Nguyen Andy I, Spencer Ryan K, Anderson Christopher L, Zuckermann Ronald N
Molecular Foundry , Lawrence Berkeley National Laboratory , Berkeley , CA 94720 , USA . Email:
Department of Chemistry , Department of Chemical Engineering & Materials Science , University of California , Irvine , CA 92697 , USA.
Chem Sci. 2018 Nov 15;9(47):8806-8813. doi: 10.1039/c8sc04240c. eCollection 2018 Dec 21.
Synthesis of biomimetic multimetallic clusters is sought after for applications such as efficient storage of solar energy and utilization of greenhouse gases. However, synthetic efforts are hampered by a dearth of ligands that are developed for multimetallic clusters due to current limitations in rational design and organic synthesis. Peptoids, a synthetic sequence-defined oligomer, enable a biomimetic strategy to rapidly synthesize and optimize large, multifunctional ligands by structural design and combinatorial screening. Here we discover peptoid oligomers (≤7 residues) that fold into a single conformation to provide unprecedented tetra- and hexadentate chelation by carboxylates to a [CoO] cubane cluster. The structures of peptoid-bound cubanes were determined by 2D NMR spectroscopy, and their structures reveal key steric and side-chain-to-main chain interactions that work in concert to rigidify the peptoid ligand. This efficient ligand design strategy holds promise for creating new scaffolds for the abiotic synthesis and manipulation of multimetallic clusters.
人们一直在寻求合成仿生多金属簇，用于太阳能高效存储和温室气体利用等应用。然而，由于目前在合理设计和有机合成方面的限制，用于多金属簇的配体匮乏，阻碍了合成工作。类肽是一种合成的序列定义寡聚物，它通过结构设计和组合筛选，实现了一种仿生策略，能够快速合成和优化大型多功能配体。在这里，我们发现类肽寡聚物（≤7个残基）折叠成单一构象，通过羧酸盐与[CoO]立方烷簇提供前所未有的四齿和六齿螯合。通过二维核磁共振光谱确定了类肽结合立方烷的结构，其结构揭示了关键的空间和侧链与主链相互作用，这些相互作用协同作用使类肽配体刚性化。这种高效的配体设计策略有望为非生物合成和操纵多金属簇创造新的支架。
