Synthesis and characterization of self-assembling block copolymers containing bioadhesive end groups
Synthesis and characterization of self-assembling block copolymers containing bioadhesive end groups
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DOI：
10.1021/bm015650p
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发表时间：
2002-03-01
影响因子：
6.2
通讯作者：
Messersmith, PB
中科院分区：
文献类型：
--
作者：
Huang, K;Lee, BP;Messersmith, PB
3，4-二羟基苯基-L-丙氨酸（DOPA）是贻贝粘附蛋白（MAPs）中发现的一种不常见的氨基酸，被认为赋予这些蛋白质粘附特性。在本文中，我们描述了DOPA部分的共轭聚（环氧乙烷）-聚（环氧丙烷）-聚（环氧乙烷）（PEOPPO-PEO）嵌段共聚物的路线。用N，N-二琥珀酰亚胺碳酸酯活化PEO-PPO-PEO嵌段共聚物的端羟基，然后与DOPA或其甲酯反应，在水和有机溶剂中均获得高偶联效率。DOPA-改性的PEO-PPO-PEO嵌段共聚物易溶于冷水，并且这些溶液的染料分配和差示扫描量热法分析揭示了共聚物在取决于嵌段共聚物组成和溶液中浓度的特征温度下聚集成胶束。振荡流变仪证实，在约20wt%的嵌段共聚物浓度以上，DOPA改性的PEO-PPO-PEO嵌段共聚物的溶液在加热时表现出溶胶-凝胶转变。凝胶化温度可以通过改变嵌段共聚物的组成、浓度和分子量在23 - 46 ℃之间调节。多巴修饰的普朗尼克和牛颌下粘蛋白之间的生物粘附相互作用的流变学测量表明，多巴修饰的普朗尼克比未修饰的普朗尼克具有更强的生物粘附性。
3,4-Dihydroxyphenyl-L-alanine (DOPA) is an unusual amino acid found in mussel adhesive proteins (MAPs) that is believed to lend adhesive characteristics to these proteins. In this paper, we describe a route for the conjugation of DOPA moieties to poly(ethylene oxide)-poly(propylene oxide) - poly(ethylene oxide) (PEOPPO-PEO) block copolymers. Hydroxyl end groups of PEO-PPO-PEO block copolymers were activated by NN-disuccinimidyl carbonate and then reacted with DOPA or its methyl ester with high coupling efficiencies from both aqueous and organic solvents. DOPA-modified PEO-PPO-PEO block copolymers were freely soluble in cold water, and dye partitioning and differential scanning calorimetry analysis of these solutions revealed that the copolymers aggregated into micelles at a characteristic temperature that was dependent on block copolymer composition and concentration in solution, Oscillatory rheometry demonstrated that above a block copolymer concentration of approximately 20 wt %, solutions of DOPA-modified PEO-PPO-PEO block copolymers exhibited sol-gel transitions upon heating. The gelation temperature could be tailored between similar to23 and 46 degreesC by changing the composition, concentration, and molecular weight of the block copolymer. Rheological measurement of the bioadhesive interaction between DOPA-modified Pluronic and bovine submaxillary mucin indicated that DOPA-modified Pluronic was significantly more bioadhesive than unmodified Pluronic.