环境水体中自由基的检测技术研究进展

卢成龙; 常红; 孙福红

doi:10.12153/j.issn.1674-991X.20210322

环境水体中自由基的检测技术研究进展

doi: 10.12153/j.issn.1674-991X.20210322

卢成龙^1,,
常红^1, ,,
孙福红^2, ,

1.
北京林业大学环境科学与工程学院
2.
中国环境科学研究院

基金项目: 国家自然科学基金项目（42077306）

详细信息

作者简介:
卢成龙（1996—），男，硕士研究生，主要从事自由基检测技术研发研究，18631668877@163.com

通讯作者:
常红（1977—），女，副教授，博士，主要从事新型污染物环境行为研究， changh@bjfu.edu.cn

孙福红（1980—），女，研究员，博士，主要从事污染物环境行为与风险评估， sunfhiae@126.com

中图分类号: X83
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出版历程
- 收稿日期: 2021-07-14

Progress on the detection technology of free radicals in waters

LU Chenglong^1
,,
CHANG Hong^{1
, ,},
SUN Fuhong^{2
, ,}

1.
College of Environmental Science and Engineering, Beijing Forestry University
2.
Chinese Research Academy of Environmental Sciences

摘要

摘要: 自由基化学性质高度活泼，极易发生得失电子的氧化还原反应，是环境水体中降解污染物的重要因素。自由基的环境鉴定和分析对揭示环境污染物降解转化机制具有重要意义。但由于自由基环境浓度极低、反应活性高、寿命短，再加上复杂环境基质的干扰效应，使其环境分析一直是研究的重点和难点。而且，目前的研究主要针对一些已知的自由基展开，对未知自由基的识别和鉴定研究较为匮乏。在系统总结典型自由基检测方法及其应用现状的基础上，阐述不同检测方法的优点和缺点，重点探讨适用于环境水体中羟基自由基等典型自由基的检测方法，并提出自旋捕获结合质谱分析技术具有特异性和高灵敏性的优点，可同时检测天然水体中多种自由基，并能够识别和鉴定未知自由基，是未来的研究方向。
- 自由基 /
- 羟基自由基 /
- 环境水体 /
- 检测方法 /
- 自旋捕获法 /
- 质谱法
Abstract: The chemical properties of free radicals are highly active and easy to cause redox reaction of gain and loss of electrons, which is an important factor for the degradation of pollutants in environmental waters. Environmental identification and analysis of free radicals are of great significance to reveal the degradation and transformation mechanism of pollutants in the environment. However, due to extremely low environmental concentration, high reactive activity and short life of free radicals, coupled with the interference of complex environmental matrices, their environmental analysis has been the focus and difficulty of the research. Meanwhile, most studies at present focus on some known free radicals, but there are few studies on the identification of unknown free radicals. In this study, on the basis of systematically summarizing the detection methods and application status of typical radicals, the advantages and disadvantages of different detection methods were expounded, especially for the detection methods suitable for typical free radicals such as hydroxyl free radicals in natural waters. It was proposed that spin capture combined with mass spectrometry, which could simultaneously detect many known radicals and identify unknown free radicals with high specificity and sensitivity, would be the research direction of radical detection in natural waters.
- free radical /
- hydroxyl radical /
- natural water /
- detection method /
- spin trapping /
- mass spectrometry

HTML全文

图 1 芬顿反应体系中·OH的ESR谱图^[57]

Figure 1. ESR spectrum of ·OH in Fenton reaction system^[57]

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图 2 Cu（Ⅱ）溶液和腐殖酸-Cu（Ⅱ）络合物溶液在光照0和120 s时的ESR谱图^[60]

Figure 2. ESR spectrum of Cu (Ⅱ) solution and humic acid- Cu (Ⅱ) complex solution under illumination for 0 and 120 s^[60]

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图 3 Fe²⁺与异丙苯过氧化氢反应中DMPO-·OH的ESI-MS谱图和MS/MS谱图^[79]

Figure 3. ESI-MS and MS/MS spectra of DMPO-·OH in the reaction of Fe²⁺ with cumene hydroperoxide^[79]

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表 1 用于ESR分析的自由基捕获剂

Table 1. Free radical trapping agents for ESR analysis

捕获剂	结构	加合物结构	优点	缺点	数据来源
DMPO			捕获速度较快，针对不同自由基其自旋加合物的ESR参数变化较大，易于区分不同自由基，对以O为中心的自由基（尤其是·OH）捕获效果好	自旋加合物寿命较短，易分解，易与微量金属离子反应	文献[62,65-67]
PBN			易与C或O为中心的基团形成相对稳定的自旋加合物，寿命较长	加合物在ESR谱图表达不清晰	文献[62,68]
4-POBN			水溶性较好	仅适用于检测pH为6~7条件下的·OH	文献[63,69]
TMPO			捕获速度较快，其波谱对自由基识别敏感（尤其是·OH）	相比DMPO少1个βH，自旋加合物提供信息有限	文献[70]
EMPO			常用于生物体系内可与氨基酸结合形成捕获效率更高的捕获体	自旋加合物不稳定，易分解	文献[71]
TEMP			对¹O₂具有良好捕获效率，其加合物稳定	对除¹O₂以外自由基捕获效率低，自旋加合物不稳定	文献[64,72]
TEMPO			对过氧自由基、烷基自由基有良好捕获效率	对¹O₂有猝灭作用，不适用于捕获¹O₂	文献[64,72]
4-氰基-2,2-二甲基-2H-咪唑-1-氧化物（CDI）			对以C为中心自由基、亚硫酸盐自由基有良好捕获效率	不适用于捕获·O₂ ⁻	文献[73]
2,2,4-三甲基-2H-咪唑 1-氧化物（TMI）			对以C为中心和以S为中心的自由基具有良好捕获效率	不适用于捕获·O₂ ⁻	文献[73]
3-吡啶基-N-叔丁基硝酮（3-PyBN）			pH为6条件下，与PBN相比，其加合物稳定性更好	加合物的寿命随着酸碱度的增加而缩短	文献[74-75]

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表 2 常用自由基检测方法对比

Table 2. Comparison of common free radicals detection methods

检测方法	原理	特点
分光光度法	利用部分自由基强氧化性改变底物的结构、性质和颜色，从而根据待测液光谱吸收的改变测定自由基浓度	经济，操作方便，分析迅速，准确性、灵敏度较低，实际环境样品中自由基的检测需考虑本底颜色带来的光谱吸收，检测限达1×10⁻⁶ mol/L
化学发光法（CL）	利用自由基与化学发光试剂反应产生化学发光，依据待测自由基的浓度与体系的化学发光强度在一定条件下呈线性定量关系的原理测定自由基浓度	灵敏度较高，检测速度快，操作简单，精度和选择性较差，检测限达1×10⁻⁹ mol/L
高效液相色谱法（HPLC）	以液体为流动相，自由基与捕获剂反应产物经色谱柱分离，进入检测器进行检测	灵敏度较高，快速，高效，反应过程复杂，干扰因素较多，检测限达10⁻¹¹~10⁻⁹ g
毛细管电泳法（CE）	以弹性石英毛细管为分离通道,以高压直流电场为驱动力分离检测自由基与捕获剂反应产物	采样体积小，分离效率高，线性范围宽，选择性好，灵敏度较高，重现性差，检测限达2×10⁻⁸ mol/L
电子自旋共振法（ESR）	利用自旋捕获剂与自由基形成稳定性更高、寿命更长的自旋加合物，经电子自旋共振法检测自旋加合物，间接测定自由基浓度	简单有效，波谱信息易受样品基质干扰、特异性不强，结构信息有限，定量分析不够精确，检测限达10⁻⁸ mol/L
质谱法（MS）	自由基与自旋捕获剂形成的自旋加合物经电场和磁场作用后，按质荷比分离后进行准确鉴定、检测	高灵敏度，高特异性，样品用量少，分析速度快，可提供丰富结构信息，检测限可达10⁻¹³ mol/L

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表 3 淬灭剂及其目标自由基

Table 3. Quenchers and their target free radicals

淬灭剂	目标自由基
甲醇（MeOH）	·OH/·SO₄⁻
乙醇（EtOH）	·OH/·SO₄⁻
异丙醇（IPA）	·OH/·SO₄⁻
亚硝酸钠（NaNO₂）	·OH/·SO₄⁻
叔丁醇（TBA）	·OH(√)/·SO₄⁻
抗坏血酸（AA）	·OH/·SO₄⁻(√)
叠氮化钠（NaN₃）	¹O₂
L-组氨酸（L-histidine）	¹O₂
糠醇（FFA）	¹O₂
苯醌（BQ）	·O₂⁻
氯仿（CF）	·O₂⁻
注：√表示主要目标自由基。

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