Rapid gel formation and adhesion in photocurable and biodegradable block copolymers with high DOPA content
Rapid gel formation and adhesion in photocurable and biodegradable block copolymers with high DOPA content
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DOI：
10.1021/ma0518959
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发表时间：
2006-03-07
期刊：
影响因子：
5.5
通讯作者：
Messersmith, PB
中科院分区：
文献类型：
--
作者：
Lee, BP;Chao, CY;Messersmith, PB
海洋贻贝锚的各种表面的湍流潮间带通过使用的粘合斑块形成硬化贻贝粘附蛋白（MAPs）。据信，3，4_二羟基苯丙氨酸（DOPA）赋予MAP防水粘合剂特性和快速固化能力。本文合成了DOPA改性的三嵌段共聚物，并将其用于形成粘合性水凝胶。制备了DOPA含量高达10wt%的两亲性嵌段共聚物，并且聚合物的水溶液通过连接到疏水链段的甲基丙烯酸酯端基的光聚合快速（< 1 min）形成水凝胶。对光固化水凝胶进行接触力学粘附测试，结果表明，将DOPA掺入聚合物结构中显著增强了对浸没在水性介质中的钛表面的粘附功。对于含有10wt%DOPA的聚合物，记录到高达410 mJ/m（2）的粘附功值，尽管以DOPA-Lys共聚肽的形式引入Lys降低了粘附功。DOPA的氧化显示出减少了对Ti的粘附功，证实了早期的研究表明，DOPA的儿茶酚形式主要负责对金属氧化物表面的粘附。在这项研究中所描述的含DOPA的嵌段共聚物是候选人使用的粘合剂生物材料的医疗应用。
Marine mussels anchor to a variety of surfaces in turbulent intertidal zones through the use of adhesive plaques formed from hardened mussel adhesive proteins (MAPs). It is believed that 3,4-dihydroxyphenylalanine (DOPA) imparts both water-resistant adhesive characteristics and rapid curing ability to MAPs. In this paper, DOPA-modified triblock copolymers were synthesized and used to form adhesive hydrogels. Amphiphilic block copolymers with DOPA content as high as 10 wt % were prepared, and aqueous solutions of the polymers rapidly (< 1 min) formed hydrogels by photopolymerization of methacrylate end groups attached to the hydrophobic segments. Contact mechanics adhesion tests were performed on the photocured hydrogels, and it was shown that incorporating DOPA into the polymer structure significantly enhanced work of adhesion to titanium surfaces submerged in an aqueous medium. Work of adhesion values as high as 410 mJ/m(2) were recorded for polymers containing 10 wt % DOPA, although the introduction of Lys in the form of a DOPA-Lys copolypeptide reduced the work of adhesion. Oxidation of DOPA was shown to reduce work of adhesion to Ti, confirming earlier studies suggesting that the catecholic form of DOPA is largely responsible for adhesion to metal oxide surfaces. The DOPA-containing block copolymers described in this study are candidates for use as adhesive biomaterials for medical applications.