Enhanced Peroxidase-like Activity of CuS Hollow Nanocages by Plasmon-Induced Hot Carriers and Photothermal Effect for the Dual-Mode Detection of Tannic Acid.

High catalytic activity is one of the necessary parameters for nanozymes to substitute for natural enzymes. It remains a great challenge to improve the specific enzyme-like activity of nanozymes as much as possible using the characteristics of nanomaterials for avoiding complexity and introducing additional uncertainties. Here, by combining the peroxidase (POD)-like activity and plasmon properties of CuS hollow nanocages (CuS HNCs), we demonstrate the feasibility of modulating the catalytic activity of nanozymes by the localized surface plasmon resonance (LSPR) effect. Rough surfaces and hollow-cage structures endow CuS HNCs with abundant hot spots to produce strong LSPR in the near-infrared (NIR) region, which makes the CuS HNCs simultaneously generate plentiful high-energy hot carriers and thermal effect to mediate H2O2 cleavage to yield the reactive oxide species (ROS) as well as speed up the reaction, leading to a dramatically enhanced POD-like activity. Based on the light-enhanced catalytic activity and high photothermal efficiency of the reaction system, a dual-mode strategy for detecting tannic acid (TA) is developed and successfully applied to determine the content of TA in different kinds of teas. This work not only provides a novel path for tuning the specific enzyme-like activity of nanomaterials but also shows a perspective for dual-mode sensing based on a photoinduced plasmon-enhanced effect.

[1]  J. Hong,et al.  Exploiting Plasmonic Hot Spots in Au-Based Nanostructures for Sensing and Photocatalysis. , 2022, Accounts of chemical research.

[2]  William W. Yu,et al.  Plasmonic Nanozyme of Graphdiyne Nanowalls Wrapped Hollow Copper Sulfide Nanocubes for Rapid Bacteria‐Killing , 2022, Advanced Functional Materials.

[3]  H. Fan,et al.  Fabrication of 3D CuS@ZnIn2S4 Hierarchical Nanocages with 2D/2D Nanosheet Subunits p-n Heterojunctions for Improved Photocatalytic Hydrogen Evolution , 2022, Chemical Engineering Journal.

[4]  Sang‐Ok Kim,et al.  Ultrafast and Ultrastable Heteroarchitectured Porous Nanocube Anode Composed of CuS/FeS2 Embedded in Nitrogen-Doped Carbon for Use in Sodium-Ion Batteries. , 2021, Small.

[5]  Wentao Xu,et al.  Nanozymes: Activity origin, catalytic mechanism, and biological application , 2021 .

[6]  Pengfei Yu,et al.  Starch Capped Atomically Thin CuS Nanocrystals for Efficient Photothermal Therapy. , 2021, Small.

[7]  Lizeng Gao,et al.  Nanozymes: A clear definition with fuzzy edges , 2021 .

[8]  Wenxi Zhao,et al.  Structural Engineering of Hollow Microflower-like CuS@C Hybrids as Versatile Electrochemical Sensing Platform for Highly Sensitive Hydrogen Peroxide and Hydrazine Detection. , 2021, ACS applied materials & interfaces.

[9]  Yunchao Li,et al.  Plasmonic Hot Hole Extraction from CuS Nanodisks Enables Significant Acceleration of Oxygen Evolution Reactions. , 2021, The journal of physical chemistry letters.

[10]  Zhi Zheng,et al.  NIR enhanced peroxidase-like activity of Au@CeO2 hybrid nanozyme by plasmon-induced hot electrons and photothermal effect for bacteria killing , 2021 .

[11]  Hui Zhang,et al.  Enhanced peroxidase-mimicking activity of plasmonic gold modified Mn3O4 nanocomposites through photo-excited hot electron transfer. , 2021, Chemistry, an Asian journal.

[12]  D. Ling,et al.  Chemical Design of Nanozymes for Biomedical Applications. , 2021, Acta biomaterialia.

[13]  Shun Wang,et al.  Fabrication of Bioresource-Derived Porous Carbon-Supported Iron as an Efficient Oxidase Mimic for Dual-Channel Biosensing. , 2021, Analytical chemistry.

[14]  Haotian Wang,et al.  Direct and continuous generation of pure acetic acid solutions via electrocatalytic carbon monoxide reduction , 2020, Proceedings of the National Academy of Sciences.

[15]  Guangfang Li,et al.  Plasmonic Nanozymes: Engineered Gold Nanoparticles Exhibit Tunable Plasmon-Enhanced Peroxidase-Mimicking Activity. , 2020, The journal of physical chemistry letters.

[16]  Zhuoran Wang,et al.  Structure and activity of nanozymes: Inspirations for de novo design of nanozymes , 2020, Materials Today.

[17]  Naseeb Ullah,et al.  A Hybrid VOx Incorporated Hexacyanoferrate Nanostructured Hydrogel as a Multienzyme Mimetic via Cascade Reactions. , 2020, ACS nano.

[18]  Hui Zhang,et al.  Plasmon-enhanced oxidase-like activity and cellular effect of Pd-coated gold nanorods. , 2019, ACS applied materials & interfaces.

[19]  Wei Nie,et al.  Hollow copper sulfide nanocubes as multifunctional nanozymes for colorimetric detection of dopamine and electrochemical detection of glucose. , 2019, Biosensors & bioelectronics.

[20]  Min Zhou,et al.  Light-Responsive Metal-Organic Framework as an Oxidase Mimic for Cellular Glutathione Detection. , 2019, Analytical chemistry.

[21]  Juewen Liu,et al.  Manganese as a Catalytic Mediator for Photo-oxidation and Breaking the pH Limitation of Nanozymes. , 2019, Nano letters.

[22]  F. Qu,et al.  Hollow CuS nanocube as nanocarrier for synergetic chemo/photothermal/photodynamic therapy. , 2019, Materials science & engineering. C, Materials for biological applications.

[23]  P. Camargo,et al.  Understanding plasmonic catalysis with controlled nanomaterials based on catalytic and plasmonic metals , 2019, Current Opinion in Colloid & Interface Science.

[24]  A. Benayas,et al.  Highly Efficient Copper Sulfide-Based Near-Infrared Photothermal Agents: Exploring the Limits of Macroscopic Heat Conversion. , 2018, Small.

[25]  Faheem Muhammad,et al.  Nitrogen-Doped Carbon Nanomaterials as Highly Active and Specific Peroxidase Mimics , 2018, Chemistry of Materials.

[26]  Jun Ren,et al.  Lewis Acid-Catalyzed Intramolecular [3+2] Cross-Cycloaddition of Aziridine 2,2-Diesters with Conjugated Dienes for Construction of Aza-[n.2.1] Skeletons. , 2017, Chemistry.

[27]  Guang Yang,et al.  Synergistic Effect Induced High Photothermal Performance of Au Nanorod@Cu7S4 Yolk–Shell Nanooctahedron Particles , 2016 .

[28]  Z. Chai,et al.  Crossover between Anti- and Pro-oxidant Activities of Graphene Quantum Dots in the Absence or Presence of Light. , 2016, ACS nano.

[29]  E. Wang,et al.  Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. , 2013, Chemical Society reviews.

[30]  Partha Samanta,et al.  CuS nanoparticles as a mimic peroxidase for colorimetric estimation of human blood glucose level. , 2013, Talanta.

[31]  Qingli Huang,et al.  CuS nanostructures prepared by a hydrothermal method , 2011 .

[32]  Kuang-Hua Chang,et al.  A hand-held electronic tongue based on fluorometry for taste assessment of tea. , 2010, Biosensors & bioelectronics.

[33]  S. Seal,et al.  Nanoceria exhibit redox state-dependent catalase mimetic activity. , 2010, Chemical communications.

[34]  Jun‐Jie Zhu,et al.  Plasmonic Cu(2-x)S nanocrystals: optical and structural properties of copper-deficient copper(I) sulfides. , 2009, Journal of the American Chemical Society.

[35]  F. L. Crane,et al.  Biochemical Functions of Coenzyme Q10 , 2001, Journal of the American College of Nutrition.

[36]  C. Wei,et al.  Tannins and human health: a review. , 1998, Critical reviews in food science and nutrition.