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化学进展 2023, Vol. 35 Issue (9): 1389-1398 DOI: 10.7536/PC230113 前一篇   后一篇

• 综述 •

金属有机框架纳米酶在临床检测中的应用

罗文浩1,2, 袁睿1,2, 孙金元1,2, 周连群3, 罗小河1,4,*(), 罗阳1,5,*()   

  1. 1 重庆大学医学院 重庆 400044
    2 重庆大学生物工程学院 重庆 400044
    3 中国科学院苏州生物医学工程技术研究所 苏州 215163
    4 重庆大学附属三峡医院 重庆 400044
    5 昆明医科大学生命科学与检验医学学院 昆明 650050
  • 收稿日期:2023-01-31 修回日期:2023-04-07 出版日期:2023-09-24 发布日期:2023-05-30
  • 基金资助:
    国家重点研发计划(2022YFC2009600); 国家重点研发计划(2022YFC2009603); 国家杰出青年科学基金(82125022); 国家自然科学基金项目(82202633); 国家自然科学基金项目(82072383); 重庆市高等教育教学改革研究项目(213035)
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Metal-Organic Framework-Based Nanozymes for Clinical Applications

Wenhao Luo1,2, Rui Yuan1,2, Jinyuan Sun1,2, Lianqun Zhou3, Xiaohe Luo1,4(), Yang Luo1,5()   

  1. 1 School of Medicine, Chongqing University,Chongqing 400044, China
    2 College of Bioengineering, Chongqing University,Chongqing 400044, China
    3 Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences,Suzhou 215163, China
    4 Chongqing University Three Gorges Hospital,Chongqing 400044, China
    5 College of Life Science and Laboratory Medicine, Kunming Medical University,Kunming 650050, China
  • Received:2023-01-31 Revised:2023-04-07 Online:2023-09-24 Published:2023-05-30
  • Contact: *e-mail: Luoy@cqu.edu.cn(Yang Luo); xiaoheluo@163.com(Xiaohe Luo)
  • Supported by:
    The National Key Research and Development Program of China(2022YFC2009600); The National Key Research and Development Program of China(2022YFC2009603); The National Science Fund for Distinguished Young Scholars(82125022); The National Natural Science Foundation of China(82202633); The National Natural Science Foundation of China(82072383); The Chongqing Higher Education Teaching Reform Research Project(213035)

酶作为天然的生物催化剂,在生物化学反应中发挥着重要的作用。由于天然酶受限其固有的缺点(稳定性低、成本高、储存困难等),具有催化活性的人工模拟酶应运而生。近年来,随着纳米材料迅速发展,仿酶催化纳米材料(纳米酶)逐渐受到研究者们的关注。纳米酶是一类具有类似天然酶活性的纳米材料,其制备过程简单、成本较低,有一定环境耐受性。然而大多数纳米酶类酶活性较低,稳定性相对较差,在生物分析应用中存在诸多困难。其中,金属有机框架(MOF)纳米酶具有高比表面积及孔隙率、活性位点均匀、较强的催化活性及稳定性等性质,且合成简单可控、成本低;此外,较天然酶而言,MOF纳米酶也以其独特的生物化学优势,在临床检测中发挥着巨大应用价值。本文主要基于MOF纳米酶的不同酶活性分类(过氧化物酶、氧化酶、过氧化氢酶、超氧化物歧化酶、水解酶),对其在核酸、蛋白质及小分子三大生物标志物在临床检测中的应用进行概述,并进一步展望了其在临床检测中面临的机遇与挑战,以推动MOF纳米酶的临床应用转化。

关键词： 金属有机框架, 纳米酶, 临床检测, 核酸检测, 蛋白质分析

Enzymes are considered as natural biocatalysts, which catalyze many biochemical reactions with good catalytic efficiency, biocompatibility, and substrate specificity. The intrinsic limitations of natural enzymes such as low stability, high cost, and storage difficulty have led to the introduction of artificial enzymes that imitate the activity of natural enzymes. With the rapid development of nanomaterials in the recent decade, novel enzyme-mimicking nanomaterials (nanozymes) have attracted considerable attention from researchers. Nanozymes are defined as a class of artificial nanomaterials possessing intrinsic enzymes-like activities, which have the advantages of simple preparation processes, low cost and some environmental tolerance. However, most of them are limited by their low activity and relatively poor stability, leading to many difficulties in the application of biochemical analysis. Among them, metal-organic framework nanozymes (MOFs) have demonstrated a wide range of uses because of their evident favorable circumstances, including the large surface area and porosity for functionalization, uniform active sites, high catalytic activity and stability, simple and controllable synthesis and low cost. In this review, we provide a summary of the clinical detection application of MOFs in nucleic acid, protein and small molecules based on their different activity classification (peroxidase, oxidase, catalase, superoxide dismutase, and hydrolase). Finally, we look forward to the opportunities and challenges that MOFs will face in clinical detection, promoting their clinical application transformation.

Contents

1 Introduction

2 Classification of MOF nanozymes

2.1 Peroxidase

2.2 Oxidase

2.3 Catalase

2.4 Superoxide dismutase

2.5 Hydrolase

3 Application of MOF nanozymes in clinical detection

3.1 Application of MOF nanozymes in nucleic acid detection

3.2 Application of MOF nanozymes in protein detection

3.3 Application of MOF nanozymes in the detection of small molecule

4 Conclusion and outlook

4.1 Strengthening environmental stability

4.2 Enhancing substrate specificity

4.3 Enhancing the enzymes-like catalytic activity

Key words: clinical tests, metal-organic framework, nanozymes, nucleic acids testing, protein analysis
()
表1 MOF 纳米酶的主要分类[8,11???????????? ~24]
Table 1 The main classification of MOF nanozymes[8,11???????????? ~24]
Classification Advantages Disadvantages Reaction principle Examples ref
Peroxidase Higher catalytic activity than natural peroxidase, and adjusted active sites The high activity is only in weak acidity condition (pH is about 4). Fenton-like reaction Zr-MOF,Fe-MOF,
Ni-MOF		 8,11,12
Oxidase Higher catalytic activity than natural oxidase, and H2O2 is not required for the reaction The selectivity and specificity of substrate are insufficient in
complex samples		 Activating O2 to
produce ROS		 some Ce-MOF,Co-MOF,Cu-MOF 13⇓⇓~16
Catalase High stability, adjustable enzyme activity, simple preparation, good biocompatibility The high catalytic activity is only at specific pH. Accelerating the
dismutation of H2O2 into water and oxygen		 Ce-MOF,Mn-MOF 17⇓~19
Superoxide dismutase Higher stability than natural superoxide dismutase, and high catalytic activity Certain cytotoxicity Disproportionation of
superoxide anion to oxygen and hydrogen peroxide		 Cu/Zr-MOF,Sn-MOF 8,20,21
Hydrolase Higher stability than natural hydrolase, wide range of applications, and flexible design The activity of catalyst is easily affected by strong acid and alkali The hydrolysis of the metal nodes and
coordination structures		 Zr-MOF,Ce-MOF 8,22⇓~24
图1 MOF纳米酶在核酸检测中的应用。(A)ZIF-8纳米酶触发级联催化反应,实现miRNA-21灵敏检测[54];(B)MOF级联核酸电路用于准确、灵敏地检测血清循环miRNA[57];(C)新型多功能铁基金属有机框架(PdNPs@Fe-MOFs)用于药物性肝损伤标记物miRNA-122超敏检测[58];(D)基于MOF纳米酶的miRNA流动均相电化学检测系统[59]
Fig.1 Application of MOF nanozymes in nucleic acid detection.(A)ZIF-8 nanozymes triggered cascade catalytic reaction for miRNA-21 detection[54];(B)MOF cascade nucleic acid circuit for circulating miRNA analyzing in serum[57];(C)multifunctional iron-based metal-organic framework (PdNPs@Fe-MOFs) for miRNA-122 identification[58];(D)MOF nanozymes assisted homogeneous electrochemical system for miRNA discrimination[59]
图2 MOF纳米酶在蛋白检测中的应用。(A)过氧化物酶模拟物Fe-MIL-88A用于凝血酶的检测[62];(B)碳布纤维表面合成的MOF-818用于凝血酶的检测[63];(C)模拟过氧化物酶的二维MOF用于碱性磷酸酶测定[68];(D)合成的MIL53(Fe)/G4-氯化血红素用于碱性磷酸酶检测[69]
Fig.2 Application of MOF nanozymes in protein detection. (A)peroxidase mimic Fe-MIL-88A for thrombin detection[62];(B)MOF-818 synthesized with the surface of carbon cloth fiber for the identification of thrombin[63];(C)Peroxidase mimic two-dimensional MOF for Alkaline Phosphatase determination[68];(D)MIL53 (Fe) / G4-hemin for the discrimination of alkaline phosphatase[69]
图3 MOF纳米酶在小分子检测中的应用。(A)Fe-MOF-Gox 级联催化检测葡萄糖[74];(B)合成的MOF纳米酶用于葡萄糖和半胱氨酸的检测[75];(C)ELISA中引入MOF纳米酶进行催化显色以测定黄曲霉毒素B1[78];(D)高过氧化物酶活性的Hemin@BSA@ZIF-8用于过氧化氢和双酚 A的检测[81]
Fig.3 Application of MOF nanozymes in the Detection of small molecules.(A)Fe-MOF-Gox cascade catalysis for glucose detection[74];(B)MOF nanozymes for the detection of glucose and Cysteine[75];(C)MOF nanozymes for the Determination of aflatoxin B1 in ELISA[78];(D)Hemin@BSA@ZIF-8 for H2O2 and bisphenol Aidentification[81]
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