神经递质类分子的电化学分析及硼酸体系与糖类作用的电化学研究
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摘要
随着神经生物学的发展,陆续在神经系统中发现了大量的神经活性物质,简称神经递质,儿茶酚胺类是其中的一种,包括多巴胺、去甲肾上腺素和。肾上腺素。血浆中儿茶酚胺水平的变化将使生物体显示不同的病态情形,因此其浓度的测定对于神经生理学、疾病诊断以及相关药物的控制都具有重要意义。近几十年来,糖类的研究已经取得了很大的进展,人们逐步了解了糖类的结构与功能,也逐渐认识到糖类对于生物体的重要性,糖类对生物体来说并非只是简单的能源物质,有关糖类的研究将成为生命科学的中心课题。糖类是生物体的主要能源物质,也是重要的信息分子,它参与许多生理和病理过程,许多疾病的发生和治疗都与糖类有密切关系。因此对糖类物质的研究与检测,也具有重要的现实意义。本工作的主要研究内容是:一、分别研究了NADH和壳聚糖参杂刚果红两种修饰电极在儿茶酚胺类物质分析方面的应用;二、硼酸体系对糖类的识别作用的研究。
主要研究工作如下:
1.NADH修饰电极在肾上腺素分析方面的应用
研究了基于邻苯二胺聚合膜的纳米金自组装NADH修饰玻碳电极的制备,并探讨了肾上腺素在此修饰电极上的电化学行为,在pH 7.2的磷酸盐缓冲液中,肾上腺素在该修饰电极上产生一个灵敏的氧化峰,峰电流与肾上腺素浓度在3.0×10~(-6)～5.0×10~(-5)mol/L范围内呈良好的线性关系,检出限为3.15×10~(-7)mol/L。该方法可用于盐酸肾上腺素注射液中肾上腺素的检测。
2.壳聚糖参杂刚果红修饰电极在同时测定多巴胺和尿酸方面研究
利用涂抹的方法,在玻碳电极上涂抹一层壳聚糖与刚果红混合物修饰膜,制成了壳聚糖参杂刚果红的修饰电极。该壳聚糖参杂刚果红的修饰电极对多巴胺(DA)和尿酸(UA)有很好的电化学活性。利用差示脉冲法探讨了壳聚糖参杂刚果红修饰电极分别测定DA、UA以及同时测定两者的最佳实验条件,建立起测定DA和UA的电化学新方法,该法可用于实际样品中DA和UA的测定。
3.3-氨基苯硼酸自组装膜修饰电极对葡萄糖等的电化学识别
采用电沉积技术将壳聚糖修饰到金电极表面,再利用戊二醛作为交联剂连接3-氨基苯硼酸(APBA),在电极表面形成带有硼酸基的自组装膜。采用循环伏安和交流阻抗技术研究了该修饰膜对葡萄糖和果糖的识别作用,探讨了时间和pH值对硼酸修饰电极与葡萄糖的相互作用的影响,研究结果表明在最佳时间和酸度条件下,该修饰电极对糖类有很好的识别作用。4.3-噻吩硼酸自组装修饰电极对葡萄糖等的电化学识别
采用电沉积技术将金纳米修饰到玻碳电极表面,借助金纳米和硫之间的强作用,3-噻吩硼酸(TBA)被自组装到玻碳电极的表面上。利用交流阻抗和扫描电子显微镜法研究了TBA自组装膜的电化学行为和表面形貌。研究表明TBA自组装膜电极对葡萄糖、甘露糖和果糖具有良好的识别作用,结果表明在最佳条件下阻抗值和糖浓度之间在一定范围有很好的线性关系,可用于糖类分子的电化学识别。
Catecholamine is a kind of the neurotransmitters, including dopamine (DA), epinephrine (EP) and norepinephrine. If the levels of catecholamine change among the blood plasma, the organism shall put up different morbidity. Therefore, the determination of catecholamine makes a very realistic significance. In recent years, a significant advance has been made in carbohydrate research, the knowledge of the structure and function of carbohydrates has been gradually obtained, and the importance of saccharides to the life, not just as a kind of simple energy substances, has also been realized. The researches of saccharides will become the emphases of life sciences. Saccharides are not only the main energy substances, but also as molecules with the function of carrying information, participate in many physiological and pathological processes. There are a lot of diseases tightly related to saccharides; thus, the analysis of saccharides is very important. In this work, one principal reaearch is about the application of NADH and chitosan congo red-polysaccharide hybrid modified electrode in the field of analysis of catecholamine, and the other is about the boronic acid system for the recognition of saccharides.
The primary reaearch work is as follows:
1. A novel sensor of NADH immobilized on poly-o-phenylenediamine film self-assembled nano gold and its application for the determination of epinephrine
The preparation of NADH-poly-o-phenylenediamine film-nano gold chemically modified glassy carbon electrode was studied, and the cyclic voltammetric behavior of epinephrine (EP) on this modified electrode was investigated. It was found that EP showed a well oxidation peak on the modified electrode in a phosphate buffer solution of pH 7.2. The linear range of EP was 3.0×10~(-6)-5.0×10~(-5)mol/L and the detection limit was 5.0×10~(-7)mol/L. This method was applied to the measurement of EP in epinephrine hydrochloride injection samples with satisfaction results.
2. Application of chitosan congo red-polysaccharide hybrid modified electrode in the field of simultaneous analysis of dopamine and uric acid
Chitosan and congon red polysaccharide hybrid can be modified onto the surface of glassy carbon electrode through daubing technique. The modified electrode shows an obvious electrochemical activity for the dopamine and uric acid. The reaction conditions were optimized carefully by differential pulse voltammetry. The modified electrode was applied to the determination in practical samples with satisfaction results.
3. 3-Aminophenylboronic acid self-assembled layer based on chitosan films for recognition of monosaccharide
Chitosan film has been successfully deposited at gold electrodes from an acidic solution and 3-aminophenylboronic acid (APBA) has been covalently bound to the chitosan film with glutaraldehyde (GD) linkage. The boronic acid groups of the APBA film could form covalent-bond with different sugars, which can change the dielectric characteristics of the APBA film. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetric (CV) were used to characterize the change of the dielectric characteristic. The CV peak current of Fe(CN)_6~(3-/4-) ion decreased and the EIS impedance increased with an increase in sugar concentration. Glucose and mannose have been detected with the CV and EIS methods. The EIS method had higher sensitivity compared with the CV method.
4. 3-Thiopheneboronic acid self-Assembled gold naoparticles monolayer-modified electrodes sensitive to saccharide
The glassy carbon electrode modified with nano-gold was prepared by the electrodeposition. Afterward the surface of nano-gold film was modified with a self-assembled monolayer (SAMs) of 3-thiopheneboronic acid (TBA). TBA can form well-packed monomolecular layers on the nano-gold modified glassy carbon electrode through a sulfur-Au bond. The boronic acids group of the TBA films can form covalent-bond with different sugars. Electrochemical impedance spectroscopy was used to display response to sugars in the presence of Fe(CN)_6~(3-/4-) ion. The dielectric characteristics of the TBA film can change with type and concentration of sugars. Three kinds of sugars have been studied by this method and good linear relationship and high sensitivity were obtained.
主要研究工作如下:
1.NADH修饰电极在肾上腺素分析方面的应用
研究了基于邻苯二胺聚合膜的纳米金自组装NADH修饰玻碳电极的制备,并探讨了肾上腺素在此修饰电极上的电化学行为,在pH 7.2的磷酸盐缓冲液中,肾上腺素在该修饰电极上产生一个灵敏的氧化峰,峰电流与肾上腺素浓度在3.0×10~(-6)～5.0×10~(-5)mol/L范围内呈良好的线性关系,检出限为3.15×10~(-7)mol/L。该方法可用于盐酸肾上腺素注射液中肾上腺素的检测。
2.壳聚糖参杂刚果红修饰电极在同时测定多巴胺和尿酸方面研究
利用涂抹的方法,在玻碳电极上涂抹一层壳聚糖与刚果红混合物修饰膜,制成了壳聚糖参杂刚果红的修饰电极。该壳聚糖参杂刚果红的修饰电极对多巴胺(DA)和尿酸(UA)有很好的电化学活性。利用差示脉冲法探讨了壳聚糖参杂刚果红修饰电极分别测定DA、UA以及同时测定两者的最佳实验条件,建立起测定DA和UA的电化学新方法,该法可用于实际样品中DA和UA的测定。
3.3-氨基苯硼酸自组装膜修饰电极对葡萄糖等的电化学识别
采用电沉积技术将壳聚糖修饰到金电极表面,再利用戊二醛作为交联剂连接3-氨基苯硼酸(APBA),在电极表面形成带有硼酸基的自组装膜。采用循环伏安和交流阻抗技术研究了该修饰膜对葡萄糖和果糖的识别作用,探讨了时间和pH值对硼酸修饰电极与葡萄糖的相互作用的影响,研究结果表明在最佳时间和酸度条件下,该修饰电极对糖类有很好的识别作用。4.3-噻吩硼酸自组装修饰电极对葡萄糖等的电化学识别
采用电沉积技术将金纳米修饰到玻碳电极表面,借助金纳米和硫之间的强作用,3-噻吩硼酸(TBA)被自组装到玻碳电极的表面上。利用交流阻抗和扫描电子显微镜法研究了TBA自组装膜的电化学行为和表面形貌。研究表明TBA自组装膜电极对葡萄糖、甘露糖和果糖具有良好的识别作用,结果表明在最佳条件下阻抗值和糖浓度之间在一定范围有很好的线性关系,可用于糖类分子的电化学识别。
Catecholamine is a kind of the neurotransmitters, including dopamine (DA), epinephrine (EP) and norepinephrine. If the levels of catecholamine change among the blood plasma, the organism shall put up different morbidity. Therefore, the determination of catecholamine makes a very realistic significance. In recent years, a significant advance has been made in carbohydrate research, the knowledge of the structure and function of carbohydrates has been gradually obtained, and the importance of saccharides to the life, not just as a kind of simple energy substances, has also been realized. The researches of saccharides will become the emphases of life sciences. Saccharides are not only the main energy substances, but also as molecules with the function of carrying information, participate in many physiological and pathological processes. There are a lot of diseases tightly related to saccharides; thus, the analysis of saccharides is very important. In this work, one principal reaearch is about the application of NADH and chitosan congo red-polysaccharide hybrid modified electrode in the field of analysis of catecholamine, and the other is about the boronic acid system for the recognition of saccharides.
The primary reaearch work is as follows:
1. A novel sensor of NADH immobilized on poly-o-phenylenediamine film self-assembled nano gold and its application for the determination of epinephrine
The preparation of NADH-poly-o-phenylenediamine film-nano gold chemically modified glassy carbon electrode was studied, and the cyclic voltammetric behavior of epinephrine (EP) on this modified electrode was investigated. It was found that EP showed a well oxidation peak on the modified electrode in a phosphate buffer solution of pH 7.2. The linear range of EP was 3.0×10~(-6)-5.0×10~(-5)mol/L and the detection limit was 5.0×10~(-7)mol/L. This method was applied to the measurement of EP in epinephrine hydrochloride injection samples with satisfaction results.
2. Application of chitosan congo red-polysaccharide hybrid modified electrode in the field of simultaneous analysis of dopamine and uric acid
Chitosan and congon red polysaccharide hybrid can be modified onto the surface of glassy carbon electrode through daubing technique. The modified electrode shows an obvious electrochemical activity for the dopamine and uric acid. The reaction conditions were optimized carefully by differential pulse voltammetry. The modified electrode was applied to the determination in practical samples with satisfaction results.
3. 3-Aminophenylboronic acid self-assembled layer based on chitosan films for recognition of monosaccharide
Chitosan film has been successfully deposited at gold electrodes from an acidic solution and 3-aminophenylboronic acid (APBA) has been covalently bound to the chitosan film with glutaraldehyde (GD) linkage. The boronic acid groups of the APBA film could form covalent-bond with different sugars, which can change the dielectric characteristics of the APBA film. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetric (CV) were used to characterize the change of the dielectric characteristic. The CV peak current of Fe(CN)_6~(3-/4-) ion decreased and the EIS impedance increased with an increase in sugar concentration. Glucose and mannose have been detected with the CV and EIS methods. The EIS method had higher sensitivity compared with the CV method.
4. 3-Thiopheneboronic acid self-Assembled gold naoparticles monolayer-modified electrodes sensitive to saccharide
The glassy carbon electrode modified with nano-gold was prepared by the electrodeposition. Afterward the surface of nano-gold film was modified with a self-assembled monolayer (SAMs) of 3-thiopheneboronic acid (TBA). TBA can form well-packed monomolecular layers on the nano-gold modified glassy carbon electrode through a sulfur-Au bond. The boronic acids group of the TBA films can form covalent-bond with different sugars. Electrochemical impedance spectroscopy was used to display response to sugars in the presence of Fe(CN)_6~(3-/4-) ion. The dielectric characteristics of the TBA film can change with type and concentration of sugars. Three kinds of sugars have been studied by this method and good linear relationship and high sensitivity were obtained.
引文
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