摘要
本论文包括以下两部分内容：
第一部分：农药的电化学分析
研究了呋喃丹的测定体系，通过对底液的选择、pH的影响、起始电位、扫描速率、线性范围、重现性、含量的测定、电极反应的可逆性和体系的吸附性等方面的研究，确定在0.2mol/L NH_3-NH_4Cl底液中(pH8.8)中，呋喃丹于单扫描示波极谱上有一灵敏的还原波，峰电位在-1.21V(vs.SCE)附近，该峰具有一定的吸附性。同时对电极反应机理进行了研究。呋喃丹的浓度在5.0×10~(-6)～1.0×10~(-4)mol/L范围内与峰电流呈良好的线性关系(r=0.9995)。建立了一种用单扫描示波极谱法测定呋喃丹的有效方法。此方法具有快速、灵敏度高、定量准确、结果稳定等优点，该方法对微生物降解呋喃丹进行监测取得满意的结果。
在玻碳电极上，0.2mol/L pH=4.0的HAc-NaAc底液中研究了福美双-Cu~(2+)配合物的伏安行为。用循环伏安法扫描时，产生两还原峰和氧化峰。峰电流和福美双的浓度在6.0×10~(-6)～8.0×10~(-5)mol/L范围内有良好的线性关系(r=0.9986)，从而建立了测定福美双的新的灵敏的方法，并用此法测定了市售样品及植物中福美双的残留量并与HPLC法进行了比较，结果满意。同时研究了Cu~(2+)对福美双的有效降解以及研究了福美双-Cu~(2+)配合物的配合性质及电极反应机理，测得配位比及稳定常数，证实电极反应是一个可逆差的过程。确定了配位物体系在玻碳电极上具有吸附性，并测出吸附量，计算出电极反应速率常数(k)及电极越迁系数(α)。
第二部分：用胶束毛细管电动色谱法(MEKC)分离多组分农药
用胶束毛细管电动色谱法(MEKC)分离了结构相似的两种氯代烟碱类杀虫剂吡虫啉、吡虫清和三种磺酰脲类除草剂甲磺隆、氯磺隆、氯嘧磺隆。研究了背景电解质，表面活性剂十二烷基硫酸钠(SDS)浓度，有机改性剂甲醇含量，pH值等对分离的影响，找出最佳条件。在以上五种农药已经达到基线分离的条件下，加入氨基甲酸酯类杀虫剂呋喃丹、扑蚜威，菊酯类杀虫剂氰戊菊酯、氯氰菊酯，有机磷类杀虫剂三唑磷、毒死蜱，优化分离条件，使这十一种农药达到基线分离。
Two parts are given in thesis, the main results are expressed as follows:
1. Electrochemical analysis of pesticide
Investigations had been performed on the determination of carbofuran. In a supporting
electrolyte containing 0.2mol/LNH3-NH4Cl at pH8.8, carbofuran produced a sensitive reduction peak by cyclic voltammetry and linear scanning voltammetry. The peak potential was -1.21V (vs.SCE) . The linear relationship of the peak current and the carbofuran concentration was in the range of 5.0 × 10-6 mol/L to 1.0×10-4 mol/L(r = 0.9995). The relative standard deviation of 5.0×10-5 mol/L carbofuran for 6 parallel determinations was 0.2%. The peak also showed adsorptive characteristics. The mechanism of electrode reduction was discussed. The method had been applied to the determination of biodegradation of carbofuran products with satisfactory result. Degradation percentage of carbofuran was 98% during 96 hours.
A new method was developed for determination of tetramethylthiuram disulfide (thiram) based on the formation of thiram- Cu2+ complex by square-wave voltammetry on a glassy carbon electrode. There was a good linear relationship between peak current and concentration of thiram in the range of 6.0 × 10-6 - 8.0 × 10-5 mol/L (r = 0.9986). The method was applied to the determination of thiram residue hi plant with satisfactory results, compared with results achieved by using HPLC. Two oxidation peaks and two reduction peaks were obtained by cyclic voltammetry on a glassy carbon electrode in 0.2 mol/L HAc-NaAc (pH = 4.0) solution containing thiram- Cu2+ complex. The electrode reaction process was quasi-reversible with adsorptive characteristics. The mechanism of electrode reaction and the degradation of thiram promoted by Cu2+ were discussed. The composition
and stability constant of the complex were determined. The amount adsorbed, the rate constant (k) of the electrode reaction and the electrode transfer coefficient (a) were calculated.
2. Five pesticides, acetamiprid, imidacloprid, carbofuran, triazophos,primicarb and three sulfonylurea herbicides-chlorsulfuron,metsulfuron methyl and chlorimuron ethyl were separated by MEKC in a 75cm × 50μm uncoated flexible fused silica capillary column (effective length=60cm) with buffer solution consisting of a mixture of 10 mmol/L borate buffer(pH8.0), 54 mmol/L SDS and 4% methanol in water. SDS concentration was examined for getting the best seperation.
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