摘要
毛细管电泳(Capillary Electrophoresis,CE)具有分离效率高、分析速度快、所需样品少等突出特点,是近年来发展较快的分析分离技术之一。毛细管电泳的研究物质包括无机离子、有机分子、生物大分子等,涉及分析化学、生物化学、分子生物学、药物化学、食品化学、环境化学等许多学科领域。在绪论中回顾了毛细管电泳发展的历史、现状以及发展趋势,对毛细管电泳和电化学检测技术的基本原理和特点进行了简单介绍,并介绍了其在食品安全监测、生物样品分析以及物化常数测定中的应用。
本文使用常规毛细管电泳—电化学检测技术测定了食品、日用品中的有害成分、一元弱酸的电离常数,以及分别使用常规和小型化的毛细管电泳装置测定了生物样品中的标记成分,主要内容如下:
1.毛细管电泳—电化学检测法研究有氧运动对体液中肌酐和尿酸含量变化的影响
本部分采用毛细管电泳—电化学检测法(CE—ED)研究了有氧运动对唾液和尿样中肌酐和尿酸含量变化的影响。试验中研究了电极电位、运行缓冲液浓度和酸度、分离电压等因素对分离检测效果的影响。在优化条件下,以直径450μm的铜圆盘电极为工作电极,电极电位为+0.655 mV(vs.SCE),在pH 9.24、20mmol/L的硼砂盐、70mmol/L SDS的运行缓冲液中,上述三组分在22min内可实现基线分离。肌酐和尿酸的浓度分别在8.83×10~(-6)～1.76×10~(-3)mol/L、5.94×10~(-6)～2.38×10~(-3) mol/L的范围内与峰电流呈良好线性关系,肌酐和尿酸的检测限分别为3.6μmol/L和0.86μmol/L。此方法已成功地运用于实际样品的测定。研究结果表明,在有氧运动后,唾液中肌酐的浓度下降,尿酸的浓度上升;而在尿样中,肌酐和尿酸的浓度都上升。
2.毛细管电泳—电化学检测法测定牙膏中的二甘醇
本部分运用毛细管电泳_电化学检测法(CE-ED)对牙膏中的违禁成分——二甘醇进行了分析测定。研究中主要考察了电极电位、进样时间、分离电压、运行液的pH值等因素对二甘醇、丙二醇和丙三醇的分离测定的影响,探索了检测二甘醇的最佳分析条件。使用长为75cm,内径为25μm的石英毛细管为分离通道,300μm铜电极作为工作电极,在pH9.2硼砂运行缓冲体系中,牙膏中常用的保湿剂二甘醇、丙二醇、丙三醇三组分能实现基线分离。二甘醇的检测限为1.5×10~(-6)g/mL。实验中对不同品牌、不同批号的市售牙膏进行二甘醇含量检测,回收率在96.9-102.9%之间。
3.毛细管电泳—电化学检测法测定酿造酱油中3-氯-1,2-丙二醇
本部分主要研究毛细管电泳—电化学检测法测定酱油中3-氯-1,2-丙二醇(3-MCPD)。酱油中存在多种干扰因素,实验中选取与3-MCPD结构性质相似的丙二醇和丙三醇为干扰物加以考虑。实验结果表明,在30 mmol/L、pH 9.24的硼砂缓冲溶液中三种被分析物质有较好的分离效果;用450μm铜电极在+0.65V(vs.SCE)的电极电位下,三种物质有较好的响应,能够实现定量检测酱油中3-MCPD的含量。该法对3-MCPD的线形范围为2.0×10~(-4) g/mL至6.6×10~(-6)g/mL,检测限(S/N=3)为1.3×10~(-7)g/mL。测定17种市售酱油样品中3-MCPD的平均回收率在93.8-107.7%之间。
4.小型化毛细管电泳—电化学检测法测定猪尿和猪饲料中的β—兴奋剂
本部分采用小型化毛细管电泳—电化学检测技术同时测定了猪尿和猪饲料中的克伦特罗及其替代品莱克多巴胺和沙丁胺醇。实验中考察了工作电极的氧化电位、运行缓冲液的酸度和浓度、分离电压、进样时间等因素对分离和检测的影响。结果表明,以直径300μm的碳圆盘电极为工作电极,检测电极电位为+0.95V(vs.SCE),在100 mmol/L pH 9.15的硼酸盐运行缓冲液中,上述三组分在7 min内实现了较好的分离效果。克伦特罗、莱克多巴胺和沙丁胺醇的最低检测限分别为2.06×10~(-7)g/mL、1.20×10~(-7)g/mL和1.50×10~(-7)g/mL。该方法已被成功应用于猪尿和猪饲料中的三种β—兴奋剂的测定,是一种简单便捷、有效的食品安全监测方法。
5.毛细管电泳—电化学检测法分析竹叶及竹叶饮品中的活性成分
本部分用毛细管区带电泳—电化学检测法(CE-ED)同时测定了五种不同竹叶和竹叶饮品(竹叶茶、竹叶酒)中的香兰素、顺式阿魏酸、对羟基苯甲醛、对香豆酸、对羟基苯甲酸、香草酸和咖啡酸等活性成分的含量。考察了实验参数对分离检测的影响,得到了最佳实验条件。以直径300μm的碳圆盘电极为工作电极,电极电位为+0.95 V(vs.SCE),在60 mmol/L硼酸盐缓冲溶液(pH＝8.7)中,上述七种组分在22 min内实现了较好的分离。七组分的浓度和峰电流在2～3个数量级范围内呈良好线性关系,最低检测限范围为1.9×10~(-8)g/mL～9.8×10~(-8)g/mL。该法用于实际样品的成分分析,结果令人满意。
6.毛细管电泳—电化学检测法测定水杨醇和苯酚的离解常数
离解常数(pKa)反映了弱酸、弱碱的基本性质,化合物的中性和离子状态的理化性质往往可能存在很大差异。本部分利用毛细管电泳—电化学检测法(CE—ED)的高灵敏度和良好的分辨能力,测定水杨醇和苯酚的离解常数(pKa)。实验中考察了不同pH值下水杨醇和苯酚的有效淌度随迁移时间改变的变化情况,结果表明,有效淌度随pH值的升高而增大。实验中建立了pH值和有效淌度的函数关系,并由此推算水杨醇和苯酚的电离常数分别为9.94、9.96,与文献中的数据相吻合。该实验表明CE—ED能简单方便的测定化合物的理化常数,拓宽了CE—ED的应用范围。
Capillary electrophoresis (CE), one of the most important separation techniques, has been greatly developed and improved in past two decades. The history, current situation and future trend of capillary electrophoresis are reviewed in this thesis. Capillary electrophoresis is becoming increasingly recognized as an important analytical separation technique due to its speed, efficiency, reproducibility, ultra-small sample volume and ease of clearing up the contaminants. Now it has been widely applied in analytical chemistry, biological chemistry, environmental chemistry, and so on. In combination with electrochemical detection (ED), it offers high sensitivity and good selectivity for electroactive species. In an effort to explore the application of CE-ED, the present dissertation described the studies of capillary electrophoresis with electrochemical detection in the analyses of biological samples, foods and physicalchemistry constant. The major contents are described as follows:
1. Study on creatinine and uric acid during aerobic exercises in saliva and urine by capillary electrophoresis with electrochemical detection
A simple and reliable method based on capillary electrophoresis with electrochemical detection (CE-ED) was applied to study the effect of aerobic exercises on creatinine and uric acid concentration in both saliva and urine. The pH value, the running buffer concentration, the SDS concentration, the separation voltage, the injection time and the potential applied to the working electrode were investigated to find the optimum conditions for the determination of creatinine and uric acid in saliva and urine. With a 57cm length of 25μm diameter fused-silica capillary, well-defined separation of creatinine and uric acid from background was achieved in 20 mmol/L borax (pH 9.24) including 70 mmol/L SDS (sodium dodecyl sulfate) within 22 min. The detection limits (S/N=3) for creatinine and uric acid were 3.6μmol/L and 0.86μmol/L, respectively. This method was successfully used in the rapid analysis of creatinine and uric acid in saliva samples for the first time. Notably, after aerobic exercises, creatinine concentration was decreased, and uric acid concentration was increased in saliva. While in urine, the concentrations of creatinine and uric acid were all increased after aerobic exercises.
2. Determination of diethylene glycol in toothpaste by capillary electrophoresis with electrochemical detection
A capillary electrophoresis technique with electrochemical detection (CE-ED) for the determination of diethylene glycol (DEG) in toothpaste was described. Effects of several factors, such as the pH value and the concentration of the running buffer, the separation voltage, the injection time and the potential applied to the working electrode, were investigated to find the optimum conditions. With a 75cm length of 25μm diameter fused-silica capillary, well-defined separation of diethylene glycol from propylene glycol and glycerol was achieved in the running buffer. While operated in a wall-jet configuration, a 300μm copper disc electrode used as the working electrode, the applied potential was +0.65V (vs. SCE), the separation voltage was 16 kV, the above three analytes could be well separated in an 80 mmol/1 borate buffer (pH =9.2). The linear range of DEG was from 8.4×10~(-4) g/mL to 4.2×10~(-6) ml/mL. Notably, the DEG detection limit (S/N=3) of 1.5×10~(-6) g/mL could meet the safety criterion of this compound. This method was successfully used in the rapid analysis of DEG in several toothpaste samples. The average recoveries of 96.9%-102.9% indicated that the experimental results were satisfactory.
3. Determination of 3-chloro-l,2-propanediol in soy sauces by capillary electrophoresis with electrochemical detection
A capillary electrophoresis technique with electrochemical detection (CE-ED) for determination of 3-chloro-1, 2-propanediol (3-MCPD) in soy sauces was described. Effects of several factors, such as the pH value and the concentration of the running buffer, the separation voltage, the injection time and the potential applied to the working electrode, were investigated to find the optimum conditions. With a 25μm diameter fused-silica capillary, well-defined separation of 3-chloro-l, 2-propanediol from propanediol and glycerol was achieved in 30 mmol/L borax (pH 9.24) within 13 min. Operated in a wall-jet configuration, a 450 urn copper-disk electrode used as the working electrode exhibits good response at +0.65 V (vs. SCE) for the analyte in 0.05 mol/1 sodium hydroxide solution. The linear range of 3-MCPD was from 2×10~(-4) g/mL to 6.6×10~(-6) g/mL. Notably, the 3-MCPD detection limit (S/N=3) of 1.3×10~(-7) g/mL could meet the criterion of food safety. This method was successfully used in the rapid analysis of 3-MCPD in soy samples. The average recoveries of 93.8%-107.7% indicated that the experimental results were satisfactory.
4. Determination ofβ-adenergic agonist in pig urine and pig fodder by small-sized capillary electrophoresis with electrochemical detection
A method of small-sized capillary electrophoresis with electrochemical detection has been developed for the determination ofβ-adenergic agonists in pig urine and pig fodder. Several important factors including the running buffer acidity, the separation voltage, the working electrode potential and etc, were evaluated to acquire optimum analysis conditions. Under the selected optimum conditions, these analytes can be well separated in 7 minute. Good linear relationship was established between the peak current and the concentration of each analyte over 3 orders of magnitude. And the analytes detection limit (S/N=3) were 2.06×10~(-7) g/mL, 1.20×10~(-7) g/mL and 1.50×10~(-7) g/mL, respectively. The proposed method has been successfully applied for the determination ofβ-adenergic agonist in pig urine and pig fodder with satisfactory results, providing a useful monitoring method for food safety.
5. Determination of active components in bamboo leaves and bamboo-leaf products by capillary electrophoresis with electrochemical detection
A simultaneous determination of vanillin, trans-ferulic acid, p-hydroxybenzaldehyde, p-coumaric acid, vanillic acid, 4-hydroxybenzoic acid and caffeic acid in five different kinds of bamboo leaves and bamboo-leaf products such as bamboo-leaf tea and bamboo-leaf liquor by capillary zone electrophoresis with electrochemical detection (CE—ED) was reported. The effects of several important factors were investigated to acquire the optimum analysis conditions. A 300μm diameter carbon disc electrode was used as the working electrode positioned carefully opposite the outlet of capillary at potential of +0.95 V (vs. SCE). The analytes could be well separated within 22 min at a separation voltage of 16 kV in a 60 mmol/L borate buffer (pH=8.7). There is excellent linearity between peak current and concentration of seven analytes over two or three orders of magnitude with the detection limits (S/N=3) ranging from 1.9×10~(-8)g/mL to 9.8×10~(-8) g/mL. The proposed method has been successfully applied to the analysis of real samples with satisfactory results.
6. Determination of pKa values of salicyl alcohol and phenol by capillary electrophoresis with amperometric detection
A simple and rapid method based on capillary electrophoresis with amperometric detection (CE-ED) to calculate the dissociation constant of salicyl alcohol and phenol is described. The effects of several factors, such as the potential applied to the working electrode, the injection time, and the separation voltage, were investigated to find the optimum conditions for pKa determination. Operating in a wall-jet configuration, a 300μm carbon disk electrode used as the working electrode exhibited good response at +0.86 V (vs. SCE) for salicyl alcohol and phenol. The effective mobilities of salicyl alcohol at different temperatures were determined by monitoring the migration time changes of salicyl alcohol and phenol. The dissociation constants of salicyl alcohol and phenol were calculated to be 9.94 and 9.96, respectively, which are in good agreement with the literature.
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