Department of Chemistry, Institute for Biophysical Dynamics, University of Chicago, Chicago, IL 60637, USA.
Proc Natl Acad Sci U S A. 2011 Feb 15;108(7):2651-5. doi: 10.1073/pnas.1015862108. Epub 2011 Jan 28.
Growing evidence supports a critical role of metal-ligand coordination in many attributes of biological materials including adhesion, self-assembly, toughness, and hardness without mineralization [Rubin DJ, Miserez A, Waite JH (2010) Advances in Insect Physiology: Insect Integument and Color, eds Jérôme C, Stephen JS (Academic Press, London), pp 75-133]. Coordination between Fe and catechol ligands has recently been correlated to the hardness and high extensibility of the cuticle of mussel byssal threads and proposed to endow self-healing properties [Harrington MJ, Masic A, Holten-Andersen N, Waite JH, Fratzl P (2010) Science 328:216-220]. Inspired by the pH jump experienced by proteins during maturation of a mussel byssus secretion, we have developed a simple method to control catechol-Fe(3+) interpolymer cross-linking via pH. The resonance Raman signature of catechol-Fe(3+) cross-linked polymer gels at high pH was similar to that from native mussel thread cuticle and the gels displayed elastic moduli (G') that approach covalently cross-linked gels as well as self-healing properties.
越来越多的证据表明，金属-配体配位在许多生物材料的特性中起着关键作用，包括粘附、自组装、韧性和硬度（无需矿化）[Rubin DJ、Miserez A、Waite JH（2010）《昆虫生理学进展：昆虫外骨骼和颜色》，eds Jérôme C、Stephen JS（Academic Press，London），pp 75-133]。最近，Fe 和儿茶酚配体之间的配位与贻贝足丝的壳聚糖的硬度和高延展性相关，并被认为赋予了自修复性能[Harrington MJ、Masic A、Holten-Andersen N、Waite JH、Fratzl P（2010）《科学》328:216-220]。受贻贝足丝分泌过程中蛋白质成熟时经历的 pH 跳跃的启发，我们开发了一种简单的方法来通过 pH 控制儿茶酚-Fe(3+) 共聚体交联。高 pH 下儿茶酚-Fe(3+)交联聚合物凝胶的共振拉曼特征与天然贻贝壳聚糖相似，并且凝胶表现出接近共价交联凝胶的弹性模量（G'）以及自修复性能。
