Oligomers assembled from designed building blocks to fold in novel ways have emerged as tools and allow the creation of new structures and molecular properties. Herein, we describe the use of a highly constrained adamantane moiety with one amino group and three carboxylic acids as a monomer. It can be viewed as a constrained, α,α-dialkylated ?-amino tri-acid with side-chains that mimic glutamic acid. We alternated this amino acid with glycine to synthesize a heteropeptide adamantane-based oligomer. An N-terminal l- or d-tyrosine was included to investigate possible chirality induction. The oligomer was assembled by solid-phase peptide synthesis using Fmoc- and Boc-protection strategies. This novel oligomer was characterized by circular dichroism spectroscopy, which revealed a clear effect from the chirality of the N-terminal tyrosine. Molecular dynamics simulation indicated that the adamantane oligomers populated compact conformations, with a subset forming cyclic geometries by hydrogen bonding. Through these interactions the chirality of Tyr induced an overall chirality in the cyclic conformations, which is in agreement with the spectroscopic data. This points to the use of adamantane building blocks in novel chirality switches.

中文翻译：

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具有手性开关的含金刚烷杂肽的合成与表征

由设计的积木组装而成的低聚物以新颖的方式折叠已成为工具，并允许创建新的结构和分子特性。在此，我们描述了使用具有一个氨基和三个羧酸的高度受限的金刚烷部分作为单体。它可以被视为一种受约束的 α,α-二烷基化 α-氨基三酸，其侧链模拟谷氨酸。我们将这种氨基酸与甘氨酸交替，以合成基于杂肽金刚烷的寡聚体。包括 N 端 l-或 d-酪氨酸以研究可能的手性诱导。使用 Fmoc 和 Boc 保护策略通过固相肽合成来组装低聚物。这种新型寡聚体通过圆二色光谱表征，揭示了 N 端酪氨酸手性的明显影响。分子动力学模拟表明，金刚烷低聚物具有紧密的构象，其中一个子集通过氢键形成环状几何结构。通过这些相互作用，Tyr 的手性在环状构象中引起了整体手性，这与光谱数据一致。这表明在新型手性开关中使用了金刚烷构件。