Poly(Urethane)-Crosslinked Poly(HEMA) Hydrogels

Abstract

Hydrogels have been prepared from 2-hydroxyethyl methacrylate polymerized in the presence of isocyanate-terminated poly(ethylene glycol) (PEG) crosslinking agents. PEGS of molecular weights 200, 400, and 1000 were investigated. The crosslinked nature of the hydrogels was demonstrated by their insolubility in solvents which normally dissolve poly(HEMA). Hexamethylene diisocyanate (HDI) was mainly used as the isocyanate. The molecular weight of the PEG and the crosslinker content significantly influenced the equilibrium water sorption and mechanical properties of the saturated networks. It was observed that as the molecular weight of the PEG increased, the water sorption increased and the nominal modulus decreased. However, for higher levels of cross-linker, water sorption decreased and modulus increased at low molecular weight PEG; for PEG 1000, water absorption increased as crosslinker content increased. These results are explained by the competing effects of flexibility, crosslink density, and hydrophobicity contributed by the various constituents of the hydrogels.     

聚癸二酸丙三醇酯对聚乳酸的改性

以丙三醇和癸二酸为单体通过熔融缩聚制得了聚癸二酸丙三醇酯(PGS),并用其预聚物(p-PGS)对聚L-丙交酯(PLLA)进行共混改性.利用傅立叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)及凝胶渗透色谱(GPC)法对P-PGS的结构进行表征,并研究了改性后材料的力学性能、两相相容性、亲水性能和细胞相容性.结果表明:P-PGS具有支化分子结构,分散系数约为2.7;共混改性后的材料弹性模量和拉伸强度均有所下降,而断裂伸长率从7 %显著提高到150%左右;PLLA/PGS属于海岛式共混结构,PGS以小于10μm的尺寸均匀分布在PLLA基体中;共混后材料的亲水性也有一定的提高,且几乎保持了PLLA原有的细胞相容性.     

Secondary Structures in Synthetic Poly(Amino Acids): Homo- and Copolymers of Poly(Aib), Poly(Glu), and Poly(Asp)

The secondary structure of poly(amino acids) is an excellent tool for controlling and understanding the functionality and properties of proteins. In this perspective article the secondary structures of the homopolymers of oligo- and poly-glutamic acid (Glu), aspartic acid (Asp), and α-aminoisobutyric acid (Aib) are discussed. Information on external and internal factors, such as the nature of side groups, interactions with solvents and interactions between chains is reviewed. A special focus is directed on the folding in hybrid-polymers consisting of oligo(amino acids) and synthetic polymers. Being part of the SFB TRR 102 “Polymers under multiple constraints: restricted and controlled molecular order and mobility” this overview is embedded into the cross section of protein fibrillation and supramolecular polymers. As polymer- and amino acid folding is an important step for the utilization and design of future biomolecules these principles guide to a deeper understanding of amyloid fibrillation.     

Functionalization of Conductive Poly(thiophenes) and Poly(pyrroles)

New methods for functionalization of conductive poly(thiophenes) and poly(pyrroles) using fused aromatics or crown ethers are discussed.     

Poly(dimethylsilylene-co-diphenylsilylene)

In this work several polyorganosilylenes were synthesized including homo-and copolymers containing SiMe₂ and SiPh₂ units. A Wurtz-type coupling reaction of the respective dichlorodiorganosilanes with sodium metal, varying the Ph₂SiCl₂/Me₂SiCl₂ ratio was the chosen synthesis method. Products with different characteristics for solubility, structure (cyclic or linear), composition, and molecular weight distribution could be obtained depending on the comonomer ratios employed. The polysilane derivatives were characterized by infrared spectroscopy (IR), proton nuclear magnetic resonance (¹H-NMR), and gel permeation chromatography (GPC). Valuable information related to the comonomers' reactivities was obtained, such as molecular weight distribution, composition, and relationships between yields of soluble, insoluble, and cyclic materials of each polycondensation reaction. © 1992 John Wiley & Sons, Inc.     

聚L-丙氨酸-聚乙二醇嵌段共聚物纳米胶束的研究

分别以氨基聚乙二醇和氨基聚乙二醇单甲醚为大分子引发剂,采用开环聚合的方法合成了两亲性聚L-丙氨酸-聚乙二醇(PAE)和聚L-丙氨酸-聚乙二醇单甲醚(PAME)两种嵌段共聚物,其结构经1H NMR,IR,DSC,GPC等表征;利用园二色技术研究了其在水溶液中的二级结构,用芘荧光探针技术研究了其胶束的形成及其临界胶束浓度(CMC),利用透射电镜研究了胶束的形态。结果表明,在水溶液中共聚物链以α-螺旋构象形式存在,在一定条件下嵌段共聚物PAE-1,PAE-2,PAME-1和PAME-2能够形成球形的稳定胶束,PAE-1形成胶束的CMC为3.36×10-5mol.L-1,CMC值受嵌段类型和共聚物中聚L-丙氨酸链段含量的影响。     

Poly (dodecacarborane-siloxanes)

The need for elastomeric polymers which will maintain their elastic properties at high temperatures has led to a wide interest in inorganic-based polymers [l]. The development of carborane-siloxane polymers in the early 1960s was a breakthrough in the search for a high-temperature elastomer. Incorporation of a carborane moiety into the siloxane backbone significantly enhanced the overall thermal stability [2].     

Synthesis of long Poly(dA).Poly(dT) DNA without structural defects using enzymatic reaction; tailored ligated Poly(dA).Poly(dT)

Poly(dA).Poly(dT) molecules up to 1000 base pairs (bp) have been synthesized using enzymatic reaction, and characterization by STM observation shows that the DNA has no defects in the duplex structure.     

聚L-丙氨酸-聚乙二醇嵌段共聚物的胶束化行为研究

以氨基聚乙二醇单甲醚(MPEG-NH₂)为大分子引发剂, 采用开环聚合方法合成了聚L-丙氨酸-聚乙二醇嵌段共聚物(PAME), 并对其结构进行了表征; 用圆二色谱(CD)研究了嵌段共聚物在水溶液中的二级结构, 用芘荧光探针技术研究了共聚物胶束的形成及其临界胶束浓度(CMC), 利用动态光散射(DLS)和透射电镜(TEM)研究了胶束的粒径分布和形态. 结果表明, 在水溶液中共聚物链以α-螺旋构象形式存在, 在一定条件下嵌段共聚物能够形成球形的稳定胶束, PAME-1形成胶束的CMC为1.99×10^-5 mol/L, CMC值受共聚物中聚L-丙氨酸(PLA)链段含量的影响.     

高分子量聚对二氧环己酮改进聚DL-乳酸柔韧性的研究

为了提高DL-聚乳酸(PDLLA)的柔韧性,将10～20wt%不同比例的由本课题组自主合成的高分子量聚对二氧环己酮(PPDO)加入到PDLLA基体中,对共混物的微观两相形态、力学性能、热学性能和表面性质、降解性能等物化性质进行了研究.实验结果表明,PPDO加入后,在PDLLA/PPDO共混物的柔韧性得到显著提高的同时,共混物表面亲水性相应提高,降解速率也随之加快.     

聚丙烯酸/聚丙烯酰胺水溶液复合特性的研究

通过酸度、电导率、粘度、接触角的测定,研究了聚丙烯酸 (PAA) /聚丙烯酰胺 (PAM) 水溶液复合物及复合物膜的结构和性能。结果表明,酸度、温度、浓度和复合比影响PAA/PAM的复合水溶液中大分子链的构象和流体力学体积,适度的氢键作用可以形成均相的复合溶液。经过热处理和未经热处理的聚合物膜表现出了不同的亲水性能。     

Metallkomplexe von alkylsubstituierten Poly(vinylpyridin-l-oxiden) und von Poly(dimethylaminostyrol-N-oxiden)

Ohne Zusammenfassung     

Metallkomplexe von alkylsubstituierten Poly(vinylpyridin-l-oxiden) und von Poly(dimethylaminostyrol-N-oxiden)

Ohne Zusammenfassung     

Dilute Solution Properties of Poly(methacrylonitrile-co-styrene) and Poly(acrylonitrile-co-styrene)

Poly(methacrylonitrile-co-styrene) (PMANS) and Poly(acrylo-nitrile- co- styrene) (PANS) having 1:1 composition were prepared with free-radical initiators. The polymers were fractionated into fractions having narrow molecular weight distribution. The dilute solution properties of the fractionated copolymers were studied by light scattering, viscometry, and osmometry in solvents (methyl ethyl ketone, dimethylformamide, and acetone), [n]-M _w and(r²)_w ^l/2?M _w relationships have been established. The validity of the various graphical methods for the determination of Flory′s constant, K _θ were observed.

From the values of the steric factors it was noticed that the copolymer coil of PANS is stiffer than that of PMANS.     

Micellization and Thermogelation of Poly(ether urethane)s Comprising Poly(ethylene glycol) and Poly(propylene glycol)

A series of multiblock poly(ether urethane)s comprising poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized. Their aqueous solutions exhibited thermogelling behavior at critical gelation concentrations (CGC) ranging from 8 to 12 wt%. The composition and structural information of the copolymers were studied by GPC and ¹H NMR. The critical micellization concentration (CMC) and thermodynamic parameters for micelle formation were determined at different temperatures. The temperature response of the copolymer solutions were studied and found to be associated with the composition of the copolymers.     

PPDO/PLLA共混物的制备及其相容性

通过溶液共沉淀法制备了一系列不同组份比例的PPDO/PLLA共混物(Pw)。通过溶度参数、扫描电镜及差式扫描量热仪(DSC)研究了Pw的相容性。结果表明:PPDO与PLLA相容性差;Pw的脆断面扫描电镜图片显示,在不同共混比例下,PLLA在基体PPDO中成典型"海-岛"式分布,且当PLLA含量超过30%时,Pw中出现部分PLLA连续相。     

聚甲基丙烯酸甲酯/聚(异戊二烯-co-苯乙烯)核壳纳米乳液的合成与直接氢化方法的研究

利用可控微乳液法合成粒径19~200 nm,且呈球状分布均匀的聚甲基丙烯酸甲酯/聚(异戊二烯-co-苯乙烯)(PMMA/PIS)核壳纳米粒子,通过水合肼产生原位氢的技术,对合成的PMMA/PIS乳液体系进行直接常压氢化,对影响氢化度的因素、聚合物氢化前后结构、热性能进行了研究.结果显示,聚合物粒径、水合肼及双氧水用量等都是影响聚合物的氢化度的因素.研究发现,氢化以PMMA为核,PIS为壳的核壳结构乳液可以显著提高PIS氢化程度,减少氢化过程中凝胶产生.利用FTIR、~1H-NMR、Na_2S_2O_3滴定法测定了乳液的氢化度.结果表明,当聚合物粒径小于200 nm时,乳液氢化度可达到95%以上,且无凝胶现象产生.GPC结果证明了反应是氢化而非凝胶过程.利用TEM、DLS测试了氢化后乳液的核壳结构和粒径.实验结果显示,PMMA/HPIS为核壳纳米结构.TGA结果显示,当氢化度为98%时,聚合物耐热性提高41°C.