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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Photoresponsive Zn2+-specific metallohydrogels coassembled from imidazole containing phenylalanine and arylazopyrazole derivatives
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Photoresponsive Zn2+-specific metallohydrogels coassembled from imidazole containing phenylalanine and arylazopyrazole derivatives

机译：光响应Zn2 + - 特异性金属铁凝胶与含咪唑含苯丙氨酸和芳基吡唑衍生物的

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摘要

Stimuli-responsive supramolecular gels and metallogels have been widely explored in the past decade, but the fabrication of metallogels with reversible photoresponsive properties remains largely unexplored. In this study, we report the construction of photoresponsive hybrid zinc-based metallohydrogel systems coassembled from an imidazole functionalized phenylalanine derivative gelator (ImF) and carboxylic acid functionalized arylazopyrazole (AzoPz) molecular photoswitches in the presence of Zn(2+)ions. Unlike traditional covalent conjugation, noncovalent introduction of small molecular switches into the gel matrix provides a convenient route to generate photoresponsive functional materials with tunable properties and expands the scope of optically controlled molecular self-assemblies. It has been found that the carboxylic acid functionalized AzoPz derivatives alone or mixed with the ImF moiety could not self-assemble to form any gels. However, in the presence of Zn(2+)ions they readily formed the coassembled hybrid metallogels in an alkaline aqueous solution with various morphologies. These results suggest that the gelation process was triggered by the Zn(2+)ions. In addition, the ImF gelator shows specific response to Zn(2+)ions only. The presence of the AzoPz moiety in the gel matrix makes the metallogel coassemblies photoresponsive and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gels showed a slow reversible light-induced gel-to-sol phase transition under UV (lambda= 365 nm) and then sol-to-gel transition by green light (lambda= 530) irradiation resulting in the reformation of the original gel state. The morphology and viscoelastic properties of the fibrillar opaque metallogels have been characterized by transmission electron microscopy (TEM) and rheological measurement, respectively.
机译：刺激响应超分子凝胶和metallogels已广泛在过去的十年，但可逆的光响应特性metallogels的制造在很大程度上仍然未知。在这项研究中，我们报告中（2+）离子的锌的存在下从咪唑官能苯丙氨酸衍生物的胶凝剂（IMF）和羧酸官能化arylazopyrazole（AzoPz）分子光电继电器coassembled光响应混合锌基metallohydrogel系统的建设。不同于传统的共价缀合，非共价引入小分子开关的入凝胶基质提供了一种方便的途径，以产生具有调谐性能光响应功能材料，扩大的光控制分子自组装的范围。已经发现的是，羧酸官能化AzoPz衍生物单独或与IMF部分混合不能自组装以形成任何凝胶。然而，在锌的存在下（2+）离子它们容易形成coassembled混合metallogels与各种形态的碱性水溶液。这些结果表明，凝胶化过程是由锌（2+）离子触发。此外，（2+）离子只对于Zn的IMF胶凝剂显示特异性反应。在凝胶基质中的AzoPz部分的存在使得metallogel coassemblies光响应并通过UV-vis光谱可逆凝胶到溶胶相转变进行了研究。凝胶呈缓慢可逆光诱导凝胶到溶胶相UV（波长= 365纳米），然后通过绿色光溶胶至凝胶转变下转变（波长= 530），从而导致原始凝胶状态的改革照射。纤维状不透明metallogels的形态和粘弹性质已经分别用透射电子显微镜（TEM）和流变测量。

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