聚乙二醇对淀粉原位熔融接枝聚乳酸的影响

研究了在聚乙二醇(PEG)存在下,淀粉与丙交酯的原位熔融接枝反应。较系统地考察了PEG的加入量及分子量的变化对淀粉一聚乳酸原位熔融接枝反应的影响。结果表明,当有PEG存在时,丙交酯可以有效地接枝到淀粉链上,得到淀粉一聚乳酸接枝共聚物。PEG对淀粉的增塑效果是影响淀粉与丙交酯熔融接枝反应至关重要的因素。     

聚乙二醇改性聚乳酸的合成与性能表征

以外消旋乳酸(D,L-LA)和不同数均分子量(Mn)的聚乙二醇(PEG)为原料,通过熔融缩聚法,合成了系列聚乳酸聚乙二醇(PLEG)。最佳工艺条件为:以(Sn(Oct)2)为催化剂,m(Sn(Oct)2)为0.8%,n(PEG)∶n(D,L-LA)=1∶600,聚合温度170℃,压力0.096 MPa条件下,反应8h。用特性粘度测试、FT-IR、XRD、接触角等对其进行表征,实验结果表明系列PLEG中PLEG-800接触角为63°,表明其亲水性能最好;PEG-800和乳酸共聚合成的PLEG的粘均分子量最大,可达48997,与PDLLA相比,结晶度有较大提高,亲水性得到改善。     

环糊精改性聚乳酸及其体外降解性研究

环糊精改性聚乳酸(PLA-β-CD)是一种全生物降解的新型生物材料.考察了环糊精改性聚乳酸基生物材料的体外降解行为,包括材料在蒸馏水中的pH值变化和在pH=7.4 PBS中的失重率变化.结果表明,PLA-β-CD与PLA的降解行为相似,PLA-β-CD的分子主链没有被破坏,没有出现引入酸酐导致材料酸性进一步增强的现象.     

新型改性聚乳酸及其亲/疏水性研究

合成了基于马来酸酐改性聚乳酸（MPLA）和丁二胺的新型改性聚乳酸（BM-PLA），旨在提高聚乳酸的亲水性，克服乳酸和MPLA在降解过程中的酸性，并为进一步引入多肽和胶原等生物信号分子提供活性基团。通过红外光谱测定到了丁二胺已成功引入到MPLA中，利用接触角和吸水率评价了BMPLA的亲/疏水性变化，表明丁二胺改性所得BMPLA的亲水性相对于PDLLA和MPLA已大大改善，测定了材料在12周降解过程中的pH变化。表明丁二胺改性聚乳酸不表现酸致自加速降解特征，未出现pH陡降现象，已完全克服了聚乳酸和马来酸酐改性聚乳酸降解过程中的酸性，上述研究结果提示，丁二胺改性聚乳酸是一族新型的具有优良亲水性和良好降解行为的组织工程材料，预示着它可望具有优良的细胞亲和性，在组织工程中具有重要的应用潜力。     

聚丙烯接枝聚乙二醇改性聚丙烯微孔膜

以聚丙烯接枝聚乙二醇(PP-g-PEG)对聚丙烯共混改性,通过单向拉伸工艺制备亲水性聚丙烯微孔膜。使用压汞仪、扫描电镜、Gurley值和水蒸气透过率表征微孔膜的孔结构和透过性能,研究PP-g-PEG含量、PEG接枝率及链长对微孔膜孔结构、水蒸汽透过率及锂电池性能的影响。结果表明,对于接枝率为0.78%的PP-g-PEG,随着添加剂PP-g-PEG含量增加,微孔膜孔隙率和微孔尺寸下降,反映孔道结构的曲挠度及喉孔比上升;微孔膜孔结构与亲水性的综合作用导致水蒸气透过率在PP-g-PEG含量为2.5%时达到最大值。PP-g-PEG含量为2.5%和5.0%的微孔膜组装的锂电池具有较低的电荷转移电阻和较高的充放电比容量,电池性能优于未改性微孔膜组装的电池。提高PEG接枝率使得改性微孔膜孔结构有所变差,但是水蒸气透过率提高,组装电池的性能也更好。长PEG侧链PP-g-PEG对微孔膜孔结构的破坏程度大于短PEG侧链PP-g-PEG,导致组装电池的性能变差。     

聚乙二醇改性聚乳酸嵌段共聚物的合成与亲水性研究

以DL-丙交酯和分子量Mn=400、1000和2000聚乙二醇(PEG)为原料,在辛酸亚锡催化下开环聚合制备了聚乳酸(PLA)-聚乙二醇-聚乳酸三嵌段共聚物(PLEG)。考察了催化剂用量、反应时间对产率和[η]的影响。用FT-IR、1 H-NMR、GPC、DSC、XRD、静态水接触角等对共聚物进行了表征和性能测试。结果表明,催化剂用量为0.2%、反应时间分别为PLEG400共聚物2～4h、PLEG1000共聚物4～8h和PLEG2000共聚物8～12h较宜;共聚物组成比与投料比较一致,共聚物的数均分子量与理论计算值较一致;共聚物为无定形态,PEG的引入使共聚物Tg明显低于PLA均聚物,且随PEG的Mn减小,共聚物的Tg随之降低;而且PEG的引入明显提高了PLA的亲水性,PEG的Mn越小,PLA亲水性的提高程度越大。通过控制催化剂用量和反应时间,150℃可以得到分子量符合投料组成比要求、亲水性有明显提高的PLA-PEG-PLA三嵌段共聚物。     

熔融缩聚合成聚乳酸-聚乙二醇共聚物及其性能研究

采用羧基封端乳酸预聚物与聚乙二醇熔融缩聚合成了聚乳酸-聚乙二醇共聚物,并用GPC、FTIR、1H-NMR等方法表征了预聚物与共聚物,结果表明,预聚物的羧基封端率高于95%,预聚物的相对分子质量可由投料比(物质的量比)控制.热分析结果表明,共聚物中聚乳酸链段呈无规分布,而聚乙二醇链段能够形成结晶微区.力学性能测试结果表明,共聚物的断裂伸长率达371%,有望在聚乳酸韧性改性方面得到应用.     

聚乳酸接枝共聚物的研究进展

接枝共聚改性是提高聚乳酸性能的一种常用方法,能够扩展其使用范围。从共聚材料种类及性能的角度,分类介绍了近年来利用纤维素、淀粉、壳聚糖、葡聚糖等天然材料和亲水性、温敏性、聚氨基酸类聚合物等合成材料接枝改性聚乳酸的研究进展,分析了各类接枝改性聚乳酸材料的优缺点和应用,展望了该领域未来的发展方向和产业化应用中应该注意的问题,指出在今后聚乳酸基接枝共聚物材料的推广应用中应该关注产品的成本问题。     

聚乳酸的合成与性能研究

以乳酸单体为原料,采用直接缩聚法合成了具有较高粘均分子质量的聚乳酸,用红外光谱、H—NMR等方法初步表征了聚乳酸的结构。研究了聚乳酸的亲水性和降解性。结果表明,聚乳酸的水接触角和吸水率分别为79．30和2．8％,说明聚乳酸具有一定的亲水性。聚乳酸在降解过程中表现为体型降解特点。粘均分子量和降解温度对聚乳酸的降解规律影响不大,但低分子量聚乳酸及聚乳酸在较高降解温度下的降解程度和初期降解速率明显大于高分子量聚乳酸及较低降解温度。本文还研究了聚乳酸粘均分子量在降解过程中的变化情况。     

一种可阻止非特异性蛋白质吸附的新型聚乳酸材料——聚乙二醇接枝聚乳酸

通过直接酰胺化反应,用氨基封端聚乙二醇(H2N-PEG-NH2)对马来酸酐改性聚乳酸(MPLA)进行了本体改性。用红外、核磁和差示扫描技术对改性材料进行了表征,用FITC荧光标记牛血清白蛋白(FITC-BSA)对材料的非特异性吸附进行了检测。结果表明,聚乙二醇被成功地接枝到MPLA上,与聚乳酸(PLA)和MPLA相比,得到的产物(PPLA)明显降低了对牛血清白蛋白的非特异性吸附,仅为PLA的37.3%。     

两亲性嵌段共聚物聚乳酸-聚亮氨酸-聚乙二醇的合成及性能研究

具有温度敏感的生物水凝胶因可根据温度变化发生相变而受到人们重视。采用直接熔融聚合法,先以外消旋乳酸(D,L-LA)和L-亮氨酸(Leu)为原料,辛酸亚锡为催化剂,合成了聚乳酸-聚亮氨酸;再以一定比例将上述两组分共聚物与一定分子量的聚乙二醇(PEG)混合,在辛酸亚锡为催化剂的情况下熔融聚合制备聚乳酸-聚亮氨酸-聚乙二醇三组分嵌段共聚物。采用傅里叶红外光谱(FTIR)、核磁共振波谱仪(1 H-NMR)和凝胶渗透色谱仪(GPC)对两组分和三组分共聚物进行了系统表征,所得三组分共聚物的一定浓度的水溶液在20～35℃时具有溶胶-凝胶转变特性,能够满足该生物友好材料在药物缓释领域中的应用。     

Synthesis and characterization of cholesterol-poly(ethylene glycol)-poly(D,L-lactic acid) copolymers for promoting osteoblast attachment and proliferation

A novel cholesterol-poly(ethylene glycol)-poly(D,L-lactic acid) copolymer (CPEG-PLA) has been synthesized as a potential surface additive for promoting osteoblast attachment and proliferation. The gel permeation chromatography (GPC) and nuclear magnetic resonance spectroscopy (NMR) results indicated the product had expected structure with low polydispersities in the range of 1.1–1.5. By blending the poly(D,L-lactic acid) (PLA) with CPEG-PLA, the surface of modified PLA membrane was investigated by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and contact angle. The results revealed the enrichment of PEG chain on the surface. Osteoblast cell line (MC3T3) was chosen to test the cell behavior on modified PLA membranes. The osteoblast test about cell attachment, proliferation, cell viability and cell morphology investigation on CPEG-PLA modified PLA substrates showed the CPEG-PLA with 15 and 5 ethylene glycol units promoted osteoblast attachment and growth, while the CPEG-PLA with 30 ethylene glycol units prevent osteoblast adhesion and proliferation. This simple surface treatment method may have potentials for tissue engineering and other biomedical applications.     

Synthesis,characterisation and non-isothermal degradation kinetics of novel poly(mono ethylene glycol dimethacrylate-co-4-aminobenzoate)

Synthesis of a novel co-polymer made by the addition polymerisation between MEGDMA and 4-AB by aza-Michael addition (AMA) polymerisation method is a fascinating field of research. The present investigation yielded a hazardous metal catalyst-free and toxic solvent-free methodology. The AMA polymerisation was carried out at five different [ M ₁/M ₂] values under N₂ atmosphere at 100^°C for 2 h. Thus, obtained co-polymer was characterized by Fourier transform infrared spectroscopy, UV–visible reflectance spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and scanning electron microscopy (SEM). The SEM image confirmed the formation of polymer nanoparticles. The non-isothermal degradation kinetics was followed with four different models, such as Flynn-Wall-Ozawa, Auggis-Bennet, Kissinger and Friedman method. Among the models used, the Kissinger method yielded the lowest degradation kinetics. The degradation kinetics of the co-polymer was followed with the help of model-free methods. Moreover, it was critically compared with the literature.     

Synthesis, characterization and hydrolytic degradation of degradable poly(butylene terephthalate)/poly(ethylene glycol) (PBT/PEG) copolymers

Hydrolytic degradable PBT/PEG copolymer was synthesized by macromolecular transesterification method from PBT and PEG macromonomers. The resultant copolymers were characterized by ¹H-NMR and GPC. The non-isothermal crystallization behavior of these copolymers was studied by differential scanning calorimetry (DSC). The water absorption and hydrolytic degradation behavior of PBT/PEG copolymers were also studied in detail. This work was partly presented in 6^th ASBM, July 19–22, 2004, Emei City, Chingdu, China. Fan LY is the co-first author for this work.     

聚(D,L-乳酸)基仿生聚合物材料的合成与表征

探索一种新型聚乳酸基仿生聚合物材料的制备新方法.具体实验步骤是:利用聚乳酸上叔碳原子的自由基反应活性,在过氧化二苯甲酰的催化作用下,将马来酸酐引入聚乳酸侧链上,以此提供高反应活性的酸酐键;然后利用酸酐基团与-NH2发生N-酰化反应这一特点,将脂肪族二胺引入聚乳酸侧链上,从而克服聚乳酸降解产物的体液环境呈酸性的缺陷;再用碳二亚胺作缩合剂,在二胺改性聚乳酸材料中共价引入一种细胞粘附肽段Arg-Gly-Asp-Ser(RGDS),赋予材料生物活性和生物特异性,这样就制备了一种新型聚乳酸基仿生材料.采用MALLS、FTIR和XPS对仿生材料进行结构表征;采用罗丹明比色法、茚三酮显色法和氨基酸分析仪检测法对仿生材料中的马来酸酐、二胺和粘附肽RGDS进行定量测定.结果表明,按文中所述之制备技术,在不改变聚乳酸材料主链结构的前提下,该仿生材料中粘附肽RGDS的含量是5.12μmol/g.这就形成了一种具有类似细胞外基质的新型仿生材料.     

端氨基聚乙二醇-聚乳酸嵌段共聚物的合成及表征

以聚乙二醇为原料,采用四步反应,合成了二碳酸二叔丁酯单保护的氨基聚乙二醇(BOC-PEG-NH2);并以DOe-PEG-NH2为引发剂,引发丙交酯开环聚合,得到了叔丁氧基酰胺基聚乙二醇-聚乳酸嵌段共聚物(BOC-PEG-PLA).在三氟乙酸二氯甲烷溶液中,脱去保护基团,得到了端氨基聚乙二醇-聚乳酸嵌段共聚物(NH2-PEG-PLA).采用核磁共振氢谱(1H-NMR)、紫外光度仪(UV)表征各聚合物的结构,由凝胶色谱仪(GPC)测定嵌段共聚物的分子量以及分子量分布.结果表明:合成的氨基引发在无催化剂条件下能够引发丙交酯开环聚合,制得分子量高、分子量分布窄的双亲性共聚物.通过三氟乙酸脱保护得到了端氨基聚乙二醇-一聚乳酸(NH2-PEG-PLA),且对分子量没有影响.     

Grafting of poly(ethylene glycol) onto poly(acrylic acid)-coated glass for a protein-resistant surface

The surface of solid glass supports for samples in optical microscopy and for biosensors needs to be protein-resistant. A coating of a poly(ethylene glycol) monomethyl ether (mPEG) on the surface of the glass is one promising method for preventing the nonspecific adsorption of proteins. In this study, we have developed a novel technique for achieving an optimal coverage of a glass surface with mPEG to prevent protein adhesion. A clean glass substrate previously treated with (3-aminopropyl)dimethylethoxysilane (APDMES) was treated sequentially with poly(acrylic acid) and subsequently a primary amine derivative of mPEG in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide. The resultant glass surface was demonstrated to be highly protein-resistant, and the adsorption of bovine serum albumin decreased to only a few percentage points of that on a glass surface treated with APDMES alone. Furthermore, to extend the present method, we also prepared a glass substrate on which biotinylated poly(ethylene glycol) was cografted with mPEG, and biotinylated myosin subfragment-1 (biotin-S1) was subsequently immobilized on this substrate by biotin/avidin chemistry. Actin filaments were observed to glide on the biotin-S1-coated glass surface in the presence of ATP, and thus, the method is capable of immobilizing the protein specifically without any loss in its biological function.