摘要
本论文回顾了电化学发光分析法的发展历史,介绍了电化学发光反应的基本原理、优点、主要反应类型及其应用,评述了电化学发光分析法与流动注射、高效液相色谱、毛细管电泳联用技术和微流控芯片电泳的联用技术,详细讲述了电化学发光传感器及其应用。在已有文献的基础上,成功地建立了羟基脲片、精胺以及生物体中NO的顺序注射-电化学发光测定新方法,并研制成了用介孔材料固定联吡啶钌的修饰电极。具体开展了以下几方面工作:
1.基于羟基脲对联吡啶钌-正三丙胺体系电化学发光的抑制作用及精胺对联吡啶钌电化学发光的增强效应,建立了顺序注射-电化学发光分析法在线测定羟基脲和精胺的新方法。结果表明,在最优条件下,本法测定羟基脲的线性范围为2×10~(-6)~1×10~(-3) mol/L,检出限为3.63×10~(-7) mol/L,对羟基脲浓度为2×10~(-6) mol/L平行测定11次,相对标准偏差为1.0%,对羟基脲进行样品测定,误差范围均在2%以内,对羟基脲片及羟基脲在健康人血清和健康人尿液中含量进行了加标回收分析,加标回收率均在94.9%~108.6%之间;本法测定精胺时相对电化学发光值与精胺浓度在5×10~(-7)~5×10~(-4) mol/L范围内呈现良好的线性关系,对5×10~(-7) mol/L浓度的精胺进行11次平行测定,其相对标准偏差为3.0%,检出限为3.03×10~(-7) mol/L。
2.固定发光试剂的优点是节省昂贵试剂联吡啶钌的耗费。价格低廉的高分子聚合物壳聚糖/介孔材料是一种有效的制备复合物膜的方法,通过离子交换采用壳聚糖/MCM-41成功地将联吡啶钌固定在铂电极表面。此修饰电极在磷酸缓冲溶液中有良好的电化学发光特性,并对正三丙胺电化学发光响应较快,而且电化学发光稳定性较强,测定羟基脲及精胺溶液效果较好。这种电极的修饰方法为其他固态ECL的检测开辟了道路。
3.基于[Ru(bpy)_2(dabpy)]~(2+)电化学发光较弱,但其与NO反应生成的[Ru(bpy)2(T-bpy)]2+电化学发光较强,建立了一种使用联吡啶钌衍生物检测水溶液和生物样品中NO含量的ECL方法,该方法灵敏度高且具有较高的选择性,可在复杂生物体系中检测NO。并将这种探针用于羟基脲溶液的测定,效果较好。在最优条件下,测定HU的线性范围为2×10~(-6)~5×10~(-4) mol/L,检出限为6.86×10~(-7) mol/L,对HU浓度为2×10~(-6) mol/L平行测定11次,相对标准偏差为3.7%,对羟基脲片、及羟基脲在健康人血清和健康人尿液中含量进行了加标回收分析,加标回收率均在95.6%~109.2%之间。
In this thesis, the principles, main reaction systems, mechanism and the application of electrochemiluminesence (ECL) were reviewed. New methods based on SI-ECL have been developed for determining hydroxyurea, spermine and NO. The work was summarized as follows:
1. The development of a sequential injection electrochemiluminescence(SI-ECL) method for the determination of hydroxyurea and spermine. It is based on the facts that hydroxyurea could inhibit the ECL of Ru(bpy)_3~(2+) and spermine could enhance the ECL of Ru(bpy)_3~(2+). Under the optimal conditions, the determination of hydroxyurea: a linear range of 2×10~(-6)~1×10~(-3) mol/L was derived along with RSD values of 1.0% at 2×10~(-6) mol/L, and a detection limit of 3.63×10~(-7) mol/L was achieved; the determination of spermine: a linear range of 5×10~(-7)~5×10~(-4) mol/L was derived along with RSD values of 3.0% at 5×10~(-7) mol/L, and a detection limit of 3.03×10~(-7) mol/L was achieved. The recoveries were in the range of 94.9%~108.6% for the determination of hydroxyurea in hydroxyurea tablet, human blood serum and urine samples.
2. A novel ECL sensor with high sensitivity and long-term stability was prepared by immobilizing Ru(bpy)_3~(2+) on the surface of Chitosan/MCM-41 composite films modified Pt electrode via an ion-exchange process and their electrogenerated chemiluminescence were investigated.The experimental results showed that the immobilized Ru(bpy)_3~(2+) maintained its electrochemistry behaviors very well. The modified electrode showed a fast ECL response to TprA. Meanwhile, the modified electrode was applied to the detection of hydroxyurea and spermine. The electrode could be easily regenerated and exhibited good stability which make it a promising candidate for sensitive electrochemical sensors for hydroxyurea and spermine.
3. A ruthenium(II) complex based turn-on ECL probe for the detection of nitric oxide and turn-off ECL probe for the detection of hydroxyurea. A selective and sensitive ECL method for the detection of NO in aqueous and biological samples using a modified Ru(bpy)_3~(2+) complex, [Ru(bpy)_2(dabpy)]~(2+), as a probe was described. Compared to the reported ECL quenching method, the new ECL enhancement method has the advantages of higher selectivity and sensitivity, and wider linear range, which allows it to be favorably useful for the ECL detection of NO in complicated biological samples. Additionally, the ECL probe was successfully applied to the detection of hydroxyurea. Under the optimal conditions, a linear range of 2×10~(-6)~5×10~(-4) mol/L was derived along with RSD values of 3.7% at 2×10~(-6) mol/L. The recoveries were in the range of 95.6%~109.2% for the determination of hydroxyurea in hydroxyurea tablet, human blood serum and urine samples.
引文
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