The construct of artificial nanocatalyts by simulating natural enzymes and thereby bringing new properties for practical applications is still a challenging task to date. In this study, chiral tetrapeptide (L-phenylalanine-L-phenylalanine-L-cysteine-L-histidine)-engineered copper nanoparticles (FFCH@CuNPs) were fabricated as an artificial peroxidase (POD). More interestingly, the nano-catalysts exhibited chiral identification function. In comparison with other nanocatalysts like L-cysteine-, L-histidine-, chiral dipeptide (L-cysteine-L-histidine)-, or chiral tripeptide phenylalanine-L-cysteine-L-histidine)-modified CuNPs, FFCH@CuNPs demonstrated a higher POD-mimetic catalytic activity in the 3,3′,5,5′-tetramethylbenzidine (TMB)-H₂O₂ system and stronger enantioselectivity in the recognition of 3,4-dihydroxy-D,L-phenylalanine (D,L-DOPA) enantiomers. Considering the strength difference between the intermolecular hydrogen bonding and the π-π interactions, the principle behind the chiral discrimination of D,L-DOPA was explored. Furthermore, contents levels of surface Cu²⁺ ions and hydroxyl radicals were found in the FFCH@CuNPs-D-DOPA-TMB-H₂O₂ system than in the FFCH@CuNPs-L-DOPA-TMB-H₂O₂ system. Based on these results, a protocol for distinguishing between D,L-DOPA enantiomers through colorimetric recognition was established. This study provides a new insight into design and fabrication of oligopeptides@CuNPs-based chiral nanozymes with improved catalytic performance and features additional to those of natural enzymes.

通过模拟天然酶构建人工纳米催化剂，从而为实际应用带来新的性能，迄今为止仍然是一项具有挑战性的任务。在这项研究中，手性四肽（L-苯丙氨酸-L-苯丙氨酸-L-半胱氨酸-L-组氨酸）工程铜纳米颗粒（FFCH@CuNPs）被制造为人工过氧化物酶（POD）。更有趣的是，纳米催化剂表现出手性识别功能。与其他纳米催化剂如L-半胱氨酸-、L-组氨酸-、手性二肽( L-半胱氨酸-L-组氨酸)-或手性三肽苯丙氨酸-L-半胱氨酸-L-组氨酸)修饰的CuNPs相比，FFCH@CuNPs表现出在 3,3',5,5'-四甲基联苯胺 (TMB)-H ₂ O ₂体系中具有更高的 POD 模拟催化活性，并且在识别 3,4-二羟基-D,L-苯丙氨酸 ( D, L -DOPA）对映体。考虑分子间氢键和π-π相互作用的强度差异，探讨了D,L - DOPA的手性判别原理。此外， FFCH@CuNPs-D-DOPA-TMB-H ₂ O _{2体系中表面Cu} ²⁺离子和羟基自由基的含量水平高于FFCH@CuNPs-L-DOPA-TMB-H ₂ O ₂体系。基于这些结果，建立了通过比色识别区分D,L -DOPA 对映体的方案。这项研究为基于寡肽@CuNPs的手性纳米酶的设计和制造提供了新的见解，该纳米酶具有改进的催化性能和天然酶的附加功能。