| 引用本文: | 王鹏鸽，张静，王震宇，赵宇蕾，黄宇.2023.光催化反应中活性氧物种产生及抗菌机制研究[J].地球环境学报,14(5):539-556 |
| WANG Pengge, ZHANG Jing, WANG Zhenyu, ZHAO Yulei, HUANG Yu.2023.Generation and antimicrobial mechanisms of reactive oxygen species in photocatalysis[J].Journal of Earth Environment,14(5):539-556 |
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| 光催化反应中活性氧物种产生及抗菌机制研究 |
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王鹏鸽，张静，王震宇，赵宇蕾，黄宇
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1.中国科学院地球环境研究所 黄土与第四纪地质国家重点实验室，中国科学院气溶胶化学与物理重点实验室，西安 710061
2.西安地球环境创新研究院，西安 710061
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| 摘要: |
| 空气中的致病菌引发的流行性疾病严重威胁人类生命安全。近年来，光催化微生物灭活技术作为一种广谱高效、安全稳定、持久耐热、不易产生耐药性、杀菌彻底的方法受到广泛关注。光催化反应中产生的活性氧物种（reactive oxygen species，ROS）在光催化抗菌中发挥着不可替代的作用，但特定类别ROS的产生和杀菌机制的研究较少，尚未有综述对其进行系统概述。本文重点从光催化半导体的能带结构与特定ROS（∙O2−、∙OH、H2O2）氧化还原电势的关系综述了三种自由基的产生机制，从氧化能力、存在寿命、主要作用对象等方面简要讨论了自由基对细菌造成氧化损伤和功能失调的具体过程，另外还涉及ROS的检测方法和抗菌性能评价方式，进一步对光催化抗菌技术在环境消杀领域的应用前景进行了展望。 |
| 关键词: 光催化 ROS 产生机制 检测技术 抗菌机理 |
| DOI：10.7515/JEE221022 |
| CSTR：32259.14.JEE221022 |
| 分类号: |
| 基金项目:国家重点研发计划（2017YFC0212200） |
| 英文基金项目:National Key Research and Development Program of China (2017YFC0212200) |
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| Generation and antimicrobial mechanisms of reactive oxygen species in photocatalysis |
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WANG Pengge, ZHANG Jing, WANG Zhenyu, ZHAO Yulei, HUANG Yu
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1. Key Laboratory of Aerosol Chemistry and Physics, State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, Chinese Academy of Sciences, Xi’an 710061, China
2. Xi’an Institute for Innovative Earth Environment Research, Xi’an 710061, China
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| Abstract: |
| Background, aim, and scope Epidemic diseases caused by bacterial and viral infections remain a growing health threat to people around the world. Compared to traditional disinfection techniques, photocatalysis has drawn tremendous attention for its high efficiency, good biocompatibility, little resistance, and broad-spectrum antibacterial performance. Oxidative stress induced by reactive oxygen species (ROS) in a photocatalytic process was considered as major antibacterial mechanism. While, the generation and disinfection mechanisms of ROS in photocatalysis have not been clearly elucidated yet at the molecular level. In this review, we surveyed on the processes of mainly forms of ROS generation, oxidative damage and dysfunction in biological systems. Based on the present reviews, the generation process, detection methods, antibacterial mechanisms of the three major ROS and evaluation methods on antibacterial performance in photocatalysis were summarized. Materials and methods This review discussed the generation and detection mechanisms of the individual ROS including superoxide (∙O2−), hydroxyl radical (·OH) and hydrogen peroxide (H2O2) in some typical photocatalytic antibacterial nanomaterials, analyzed the main processes of biological damages caused by ROS in photocatalysis disinfection, and evaluated the antibacterial effects through different antibacterial mechanisms. Results (1) Induced by solar irradiation, e− and h+ migrated on the surfaces of photocatalysts possess reduction and oxidation properties, respectively, which can react with absorbed O2 and H2O/OH− to produce ∙O2−, ·OH, H2O2 and etc. The absorbed O2 is reduced to generate ∙O2−, H2O2, and ·OH; H2O is oxidized to produce ∙O2−, ·OH, and H2O2. (2) The ROS generated in photocatalysis are mainly detected by vibration spectroscopy, UV-visible spectrophotometry, and fluorescence emission technology. (3) Oxidative stress induced by ROS generated in photocatalysis is considered as one of the major mechanisms for photoinduced sterilization. All ROS, including ∙O2−, ·OH and H2O2, are strongly oxidizing and have established antimicrobial activity which cause obvious damage to cell membrane, protein and life genetic material. (4) The antibacterial properties of photocatalytic materials can be qualitatively and quantitatively evaluated by the bacteriostatic circle and minimum inhibitory concentration (MIC) methods. Discussion (1) The generated radical species are related to the band structures of the semiconductors and redox potentials (EH) of that. In aqueous phase, considering the effect of pH on the band edges of semiconductors, the relevant EC and EV can be calculated by the Nerstian relation. (2) Optical absorption, direct electron spin resonance (ESR), spin-trapping ESR, and chemiluminescence methods are applicable to detect ∙O2−, ·OH, and H2O2 in photocatalytic processes. Coloration, fluorescence probe methods, and analysis of the reaction products with DMSO (dimethyl sulfoxide), benzene, 4-chlorobenzoic acid, and 4-chlorophenol are also used to detect ∙O2−, ·OH, and H2O2, respectively. (3) Lipids, proteins, and DNA could be damaged by ROS, which causes oxidative stress leading to bacterial apoptosis. ∙O2− is more conducive to killing bacteria due to its long lifetime, causing damages to cell membrane, protein and genetic materials. ·OH can oxidize all organic cell constituents at close to diffusion-controlled rates virtually as a strong and nonselective oxidant with oxidation potential of 2.78 V (vs. NHE). Protein is the main initial target of intracellular hydroxyl radicals in the process of interaction with cells. H2O2 can cross the bacterial cell wall directly, and exert a signaling effect to call leukocytes to a point of infection or tissue trauma. (4) The disinfection performance is evaluated qualitatively and quantitatively by agar disk diffusion and the agar dilution methods. The antimicrobial activity of the photocatalytic materials and products can be assessed by GB/T 30706—2014 and GB/T 23763—2009, respectively. Conclusions Generation of the three types of ROS (∙O2−, ·OH, and H2O2) in photocatalysis is related to the electronic structures of semiconductor. Detection methods of the typical ROS mainly depend on their particular features, including vibration spectroscopy absorption spectrum emission spectrum and electrochemical techniques, etc. The three types of ROS (∙O2−, ·OH, and H2O2) may coexist and exert complex oxidative stress on biological systems. ∙O2− is an effective antimicrobial reactive oxygen species for photocatalytic nanomaterials due to its long-life span, which could cause obvious damage to cell membrane, protein and life genetic material. The ·OH radicals with highly reactive potential can oxidize virtually all organic cell constituents at close to diffusion-controlled rates, leading to the peroxidation of protein and cell apoptosis. H2O2 works on the lysosomes of cells, causing lipid peroxidation, lysosomal membrane permeability, and cell apoptosis. In addition, the evaluation of photocatalytic antibacterial performance is discussed from qualitative and quantitative perspectives, respectively. Recommendations and perspectives Oxidative stress induced by ROS is one of the major antimicrobial mechanisms in photocatalysis, which can be utilized for photoinduced antibacterial applications. While, the current researches and applications of photocatalytic antibacterial agents mainly focus on powder materials, which limits their practical application in general disinfection and environmental sanitation. Therefore, expand the visible-light-driven photocatalytic collosol as “sterilization spray” with strong bactericidal capability and high biological safety may be an urgent need for photoinduced sterilization to more application scenarios. |
| Key words: photocatalysis ROS generation mechanism detection technology antibacterial mechanism |
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