毒物的化学发光分析研究
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摘要
本文分为两部分，第一部分为综述，第二部分为研究报告。
第一部分综述了有机磷毒物分析的现状，对当前用于有机磷毒物分析的主要方法作了简单评述。较为详细地总结了化学发光法在有机磷毒物分析中的应用及进展情况，并提供了近年来几种测定有机磷农药的化学发光分析方法。
当前用于有机磷毒物分析的方法主要有波谱法，色谱法和生物传感器等。波谱法是较早时期用于有机磷毒物分析的方法，其存在的缺点是灵敏度不高。色谱法是分析有机磷毒物最主要的手段。其优点是分离效能好，灵敏度高。存在的局限性有仪器昂贵，样品前处理过程复杂等。生物传感器用于有机磷毒物分析具有响应灵敏、快速，选择性高等优势，而存在的问题是分析结果的稳定性差，使用寿命较短。
化学发光法用于有机磷毒物分析可追溯到1944年。在这一年，Schoenemann首次报道了应用化学发光法测定有机磷神经毒剂的方法，方法的原理是基于神经毒剂能与鲁米诺-过氧化氢产生化学发光。此后，又有一些机磷神经毒剂的化学发光分析法问世。Goldenson和Frische都采用鲁米诺-过硼酸钠体系直接化学发光法测定了神经毒剂，Frische所用的方法中因加入NaCl而使测定灵敏度大为提高。
近年来，化学发光法因为灵敏度高和仪器简单等优势在有机磷农药分析中引起了更多的关注，并且有一些新方法出现。概括近年来用于有机磷农药分析中的化学发光分析法，有①基于农药与鲁米诺-H_2O_2反应的直接化学发光分析法，这类方法已用于敌敌畏、甲基对硫磷等农药的测定。②基于农药对乙酰胆碱酶活性抑制的化学发光分析法，已用于对氧磷和乐果等的测定。③基于碱性磷酸酯酶催化的化学发光法，这类方法已应用于测定乐果和甲基对硫磷。
第二部分详细研究了有机磷农药对硫磷、杀螟硫磷和久效磷在增敏剂存在的条件下，与鲁米诺-过氧化氢的化学发光反应行为，建立了三种农药的化学发光分析新方法。
1．流动注射化学发光法测定对硫磷的研究
研究发现，在表面活性剂聚乙二醇-400存在的条件下，有机磷农药对硫磷能极大地增强碱性溶液中鲁米诺和过氧化氢的化学发光反应。据此建立了测定对硫磷的流动注射化学发光分析新方法。测定对硫磷的线性范围为2.0×10~(-8)～1.0×
10“g／niL，检出限为8 X 10－’g／niL。对浓度为2．0 X 10Jg／InL对梆断T 11
次平行测定，相对标准偏差为2．8％。本方法用于大米中对硫磷残留量的测定，结
果满意。
2．流动注射化学发光法测定杀螟硫磷的研究
研究发现，在无机盐NaCI存在的条件下，农药杀螟硫磷在碱性鲁米诺和过
氧化氢中能产生很强的发光信号，结合流动注射枝术，基于此建立了测定杀螟硫
磷的流动注射化学发光新方法。测定杀螟硫磷的检出限为 4X10’g／InL，线性范
围为 10 X 10“’－20 X 10“g／InL，对浓度为 10 X 10“’g／InL杀螟硫磷进行＊ 次平
行测定，相对标准偏差为2．gO／。本法用于水样中杀螟硫磷含量的测定，结果满意。
3．流动注射化学发光法测定久效磷的研究
发现在无机盐NaCI存在的条件下，农药久效磷能增强碱性溶液中鲁米诺和
过氧化氢的化学发光反应。在此基础上建立了测定久效磷的流动注射化学发光的
新方法。测定久效磷的线性范围为 2．0 XIO”－10 XIO“g ／rnL 检出限为 7 XIO－’
g／InL，对浓度为 1刀 X 10“’g ／InL久效磷进行u次平行测定，相对标准偏差小于
3％。该法巳成功地用于水样中久效磷含量的测定。
This thesis is consists of two parts. Part one is review. Part two is research reports.
In part one, the present condition of chemiluminescence (CL) assays in the analysis of organophosphorous poisons and the main analytical methods of organophosphorous poisons are reviewed. The focus of this part is to summarize the application and the development of chemiluminescence assays in the analysis of organophosphorous poisons in detail. The new chemiluminescence methods for the determination of organophosphorous poisons in recent years have also been provided in this paper.
Wave spectrum, chromatography and biosensors are major analytical tools of organophosphorous poisons in present time. Wave spectrum was applied to the analysis of organophosphorous poisons in earlier time. The shortcoming of this method is that the sensitivity is not very high. Chromatography is the most important tool in the analysis of organophosphorous poisons because it owns high sensitivity and good separation function. But the instrument is very expensive and the pre-handling process for sample is much complicated. Biosensors possess many advantages such as sensitive, fast and high selectivity. The weakness of biosensors is that the reproducibility is poor and the lifetime is short comparatively.
In 1944, schoenemann first reported the CL method for the determination of organophosphorous nerve agent. After that, there are other CL methods applying to the determination of nerve agents.
There are some novel CL methods in the analysis of organophosphorous pesticides during recently years, (a) The CL method based upon the reaction of lumino with H2O2 This method has also been applied to the determination of dichlorvos and methyl parathion. (b) The CL method based on the inhibition of acetylcholinesterase. The method has also been applied to the determination of paraoxon and dimethoate.(c) The CL method based upon the catalysis of alkaline phosphatase This method has also been applied to the determination of dimethoate and methyl parathion.
Part two is mainly focused on developing of novel chemiluminescence method for the direct determination of three organophosphorous pesticides based upon the CL
reaction of pesticides with lumino-H2O2 in .the presence of sensitizer.
I Study of flow-injection chemiluminescence analysis of parathion
A novel sensitive flow-injection chemiluminescence method for the determination of parathion based on the reaction of luminol and IkOi in the presence of neutral surfactant polyethylene glycol-400 has been established. Under the optimal conditions, the CL intensity is linear to the parathion concentration in the range of 2.OX 10~8~1.0 X lO^g/mL. The detection limit is 8 x 10"9 g /mL and the relative standard deviation is 2.8% for 2.OX 10~8g/mL parathion (n=ll). This method has been successfully applied to the determination of parathion residue in rice samples.
II Study of flow-injection chemiluminescence method for the determination of
fenitrothion
A novel flow-injection chemiluminescence method for the direct determination of fenitrothion has been developed .It is based on the reaction of fenitrothion with luminol-H2O2 in alkaline medium. The chemiluminescence signal is enhanced by sodium chloride greatly. Under the optimal conditions, the detection limit is 4 x 10-9 g /mL for fenitrothion. The linear range is 1.0 10-8~ 2.0 10-6g/mL. The relative standard deviation was 2.9% for 1.0 X 10"7g/mL fenitrothion (n=11). The method has been applied to determination of fenitrothion in water samples with satisfactory results.
Study of flow-injection chemiluminescence method for the determination of monocrotophos
A novel sensitive flow-injection chemiluminescence method for the determination of monocrotophos has been developed in the first time. It is based on the reaction of monocrotophos with luminol-H2O2 in alkaline medium in the presence of sodium chloride as sensitizer. Under the optimal conditions, the CL intensity is linear to the monocrotophos concentration in the range of 2.0 X 10- 8~
第一部分综述了有机磷毒物分析的现状，对当前用于有机磷毒物分析的主要方法作了简单评述。较为详细地总结了化学发光法在有机磷毒物分析中的应用及进展情况，并提供了近年来几种测定有机磷农药的化学发光分析方法。
当前用于有机磷毒物分析的方法主要有波谱法，色谱法和生物传感器等。波谱法是较早时期用于有机磷毒物分析的方法，其存在的缺点是灵敏度不高。色谱法是分析有机磷毒物最主要的手段。其优点是分离效能好，灵敏度高。存在的局限性有仪器昂贵，样品前处理过程复杂等。生物传感器用于有机磷毒物分析具有响应灵敏、快速，选择性高等优势，而存在的问题是分析结果的稳定性差，使用寿命较短。
化学发光法用于有机磷毒物分析可追溯到1944年。在这一年，Schoenemann首次报道了应用化学发光法测定有机磷神经毒剂的方法，方法的原理是基于神经毒剂能与鲁米诺-过氧化氢产生化学发光。此后，又有一些机磷神经毒剂的化学发光分析法问世。Goldenson和Frische都采用鲁米诺-过硼酸钠体系直接化学发光法测定了神经毒剂，Frische所用的方法中因加入NaCl而使测定灵敏度大为提高。
近年来，化学发光法因为灵敏度高和仪器简单等优势在有机磷农药分析中引起了更多的关注，并且有一些新方法出现。概括近年来用于有机磷农药分析中的化学发光分析法，有①基于农药与鲁米诺-H_2O_2反应的直接化学发光分析法，这类方法已用于敌敌畏、甲基对硫磷等农药的测定。②基于农药对乙酰胆碱酶活性抑制的化学发光分析法，已用于对氧磷和乐果等的测定。③基于碱性磷酸酯酶催化的化学发光法，这类方法已应用于测定乐果和甲基对硫磷。
第二部分详细研究了有机磷农药对硫磷、杀螟硫磷和久效磷在增敏剂存在的条件下，与鲁米诺-过氧化氢的化学发光反应行为，建立了三种农药的化学发光分析新方法。
1．流动注射化学发光法测定对硫磷的研究
研究发现，在表面活性剂聚乙二醇-400存在的条件下，有机磷农药对硫磷能极大地增强碱性溶液中鲁米诺和过氧化氢的化学发光反应。据此建立了测定对硫磷的流动注射化学发光分析新方法。测定对硫磷的线性范围为2.0×10~(-8)～1.0×
10“g／niL，检出限为8 X 10－’g／niL。对浓度为2．0 X 10Jg／InL对梆断T 11
次平行测定，相对标准偏差为2．8％。本方法用于大米中对硫磷残留量的测定，结
果满意。
2．流动注射化学发光法测定杀螟硫磷的研究
研究发现，在无机盐NaCI存在的条件下，农药杀螟硫磷在碱性鲁米诺和过
氧化氢中能产生很强的发光信号，结合流动注射枝术，基于此建立了测定杀螟硫
磷的流动注射化学发光新方法。测定杀螟硫磷的检出限为 4X10’g／InL，线性范
围为 10 X 10“’－20 X 10“g／InL，对浓度为 10 X 10“’g／InL杀螟硫磷进行＊ 次平
行测定，相对标准偏差为2．gO／。本法用于水样中杀螟硫磷含量的测定，结果满意。
3．流动注射化学发光法测定久效磷的研究
发现在无机盐NaCI存在的条件下，农药久效磷能增强碱性溶液中鲁米诺和
过氧化氢的化学发光反应。在此基础上建立了测定久效磷的流动注射化学发光的
新方法。测定久效磷的线性范围为 2．0 XIO”－10 XIO“g ／rnL 检出限为 7 XIO－’
g／InL，对浓度为 1刀 X 10“’g ／InL久效磷进行u次平行测定，相对标准偏差小于
3％。该法巳成功地用于水样中久效磷含量的测定。
This thesis is consists of two parts. Part one is review. Part two is research reports.
In part one, the present condition of chemiluminescence (CL) assays in the analysis of organophosphorous poisons and the main analytical methods of organophosphorous poisons are reviewed. The focus of this part is to summarize the application and the development of chemiluminescence assays in the analysis of organophosphorous poisons in detail. The new chemiluminescence methods for the determination of organophosphorous poisons in recent years have also been provided in this paper.
Wave spectrum, chromatography and biosensors are major analytical tools of organophosphorous poisons in present time. Wave spectrum was applied to the analysis of organophosphorous poisons in earlier time. The shortcoming of this method is that the sensitivity is not very high. Chromatography is the most important tool in the analysis of organophosphorous poisons because it owns high sensitivity and good separation function. But the instrument is very expensive and the pre-handling process for sample is much complicated. Biosensors possess many advantages such as sensitive, fast and high selectivity. The weakness of biosensors is that the reproducibility is poor and the lifetime is short comparatively.
In 1944, schoenemann first reported the CL method for the determination of organophosphorous nerve agent. After that, there are other CL methods applying to the determination of nerve agents.
There are some novel CL methods in the analysis of organophosphorous pesticides during recently years, (a) The CL method based upon the reaction of lumino with H2O2 This method has also been applied to the determination of dichlorvos and methyl parathion. (b) The CL method based on the inhibition of acetylcholinesterase. The method has also been applied to the determination of paraoxon and dimethoate.(c) The CL method based upon the catalysis of alkaline phosphatase This method has also been applied to the determination of dimethoate and methyl parathion.
Part two is mainly focused on developing of novel chemiluminescence method for the direct determination of three organophosphorous pesticides based upon the CL
reaction of pesticides with lumino-H2O2 in .the presence of sensitizer.
I Study of flow-injection chemiluminescence analysis of parathion
A novel sensitive flow-injection chemiluminescence method for the determination of parathion based on the reaction of luminol and IkOi in the presence of neutral surfactant polyethylene glycol-400 has been established. Under the optimal conditions, the CL intensity is linear to the parathion concentration in the range of 2.OX 10~8~1.0 X lO^g/mL. The detection limit is 8 x 10"9 g /mL and the relative standard deviation is 2.8% for 2.OX 10~8g/mL parathion (n=ll). This method has been successfully applied to the determination of parathion residue in rice samples.
II Study of flow-injection chemiluminescence method for the determination of
fenitrothion
A novel flow-injection chemiluminescence method for the direct determination of fenitrothion has been developed .It is based on the reaction of fenitrothion with luminol-H2O2 in alkaline medium. The chemiluminescence signal is enhanced by sodium chloride greatly. Under the optimal conditions, the detection limit is 4 x 10-9 g /mL for fenitrothion. The linear range is 1.0 10-8~ 2.0 10-6g/mL. The relative standard deviation was 2.9% for 1.0 X 10"7g/mL fenitrothion (n=11). The method has been applied to determination of fenitrothion in water samples with satisfactory results.
Study of flow-injection chemiluminescence method for the determination of monocrotophos
A novel sensitive flow-injection chemiluminescence method for the determination of monocrotophos has been developed in the first time. It is based on the reaction of monocrotophos with luminol-H2O2 in alkaline medium in the presence of sodium chloride as sensitizer. Under the optimal conditions, the CL intensity is linear to the monocrotophos concentration in the range of 2.0 X 10- 8~
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