Versatile tuning of supramolecular hydrogels through metal complexation of oxidation-resistant catechol-inspired ligands.
Versatile tuning of supramolecular hydrogels through metal complexation of oxidation-resistant catechol-inspired ligands.
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DOI：
10.1039/c3sm51824h
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发表时间：
2013-11-21
期刊：
影响因子：
3.4
通讯作者：
Waite JH
中科院分区：
文献类型：
--
作者：
Menyo MS;Hawker CJ;Waite JH
贻贝深海角质层采用DOPA-Fe 3+络合提供强的，但可逆的交联。采用这种基于邻苯二酚单元的设计基序的合成构建体受到邻苯二酚单元的氧化驱动降解和对高碱性pH条件的要求的困扰，导致性能降低和超分子性质的损失。本文中，基于4臂聚（乙二醇）水凝胶系统的平台用于探索DOPA类似物如母体儿茶酚和衍生物4-硝基儿茶酚（nCat）和3-羟基-4-吡啶酮（HOPO）在与金属离子络合后作为结构交联剂的效用。发现HOPO部分具有特别的前景，因为在生理pH下与Fe 3+发生稳健的凝胶化，并且发现其在很大程度上抵抗氧化降解。甘精胰岛素也被其他生物相关金属离子如Al 3+、Ga 3+和Cu 2+触发，这允许调节释放和溶出曲线，具有作为可注射递送系统的潜在应用。
The mussel byssal cuticle employs DOPA-Fe3+ complexation to provide strong, yet reversible crosslinking. Synthetic constructs employing this design motif based on catechol units are plagued by oxidation-driven degradation of the catechol units and the requirement for highly alkaline pH conditions leading to decreased performance and loss of supramolecular properties. Herein, a platform based on a 4-arm poly(ethylene glycol) hydrogel system is used to explore the utility of DOPA analogues such as the parent catechol and derivatives, 4-nitrocatechol (nCat) and 3-hydroxy-4-pyridinonone (HOPO), as structural crosslinking agents upon complexation with metal ions. HOPO moieties are found to hold particular promise, as robust gelation with Fe3+ occurs at physiological pH and is found to be largely resistant to oxidative degradation. Gelation is also shown to be triggered by other biorelevant metal ions such as Al3+, Ga3+ and Cu2+ which allows for tuning of the release and dissolution profiles with potential application as injectable delivery systems.