聚右旋丙交酯和聚左旋丙交酯乙交酯的制备及其共混物的结晶行为

以辛酸亚锡为催化剂,十八醇为引发剂,分别以右旋丙交酯和左旋丙交酯与乙交酯为原料,在真空条件下经本体熔融开环聚合制备了系列右旋丙交酯聚合物(E)和左旋丙交酯乙交酯共聚物(F),其结构经1H NMR和IR表征。利用DSC研究了E和F共混物(M)的结晶性能,结果表明,E和F能形成具有较高熔点的立构复合物(SC),其形成能力随E分子量的增加而降低,且SC的含量在E和F共混比为49∶51附近出现极大值。     

生物可降解封堵器材料的合成及表征

以L型丙交酯(LLA)、乙交酯(GA)和三亚甲基碳酸酯(TMC)为原料,辛酸亚锡为催化剂,通过开环聚合制备了丙交酯-三亚甲基碳酸酯二元共聚物(PLT)和丙交酯-三亚甲基碳酸酯-乙交脂(PLTG)三元共聚物。采用核磁共振氢谱、傅里叶红外光谱、体积排阻色谱、差热扫描、力学性能测试、血液相容性实验表征了产物的结构与性能,研究了共聚物组成对其结晶能力、热性能和力学性能的的影响。结果表明:所得聚合物的数均分子量均在8×10~4以上,多分散系数在2.0以下。共聚物中的TMC和GA链段使其结晶能力、玻璃化转变温度和拉伸强度与L型聚丙交酯相比均有所下降。三元共聚物PLTG的拉伸强度可达到22.3 MPa,断裂伸长率达到168.7%。另外,共聚物的血液相容性优良。     

乙交酯、L-丙交酯均聚物及其共聚物的制备和性能研究

以辛酸亚锡为催化剂、1,4-丁二醇为引发剂,在高温、高真空条件下本体熔融开环聚合制备了聚乙交酯(PGA)、聚L-丙交酯(PLLA)及其不同比例的共聚物(PLGA).通过红外光谱(IR)、核磁共振(1H-NMR)对聚合物的结构进行了表征,用乌氏黏度计、凝胶渗透色谱仪(GPC)、示差扫描量热仪(DSC)、热重分析仪(TGA)、X射线粉末衍射仪(XRD)、流变仪等对聚合物的特性黏数、分子量与分子量分布、热性能、结晶性、流变性能进行了研究.结果表明PLGA和PLLA具有较高的分子量和窄的分子量分布;PGA、PLLA、PLGA均具有较高的热稳定性,随着PLGA中PGA单元的增加,分解温度逐渐升高.直接熔融合成的PGA在各有机溶剂中溶解性都不理想,用二甲基亚砜(DMSO)重结晶后的PGA在六氟异丙醇(HFIP)中的溶解度增大;PGA、PLLA具有较高的结晶度,而PLGA以非晶态存在,DMSO重结晶后的PGA的结晶度降低.PGA、PLLA、PLGA的熔体均是剪切变稀流体,但PGA、PLLA具有较高的储能模量,PLGA具有较高的损耗模量.相对于PGA和PLLA,无规共聚的PLGA易纯化,并且柔性较好,更易加工,因此PLGA是更适宜的生物可降解材料.     

聚(L-丙交酯)/聚(DL-丙交酯)的结晶性能及相溶性

用共溶液沉淀法制备了聚 (L 丙交酯 ) 聚 (DL 丙交酯 )共混物 (PLLA PDLLA) ,然后用成纤模压法压制成3 2mm的棒材 .用差示扫描量热法研究了共混物的结晶性能和相溶性 .结果表明 ,PLLA组分在共溶液沉淀过程中可生成结晶 ,共混物中PDLLA含量直到 30 %时 ,PLLA组分的结晶熔融温度和结晶度与纯PLLA相同 ,但PDLLA含量为 5 0 %时 ,PLLA组分的结晶熔融温度和结晶度明显下降 .由于加工成型条件的不一致性 ,共混物棒材中的PLLA组分的结晶熔融温度和结晶度呈较大的分散性 .共混物从熔体降温 ,在其后的升温DSC扫描中出现分别相应于PDLLA和PLLA的玻璃化转变 ,表明PDLLA与未结晶的PLLA形成的非晶相是不相溶的     

高热稳定Lewis酸碱对催化L-丙交酯均聚及与乙交酯共聚的本体开环聚合研究

聚丙交酯(PLA)和乙交酯-丙交酯共聚酯(PLGA)是性能优异的可降解聚酯材料,发展绿色、环境友好的催化剂实现丙交酯和乙交酯的本体熔融聚合具有重要的科学意义和实际应用价值.本文研究了ZnCl₂、MgCl₂和FeCl₃与3种有机碱构成的Lewis酸碱对在丙交酯(LA)本体熔融聚合的催化作用.研究了包括Lewis酸碱对类型、比例和反应时间对LA开环聚合反应的影响.这3类Lewis酸碱对在180℃高温下表现出较好的热稳定性和催化活性.其中FeCl₃/DBU催化体系能够同时实现高单体转化率和分子量.同时,FeCl₃/DBU能够有效催化LA和GA的随机共聚,通过调控LA和GA的单体投料比可以制备不同摩尔组成的PLGA共聚酯.     

聚(丁二酸丁二酯-co-丁二酸丙二酯)的等温结晶行为研究

以1,4-丁二酸、1,4-丁二醇和1,3-丙二醇为原料通过直接熔融缩聚法合成了聚丁二酸丁二酯(PBS),聚丁二酸丙二酯(PPS)和聚(丁二酸丁二酯-co-丁二酸丙二酯)(PBSPS)等脂肪族聚酯.利用1H-NMR,WAXD,DSC和POM等研究了聚酯的结晶结构和结晶动力学过程等结晶行为.PBSPS的结晶晶型与PBS一致,说明只有丁二酸丁二酯(BS)单元结晶而丁二酸丙二酯(PS)单元处于无定形区.聚酯等温结晶后,在升温熔融过程中出现了多重熔融峰.分析表明多重熔融峰主要来自于聚酯升温过程中的熔融-重结晶行为.利用Avrami方程分析了聚酯的等温结晶动力学,Avrami指数n为2.2~2.8,说明聚酯等温结晶时主要以异相成核的三维生长方式进行;随着PS单元的增多,聚酯的表观结晶活化能升高,也就是说BS单元的结晶变得困难.POM观察到聚酯等温结晶时都出现了环带球晶现象,球晶形态会随着结晶温度和化学结构差异而改变.     

聚乳酸接枝改性纳米生物玻璃/PLGA复合材料的制备、表面性质及生物活性

以丙交酯开环聚合原位接枝改性的纳米生物玻璃(PLLA-g-BG)与聚丙交酯-乙交酯(PLGA)复合材料为研究对象, 采用TGA, ESEM和EDX分析其接枝率, 粒子分散性和表面元素分布, 通过将兔成骨细胞种植于材料膜表面进行体外培养, 采用荧光染色法、NIH Image J图像分析软件、MTT法和流式细胞术等手段检测细胞在材料表面的平均黏附数量、扩展面积比、增殖能力和细胞周期的变化, 综合评价新型改性纳米复合材料的生物相容性和生物活性. 结果表明, 聚乳酸表面接枝改性可明显改善纳米生物玻璃粒子的团聚; PLGA中掺入一定比例的改性PLLA-g-BG可明显促进兔成骨细胞的黏附、扩展与增殖; 改性纳米生物玻璃的应用可提高生物可降解聚酯材料的生物相容性和生物活性.     

热熔挤出法联合静电纺丝法制备新型抗炎缓释系统

报道了一种制备具有“核-壳”结构和双重释放过程的可降解抗炎缓释系统(3)的新方法。以聚（乙交酯-丙交酯）（PLGA50）为药物载体,先通过热熔挤出法将绿原酸（CA）与PLGA50共挤出得挤出物（1）;利用静电纺丝法在1表面包裹一层“PLGA50+CA”静电纺丝膜（2）,制得具备“核-壳”结构的材料（3）。采用SEM, TGA, DSC和LC-MS研究了CA的热稳定性,1的热力学性能,3的微观形态和体外药物释放行为。结果表明：3具有“核-壳”结构;引入CA,降低了PLGA50的玻璃化转变温度;3的药物释放为双重释放过程。     

淀粉/DL-丙交酯接枝共聚物的合成和生物降解性能研究

以淀粉为接枝骨架 ,DL 丙交酯为接枝单体 ,在无水LiCl存在下 ,合成了淀粉 /DL 丙交酯接枝共聚物 .研究了接枝反应的投料比、反应时间、反应温度对单体转化率 (C % )、接枝率 (G % )和接枝效率 (GE % )的影响 .当DL 丙交酯与淀粉结构单元的摩尔比为 10∶1,反应温度为 80～ 85℃ ,反应时间为 4h ,C % ,G %和GE %可分别达到 37 3 %、179 7%和 6 8 0 % .用差示扫描量热 (DSC)分析仪、红外光谱仪和X 射线衍射仪对合成的接枝共聚物进行了表征 ,结果表明 ,淀粉和DL 丙交酯反应生成了淀粉 /DL 丙交酯接枝共聚物 .防水实验结果表明 ,该产物在给定条件下可使纸板的吸水率由 41 1%降低到 1 0 % .降解实验表明该接枝共聚物能够被酸、碱及微生物完全降解     

聚(丙交酯-co-乙交酯)/β-磷酸三钙复合物的电纺研究

对生物可吸收聚(丙交酯-co-乙交酯)(poly(lactide-co-glycolide),PLGA)与β-磷酸三钙(-βTCP)复合物体系进行了电纺.研究了PLGA的浓度,-βTCP与PLGA比例,加料速度,电压,喷头与接收体之间的距离等因素对电纺过程的影响,制备出纳米纤维膜,并用扫描电镜(SEM)等对纤维膜进行表征.结果表明,电纺溶液浓度越高,或者加料速度越快,纳米纤维的直径越粗.力学实验显示,复合物中-βTCP的含量增加使纳米纤维膜的拉伸强度和杨氏模量下降.     

Thermal Properties of Copoly(L‐lactic acid/glycolic acid) by Direct Melt Polycondensation

Poly(L‐lactic acid‐co‐glycolic acid) (PLGA) was prepared from hydroxy‐acids with melt polymerization. In this way, the copoly(L‐LA/GA) (PLGA) was synthesized directly using a binary catalyst (tin chloride dihydrate/p‐toluenesulfonic acid). The thermal properties of PLGA were studied by differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). The results show that the melting point of PLGA decreases with increasing mole fraction of GA units in the copolymer. In addition, the melting point of polymer also decreases with increasing degree of racemization of the polymer.     

聚甲基丙烯酸胆甾醇酯共聚物的合成、结构与性能研究 Ⅳ.PMACE的相态转变及光学性质

Finkelmann和等人对侧链胆甾型高分子液晶的研究表明,将具有液晶功能的低分子基团,经过一个软段连接到柔性高分子主链上的梳型高分子在一定的温度下可以形成液晶态,调节侧链高分子液晶的分子结构、软段长度,可以改变其相态转变温度及微区形态。前已报导具有不同侧链结构的聚甲基丙烯酸胆甾醇酯共聚物的合成、相态转变及光学性质,本文通过对聚甲基丙烯酸胆甾醇乙烯酯共聚物(PMACE)的液晶态及结晶态的微细结构及相态转变与胆甾侧链含量关系的研究,给出了液晶态的形成条件及结构特征。     

Synthesis and characterization of novel ferroelectric liquid crystal polysiloxane containing undecanoyloxy spacer (I)

A novel side-chain liquid crystal polysiloxane and its corresponding monomer were synthesized by the standard method. We ensured their structures were as expected and their purities were high by ¹H nuclear magnetic resonance and infrared measurements. They were studied by differential scanning calorimetry (DSC) for their thermal analysis and polarizing optical microscopy (POM) with hot stage for their textures and transition temperatures. The results showed good liquid crystal properties and low transition temperatures of the mesophase. X-ray diffractions were done to research their layer structure and SmA and SmC^* phases were assured, in good agreement with the results of the POM and DSC measurements. The optical rotation degree was also measured.     

Properties of poly(lactic acid-co-glycolic acid) film modified by blending with polyurethane

A number of poly(lactic acid-co-glycolic acid)/polyurethane (PLGA/PU) blend films with various PU mole contents were prepared by casting the polymer blend solution in chloroform. The surface morphologies of the PLGA/PU blend films were studied by scanning electron microscopy (SEM). The thermal, mechanical and chemical properties of the PLGA/PU blend films were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile tests and surface contact angle tests. The results revealed that the introduction of PU could markedly modify the properties of PLGA films.     

Plasma surface modification of poly (l-lactic acid) and poly (lactic-co-glycolic acid) films for improvement of nerve cells adhesion

Radio frequency (RF) plasma treatment in O₂ was applied to modify the surface of poly (l-lactic acid) (PLLA) and poly (d,l-lactic acid-coglycolic acid) (PLGA) as biodegradable polymers. The surface structure, morphology, wettability and surface chemistry of treated films were characterized by water drop contact angle measurement, scanning electron microscope (SEM), optical invert microscope, differential scanning calorimetry (DSC) and ATIR–FTIR spectroscopy. The cell affinity of the oxygen plasma treated film was evaluated by nervous tissue B65 cell culture in stationary conditions. The results showed that the hydrophilicity increased greatly after O₂ plasma treatment. The results showed that improved cell adhesion was attributed to the combination of surface chemistry and surface wettability during plasma treatment. Cell culture results showed that B65 nervous cell attachment and growth on the plasma treated PLLA was much higher than an unmodified sample and PLGA. Surface hydrophilicity and chemical functional groups with high polar component play an important role in enhancing cell attachment and growth.     

The effect of the linear charge density of carrageenan on the ion binding investigated by differential scanning calorimetry, dc conductivity, and kHz dielectric relaxation

The effect of the linear charge density of natural polyelectrolyte, carrageenan, on the ion binding to carrageenan molecules in relation to the gelation was investigated by using the dielectric relaxation spectroscopy, dc conductivity, optical rotation, and differential scanning calorimetry (DSC). Although carrageenan is an anionic polysaccharide, carrageenan molecules in the helix state at low temperatures can bind not only cation, such as potassium and cesium, but also anion, such as iodide. The dc conductivity steeply decreases just below the coil–helix transition temperature, which indicates the binding of ion to the carrageenan molecules in the helix state due to the increase of the linear charge density compared with that in the coil state. The addition of NaI promotes the helix formation, and prevents from aggregation of helices, which was suggested by the results of the dynamic shear modulus and the DSC, and resulted in an increase of the relaxation amplitude of the lowest frequency relaxation (kHz) attributed to the fluctuation of the tightly bound counter ions along the high charge density region (helix). It is concluded that binding of iodide induces (1) the increase in the amount of tightly bound counterions to carrageenan molecules and (2) the formation of non-aggregated helix.     

聚[(双-甘氨酸乙酯)膦腈]/聚酯共混相容性研究

采用溶液混合法制备了聚[(双－甘氨酸乙酯）膦腈]（PGP）与丙交酯均聚物（PLA）或丙交酯／乙交酯共聚物（PLGA）的共混体系，利用示差扫描量热仪、傅里叶红外光谱仪和相差显微镜研究了两体系的共混相容性。实验结果表明，PGP与PLA不相容，但通过氢键相互作用可与PLGA达到部分相容，且PGP／PLGA的共混相容性随着PLGA含量的增加而有所改善。     

The influence of radiation sterilization on thiamphenicol

The effect of ionising radiation, applied in the form of an electron beam, in the doses of 25, 100 and 400 kGy on the physical and chemical properties of thiamphenicol in solid phase has been studied by organoleptic analysis (form, colour, smell, solubility, clarity) and spectroscopic methods (UV, IR, EPR), chromatography (TLC), SEM observations, X-ray diffraction, polarimetry and thermal method (DSC). The above-discussed results have proved that on irradiation with a dose of 25 kGy no significant changes appear in thiamphenicol, apart from the formation of free radicals of the lifetime of over 352 days. On irradiation with much higher doses (100 and 400 kGy) no changes were observed in the IR spectra but the UV line intensities slightly increased at lambda(max)=266 and 273 nm, the colour of the powder changed, the radiolysis products appeared as detected by TLC, changes were also observed in the XRD, SEM pictures, the melting point values (DSC) and optical rotation. On the basis of DSC results a linear relation was found between the irradiation dose and the decrease in the melting point and increase in the enthalpy of melting, characterised by high correlation coefficients of r=0.9839 and 0.9622, respectively. Moreover, a linear relation was established between the optical rotation angle and the irradiation dose, alpha(D) ( degrees )=f(dose), characterised by the correlation coefficient r=0.9874. The results obtained indicate that thiamphenicol can be safely subjected to radiation sterilization by the standard dose of 25 kGy.     

Engineering of lipid-coated PLGA nanoparticles with a tunable payload of diagnostically active nanocrystals for medical imaging

Polylactic-co-glycolic acid (PLGA) based nanoparticles are biocompatible and biodegradable and therefore have been extensively investigated as therapeutic carriers. Here, we engineered diagnostically active PLGA nanoparticles that incorporate high payloads of nanocrystals into their core for tunable bioimaging features. We accomplished this through esterification reactions of PLGA to generate polymers modified with nanocrystals. The PLGA nanoparticles formed from modified PLGA polymers that were functionalized with either gold nanocrystals or quantum dots exhibited favorable features for computed tomography and optical imaging, respectively.