Programmable Bio‐Derived Noncovalent Glass via Reconfigurable H‐Bonding Networks

Abstract Glass has served as a cornerstone of modern civilization due to its exceptional optical transparency and structural integrity. Yet, its static covalent/ionic network fundamentally restricts environmental adaptability, presenting a critical challenge for next‐generation sustainable technologies. Here, we report a programmable, bio‐derived noncovalent glass (BNG) engineered through multivalent, reconfigurable H‐bonding networks composed of natural building blocks (e.g., amino acids, peptides, biomacromolecules) and organic acids with multiple H‐bond donors and acceptors. Molecular programming of these networks enables unprecedented four‐dimensional control: hydration‐tunable mechanical stiffness, amino acid‐guided refractive index modulation, humidity/temperature‐activated self‐healing, and closed‐loop aqueous recyclability. This molecularly encoded programmability distinguishes BNG from conventional smart materials, which typically rely on single stimulus–response modes. Critically, the configurability of H‐bonding network further endows BNG with versatile processability (e.g., 3D printing, thermal pressing, and mold‐casting) for functional architectures. Moreover, the programmable disassembly allows seamless integration into transient electronics as an energy‐efficient alternative to energy‐intensive glass recycling. By leveraging naturally abundant, metabolically benign building blocks, BNG establishes a sustainable paradigm for adaptive soft electronics and circular packaging—transforming glass from a passive structural medium to a dynamically programmable material.