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基于聚(3-羟基丁酸酯-共-4-羟基丁酸酯)和聚(3-羟基己酸酯-共-3-羟基辛酸酯)的嵌段聚(酯-聚氨酯)。

Block poly(ester-urethane)s based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and poly(3-hydroxyhexanoate-co-3-hydroxyoctanoate).

作者信息

Chen Zhifei, Cheng Shaoting, Xu Kaitian

机构信息

Multidisciplinary Research Center, Shantou University, Daxue Lu 243, Shantou, Guangdong 515063, China.

出版信息

Biomaterials. 2009 Apr;30(12):2219-30. doi: 10.1016/j.biomaterials.2008.12.078. Epub 2009 Jan 23.

Abstract

A series of block poly(ester-urethane) poly(3/4HB-HHxHO) urethanes (abbreviated as PUHO) based on poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3/4HB-diol) and poly(3-hydroxyhexanoate-co-3-hydroxyoctanoate) (PHHxHO-diol) segments were synthesized by a facile way of melting polymerization using 1,6-hexamethylene diisocyanate (HDI) as the coupling agent, with different 3HB, 4HB, HHxHO compositions and segment lengths. The chemical structure, molecular weight and distribution were systematically characterized by (1)H, (13)C nuclear magnetic resonance spectrum (NMR), two-dimensional correlation spectroscopy (COSY ((1)H, (13)C) NMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The thermal property was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The hydrophilicity was investigated by static contact angle of water and CH(2)I(2). DSC revealed that the poly(3/4HB-HHxHO) urethanes are almost amorphous with a little crystallinity (less than 6%) and T(g) from -23 degrees C to -3 degrees C. The polyurethanes are more hydrophobic (water contact angle 88 degrees -117 degrees ) than the P3/4HB and PHHxHO raw materials. The lactate dehydrogenase (LDH) assay and platelet adhesion determination showed that the obtained polyurethanes have much higher platelet adhesion property than raw materials and common biodegradable polymers polylactic acid (PLA) and poly(3-hydroxybutyrate) (PHB). Hydrophobicity and crystallinity degree are important factors to affect the platelet adhesion. All the properties can be tailored by changing the composition and segment length of prepolymers P3/4HB-diol and PHHxHO-diol.

摘要

基于聚(3-羟基丁酸酯-共-4-羟基丁酸酯)(P3/4HB-二醇)和聚(3-羟基己酸酯-共-3-羟基辛酸酯)(PHHxHO-二醇)链段,通过以1,6-六亚甲基二异氰酸酯(HDI)为偶联剂的简便熔融聚合法,合成了一系列嵌段聚(酯-聚氨酯)聚(3/4HB-HHxHO)聚氨酯(简称为PUHO),其具有不同的3HB、4HB、HHxHO组成和链段长度。通过(1)H、(13)C核磁共振谱(NMR)、二维相关光谱(COSY((1)H,(13)C)NMR)、傅里叶变换红外光谱(FTIR)和凝胶渗透色谱(GPC)对化学结构、分子量和分布进行了系统表征。通过差示扫描量热法(DSC)和热重分析(TGA)研究了热性能。通过水和CH(2)I(2)的静态接触角研究了亲水性。DSC显示聚(3/4HB-HHxHO)聚氨酯几乎为无定形,具有少量结晶度(小于6%),玻璃化转变温度(T(g))为-23℃至-3℃。这些聚氨酯比P3/4HB和PHHxHO原料更疏水(水接触角为88°-117°)。乳酸脱氢酶(LDH)测定和血小板粘附测定表明,所获得的聚氨酯比原料以及常见的可生物降解聚合物聚乳酸(PLA)和聚(3-羟基丁酸酯)(PHB)具有更高的血小板粘附性能。疏水性和结晶度是影响血小板粘附的重要因素。通过改变预聚物P3/4HB-二醇和PHHxHO-二醇的组成和链段长度,可以调整所有性能。

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