几种降解性脂肪族聚酸酐的合成及性能表征

通过高真空熔体缩聚法合成了下列几种基于脂肪癸二酸的共聚物：癸二酸－间苯二酸共聚物（ＰＳＡ－ＰＩＰＨ）、癸二酸－聚乙二醇共聚物（ＰＳＡ－ＰＥＧ）、癸二酸－酒石酸共聚物（ＰＳＡ－ＰＴＴＡ）、癸二酸与四氢呋喃－环氧乙烷共聚醚（Ｍｒ＝１５００）的共聚物（ＰＳＡ－ＰＥＧ／ＴＨＦ）．采用１Ｈ或１３Ｃ核磁共振分析、红外光谱分析、差示扫描量热法（ＤＳＣ）对获得的聚合物进行了分析和表证．测定了聚合物的熔点及特性粘数．ＤＳＣ测定结果表明ＰＳＡ－ＰＥＧ和ＰＳＡ－ＰＥＧ／ＴＨＦ具有较低的结晶度．实验表明ＰＳＡ－ＰＩＰＨ、ＰＳＡ－ＰＴＴＡ比ＰＳＡ具有更好的成膜性质．     

Ce_(0.6)Zr_(0.4)O_2和BaSO_4微纳米粒子的水热合成与表征

具有高热稳定性和高比表面积的铈锆固溶体和硫酸钡在催化中有重要用途.采用以三嵌段共聚物EO20PO70EO20(P123)、十六烷基三甲基溴化铵(CTAB)或聚乙二醇(PEG)为表面活性剂的水热法合成了高比表面积的Ce0.6Zr0.4O2固溶体纳米粒子和BaSO4微纳米粒子.利用X射线衍射、N2吸附-脱附、扫描电子显微镜、高分辨透射电子显微镜以及选区电子衍射等技术研究了这些材料的物理性质.结果表明,以P123、CTAB或PEG为表面活性剂所合成的Ce0.6Zr0.4O2粒子呈不规则类球状表面形貌,兼有单晶与多晶(混晶)的面心立方结构,粒径为15~30 nm,比表面积为45~64 m2/g;以PEG或P123为表面活性剂所合成的BaSO4微纳米粒子呈多面体状表面形貌,具有单晶正交结构,晶粒边长为80~200 nm,比表面积为6~11 m2.g-1.     

刚柔嵌段共聚物在水溶液中的温度响应自组装

环氧乙烷链具有低临界溶解温度(LCST)效应,其在水溶液中会随着温度变化在水合作用-脱水作用之间进行可逆的转化,从而引发分子构象的变化,并最终改变分子聚集体的形貌和性质.本文将介绍基于聚环氧乙烷链为柔性链段的刚柔嵌段小分子在水溶液中形成的多种热响应纳米结构以及它们的自组装行为原理,为热响应纳米材料的制备和研究提供参考.     

聚乳酸/醋酸淀粉薄膜的制备及性能研究

采用溶剂挥发成膜法分别制备了聚乳酸(PLA)/淀粉(DPS)和聚乳酸(PLA)/醋酸淀粉(AS)复合薄膜,并通过添加增塑剂改善复合薄膜的力学性能.对样品薄膜进行SEM、TG、DMA和机械性能测试,结果表明:PLA/AS复合薄膜与PLA/DPS复合薄膜相比,各组分的相容性以及薄膜的断裂伸长率得到了改善,尤其是增塑剂的添加使复合薄膜的力学性能得到了明显提高.     

Matrix metalloproteinase-sensitive poly(ethylene glycol)/peptide hydrogels as an interactive platform conducive to cell proliferation during 3D cell culture

The response of extracellular matrix(ECM) to dynamic cell signals is of great significance for the regulation of cell behavior. In the present study, we prepared a type of matrix metalloproteinase(MMP)-sensitive degradable hydrogels(MSDHs) via the catalyst-free o-phthalaldehyde(OPA)/amine cross-linking reaction between o-phthalaldehyde-grafted four-arm poly(ethylene glycol)(4aPEG-OPA) and an MMP-sensitive degradable peptide. The gelation rates and storage moduli of MSDHs and the MMP-insensitive hydrogels(MIHs) based on an MMP-insensitive scramble peptide were comparable and dependent on the concentrations of precursor polymers. MSDHs were degradable while MIHs were stable in the presence of proteinase in vitro.The degradation of MSDHs was obviously faster than that of MIHs after subcutaneous injection into rats. In addition, both types of poly(ethylene glycol)/peptide hydrogels displayed excellent cytocompatibility in vitro, and showed good histocompatibility in vivo in the subcutaneous layer of rats. Furthermore, the proliferation of several MMP-expressing cell lines including MDA-MB-231 cells within MSDHs was obviously faster than that in MIHs, indicating the influence of metabolism-mediated scaffold degradation on the cell proliferation. This study provides a new biocompatible and biodegradable 3 D cell culture interactive platform for regulation of cell behavior.     

1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷与高分子粘合剂的相互作用

运用MO-PM3方法和MM-UFF方法分别计算1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)与环氧乙烷/四氢呋喃共聚醚(PET)、聚乙二醇(PEG)、端羟基聚丁二烯(HTPB)、缩水甘油叠氮基聚醚(GAP)、3-叠氮甲基-3-甲基环氧丁烷聚合物(AMMO)和3,3-双(叠氮甲基)环氧丁烷聚合物(BAMO)六种高分子粘合剂所形成的混合体系模型,求得稳定几何构型和结合能(ΔE)。对两种计算方法得出的结合能(ΔE)进行相关性分析。在PM3方法得出的结合能中,GAP、BAMO与HMX的结合能(绝对值)随高分子聚合度的增加而增加。PET与HMX的结合能明显大于GAP与HMX的结合能;另外PEG与HMX的结合能也大于HTPB与HMX的结合能。此结果为HMX与高分子粘合剂之间的相容性研究提供基础数据。     

可生物降解多嵌段聚乳酸共聚物合成研究

以氧化锌为催化剂,使左旋丙交酯(LLA)与聚乙二醇(PEG600)开环共聚,得到三嵌段(HO PLLA PEG PLLA OH)预聚物;再以甲苯二异氰酸酯TD1 80为扩链剂对其进行扩链,得到多嵌段共聚物.采用核磁共振、红外光谱、凝胶渗透色谱等对目标产物的结构、分子量分布进行了表征;同时用变温红外法研究了与LLA结晶相关谱带的位置,并对其进行了归属.     

Ag(I)与乙酰丙酮、乙酰乙酸乙酯、丙二腈及中性膦配合物的电化学合成

用牺牲金属阳极的电化方法合成了三种新的一价银配合物Ag(I)(dppe)(CH(CN)2),Ag(I)(dppe)(CH3COCHCOOEt)及Ag(I)(dppe)(CH3COCHCOCH3)，对配合物进行了元素分析，红外光谱测试及表征，并研究反应的机理。     

聚合物反胶团萃取氨基酸的研究

利用德国BASF公司生产的Pluronic型和PluronicR型两类嵌段聚合物制备聚合反应胶团萃取氨基酸（L－苯丙氨酸和L－异亮氨酸）， 聚合物反胶团对氨基酸的萃取平衡特性，实验表明，聚合物反胶团对氨基酸的萃取平衡时间与纯有机溶剂的物理萃取相比差别很小，溶质在反胶团外壳部分与其内部水池间的平衡分配系数K都普遍较大，另外，当氨基酸水溶液的PH值接近等电点时，反胶团萃取达到最佳效果。通过理论分析得到如下推断，聚合物反胶团对两亲性氨基酸的增溶主要在基外壳部分，很可能是包裹在聚氧丙烯外壳内或缠绕在聚氧丙烯链之间，亲油作用和氢键作用是聚合物反胶团萃取的主要推动力。     

Electrochemical behaviors of novel composite polymer electrolytes for lithium batteries

A novel composite polymer electrolyte was prepared by blending an appropriate amount of LiC104 and 10% (mass fraction) fumed SiO2 with the block copolymer of poly (ethylene oxide) (PEO) synthesized by poly (ethylene glycol) (PEG) 400 and CH2CI2.The ionic conductivity, electrochemical stability, interfacial characteristic and thermal behavior of the composite polymer electrolyte were studied by the measurements of AC impedance spectroscopy, linear sweep voltammetry and differential scanning calorimetry (DSC), respectively. The glass transition temperature acts as a function of salt concentration, which increases with the LiC104 content.Lewis acid-base model interaction mechanism was introduced to interpret the interactive relation between the filled fumed SiO2 and the lithium salt in the composite polymer electrolyte. Over the salt concentration range and the measured temperature, the maximum ionic conductivity of the composite polymer electrolyte (10^4.41 S/cm) appeared at EO/Li=25 (mole ratio) and 30~C, and the beginning oxidative degradation potential versus Li beyond 5 V.     

氯化聚丙烯接枝聚乙二醇的合成与性能

以氯化聚丙烯（ＭＣＰＰ）与聚乙二醇（ＰＥＧ）为原料,在金属钠作用下,合成了ＭＣＰＰ为主链,ＰＥＧ为支链的梳形两亲性高聚物．用ＦＴＩＲ表征了高聚物的结构,并测定了ＭＣＰＰ接枝ＰＥＧ前后的吸水性,水在其表面的接触角及乳液分散性．结果表明：两亲性高聚物的吸水性能随着ＰＥＧ含量的增加而增强,水在其表面的接触角随着ＰＥＧ含量的增加而减少,它的乳液分散性能与其浓度及支链ＰＥＧ分子量有关．     

六氯环三磷腈基类聚合物的合成

在线状、环状聚磷腈类聚合物的主链结构中磷原子可以与不同的取代基相连接,使此类聚合物材料的物理、化学性质各不相同而表现出性能的多样性.本论文用碳酸钾为质子吸收剂,二氧六环做溶剂,以金属钠、六氯环三磷腈和一缩二乙二醇、二缩三乙二醇为原料,合成出以环状聚磷腈和缩乙二醇类为基本结构单元的二维网状聚合物:一缩二乙二醇缩聚环三磷腈[P3N3C l3(OCH2CH2OCH2CH2O)3]n和二缩三乙二醇缩聚环三磷腈[P3N3C l3(OCH2CH2OCH2CH2OCH2CH2O)3]n,并对其进行了表征,实验结果表明该类聚合物具有对酸(盐酸、硫酸和硝酸)、碱(氢氧化钠、氢氧化钾)和有机溶剂的耐腐蚀性.     

The Synthesis and Electrorheological Properties of BaTiO_3-coated PMMA Microspheres

Coated-PMMA microspheres consisting of poly (methyl methacrylate)(PMMA) core and barium titanate (BaTiO3) shell were synthesized by the modified sol-gel processing and then adopted as an electrorheological (ER) materials. The structure and morphology of coated powders were characterized by SEM and FT-IR; the shear stress of the suspensions of coated-PMMA particles and pure PMMA particles in silicone oil with a 20 vol% were investigated. The results show that the BaTiO3 coated PMMA microspheres based suspension in silicone oil exhibited typical ER behavior and stronger ER effects.     

聚碳酸酯纳米药物的制备与性能

采用可生物降解高分子材料链接或包埋抗癌药物制备高分子纳米或微米药物,不仅可以提高药物的抗癌功效而且能减小药物对正常组织的毒副作用.以9 苯基 2,4,8,10 四氧螺\[5,5\]十一烷 3 酮与2,2 二甲基二亚甲基合成的羟基化的碳酸酯共聚物P(PTC co DTC)为载体,将肿瘤靶向基团叶酸通过化学反应键连在聚碳酸酯的侧链,从而制备肿瘤靶向性高分子载体,并进行了傅立叶红外光谱、核磁共振氢谱、紫外 可见光谱等结构表征.再将靶向高分子载体与5 氟尿嘧啶复合,采用高压电场喷雾法与透析法分别制得两种肿瘤靶向聚碳酸酯纳米抗癌药物,并初步研究了纳米抗癌药物的体外药物控制释放性能.研究结果表明碳酸酯纳米药物具有较好的药物释放性能,且高压电场喷雾法制备的纳米药物比透析法制备的纳米药物释放药物速率快.     

PBT-PA_6嵌段共聚物的合成、结晶与熔融

本文探讨通过溶剂溶解后,达到均匀混合的聚对苯二甲酸丁二酯(简称PBT)和聚己内酰胺(简称 PA_6)均聚物间,通过固相聚合反应合成 PBT-PA_6嵌段共聚物的新方法。并以 DSC、WAXD 和 TG 方法探讨了 PBT-PA_6的结晶、熔融及热稳定性。     

一类泛函微分方程单增解的存在性

本文利用Schauder不动点定理,研究了自治迭代泛函微分方程x'(t)=f(x~(N)(t))的解的情况,给出了解存在的条件.     

Synthesis and Characterization of Novel Biodegradable Poly (butylene succinate-co-triethylene glycol succinate)Copolymers

Novel biodegradable aliphatic polyesters,poly(butylene succinate-co-triethylene glycol succinate)(P(BS-co-TEGS))and poly(butylene succinate)(PBS),were synthesized through a two-step procedure of esterification and polycondensation with succinic acid and1,4-butanediol/triethylene glycol as raw materials as well as tetrabutyl titanate and diphenylphosphinic acid as the co-catalysts.The chemical structure and molecular weight of the copolymers were characterized by 1~H nuclear magnetic resonance(~1H NMR)and gel permeation chromatography(GPC),respectively.In addition,thermal properties,crystal structure and mechanical properties were also analyzed with various techniques.P(BS-co-TEGS)exhibited more excellent mechanical properties than PBS,especially in elongation at break.Meanwhile,the crystal structure and thermal stability of the P(BS-co-TEGS)have hardly changed.The crystallinity of P(BS-co-TEGS)was lower than that of PBS and decreased with the increase of mole ratio of triethylene glycol.With the increase of TEGS unit molar composition,the melting point(T_m),crystallization temperatures(T_c)and heat of fusion(ΔH_m)of P(BS-co-TEGS)decreased,while glass transition temperature(T_g)increased.     

The Synthesis and Eleetrorheologieal Properties of BaTiO3-coated PMMA Mierospheres

Coated-PMMA microspheres consisting of poly （methyl methacrylate）（PMMA） core and barium titanate （BaTiO3） shell were synthesized by the modified sol-gel processing and then adopted as an electrorheological （ER） materials. The structure and morphology of coated powders were chyfecterized by SEM and FT-IR; the shear stress of the suspensions of coated-PMMA particles and pure PMMA particles in silicone oil with a 20 vol% were investigated. The results show that the BaTiO3 coated PMMA microspheres based suspension in silicone oil exhibited typical ER behavior and stronger ER effects.     

Rheology-morphology relationship in polystyrene/poly(methyl methacrylate) blends

The relationship between rheological properties and morphology of immiscible polystyrene(PS)/poly(methyl methacrylate)(PMMA) blends was studied.The blends were prepared using a twin screw extruder.A single screw extruder equipped with a slit die was used to perform shear flow measurements of PS/PMMA blends.Morphological examinations were conducted on the cryogenically fractured and extracted samples by scanning electron microscopy.The results show that the melt viscosity of PS/PMMA blend decreases with increasing shear stress,which is attributed to not only the disentanglement of macromolecules but also the reduction in the domain size and the resultant increase of the interfacial area.The power-law index of the blend melt is lower than any of its component melt,suggesting that deformation and breakup of the dispersed phase increase the dependence of the melt viscosity on the shear stress.The blend whose domain size decreases at a faster rate with increasing shear stress,exhibits a strong shear rate dependence on the melt viscosity.The comparison of the morphologies of samples before and after the slit section of the die indicates that the morphology of the blend has a quick response to shear flow,the coalescence of the dispersed drops is predominant for blends at low shear rates.     

Preparation and characterization of cationic PLGA-PEGLf/DOPE nanoparticles for HO-1 gene delivery

Cationic nanoparticles(NPs)for gene delivery were successfully prepared by assembling carboxylation poly(lactic-co-glycolic acid)(PLGA),polyethylene glycol(PEG),L-α-Phosphatidylethanolamine(DOPE)and octadecyl quaternized carboxymethyl chitosans(OQCMC).Lactoferrin(Lf)was selected as a targeting ligand conjugated to PLGA via bifunctional PEG,yielding PLGA-PEG-Lf/DOPE NPs to be used for gene vectors.Fourier transform infrared spectroscopy(FTIR),UV and nuclear magnetic resonance(NMR)spectroscopy were performed to evaluate the synthesis of the vectors.The characteristics of the vectors loaded heme oxygenase(HO-1)gene were evaluated by transmission electron microscope(TEM),particle size analyser and fluorescent microscopy.The experimental results showed that the obtained vectors were spherical in shape with average particle size of 142.2 nm and zeta potentials of +16.4 mV.The vectors could protect the loaded gene from the degradation by nuclease.For 293T cells,there is high transfection eff iciency of the vectors similar to liposome-2000.It can be concluded that the established cationic PLGA-PEG-Lf/DOPE NPs have potential gene delivery ability for gene therapy.