对二氧环己酮与丙交酯共聚反应的~1H-NMR分析

由对二氧环己酮（PDO）和丙交酯（LA）单体,在不同温度下合成了PDO-co-LA共聚物,采用核磁共振（1H-NMR）研究了共聚反应动力学和共聚物分子链结构,提出了一种链段平均序列长度的计算方法。结果显示,丙交酯在共聚反应中的聚合能力要比对二氧环己酮强;实验条件下LA/PDO投料物质的量比为2/3时,共聚物中PDO与L...     

哌嗪扩链的形状记忆医用材料聚氨酯脲的合成与表征

研究了以二元环状仲胺哌嗪(PPZ)替代二元伯胺作为扩链剂,以六亚甲基二异氰酸酯(HDI)为偶联剂,以端羟基聚(丙交酯-co-对二氧环己酮)(HO-P(LA-co-PDO)-OH)为软段,采用溶液法合成了一系列新型聚氨酯脲(P(LA-co-PDO)-PPZ-PUU)。1 HNMR表征结果证实了P(LA-co-PDO)-PPZ-PUU的结构。比较了以PPZ和BDA为扩链剂时两反应体系的粘度变化,产物在氯仿中的溶解性、热熔性及其玻璃化转变温度(Tg)随NCO/OH摩尔比的变化。同时研究了其形状记忆性能。结果表明,PPZ反应体系的粘度更低,产物的溶解性和热熔性更好,PPZ可明显减少交联;而且,PPZ的环状结构可明显提高PUU硬段的刚度,从而提高Tg。形状回复时间受温度的影响,回复温度越高,形状回复时间越短。该材料呈现良好的形状记忆性能且形状回复率均可达到95%以上。     

不同比例及旋光结构的MPEG-PLGA合成与性能研究

以乙交酯(GA)和两种不同旋光结构的丙交酯(LA)∶外消旋丙交酯(D,L-LA)和左旋丙交酯(L-LA)为原料,在聚乙二醇(PEG)引发下合成了一系列不同LA/GA摩尔比的聚乙二醇-聚丙交酯乙交酯(MPEG-PLGA)嵌段共聚物,并对其结构、结晶性、热性能和力学性能进行了分析测试。结果表明:由D,L-LA合成的共聚物均为非晶态,LA/GA的变化对其各方面性能影响较小;而L-LA合成的共聚物在LA/GA为75∶25时出现结晶性,90∶10时结晶度进一步增大,玻璃化转变温度及拉伸强度也随之明显提高。     

一种生物可降解材料PDLLA-(MAh-PEG)_n-PDLLA的合成与表征

丙交酯(LA)开环聚合时同时引入功能性单体合成含活性基团的可降解聚合物,是目前对聚乳酸(PLA)类材料进行改性的一个重要研究方向。文中首先以聚乙二醇(PEG)和马来酸酐(MAh)为原料,采用溶液缩聚法制得聚乙二醇与马来酸酐的交替预聚物(MAh-PEG)n;然后以辛酸亚锡为催化剂,(MAh-PEG)n为引发剂,引发D,L-丙交酯(D,L-LA)开环聚合,制得聚(D,L-乳酸)(PDLLA)与(MAh-PEG)n的共聚物PDLLA-(MAh-PEG)n-PDLLA。采用凝胶渗透色谱(GPC)、傅里叶红外(FT-IR)、核磁共振(NMR)等方法对共聚物的结构和性质进行研究。结果发现,随着(MAh-PEG)n用量的增加,共聚物的分子量有所下降。这种聚合物的主链含有不饱和双键和亲水性的链段,预计将成为一种新的生物可降解材料。     

医用聚乳酸的合成及其管型材料性能的测定

本文以无毒的辛酸亚锡作催化剂,将丙交酯聚合成聚乳酸(PLA)。研究了在760～0.05mmHg范围内压力改变对PLA分子量的影响,并将PL制成内径为2mm的管型材料,经热稳定性、机械强度和降解性能等试验,结果都表明此管材可用作引导神经再生导管材料。     

含生物功能基团磷脂胆碱的聚乳酸的合成反应

用天然甘油磷脂胆碱开环丙交酯,以获得具有仿生功能的生物降解聚乳酸.采用1H-NMR、FT-IR确证在聚合物结构中引入了生物功能基团磷脂胆碱.通过1H-NMR和GPC测定分子量及其分布,研究了反应时间和温度对聚合物分子量扣产率的影响,聚合物产率达80%以上.将磷脂引入聚乳酸链段中得到可全降解的、生物相容性好的磷脂高分子.这一新的思路可以用于合成一系列新型的药物载体和组织工程支架材料.     

MPEG-PLLGA多孔支架制备影响因素研究

采用热致相分离法制备了MPEG-PLLGA(单甲氧基聚乙二醇-聚左旋丙交酯乙交酯)多孔支架。讨论了丙交酯/乙交酯(LA/GA)配比、聚合物质量浓度、预冻温度等因素对支架的孔径、孔隙率和力学性能的影响。结果表明,当聚合物质量浓度为0.03g/mL时,不同n(LA)/n(GA)比的MPEG-PLLGA支架的孔形貌相差较大,而当聚合物质量浓度为0.04g/mL和0.05g/mL时,3种n(LA)/n(GA)比的MPEG-PLLGA支架的孔形貌和孔径没有明显差异,且在相同聚合物质量浓度下,随着n(LA)/n(GA)比升高,所得支架的压缩强度增大;随聚合物溶液质量浓度的提高,3种n(LA)/n(GA)比支架的孔隙率、孔径均呈变小趋势,压缩强度逐渐增大;随预冻温度的降低,所得支架的孔径、孔隙率逐渐变小,压缩强度逐渐增大。     

药物缓释材料聚(乳酸-丙氨酸)的直接法合成与表征

直接以外消旋乳酸(LA)、L-丙氨酸(Ala)为原料[n(LA):n(Ala)=9:1],采用熔融聚合法合成药物缓释材料聚(乳酸-丙氨酸)共聚物[P(LA-co-Ala)],并用特性黏数、FTIR、1H NMR、GPC、DSC、XRD等手段进行系统表征.熔融共聚中采用一次投料并分次预聚,可生成重均相对分子质量(Mw)达3200(分散度Mw/Mn＝1.23)的共聚物,相对分子质量可以达到丙交酯开环共聚法的水平.首次报道了P(LA-co-Ala)]药物缓释材料的DSC与XRD表征结果,其与聚外消旋乳酸(PDLLA)相比,共聚物具有较低的Tg、Tm和结晶度.新方法步骤少、操作简便,且成本更加低廉.     

TBCL对PLA及LA/CL共聚物预聚体的扩链反应

以乳酸或乳酸及ε-己内酯,与二元醇如丁二醇或一缩二乙二醇在催化剂的存在下缩聚,合成端羟基聚乳酸预聚体(HO-PLA-OH)或乳酸-ε-己内酯共聚物预聚体(HO-P(LA/CP)-OH)。以对苯二甲酰双己内酰胺(TBCL)为扩链剂,研究了扩链温度、预聚体结构、扩链剂/预聚体配比、扩链时间等对扩链反应的影响。结果表明,在扩链温度为150℃,酸值为0.9、黏均分子量为1120的(HO-P(LA/CP)-OH)预聚体,在扩链剂/预聚体的摩尔比为1.2时,经2 h扩链反应后,黏均分子量达到8630。并采用凝胶渗透色谱法对扩链前后聚合物的分子量变化进行了表征。     

聚L-丙交酯合成工艺条件研究

在超声波辐射条件下 ,以丙交酯为原料、辛酸亚锡为催化剂 ,通过开环聚合反应制得聚L 丙交酯 (PLLA)。应用红外光谱 (IR)表征聚合物的结构 ,详细讨论了丙交酯纯度、聚合温度、聚合时间和超声辐射对聚合物分子质量的影响。优化聚合条件可获得粘均分子量 >1 80× 1 0 3的聚丙交酯材料 ,聚合结果具有良好的重复性     

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.     

5-Fluorouracil-loaded PLA/PLGA PEG–PPG–PEG polymeric nanoparticles: formulation,in vitro characterization and cell culture studies

In this study, 5-FU, a potent anticancer drug, is planned to be delivered via a new and promising drug delivery system, nanoparticles formed with hydrophobic core polymer and triblock copolymers; Poly(DL-lactic acid), Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) copolymer (PLA/PEG-PPG-PEG) and Poly(D,L-lactide–co-glycolide)/Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) copolymer (PLGA/PEG-PPG-PEG) nanoparticles. Particle size range of nanoparticles was found to be between 145 and 198?nm, which would promote the passive targeting of the nanoparticles to tumor cells based on the enhanced permeability and retention (EPR) effect. SEM images revealed all nanoparticles formulations to be spherical and without pores. Zeta potential, yield value and encapsulation efficiencies of 5-FU-loaded nanoparticles were within the range of ?11.1 and ?13.7?mV, 72.7–87.7% and 83.6–93.9%, respectively. Cumulative release of 5-FU was observed between 90% and 94.4% in all nanoparticle formulations by the end of 72?h, and fitness of release profiles to Higuchi model indicated matrix-controlled diffusion of the 5-FU from polymeric nanoparticles. Cell viability values of the cells treated with 5-FU-loaded nanoparticles were obtained as low as 47% and 52% with tetrazolium dye assay, suggesting that delivery of 5-FU via amphiphilic triblock copolymer nanoparticles would be a promising delivery system because of the EPR effect.     

新型生物降解交联剂的制备及其在壳聚糖交联膜中的应用

本文用聚乙二醇和丙交酯在辛酸亚锡的催化作用下合成了可降解的二羟基中间体,再与2,4-甲苯二异氰酸酯(2,4-TDI)反应,合成了异氰酸酯基封端的一系列生物降解型交联剂.并且对中间体和交联剂进行了 FTIR分析表征.应用交联剂对壳聚糖膜材料进行交联,并对交联材料进行了吸水率,表面接触角及力学性能的测定,结果表明新型生物降解交联剂的运用不仪改善了材料吸水性,也提高了材料的力学性能.     

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.     

Evaluation of two polymeric blends (EVA/PLA and EVA/PEG) as coating film materials for paclitaxel-eluting stent application

The ethylene vinyl acetate copolymer (EVA)/Poly (lactic acid) (PLA) blend and EVA/Poly (ethylene glycol) (PEG) blend were applied as the drug carrier materials for a bi-layer drug-loaded stent coating film, which consisted of a paclitaxel (PTX)-loaded layer and a drug-free EVA layer. The changes of weight and appearance of the drug-free polymeric blend films with increasing time were examined by X-ray diffraction analysis (XRD), gel permeation chromatography (GPC) tests and scanning electronic microscopy (SEM), and the results showed the degradation of PLA and the leaching of PEG from the films. The effects of PLA, PEG and drug contents on in vitro drug release were investigated, and the results demonstrated that the addition of PLA promoted the drug release while the addition of PEG almost did not. Franz cells diffusion test results indicated that the bi-layer structure successfully endowed the stent coating with the release of drug in a unidirectional fashion. The release profiles of films incorporated PTX and the mechanical performance of the film could be customized by readily adjusting the contents of the blend components. Therefore, the polymeric blends could be useful drug carrier materials for drug-loaded stent coating capable of releasing drug in a highly tunable manner.     

冷冻抽提相分离法制备聚乳酸多孔支架

为了制备结构和性能满足骨组织工程支架要求的聚乳酸(PLA)多孔支架材料,采用冷冻抽提相分离法,以1,4-二氧六环和水为混合溶剂,聚乙二醇(PEG)为致孔剂,制得一系列PLA多孔支架,探讨了溶剂组成、PLA浓度、PEG添加量对PLA多孔支架结构和性能的影响,结果表明添加PEG有利于形成多孔三维支架,随着PEG含量的增加,...     

Influence of Ethylene Glycol on the Formation of Calcium Phosphate Nanocrystals

A synthesis route of using calcium hydroxide Ca(OH)2 with ethylene glycol solvent and orthophosphoric acid (H3PO4) as reagents is described. Three ratios of ethylene glycol to distilled water 1:0, 1:1 and 0:1 are used as diluting media for Ca(OH)2. Crystals of different morphology and composition are formed under weak alkaline circumstance at pH 7.0～8.0. Acicular calcium phosphate nanocrystals are prepared in pure ethylene glycol while rod-like calcium phosphate nanocrystals form in pure distilled water. The nanograde size of the former is smaller than that of the latter. Calcium-deficient apatite (CDAP) is obtained with a Ca/P molar ratio of 1.66. Therefore, it was deduced that the usage of ethylene glycol solvent could influence the formation of calcium phosphate crystal lattice.     

PLA-PEG-PLA copolymer-based polymersomes as nanocarriers for delivery of hydrophilic and hydrophobic drugs: preparation and evaluation with atorvastatin and lisinopril

Tri-block poly(lactide)–poly(ethylene glycol)–poly(lactide) (PLA–PEG–PLA) copolymers were synthesized and used to prepare polymersomes loaded separately by the hydrophobic and hydrophilic model drugs, atorvastatin and lisinopril, respectively. The resulting nanostructures were characterized by various techniques such as FTIR, DSC, PCS and AFM. The polymersomes exhibited high encapsulation efficiencies of almost 78% and 70.8% for atorvastatin and lisinopril, respectively. Investigation on FTIR and DSC results revealed that such a high encapsulation efficiency is due to strong interaction between atorvastatin and the copolymer. The impact of drug/copolymer ratio and copolymer composition on drug-loading efficiency and drug release behavior were also studied. The results showed that in case of lisinopril, polymersomes exhibited a triphasic drug release, while for atorvastatin a biphasic release profile was obtained. Overall, the results indicated that PLA–PEG–PLA polymersomes can be considered as a promising carrier for both hydrophilic and hydrophobic drugs.     

聚乙二醇增容纳米纤维素/聚乳酸共混体系的研究

采用溶液浇铸法制备纳米纤维素/聚乳酸/聚乙二醇三元复合材料,与纯聚乳酸相比,该复合材料的抗张强度和断裂伸长率分别提高了41.2%和38.4%.傅立叶红外(FT-IR)表明聚乙二醇的存在使纳米纤维素和聚乳酸之间形成了强烈的氢键作用,明显改善了纳米纤维素和聚乳酸之间的相容性,提高了界面黏结力.扫描电子显微镜(SEM)观察了...     

pH值对聚乙二醇渗透材料的影响及NMR的分析

为了探讨聚乙二醇(PEG)渗透材料在不同pH条件下的性能,用NaOH溶液和稀盐酸调节PEG渗透材料的pH值.采用核磁共振研究不同pH值条件对PEG结构的影响.研究表明:当pH值在2~8时,PEG渗透材料放置7d可以保持稳定的pH值;在酸性条件下,由于PEG中的O对酸中H+形成作用,削弱了O原子对与O间接相连的-CH2基团的引力,使该-CH2基团中的H原子的化学位移向低场偏移,但PEG的结构不变;在pH值大于8的条件下,氢键的形成导致线状的PEG发生立体扭结,从而产生沉淀.因此,在pH值为2~8的范围内,可以稳定使用PEG渗透材料.