Plasmonic nanostructures acting as a light-driven O_(2)-sensitive nitroreductase mimic for enhanced photochemical oxidation of para-aminothiophenol  

作　　者：Xinshuang Gao Jia-jia Zheng Hanbo Li Rui Cai Xingfa Gao Xiaochun Wu 

机构地区：[1]CAS Key Laboratory of Standardization and Measurement for Nanotechnology,National Center for Nanoscience and Technology,Beijing 100190,China [2]Laboratory of Theoretical and Computational Nanoscience,National Center for Nanoscience and Technology,Beijing 100190,China [3]University of Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Nano Research》2023年第11期12697-12705,共9页纳米研究（英文版）

基　　金：supported by the National Key Basic Research Program of China(No.2021YFA1202803);the National Natural Science Foundation of China(No.22072032);the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)。

摘　　要：Nanozymes,as a novel form of enzyme mimics,have garnered considerable interest.Despite overcoming the main disadvantages of their natural analogs,they still face challenges such as restricted mimic types and low substrate specificity.Herein,we introduce a reactive ligand modification strategy to diversify enzyme mimic types.Specifically,we have utilized helical plasmonic nanorods(HPNRs)modified with para-nitrothiophenol(4-NTP)to create an oxygen-sensitive nitroreductase(NTR)with light-controllability.HPNRs act as a light-adjustable source of nicotinamide adenine dinucleotide/nicotinamide adenine dinucleotide phosphate(NAD(P)H),providing photon-generated energetic electrons to adsorbed 4-NTP molecules.In the presence of O_(2),the activated 4-NTP transfers the captured electron to the adsorbed O_(2),mimicking the electron transfer process in its natural counterpart.This enhanced O_(2)activation notably boosts the oxidative coupling of para-aminothiophenol(4-ATP).Density functional theory(DFT)calculations reveal that hot electrons injected into the lowest unoccupied molecular orbital(LUMO)energy level of 4-NTP can be transferred to that of molecular oxygen.In conclusion,our findings underline the potential of the reactive ligand modification strategy in developing new types of enzyme reactions,which opens up promising avenues for the enhancement and diversification of nanozyme functionalities.

关 键 词：plasmonic nanostructure nanozyme NITROREDUCTASE para-nitrothiolphenol hot electron injection para-aminothiolphenol 

分 类 号：O62[理学—有机化学]