Despite great progress on the construction of non‐equilibrium systems, most approaches do not consider the structure of the fuel as a critical element to control the processes. Herein, we show that the amino acid side chains (A, F, Nal) in the structure of abiotic phosphates can direct assembly and reactivity during transient structure formation. The fuels bind covalently to substrates and subsequently influence the structures in the assembly process. We focus on the ways in which the phosphate esters guide structure formation and how structures and reactivity cross regulate when constructing assemblies. Through the chemical functionalization of energy‐rich aminoacyl phosphate esters, we are able to control the yield to esters and thioesters upon adding dipeptides containing tyrosine or cysteine residues. The structural elements around the phosphate esters guide the lifetime of the structures formed and their supramolecular assemblies. These properties can further be influenced by the peptide sequence of substrates, incorporating anionic, aliphatic and aromatic residues. Furthermore, we illustrate that oligomerization of esters can be initiated from a single aminoacyl phosphate ester incorporating a tyrosine residue (Y). These findings suggest that activated amino acids with varying reactivity and energy contents can pave the way for designing and fabricating structured fuels.

中文翻译：

---

利用嵌入非生物磷酸盐燃料中的结构元件引导瞬时肽组装

尽管在非平衡系统的构建方面取得了巨大进展，但大多数方法并未将燃料的结构视为控制过程的关键要素。在此，我们证明非生物磷酸盐结构中的氨基酸侧链（A、F、Nal）可以在瞬时结构形成过程中指导组装和反应性。燃料与基材共价结合，随后影响组装过程中的结构。我们重点研究磷酸酯引导结构形成的方式以及构建组件时结构和反应性如何交叉调节。通过富含能量的氨酰基磷酸酯的化学功能化，我们能够在添加含有酪氨酸或半胱氨酸残基的二肽时控制酯和硫酯的产率。磷酸酯周围的结构元素决定所形成的结构及其超分子组装体的寿命。这些特性还可能受到底物肽序列的影响，其中包含阴离子、脂肪族和芳香族残基。此外，我们还说明了酯的低聚可以从包含酪氨酸残基（Y）的单个氨基酰基磷酸酯引发。这些发现表明，具有不同反应性和能量含量的活化氨基酸可以为设计和制造结构化燃料铺平道路。