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Stimuli-Responsive Supramolecular Gelation in Ferrocene–Peptide Conjugates

机译:二茂铁-肽缀合物中的刺激响应超分子凝胶化。

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Smart and functional materials have attracted a lot of attention in the last three decades because of their potential applications in the development of new molecular devices.~([1]) In this regard, organogels represent an important medium for the preparation of stimuli-responsive materials.~([2]) The concept of supramolecular devices is still in its infancy and much research is required to develop systems that possess the same responsive behavior that is present in nature. Peptides and proteins are capable of demonstrating multistimuli responsive behavior, and naturally occurring amino acids can be attractive building blocks to extend the same stimuliresponsive features to the development of functional materials.~([3]) Owing to its redox-active properties, ferrocene has been found to be useful in a plethora of applications including sensing, catalysis, and in responsive materials.~([4]) Importantly, ferrocene–peptide conjugates have attracted tremendous attention in designing secondary-structure mimics of peptides because these conjugates have the ability to form hierarchical assemblies driven by weak non-covalent interactions.~([5]) Despite these interesting features, the application of ferrocene–peptide foldamers in forming supramolecular gels has not yet been explored. Herein, we report two novel ferrocene– dipeptide organogelators that are capable of forming gels in various solvents. The prepared gels demonstrate reversible responses to various external signals including thermal, sound, redox, and mechanical stress. Considering the fact that serendipity is one of the main pathways to discovery in organogel research, organometallic-based gelators are not abundant; the ferrocene–dipeptide conjugates reported here are intriguing organometallic gelators.~([6]) We have previously reported Boc-l-Phe-l-Lys(Z)-OMe to have a robust self-organization property that can lead to hierarchical selfassembly and gel formation. Owing to these attractive features, we have coupled this dipeptide, and its analogue Bocl-_L-ys(Z)-l-Phe-OMe, to ferrocene monocarboxylic acid to induce gel formation in the respective ferrocene–peptide conjugates (see Scheme 1).~([7])
机译:在过去的三十年中,智能和功能性材料因其在开发新的分子装置中的潜在应用而引起了广泛的关注。〜([1])在这方面,有机凝胶是制备刺激响应性物质的重要介质材料[2]。超分子器件的概念仍处于起步阶段,需要大量研究来开发具有与自然界相同的响应行为的系统。肽和蛋白质能够表现出多种刺激响应行为,天然氨基酸可以成为有吸引力的构建基,以将相同的刺激响应功能扩展到功能材料的开发中。[[3])由于其氧化还原活性,二茂铁具有[4]重要的是,二茂铁-肽共轭物在设计肽的二级结构模拟物中引起了极大的关注,因为这些共轭物具有〜([5])尽管有这些有趣的功能,但尚未探索在形成超分子凝胶中使用二茂铁-肽折叠剂的应用。在这里,我们报道了两种新颖的二茂铁-二肽有机胶凝剂,它们能够在各种溶剂中形成凝胶。制备的凝胶显示出对各种外部信号(包括热,声音,氧化还原和机械应力)的可逆响应。考虑到偶然性是有机凝胶研究中发现的主要途径之一,基于有机金属的胶凝剂并不丰富。 〜([6])我们之前已经报道过Boc-1-Phe-1-Lys(Z)-OMe具有强大的自组织特性,可以导致分层的自组装,这是有趣的有机金属胶凝剂。和凝胶形成。由于具有这些吸引人的特征,我们将该二肽及其类似物Bocl-_L-ys(Z)-1-Phe-OMe与二茂铁一元羧酸偶联,以诱导在相应的二茂铁-肽共轭物中形成凝胶(参见方案1) 。〜([7])

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