Tailored Degradation and Dye Release from Poly(ester amides)

Poly(ester amides) based on L-valine and adipic acid with different aliphatic and aromatic diols were synthesized by interfacial polymerization. Four different diols such as ethylene glycol, 1,5-pentanediol, resorcinol, and catechol were used to systematically vary the chain lengths and position of the hydroxyl groups. The chemical structures, thermal properties, degradation, and dye release of these polymers were investigated. This study demonstrates that the release kinetics can be tailored through the control of the chain length of the diol and the position of the hydroxyl groups. These findings have important implications for designing biodegradable polymers for tailored release.     

聚对苯乙烯磺酸微球的绿色制备及催化合成生物柴油

以水为介质、苯乙烯（St）为基体单体、二乙烯苯（DVB）为交联单体、对苯乙烯磺酸钠（Na SS）为功能单体、甲基丙烯酸（MAA）为水溶性单体、过硫酸钾（KPS）为引发剂，采用无皂乳液聚合法制备了聚对苯乙烯磺酸微球（PSS）。利用FTIR、XPS、SEM、TGA和DSC对其进行了表征，并对其粒径、Zeta电位、比表面积、酸密度进行了考察，探讨了Na SS、DVB和KPS用量对PSS结构、性能的影响。当H2O为90m L、St为76.9 mmol、MAA为9.3 mmol、NaSS为0.7mmol、DVB为7.7 mmol、KPS为0.7mmol时，制备的PSS-3粒径均匀且酸密度较高。然后，将PSS-3作为固体酸催化剂，用于催化油酸/甲醇酯化合成生物柴油（油酸甲酯）。结果表明，当甲醇/油酸的物质的量比为10∶1、PSS-3用量为油酸质量的2%、反应温度为80℃、反应时间为6h时，油酸的转化率可达86.4%。PSS-3作为固体酸催化剂具有较好的重复使用性能，循环使用4次后油酸转化率没有明显下降。     

Effect of Poly(L-lactic acid) on Hydrolytic Degradation of Poly(glycolic acid)

The in-vitro degradation behavior of poly(glycolic acid) (PGA) rods and the composite rods containing poly(L-lactic acid) (PLLA) were investigated via mass loss, pH value change, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Since the degradation rate of PLLA is lower than that of PGA, PLLA/PGA composite rods exhibit a slower degradation rate in comparison with PGA. This finding indicated that it was possible to control the degradation rate of the composites by changing their composition. This result indicates that this kind of composite biomaterial may be applicable to devices for the need of prolonged degradation.     

壳聚糖/聚丙烯酸共聚物微球的制备及性能

以环己烷为油相,壳聚糖溶液为水相,运用反相乳液聚合法制得了具有pH敏感性的壳聚糖/聚丙烯酸共聚物微球。讨论了微球在pH=1～10缓冲溶液中的溶胀率变化,研究表明,微球在强酸性(pH≈1)和碱性(pH>7)条件下,溶胀率均在10倍以上;而在pH=2～6时溶胀较差,当pH=4时出现最低值,溶胀率低于1倍。光学显微镜所观察到的微球粒径均在40μm以内,且大小均匀。采用傅里叶红外光谱仪分析了不同配比样品特征峰的峰值和峰面积的变化。用722光栅分光光度计研究了共聚物微球包埋考马斯亮蓝的溶胀释放过程。     

超大孔聚(苯乙烯-甲基丙烯酸缩水甘油酯)共聚微球的制备及孔结构的调控

使用表面活性剂反胶团法制备超大孔聚(苯乙烯-甲基丙烯酸缩水甘油酯)[P(ST-GMA)]共聚微球,考察了功能单体GMA含量、油溶性表面活性剂、稀释剂、交联剂对微球孔径的影响. 结果表明,随GMA含量增加,微球孔径显著增大;表面活性剂用量从1.6 g增加到2.0 g时,微球孔径由100 nm增加到720 nm;随稀释剂疏水性增强,微球孔径增大;交联剂用量由1.0 g增加到2.0 g,微球孔径由550 nm变为100 nm左右. 在此基础上,通过条件优化合成了具有特定孔径的不同功能单体GMA含量的超大孔P(ST-GMA)共聚微球,可连接不同配基,用于色谱分离介质及酶的固定化.     

5-氟尿嘧啶明胶微球的制备、表征及释药性能

为了获得粒径为50～100μm的5-氟尿嘧啶／明胶微球（5-Fu／GMs）,采用乳化一化学交联法,讨论了5-Fu用量、乳化剂浓度和水／油比等因素对微球平均粒径、载药量及包封率等的影响。结果表明,5-Fu／明胶质量比为0．5,乳化剂浓度为0．5％和水／油相体积比为1／10时,可获得最大的载药量30．1％和包封率90．2％。体外释药性能表明5-氟尿嘧啶明胶微球具有明显的药物缓释作用。     

可生物降解聚乳酸纳米粒的制备及表征

采用乳化 -溶剂蒸发法 ( O/W)制备聚乳酸 ( PLA)纳米粒 ,用透射电子显微镜和激光粒度仪对纳米粒进行了表征 ,纳米粒具有规整的球形且正态分布 ,同时从有机相和水相的体积比、聚合物的浓度、表面活性剂的选择及表面活性剂的浓度等几个因素对纳米粒粒径大小的影响作了较详细地讨论。有机相与水相的体积比从 1∶ 3减小到 1∶ 30 ,纳米粒的粒径从 ( 30 6.2 + 1 1 ) nm减小到( 1 87.1 + 2 .4) nm;聚合物在有机相的浓度从 1 %(质量分数 )增加到 5 %(质量分数 ) ,纳米粒的粒径从 1 94nm增加到 32 1 nm;随着水相中表面活性剂浓度从 0 .5 (质量体积分数 )增大到 3.5 %(质量体积分数 ) ,纳米粒粒径从 2 0 2 nm减小 1 78nm且有一个低的多分散指数。而且还比较了搅拌蒸发法和减压抽提法对纳米粒表面形态的影响     

Hydrolytic Degradation of Aliphatic Polyesters Copolymerized with Poly(ethylene glycol)s

Poly(1,4-butanediol succinate) copolymers were prepared by melt polycondensation of succinic acid and 1,4-butanediol with 10–50mol% (in feed) of poly(ethylene glycol) (PEG), where molecular weight (MW) of PEG is 200–2000. The reduced specific viscosity of the copolymers increased with incorporation of the PEG component, but a higher PEG content in the copolymers reduced it. The temperature of melting (T_m) and crystallinity decreased with increasing PEG content. T_m depression of the copolymers followed approximately Flory’s equation, suggesting that these are random type copolymers. Tensile strength and elongation decreased with increasing MW and content of PEG. The weight loss of copolymer films in a buffer solution with or without lipase at 37°C, as well as water absorption, increased with increasing PEG content, implying that higher water absorption contributes to hydrolytic degradation of the films. However, the weight loss of copolymers with PEG of lower MW increased greatly in spite of lower water absorption, demonstrating that hydrolytic degradation is influenced by the concentration of degradable ester linkages between succinic acid and PEG segments rather than water absorption. © of SCI.     

Synthesis of Biodegradable Poly(butylene terephthalate)/poly(ethylene glycol) (PBT/PEG) Multiblock Copolymers and Preparation of Indirubin Loaded Microspheres

Summary Biodegradable PBT/PEG copolymers were synthesized by macromolecular transesterification method, and were characterized by 1H-NMR and DSC. Alkaline degradation behavior was studied too. Indirubin loaded microspheres were prepared by O/W solvent evaporation method.     

Anti-Inflammatory Effect of Very High Dose Local Vessel Wall Statin Administration: Poly(L,L-Lactide) Biodegradable Microspheres with Simvastatin for Drug Delivery System (DDS)

Atherosclerosis involves an ongoing inflammatory response of the vascular endothelium and vessel wall of the aorta and vein. The pleiotropic effects of statins have been well described in many in vitro and in vivo studies, but these effects are difficult to achieve in clinical practice due to the low bioavailability of statins and their first-pass metabolism in the liver. The aim of this study was to test a vessel wall local drug delivery system (DDS) using PLA microstructures loaded with simvastatin. Wistar rats were fed high cholesterol chow as a model. The rat vessels were chemically injured by repeated injections of perivascular paclitaxel and 5-fluorouracil. The vessels were then cultured and treated by the injection of several concentrations of poly(L,L-lactide) microparticles loaded with the high local HMG-CoA inhibitor simvastatin (0.58 mg/kg) concentration (SVPLA). Histopathological examinations of the harvested vessels and vital organs after 24 h, 7 days and 4 weeks were performed. Microcirculation in mice as an additional test was performed to demonstrate the safety of this approach. A single dose of SVPLA microspheres with an average diameter of 6.4 μm and a drug concentration equal to 8.1% of particles limited the inflammatory reaction of the endothelium and vessel wall and had no influence on microcirculation in vivo or in vitro. A potent pleiotropic (anti-inflammatory) effect of simvastatin after local SVPLA administration was observed. Moreover, significant concentrations of free simvastatin were observed in the vessel wall (compared to the maximum serum level). In addition, it appeared that simvastatin, once locally administered as SVPLA particles, exerted potent pleiotropic effects on chemically injured vessels and presented anti-inflammatory action. Presumably, this effect was due to the high local concentrations of simvastatin. No local or systemic side effects were observed. This approach could be useful for local simvastatin DDSs when high, local drug concentrations are difficult to obtain, or systemic side effects are present.     

Poly(2-hydroxyethylmethacrylate-co-2-folate ethylmethacrylate) and Folic acid/Poly(2-hydroxyethylmethacrylate) Solid Solution: Preparation and Drug Release Investigation

Poly(2-hydroxyethylmethacrylate-co-2-folatethylmethacrylate) was synthesized by free radical polymerization of 2-hydroxyethylmethacrylate with 2-folatethylmethacrylate and folic acid/poly(2-hydroxyethylmethacrylate) solid solutions was prepared by mixing folic acid with poly(2-hydroxyethylmethacrylate) using the solution casting method. The structure and the homogeneity distribution of folic acid in the polymer matrix are characterized by different methods. The diffusion behaviors of water and folic acid through poly(2-hydroxyethylmethacrylate-co-2-folatethylmethacrylate) and poly(2-hydroxyethylmethacrylate) matrixes were found obey to the Fick models. The in vitro cytotoxicity assessed by microculture tetrazolium test assay and the antioxidant activity of poly(2-hydroxyethylmethacrylate-co-2-folatethylmethacrylate) systems determined by 1,1-diphenyl-2-picryl-hydrazyl method revealed no significant toxicity of these systems and has excellent free radical scavenger property which can be as safe candidate in drug-carrier system. The solubility enhancement of folic acid in different pH media is also investigated and the results obtained reveal a maximum of 399–400?mg?L^?1. The release dynamic of folic acid from the poly(2-hydroxyethylmethacrylate-co-2-folatethylmethacrylate) containing 5?mol% of folic acid and that from folic acid/poly(2-hydroxyethylmethacrylate) system containing 10?mol% of folic acid have the best intestine/stomach ratio.     

浓乳液双相聚合制备聚丙烯酸丁酯粒子及其对聚氯乙烯的改性研究

用浓乳液双相法合成PBA，通过在合成过程中添加不同用量的DVB交联剂和MMA硬单体调节PBA粒子的硬度及性能，研究了不同DVB及MMA加入量的PBA对PVC力学性能的影响。并通过复合材料断面微观形态分析验证了实验结果。结果表明：在BA单体中加入硬单体MMA和交联剂DVB均可提高PBA粒子的硬度，当MMA和DVB用量较大时，会导致粒子呈现刚性，不利于PBA对PVC改性；PBA粒子与硬质PVC共混后能较好地分散在PVC中，并能在提高材料冲击强度的同时，拉伸强度也有所改善；DVB和MMA的用量均为2mL时，PBA异形粒子对硬质PVC的改性效果最好。此配方PBA粒子与PVC相容性好、界面结合力强。     

负载药物替莫唑胺的纳米羟基磷灰石/聚乳酸-羟基乙酸共聚物微球的缓释行为

以聚乳酸-基乙酸共聚物(PLGA)和纳米羟基磷灰石(nHA)作为生物降解材料制备了药物替莫唑胺(Temozolomide,TMZ)的缓释系统.采用湿法化学工艺制备了球状和棒状的nHA粉末.将TMZ药物分子负载在nHA表面(nHA-TMZ),再通过乳化溶剂挥发法将nHA-TMZ包裹在PLGA微球中,同时研究了微球中nHA的形貌和含量对缓释微球物化性能的影响.用扫描电镜、紫外分光光度计分别测定了微球的结构、形貌、药物包封率和缓释行为.相比于不含有nHA的TMZ/PLGA缓释微球,nHA的介入能够显著提高药物的包封率,并且包封率与nHA的加入量有关.此外,药物释放实验表明包裹在微球中的nHA的形貌和溶解速率能够影响微球的缓释行为.     

Synthesis,Characterization, and Release Dynamic of Acetylsalicylic Acid From Acetylsalicylic Acid/Poly(vinylalcohol-co-ethylene) Membrane

A series of poly(vinylalcohol-co-ethylene)/acetylsalicylic acid blends (PEVA/AcSa) of different AcSa contents were prepared and characterized by the solubility test, differential scanning calorimetry, and scanning electron microscopic analyses. The results revealed that AcSa was perfectly soluble in PEVA at certain composition and uniformly distributed throughout the polymer matrix. The release dynamic of AcSa from PEVA/AcSa material was studied at body temperature during 92 h in which the influence of AcSa initially incorporated in PEVA, the pH of media, the membrane thickness, and the stability of AcSa release rate on the release dynamic were detailed.     

Preparation and Characterization of Poly (Hydroxy Ethyl Methyl Acrylate-Co-Acrylic Acid) Microspheres for Drug Delivery Application

Poly (hydroxy ethyl methyl acrylate-co-acrylic acid) pH sensitive microspheres crosslinked with N,N′-Methylenebisacrylamide were prepared by free radical emulsion polymerization. Different formulations was prepared by varying amounts of 2-hydroxy ethyl methacrylate (HEMA) acrylic acid (AA) and N,N′-Methylenebisacrylamide (NNMBA), Triprolidine hydrochloride (TPH), and hypertensive drug was loaded during in situ polymerization and in vitro release studies was performed at 37°C. DSC analysis reveals that the drug is molecularly dispersed in the microspheres. SEM studies indicate the formation of microspheres with smooth surface and spherical shape. The in vitro release studies of the microspheres were carried out in pH 1.2 and 7.4 media.     

聚乙烯醇降解特性研究

采用凝胶色谱法（GPC）和紫外分光光度法（UV）研究了聚乙烯醇（PVA）微生物降解和化学氧化降解效果。GPC实验表明，PVA经过本实验室筛选的微生物菌株降解后，保留9min左右产生了一个小相对分子质量的峰，其峰面积约占总面积的一半；UV实验也表明了PVA在降解菌株的作用下，其浓度呈下降趋势；采用Fenton试剂（FR）对PVA进行预先氧化处理，然后再进行微生物降解。结果表明FR预处理有利于PVA的快速有效降解。     

Chemical Degradation of Poly(Ethylene Terephthalate)

The possibility of converting polyethylene terephthalate (PET) waste into terephthalic acid as a primary material by using different techniques through trans-esterification, with an alcohol and through hydrolysis in basic medium, has been investigated. In addition, utilization of activating agents such as inorganic salts and phase transfer catalysts has been investigated.Mineral water and beverage bottles were collected, cleaned and crushed into flakes suitable for the intended experiments. Also, the main products of chemical conversion of such wastes were isolated and confirmed by authentication with standard terephthalic acid through Thin Layer Chromatography (TLC) technique. The reaction yield % was determined to optimize the corresponding experimental conditions and the obtained results have been presented and discussed.     

新型聚氨酯微球制备及其药物释放规律的研究

以低相对分子质量生物可降解DL-聚乳酸二醇和六亚甲基二异氰酸酯为原料,通过悬浮聚合法合成了一种新型聚氨酯微球(PUMS),考察了扩链剂1,4-丁二醇(BDO)的含量对微球表面形态和药物包封率的影响。用傅立叶变换红外光谱(FFIR)、扫描电子显微镜(SEM)以及激光粒度分析仪对微球的化学结构、表面形态、粒径及其分布进行了表征,并以溴百里酚兰为亲水性模型药物,初步研究了微球的药物释放行为。结果表明,合成的微球的平均粒径47um,粒径分布在10～90um之间;微球表面有孔,但随着BDO含量的增加,微球表面变得相对粗糙,孔数减少,孔径减小,直至孔消失;BDO含量的增加也使模型药物的包封率减小,释放速率变慢;药物释放初期出现程度不同的“暴释”现象,但随后近似于零级释放。