Chiral Cryptographic Key‐Based Fluorescence Encryption Enabled by Stimuli‐Responsive Metal–Organic Frameworks

作者：Xie Han, Weiqi Wang, Yan Liu, Hao Han, Rong Shao, Zhaojin Wang, Xiu‐Li Yang, Ming‐Hua Xie, Yong Cui · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202510219 · 被引用次数：17 · 研究领域：Molecular Sensors and Ion Detection、Luminescence and Fluorescent Materials、Metal-Organic Frameworks: Synthesis and Applications

Increasing threats of data forgery breaches necessitate the development of advanced encryption strategies beyond traditional cryptographic methods. Fluorescence encryption has emerged as a promising alternative, yet current systems suffer from low security due to simple, reversible stimuli responses. Here, we introduce a novel lock-and-key encryption system using a chiral cyclodextrin metal-organic framework (CDMOF), termed Zole@CDMOF (Zole = acetylated benzoimidazole), for enantioselective discrimination of phenylethylamine (PEA) enantiomers.Confined Zole serves as the lock, while PEA enantiomers act as the key, selectively triggering fluorescence turn-on via acetyl─O bond cleavage and restoring excited-state intramolecular proton transfer (ESIPT) of deacetylated Zole. Mechanistic studies reveal that enantioselectivity arises from thermodynamic differences and distinct hydrogen-bonding interactions between PEA enantiomers. To enhance practical application, Zole@CDMOF is fabricated into a flexible sensor via scotch tape strategy, enabling visual indexing of enantiomeric excess. Additionally, we propose a barcode chiral encryption model, establishing a quadruply encrypted system with ultra-high security-allowing only one out of approximately two million keys to decrypt. This study pioneers the first chiral cryptographic key in fluorescence encryption, paving the way for ultra-secure encryption, advanced chiral sensing, and stimuli-responsive materials.