含有4,4′-双(甲基丙烯酰胺基)偶氮苯水凝胶的合成及其在结肠位药物释放的动物实验

合成了不同链长的甲基丙烯酸酯、甲基丙烯酰胺及丙烯酸与4,4′-双(甲基丙烯酰胺基)偶氮苯交联共聚的功能凝胶.三维网络结构通过压缩弹性模量、有效交联密度及聚合物与溶剂间的相互作用参数进行了表征.主要研究了这类凝胶在pH2.2和pH7.4的缓冲溶液的平衡溶胀特性及其偶氮交联基团在体内的降解行为,并讨论了其降解机制.凝胶在胃部的性能稳定,既不发生溶胀,亦不发生降解;但在盲肠内偶氮交联基因可发生降解.其降解率与凝胶的平衡溶胀程度有一个很好的关联:交联程度、疏水基侧链的长度及含量对凝胶溶胀行为的影响结果与这些因素对偶氮交联基团体内降解的影响结果完全一致.通过调节这些因素不仅可以控制凝胶的溶胀程度,而且可以控制偶氮交联基团在体内的降解行为.     

含有4,4′-双(甲基丙烯酰胺基)偶氮苯水凝胶的合成及其在结肠位药物释放的动物实验

合成了不同链长的甲基丙烯酸酯、甲基丙烯酰胺及丙烯酸与 4 ,4′ 双 (甲基丙烯酰胺基 )偶氮苯交联共聚的功能凝胶 .三维网络结构通过压缩弹性模量、有效交联密度及聚合物与溶剂间的相互作用参数进行了表征 .主要研究了这类凝胶在pH2 2和pH7 4的缓冲溶液的平衡溶胀特性及其偶氮交联基团在体内的降解行为 ,并讨论了其降解机制 .凝胶在胃部的性能稳定 ,既不发生溶胀 ,亦不发生降解 ;但在盲肠内偶氮交联基因可发生降解 .其降解率与凝胶的平衡溶胀程度有一个很好的关联 :交联程度、疏水基侧链的长度及含量对凝胶溶胀行为的影响结果与这些因素对偶氮交联基团体内降解的影响结果完全一致 .通过调节这些因素不仅可以控制凝胶的溶胀程度 ,而且可以控制偶氮交联基团在体内的降解行为 .     

可生物降解的聚磷酸异山梨醇酯的合成与表征

由异山梨醇和苯膦酰二氯经本体聚合法和溶液聚合法得到了不同分子量的新型聚磷酸酯(PPI),采用傅立叶变换红外(FTIR),核磁共振氢谱(~1H-NMR)和凝胶渗透色谱(GPC)对聚酯的组成和分子量进行表征,结果表明产物为聚磷酸酯结构.聚合物在水溶液和酶溶液中的降解和溶胀实验表明,当PPI的分子量(M_w)低于5×10~4时,聚合物具有很好的降解性能和溶胀性能,25天后其降解率达到80%,溶胀率达到150%.当M_w高于5×10~4时,其降解速率和吸水率明显下降,25天后降解率和溶胀率分别仅为25%和40%.研究了PPI的玻璃化转变温度(T_g)和分子量的关系,PPI具有较高的Tg,且随着分子量的增加,聚合物的T_g显著增加.当PPI的分子量为6×10~4时,其玻璃化转变温度达到176℃.同时研究了聚合物分子量对其热稳定性的影响,当重均分子量由2×10~4增加到6×10~4时,PPI的起始分解温度从260℃提高到315℃.结果表明提高分子量有助于提高PPI的热分解温度.     

末端为磷酰胆碱基团的聚丁二酸丁二醇酯的酶促降解和热性能

以聚丁二酸丁二醇酯(PBS)为参照, 研究了酯酶Lipase AY30对亲水磷酰胆碱(PC)基团改性的聚丁二酸丁二醇酯(PBS-PC)的生物降解性能的影响. 结果显示, 在酯酶Lipase AY30作用下, 21 d后PBS的质量损失仅为1.9%, 而PBS-PC的质量损失了9.7%. 相同条件下扣除各自水解引起的质量损失(PBS 1.4%和PBS-PC 6.5%)后, PC亲水基团的引入对聚合物的降解起到了促进作用. 示差扫描量热(DSC)研究结果表明, 改性后的聚合物熔融温度和熔融焓降低, 玻璃化转变温度升高, 表明PC端基的引入降低了PBS的结晶能力, 非晶相结构的增多对聚合物降解有促进作用. 因此PBS-PC有望作为一种新的具有良好生物降解性和生物相容性的高分子材料, 应用于药物控释、基因治疗及组织工程等生物医用材料领域.     

新型不饱和聚磷酸酯的合成、表征及性能

通过溶液聚合制备了一种新型不饱和聚磷酸酯(Polymer Ⅰ), 经季铵化得到了侧基含季铵基的不饱和聚磷酸酯(PolymerⅡ). 对聚合物的结构和热性能进行了表征. 研究了PolymerⅡ与聚丁二酸丁二醇酯(PBS)的共混片基(Polymer Ⅱ的质量分数分别为5%, 10%和20%)在pH=7.4的磷酸缓冲溶液中的溶胀和降解性能. 结果表明, 以纯三甲胺为季铵化试剂, 在V(氯仿): V(异丙醇): V(DMF)=3: 5: 5的混合溶剂中, 于60℃反应24 h可得到季铵化率高达48%的PolymerⅡ. 在PBS中PolymerⅡ的含量越多, 达到溶胀平衡时, 共混片基的溶胀率越高, 越容易降解. 磷酸酯的引入使聚合物的熔点(T_m)和热稳定性(T_d)降低.     

木质素-聚氨酯水凝胶的合成及其性能

异氰酸根封端的聚氨酯离子聚合物与乙酸木质素交联合成了一种水凝胶。研究了该水凝胶的吸水溶胀率、热稳定性能及以此凝胶包裹的硫酸铵的缓释性能。结果表明:当木质素与聚氨酯离子聚合物的质量比为0.35时,水凝胶在pH=6.86的缓冲溶液中的最大溶胀率为3.14;聚氨酯水凝胶中引入木质素,可以提高凝胶的热稳定性;木质素-聚氨酯水凝胶包裹的硫酸铵表现出明显的缓释特征。     

交联聚合物P(MMA-MAh)-PEG1500基凝胶电解质锂离子键合极性基团作用FTIR研究

用聚乙二醇(PEG1500)和甲醇先后与共聚物(P(MMA-MAh))发生酯化反应,合成得到交联聚合物P(MMA-MAh)-PEG1500.以该交联聚合物P(MMA-MAh)-PEG1500、碳酸丙烯酯(PC)和锂盐(LiClO4)为三种组分制备凝胶聚合物电解质,电解质性能必会受到这些组分间存在的微观相互作用的影响.采用FTIR来研究PC和P(MMA-MAh)-PEG1500中存在的极性基团(C=O和C—O—C)与Li+的相互作用.对于PC/LiClO4和polymer/LiClO4体系,FTIR定量分析显示,极性基团对Li+的吸收系数分别为0.113和0.267,说明在红外光谱中Li+键合C=O和C—O—C极性基团比自由极性基团吸收灵敏度高;另外,计算该二体系中Li+键合极性基团(C=O和C—O—C)的当量百分数极限值分别为94%和45%,表明极性基团与Li+间存在的相互作用是可逆的,并且体系PC/LiClO4中相互作用强度大于体系polymer/LiClO4.     

pH敏感性丙烯酸-苯乙烯-丙烯酸异辛酯共聚物水凝胶的制备及性能研究综合实验

采用乳液聚合的方法,合成了丙烯酸-苯乙烯-丙烯酸异辛酯共聚物水凝胶,通过红外光谱对水凝胶进行了表征,考察了pH对水凝胶溶胀率的影响,并以该凝胶制备了硫脲缓释体系。结果表明,该凝胶在碱性条件下的溶胀度远大于在中性和酸性条件下的溶胀度,具有pH敏感性,且缓释性能好。将该实验研究过程设计为高职学生的综合实验项目并进行了实践探索,结果表明其在提升学生专业综合能力、开阔专业视野及培养创造性与科学思维等方面效果显著。     

磺化聚苯醚酮质子交换膜的制备与表征

设计、合成了一种含氰基双氯单体,其结构特点是氰基分布在3个以间位醚键相连的苯环上。以此单体和2,5-二氯-3'-磺酸钠二苯甲酮为原料,利用Ni(0)催化偶联反应制备了微嵌段型质子交换膜材料(中等长度磺化聚苯-三氰基聚苯醚酮共聚物(m-SPP-co-PAEK 3CN x),x代表聚合物的离子交换容量)。结果表明,与相同离子交换容量的磺化聚合物相比,该类聚合物膜表现出较低的吸水、溶胀率和较低的甲醇渗透性能。以离子交换容量2.16为例,80℃下,m-SPP-co-PAEK 3CN 2.16的吸水率、溶胀率分别为29.7%、28.2%,而SPP-co-PAEK MO 2.33的吸水率、溶胀率分别为80.2%、37.2%。25℃下,二者的甲醇渗透系数分别为2.38和7.20。聚合物骨架结构中存在丰富的氰基基团,导致膜具有良好的尺寸稳定性和较低的甲醇渗透性能。基于这些优异的性能,新制备的膜材料在燃料电池领域显示了潜在的应用前景。     

干燥方式对含直链淀粉半互穿网络水凝胶溶胀和降解的影响

以4,4′-二甲基丙烯酰胺基偶氮苯(BMAAB)为交联剂,制备了丙烯酸-丙烯酰胺-甲基丙烯酸酯共聚物和直链淀粉半互穿网络水凝胶.以冷冻干燥和空气干燥两种方式,研究了干凝胶在pH2.2和pH7.4时的溶胀和降解性能.结果表明采用两种干燥方式的凝胶在不同pH的介质中都遵循二级溶胀动力学.凝胶内部水的扩散均为非Fickian机理,即扩散和链松弛协同作用的机理.但经历冷冻干燥的凝胶其扩散机制占优势.在pH=7.4的介质中,冷冻干燥凝胶的平衡溶胀比(SR)显著增大,而在pH=2.2时则无明显变化.扫描电镜(SEM)和降解实验发现,在结肠内容物的作用下,冷冻干燥凝胶在5天内降解率可达35.3%,而空气干燥凝胶的降解率为28.1%,表明冷冻干燥的方式可在一定程度上促进凝胶在结肠环境下的降解.     

Improved biocompatibility of phosphorylcholine end-capped poly(butylene succinate)

In this work, the biocompatibility of a biomimetic, fully biodegradable ionomer phosphorylcholine (PC)-functionalized poly(butylene succinate) (PBS-PC) was investigated by means of hemolysis, platelet adhesion, protein adsorption and cytotox- icity experiments. The reference materials were poly(butylene succinate) (PBS) and chloroethylphosphoryl functionalized poly(butylene succinate) (PBS-Cl). The hemolysis rates (HR) of the leaching solutions of PBS, PBS-Cl and PBS-PC were all lower than the safe value, and the rate of PBS-PC was reduced to 1.07%. Scanning electron microscopy (SEM) measurements showed that platelet adhesion and aggregation were significant on both PBS and PBS-Cl surface. In contrast, very few platelets were observed on PBS-PC surface. Bicinchoninic acid (BCA) measurements revealed that the adsorption amounts of bovine serum albumin (BSA) and bovine plasma fibrinogen (BPF) on PBS-PC surface were 52% and 72% reduction respectively compared with those on PBS surface. Moreover, non-cytotoxicity of both PBS-PC particles and its leaching solution was sug- gested by MTT assay using mouse L929 fibroblast cells. All the results demonstrated that the biocompatibility of PBS could be greatly improved by PC end-capping strategy. This PC functionalized polyester may have potential applications in biological environments as a novel carrier for controlled drug release and scaffold for tissue engineering.     

In vitro degradation and swelling behaviour of rubbery thermoplastic starch in simulated body and simulated saliva fluid and effects of the degradation products on cells

Degradation in vitro is of importance in implanted biological industry. This research investigated the swelling and degradation behaviours of glycerol plasticized thermoplastic starch (GTPS) in simulated body fluid (SBF) and simulated saliva fluid (SSF), respectively. The weight loss, swelling degree and linear extensibility as a function of time were measured. Changes in the morphology (SEM), chemical structure (FT-IR), crystal property (XRD) and thermogravimetic property (TG) during degradation were also investigated. Results show that the degradation in SSF was much quicker than that in SBF. About 1 h was needed for the swelling equilibrium in SBF, which was a little quicker than that in SSF. In alkaline solution the swelling speed and the swelling degree were larger than those in neutral and acidic solutions. The degradation in SBF was typical bulk degradation. In SSF the surface and bulk degradation took place synchronously, but the surface degradation played an important role in the first 2 h. Results from FT-IR and XRD suggest that the glycosidic linkages in starch chains were broken and the crystal structure in GTPS was destructed during degradation. Cytotoxicity test was used to investigate the effects of the short-term extracted dilutions and long-term degradation products on the cells, which illustrates that the degradation products not only had non-toxicity but also accelerated the cells' growth.     

Development of Injectable Biodegradable Multi-Arms PEG-Based Hydrogels: Swelling and Degradation Investigations

Summary : Injectable biodegradable hydrogels have been developed to determine the efficacy of biomaterials for the treatment of periodontitis through control delivery of bone-healing bioactives. The hydrogels were prepared from the PEG-ylated macromer of Boltorn™ H20 (BH20) and an acrylated triblock copolymer of polylactide-polyethylene glycol (2k)-polylactide (PLA) in various molar ratios using ammonium persulfate and sodium ascorbate as a free radical initiating system. Preliminary investigations involving the synthesis of PLA hydrogels with different PLLA block lengths were studied in order to determine the swelling ratios and degradation rates of the biodegradable component of the hydrogels prior to copolymerization with BH20. The swelling and degradation studies of PLA with PEG diacrylate (FW 700) hydrogels were established in phosphate buffered saline (PBS) at 37 °C, pH 7.4 and in water (pH ∼5.5). They have been shown to have low swelling ratios (Q_max = 4.4 to 3.6) and degradation times of 20–30 days. The swelling and degradation parameters were found to be dependent on the molar ratio of the PEG diacrylate to PLA in the copolymer.     

Behavior of intumescent epoxy resins in fireproofing applications

The thermal degradation process of a commercial intumescent epoxy resin for fireproofing applications was investigated. The changes in the morphology of the material during exposure to fire-like conditions were interpreted in the light of the degradation of single material components and of the overall swelling mechanism. An apparent kinetic model was developed to describe the thermally activated conversion and the weight loss of the material. The dramatic change in the key properties of the material (thermal conductivity, volume swelling, and apparent density) was investigated and linked with the thermal degradation phenomena governing the swelling process. Models were developed to describe material properties as a function of temperature and material conversion. The models provide the simulation of the fire-triggered degradation of the sample material at the heating rates of interest, allowing a detailed analysis of fireproofing performance.     

Synthesis, characterization and properties of biodegradable polylactic acid-β-cyclodextrin cross-linked copolymer microgels

The novel biodegradable polylactic acid-β-cyclodextrin (PLA-β-CD) cross-linked copolymer microgels were prepared by the radical copolymerization of PLA macromonomer and polymerizable β-CD derivatives. The β-CD derivatives with various numbers of polymerizable vinyl groups were synthesized from 1-allyloxy-2,3-epoxy propane (also called allylglycidyl ether, AGE) and β-CD. The chemical structures of polymerizable monomers were determined by NMR. The thermal properties, size, morphology, in vitro degradation and swelling behavior of the microgels were investigated. The results indicated that the microgels were stable under thermal conditions up to 200 °C. The microgels were spherical in aqueous solution. The hydrophilicity of the microgels increased with increasing β-CD contents, while the swelling ratios and degradation rate decreased. The more vinyl groups on β-CD, the higher cross-linked density, which resulted in a decrease of the swelling ratios and the rate of degradation.     

Hydrophobically modified hydrogels containing azoaromatic cross-links: swelling properties, degradation in vivo and application in drug delivery

Hydrogels based on n-alkyl methacrylate esters (n-AMA) of various chain lengths, acrylic acid, and acrylamide cross-linked with 4,4-di(methacryloylamino)azobenzene were synthesized. The equilibrium swelling degree of the hydrogels in buffered solutions at pH 7.4 was shown to be very low in the pH range of the stomach. The entire swelling processes of the gels in the gastrointestinal tract were mainly dependent on those in the small intestine. In the buffered solution of pH 7.4 the diffusion of water into the gel slabs was discussed on the stress relaxation model of polymer chains. The results obtained are in good agreement with Schott's second-order diffusion kinetics. The biodegradability in vivo of their azobenzene cross-linking groups as well as the mechanism of degradation by cecal bacteria was studied. The gels are stable in the stomach but degradable by ananerobes present in the colon. The extent of degradation was considerably related to the equilibrium degree of swelling. The factors influencing the swelling degree were shown to influence the in vivo degradation of the gels. By changing these factors such as the degree of cross-linking, the length and content of the n-AMA side chains, it is possible to control both the degree of swelling and the degradation of the hydrogels.