Biomolecule-based non-covalent glasses are biocompatible and biodegradable, and offer a sustainable alternative to conventional glass. Cyclic peptides (CPs) can serve as promising glass formers owing to their structural rigidity and resistance to enzymatic degradation. However, their potent crystallization tendency hinders their potential in glass construction. Here we engineered a series of CP glasses with tunable glass transition behaviours by modulating the conformational complexity of CP clusters. By incorporating multicomponent CPs, the formation of high-entropy CP glass is facilitated, which—in turn—inhibits the crystallization of individual CPs. The high-entropy CP glass demonstrates enhanced mechanical properties and enzyme tolerance compared with individual CP glass and a unique biorecycling capability that is unattainable by traditional glasses. These findings provide a promising paradigm for the design and development of stable non-covalent glasses based on naturally derived biomolecules, and advance their application in pharmaceutical formulations and smart functional materials.

基于生物分子的非共价玻璃具有生物相容性和可生物降解性，是传统玻璃的可持续替代品。环肽 （CP） 由于其结构刚性和抗酶降解性，可以作为有前途的玻璃形成剂。然而，它们强大的结晶倾向阻碍了它们在玻璃结构中的潜力。在这里，我们通过调节 CP 簇的构象复杂性，设计了一系列具有可调玻璃化转变行为的 CP 玻璃。通过掺入多组分 CP，促进了高熵 CP 玻璃的形成，进而抑制了单个 CP 的结晶。与单个 CP 玻璃相比，高熵 CP 玻璃表现出增强的机械性能和酶耐受性，以及传统玻璃无法实现的独特生物回收能力。这些发现为基于天然衍生生物分子的稳定非共价玻璃的设计和开发提供了有前途的范式，并推动了它们在药物制剂和智能功能材料中的应用。