning calorimetry. The experimental data were processed by using the Avrami equation. The relative parameters, such as the Avrami exponent and half-time crystallization, revealed that PGA fibers had positive effects on the crystallization of PLLA, but these effects had only a minimal dependence on the PGA fiber content. Moreover, at low isothermal crystallization temperatures (85°C～110°C), recrystallization during the heating scan was observed, which could lower the melting point of the samples to a certain extent.     

Effect of Metallic Salts of Phenylmalonic Acid on the Crystallization of Poly(L-lactide)

The effect of the metallic salts of phenylmalonic acid (PMA), as novel nucleating agents, on the melt and crystallization behaviors, spherulitic morphologies, and crystal structures of poly(L-lactide) (PLLA) was studied by means of differential scanning calorimetry, polarized light microscopy, and wide angle X-ray diffraction (WAXD). The results showed that calcium and cadmium salts of PMA are good nucleating agents for PLLA. Lithium, sodium, magnesium, strontium, and zinc salts of PMA are moderate nucleating agents, barium and aluminum salts of PMA are weak nucleating agents, while potassium phenylmalonate is not a nucleating agent for PLLA. The presence of nucleating agents significantly increased the number and decreased the size of the spherulites, but the crystal structures of the nucleated PLLA samples were not changed.