Metal-mediated cross-linking in the generation of a marine-mussel adhesive
Metal-mediated cross-linking in the generation of a marine-mussel adhesive
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DOI：
10.1002/anie.200352759
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发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
Wilker, JJ
中科院分区：
文献类型：
--
作者：
Sever, MJ;Weisser, JT;Wilker, JJ
4000 多年来，水手们一直在与藤壶和贻贝的顽强斗争。这些蛋白质基粘合剂表现出人类技术仍无法比拟的惊人材料特性。这种硬化基质是通过蛋白质前体的广泛交联形成的。[1-3]这种生物材料合成的交联方法是由来自贻贝、帽贝和海带的胶水、来自藤壶、牡蛎和多毛类蠕虫、珊瑚骨骼和鳐鱼卵壳的水泥所共有的。[2, 3]然而，在这些系统中，没有一个提供用于材料构造的粘合方案的详细图片。对于贻贝粘附斑（图 1），翻译后将 3, 4-二羟基苯丙氨酸 (DOPA) 掺入蛋白质（方案 1）对于随后的交联和正确粘附至关重要。[1-3] 贻贝胶的其他有趣特性包括过渡金属离子含量（例如铜、铁和锌）[4, 5] 高达开放海洋中的 100 000 倍水域。[6]最近我们发现金属离子，特别是 FeIII，可以使从贻贝中提取的粘合剂前体固化。[7]为了深入了解海洋粘合剂的粘合，我们提供了关于贻贝胶和相关系统的数据，表明金属-蛋白质相互作用参与了这些材料的生成。从缅因州沿海收集普通蓝贻贝 (Mytilus edulis)，并将其放在 68C 盐水箱（去离子水和海洋环境盐）中的玻璃板上。沉积粘合剂后（图1），将贻贝和线切掉，从玻璃上刮下粘合剂斑块，用去离子水清洗，并在真空下干燥。收集的斑块在 15K 下通过电子顺磁共振波谱（EPR，图 2a）进行检查。该光谱显示明显存在高自旋 FeIII 中心（g= 4.239, 1531 G；g= g 因子）和有机自由基（g= 1.997, 3249 G），可能伴有 CuII 或低自旋 FeIII 中心（2615, 2734, 2904, 3070 G）的微弱信号。 [8, 9]
Mariners have been contending with the tenacious holdfasts of barnacles and mussels for over 4000 years. These proteinbased adhesives exhibit striking materials properties still unmatched by human technology. Such hardened matrices are formed by extensive cross-linking of protein precursors.[1–3] This cross-linking approach to biomaterial synthesis is shared by glues from mussels, limpets, and kelp, cements from barnacles, oysters, and polychaete worms, coral skeletons, and skate egg shell cases.[2, 3] In none of these systems, however, is there available a detailed picture of the bonding schemes employed for material construction. For mussel adhesive plaques (Figure1), posttranslational incorporation of 3, 4-dihydroxyphenylalanine (DOPA) into the protein (Scheme 1) is essential for subsequent cross-linking and proper adhesion.[1–3] Other interesting properties of the mussel glues include a transition-metal-ion content (eg, copper, iron, and zinc)[4, 5] up to 100 000 times that found in open ocean waters.[6] Recently we have shown that metal ions, in particular FeIII, bring about curing of adhesive precursors extracted from mussels.[7] To gain insights on bonding of marine adhesives, we present data on mussel glues and related systems indicating that metal–protein interactions participate in the generation of these materials.Common blue mussels (Mytilus edulis) were collected from coastal Maine and placed on glass sheets in salt water tanks (deionized water and Marine Environment salt) at 68C. After deposition of adhesive (Figure 1), mussels and threads were cut free, the adhesive plaques were scraped from the glass, washed with deionized water, and dried under vacuum. Collected plaques were examined by electron paramagnetic resonance spectroscopy (EPR, Figure2a) at 15K. This spectrum showed the conspicuous presence of high-spin FeIII centers (g= 4.239, 1531 G; g= g factor) and an organic radical (g= 1.997, 3249 G), possibly accompanied by weak signals for CuII or low-spin FeIII centers (2615, 2734, 2904, 3070 G).[8, 9]