Inspired by the hydrolysis behaviors of skin cells, we exquisitely designed and synthesized a class of hydrolase mimics to develop an analytical method that can both identify and quantity antioxidant components in skin-whitening cosmetics, including ascorbic acid (AA) and its glycoside and phosphate derivatives. A series of ultra-thin CuMnO or FeMnO with rich acid-base pairs were prepared via chemical deposition and Cu/Fe self-assembly. HO and DO isotopic labeling studies and density function theory (DFT) calculations were adopted to analyze the cleaving sites of ascorbyl phosphate (AAL)/ascorbyl glucoside (AAP) and confirm that HO was involved in the new bonds. DRIFT NH-IR and −TPD further confirmed that the Fe- or Cu-substitution could increase the quantity and strength of Brønsted and Lewis acid sites. A cascade catalytic fluorescence sensor was designed for selective recognition or quantification of AA and its derivatives, which presents ultra-high-precision (≤2.5 %), stability, and selectivity in testing the target ingredients of five cosmetics from the market. Our nanozymes exhibit higher catalytic efficiency of 17.1 s for AA, 8.42 s for AAL, and 3.32 s for AAP, which are 5.6 ∼ 32.8-fold higher than those of their mimic proteases. This work provides a controllable methodology to design hydrolytic nanozymes, which sheds light on biomimetic engineering and paves the way for breakthroughs in cosmetics industrial applications in the future.

中文翻译：

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通过金属掺杂调节多种酶样活性，用于化妆品中抗氧化剂的鉴定和定量


受皮肤细胞水解行为的启发，我们精心设计并合成了一类水解酶模拟物，开发了一种分析方法，可以鉴定和定量美白化妆品中的抗氧化成分，包括抗坏血酸（AA）及其糖苷和磷酸盐衍生物。通过化学沉积和Cu/Fe自组装制备了一系列具有丰富酸碱对的超薄CuMnO或FeMnO。采用H2O和DO同位素标记研究和密度函数理论（DFT）计算来分析抗坏血酸磷酸酯（AAL）/抗坏血酸葡萄糖苷（AAP）的裂解位点，并确认H2O参与新键。 DRIFT NH-IR 和 -TPD 进一步证实 Fe 或 Cu 取代可以增加 Brønsted 和 Lewis 酸位的数量和强度。设计了级联催化荧光传感器，用于选择性识别或定量AA及其衍生物，在测试市场上五种化妆品的目标成分时表现出超高精度（≤2.5%）、稳定性和选择性。我们的纳米酶表现出更高的催化效率，AA 为 17.1 s，AAL 为 8.42 s，AAP 为 3.32 s，比模拟蛋白酶高 5.6 ∼ 32.8 倍。这项工作提供了一种可控的方法来设计水解纳米酶，为仿生工程提供了线索，并为未来化妆品工业应用的突破铺平了道路。