Ben-Zvi Oren, Grinberg Itzhak, Orr Asuka A, Noy Dror, Tamamis Phanourios, Yacoby Iftach, Adler-Abramovich Lihi
School of Plant Sciences and Food Security, The George S. Wise Faculty of Life Sciences, Tel Aviv University, Tel Aviv 6997801, Israel.
Artie McFerrin Department of Chemical Engineering. Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3122, United States.
ACS Nano. 2021 Apr 27;15(4):6530-6539. doi: 10.1021/acsnano.0c09512. Epub 2021 Apr 12.
Molecular oxygen (O) is a highly reactive oxidizing agent and is harmful to many biological and industrial systems. Although O often interacts metals or reducing agents, a binding mechanism involving an organic supramolecular structure has not been described to date. In this work, the prominent dipeptide hydrogelator fluorenylmethyloxycarbonyl-diphenylalanine is shown to encage O and significantly limit its diffusion and penetration through the hydrogel. Molecular dynamics simulations suggested that the O binding mechanism is governed by pockets formed between the aromatic rings in the supramolecular structure of the gel, which bind O through hydrophobic interactions. This phenomenon is harnessed to maintain the activity of the O-hypersensitive enzyme [FeFe]-hydrogenase, which holds promising potential for utilizing hydrogen gas for sustainable energy applications. Hydrogenase encapsulation within the gel allows hydrogen production following exposure to ambient O. This phenomenon may lead to utilization of this low molecular weight gelator in a wide range of O-sensitive applications.
分子氧（O₂）是一种高活性的氧化剂，对许多生物和工业系统都有害。尽管O₂经常与金属或还原剂相互作用，但迄今为止尚未描述涉及有机超分子结构的结合机制。在这项工作中，著名的二肽水凝胶剂芴甲氧羰基-二苯基丙氨酸被证明能够捕获O₂，并显著限制其在水凝胶中的扩散和渗透。分子动力学模拟表明，O₂的结合机制受凝胶超分子结构中芳香环之间形成的口袋控制，这些口袋通过疏水相互作用结合O₂。利用这一现象来维持对O₂高度敏感的酶[FeFe]-氢化酶的活性，该酶在利用氢气实现可持续能源应用方面具有广阔前景。将氢化酶封装在凝胶中可在暴露于环境O₂后产生氢气。这种现象可能导致这种低分子量凝胶剂在广泛的对O₂敏感的应用中得到利用。
