Facile Preparation of Homogeneous Copper Nanoclusters Exhibiting Excellent Tetraenzyme Mimetic Activities for Colorimetric Glutathione Sensing and Fluorimetric Ascorbic Acid Sensing

Nanozymes are artificial enzymes, which can substitute traditional biological enzymes for multifield applications. However, to date, it remains challenging to search novel mimic enzymes or multienzyme mimics. Herein, a facile and green method for preparing monodisperse, homogeneous copper nanocluste...

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Veröffentlicht in:ACS applied materials & interfaces 2020-09, Vol.12 (38), p.42521-42530
Hauptverfasser: Liu, Chongyang, Cai, Yuanyuan, Wang, Jin, Liu, Xuan, Ren, Han, Yan, Lu, Zhang, Yujiao, Yang, Shuqing, Guo, Jing, Liu, Aihua
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container_end_page 42530
container_issue 38
container_start_page 42521
container_title ACS applied materials & interfaces
container_volume 12
creator Liu, Chongyang
Cai, Yuanyuan
Wang, Jin
Liu, Xuan
Ren, Han
Yan, Lu
Zhang, Yujiao
Yang, Shuqing
Guo, Jing
Liu, Aihua
description Nanozymes are artificial enzymes, which can substitute traditional biological enzymes for multifield applications. However, to date, it remains challenging to search novel mimic enzymes or multienzyme mimics. Herein, a facile and green method for preparing monodisperse, homogeneous copper nanoclusters (Cu NCs) with smaller size was developed, which used cysteamine as a template and hydrazine hydrate as a reductant to reduce Cu2+. The as-prepared Cu NCs exhibited excellent tetraenzyme-like activities, including peroxidase (POD)-, catalase (CAT)-, superoxide dismutase (SOD)-, and ascorbic acid oxidase (AAO)-mimic activities. The mechanisms, kinetics, and catalytic performances of Cu NCs were systematically studied. Moreover, based on the POD-like activity of Cu NCs, sensitive and simple colorimetric sensing glutathione (GSH) was explored, with the low limit of detection of 0.89 μM GSH (S/N = 3). Additionally, a novel fluorimetric ascorbic acid (AA) sensor was developed with the linear range of 0.5–30 μM and limit of detection (LOD) of 0.144 μM, on the basis of the principle that AA is oxidized to dehydroascorbic acid (DHAA) specifically catalyzed by the AAO-like activity of Cu NCs, while DHAA can further react with o-phenylenediamine (OPDA) to generate a highly fluorescent quinoxaline (DFQ) derivative. The as-proposed colorimetric GSH sensor and the fluorimetric AA sensor were capable of detecting GSH and AA, respectively, in real samples accurately and reproducibly. Thus, the Cu NCs-based multienzyme mimic is a promising candidate for biocatalysis and biosensing.
doi_str_mv 10.1021/acsami.0c11983
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However, to date, it remains challenging to search novel mimic enzymes or multienzyme mimics. Herein, a facile and green method for preparing monodisperse, homogeneous copper nanoclusters (Cu NCs) with smaller size was developed, which used cysteamine as a template and hydrazine hydrate as a reductant to reduce Cu2+. The as-prepared Cu NCs exhibited excellent tetraenzyme-like activities, including peroxidase (POD)-, catalase (CAT)-, superoxide dismutase (SOD)-, and ascorbic acid oxidase (AAO)-mimic activities. The mechanisms, kinetics, and catalytic performances of Cu NCs were systematically studied. Moreover, based on the POD-like activity of Cu NCs, sensitive and simple colorimetric sensing glutathione (GSH) was explored, with the low limit of detection of 0.89 μM GSH (S/N = 3). Additionally, a novel fluorimetric ascorbic acid (AA) sensor was developed with the linear range of 0.5–30 μM and limit of detection (LOD) of 0.144 μM, on the basis of the principle that AA is oxidized to dehydroascorbic acid (DHAA) specifically catalyzed by the AAO-like activity of Cu NCs, while DHAA can further react with o-phenylenediamine (OPDA) to generate a highly fluorescent quinoxaline (DFQ) derivative. The as-proposed colorimetric GSH sensor and the fluorimetric AA sensor were capable of detecting GSH and AA, respectively, in real samples accurately and reproducibly. 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Mater. Interfaces</addtitle><description>Nanozymes are artificial enzymes, which can substitute traditional biological enzymes for multifield applications. However, to date, it remains challenging to search novel mimic enzymes or multienzyme mimics. Herein, a facile and green method for preparing monodisperse, homogeneous copper nanoclusters (Cu NCs) with smaller size was developed, which used cysteamine as a template and hydrazine hydrate as a reductant to reduce Cu2+. The as-prepared Cu NCs exhibited excellent tetraenzyme-like activities, including peroxidase (POD)-, catalase (CAT)-, superoxide dismutase (SOD)-, and ascorbic acid oxidase (AAO)-mimic activities. The mechanisms, kinetics, and catalytic performances of Cu NCs were systematically studied. Moreover, based on the POD-like activity of Cu NCs, sensitive and simple colorimetric sensing glutathione (GSH) was explored, with the low limit of detection of 0.89 μM GSH (S/N = 3). Additionally, a novel fluorimetric ascorbic acid (AA) sensor was developed with the linear range of 0.5–30 μM and limit of detection (LOD) of 0.144 μM, on the basis of the principle that AA is oxidized to dehydroascorbic acid (DHAA) specifically catalyzed by the AAO-like activity of Cu NCs, while DHAA can further react with o-phenylenediamine (OPDA) to generate a highly fluorescent quinoxaline (DFQ) derivative. The as-proposed colorimetric GSH sensor and the fluorimetric AA sensor were capable of detecting GSH and AA, respectively, in real samples accurately and reproducibly. Thus, the Cu NCs-based multienzyme mimic is a promising candidate for biocatalysis and biosensing.</description><subject>Ascorbate Oxidase - chemistry</subject><subject>Ascorbate Oxidase - metabolism</subject><subject>Ascorbic Acid - analysis</subject><subject>Ascorbic Acid - metabolism</subject><subject>Biological and Medical Applications of Materials and Interfaces</subject><subject>Catalase - chemistry</subject><subject>Catalase - metabolism</subject><subject>Colorimetry</subject><subject>Copper - chemistry</subject><subject>Copper - metabolism</subject><subject>Fluorometry</subject><subject>Glutathione - analysis</subject><subject>Glutathione - metabolism</subject><subject>Metal Nanoparticles - chemistry</subject><subject>Particle Size</subject><subject>Peroxidase - chemistry</subject><subject>Peroxidase - metabolism</subject><subject>Superoxide Dismutase - chemistry</subject><subject>Superoxide Dismutase - metabolism</subject><subject>Surface Properties</subject><issn>1944-8244</issn><issn>1944-8252</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNp1kE1P3DAQhq0KVCjttUfkM9Ju_ZmNj6sVC5UoIEHP0awzAaPEjmynKvwv_l-9XT5OnGZG87zvjF5CvnM250zwH2ATDG7OLOemlp_IITdKzWqhxd5br9QB-ZLSA2OVFEx_JgdS1EpVih-S5zVY1yO9jjhChOyCp6Gj52EId-gxTImuwjhipJfgg-2nlDEmevr33m1cdv6utBb7Hn2mt5gjoH96HJD-cgNmZ-nSZvengJhoF2Lx6kPcrmLZnfVThnxfTiK9QZ-2buBbuu6nd2iZbIib_06ufcW-kv0O-oTfXuoR-b0-vV2dzy6uzn6ulhczkKbKM1lbrsyiYloIBGmlQSOFbIGXccNZ1YGo9cK0LegFLJjuaqU72ypllNGayyMy3_naGFKK2DVjeQziY8NZs82_2eXfvORfBMc7wThtBmzf8NfAC3CyA4qweQhT9OX_j9z-AX1OlNw</recordid><startdate>20200923</startdate><enddate>20200923</enddate><creator>Liu, Chongyang</creator><creator>Cai, Yuanyuan</creator><creator>Wang, Jin</creator><creator>Liu, Xuan</creator><creator>Ren, Han</creator><creator>Yan, Lu</creator><creator>Zhang, Yujiao</creator><creator>Yang, Shuqing</creator><creator>Guo, Jing</creator><creator>Liu, Aihua</creator><general>American Chemical Society</general><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0003-4260-1982</orcidid></search><sort><creationdate>20200923</creationdate><title>Facile Preparation of Homogeneous Copper Nanoclusters Exhibiting Excellent Tetraenzyme Mimetic Activities for Colorimetric Glutathione Sensing and Fluorimetric Ascorbic Acid Sensing</title><author>Liu, Chongyang ; Cai, Yuanyuan ; Wang, Jin ; Liu, Xuan ; Ren, Han ; Yan, Lu ; Zhang, Yujiao ; Yang, Shuqing ; Guo, Jing ; Liu, Aihua</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a396t-38c149760522ea3c39e9323da12eab106fa28579dda57a705f845fcd449495513</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Ascorbate Oxidase - chemistry</topic><topic>Ascorbate Oxidase - metabolism</topic><topic>Ascorbic Acid - analysis</topic><topic>Ascorbic Acid - metabolism</topic><topic>Biological and Medical Applications of Materials and Interfaces</topic><topic>Catalase - chemistry</topic><topic>Catalase - metabolism</topic><topic>Colorimetry</topic><topic>Copper - chemistry</topic><topic>Copper - metabolism</topic><topic>Fluorometry</topic><topic>Glutathione - analysis</topic><topic>Glutathione - metabolism</topic><topic>Metal Nanoparticles - chemistry</topic><topic>Particle Size</topic><topic>Peroxidase - chemistry</topic><topic>Peroxidase - metabolism</topic><topic>Superoxide Dismutase - chemistry</topic><topic>Superoxide Dismutase - metabolism</topic><topic>Surface Properties</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Chongyang</creatorcontrib><creatorcontrib>Cai, Yuanyuan</creatorcontrib><creatorcontrib>Wang, Jin</creatorcontrib><creatorcontrib>Liu, Xuan</creatorcontrib><creatorcontrib>Ren, Han</creatorcontrib><creatorcontrib>Yan, Lu</creatorcontrib><creatorcontrib>Zhang, Yujiao</creatorcontrib><creatorcontrib>Yang, Shuqing</creatorcontrib><creatorcontrib>Guo, Jing</creatorcontrib><creatorcontrib>Liu, Aihua</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><jtitle>ACS applied materials &amp; 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Mater. Interfaces</addtitle><date>2020-09-23</date><risdate>2020</risdate><volume>12</volume><issue>38</issue><spage>42521</spage><epage>42530</epage><pages>42521-42530</pages><issn>1944-8244</issn><eissn>1944-8252</eissn><abstract>Nanozymes are artificial enzymes, which can substitute traditional biological enzymes for multifield applications. However, to date, it remains challenging to search novel mimic enzymes or multienzyme mimics. Herein, a facile and green method for preparing monodisperse, homogeneous copper nanoclusters (Cu NCs) with smaller size was developed, which used cysteamine as a template and hydrazine hydrate as a reductant to reduce Cu2+. The as-prepared Cu NCs exhibited excellent tetraenzyme-like activities, including peroxidase (POD)-, catalase (CAT)-, superoxide dismutase (SOD)-, and ascorbic acid oxidase (AAO)-mimic activities. The mechanisms, kinetics, and catalytic performances of Cu NCs were systematically studied. Moreover, based on the POD-like activity of Cu NCs, sensitive and simple colorimetric sensing glutathione (GSH) was explored, with the low limit of detection of 0.89 μM GSH (S/N = 3). Additionally, a novel fluorimetric ascorbic acid (AA) sensor was developed with the linear range of 0.5–30 μM and limit of detection (LOD) of 0.144 μM, on the basis of the principle that AA is oxidized to dehydroascorbic acid (DHAA) specifically catalyzed by the AAO-like activity of Cu NCs, while DHAA can further react with o-phenylenediamine (OPDA) to generate a highly fluorescent quinoxaline (DFQ) derivative. The as-proposed colorimetric GSH sensor and the fluorimetric AA sensor were capable of detecting GSH and AA, respectively, in real samples accurately and reproducibly. Thus, the Cu NCs-based multienzyme mimic is a promising candidate for biocatalysis and biosensing.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>32844641</pmid><doi>10.1021/acsami.0c11983</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0003-4260-1982</orcidid></addata></record>
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subjects Ascorbate Oxidase - chemistry
Ascorbate Oxidase - metabolism
Ascorbic Acid - analysis
Ascorbic Acid - metabolism
Biological and Medical Applications of Materials and Interfaces
Catalase - chemistry
Catalase - metabolism
Colorimetry
Copper - chemistry
Copper - metabolism
Fluorometry
Glutathione - analysis
Glutathione - metabolism
Metal Nanoparticles - chemistry
Particle Size
Peroxidase - chemistry
Peroxidase - metabolism
Superoxide Dismutase - chemistry
Superoxide Dismutase - metabolism
Surface Properties
title Facile Preparation of Homogeneous Copper Nanoclusters Exhibiting Excellent Tetraenzyme Mimetic Activities for Colorimetric Glutathione Sensing and Fluorimetric Ascorbic Acid Sensing
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