毛细管电泳-电化学发光法分离检测饮料中亮氨酸

基于亮氨酸对化学发光试剂三联吡啶钌(Ru(bpy)32+)在铂电极上电致发光信号的增敏作用,建立了一种快速测定亮氨酸的毛细管电泳-电化学发光分析方法.对实验条件进行优化,最佳实验条件如下:检测电位为1.15 V;Ru(bpy)32+浓度为7 mmol·L-1(pH=8.5);进样时间为10 s;进样高压为10 kv;分...     

基于电纺碳纳米纤维材料的阿托品固态电化学发光传感器

将电纺碳纳米纤维(CNF)掺杂于吸附有三联吡啶[RU(bpy)32+]的Nafion聚合物膜中,制成固态电化学发光(ECL)传感器,并将其用于对阿托品的检测.实验表明,CNF的加入能够增强Ru(bpy)32+/阿托品体系的电化学和ECL信号,且Ru(bpy)32+在膜中的电化学反应受扩散控制.在最佳实验条件下,ECL强...     

毛细管电泳吡啶钌电化学发光检测天仙子中生物碱

1 引言 天仙子是一种天然中草药,它的主要活性成分为阿托品和东莨菪碱 .目前,分析天仙子的方法主要有:核磁共振技术、紫外分光光度法、高效液相色谱法和毛细管电泳分离法等.毛细管电泳技术(CE)具有进样体积小、分离效率高等优势.吡啶钌(Ru(bpy)2+3)电化学发光法具有激发态寿命长、发光效率高、试剂可循环再生等优点. CE与Ru(bpy)2+3电化学发光联用技术(CE-ECL)将二者优势有机组合,已成为分析化学领域中很好的分析工具.     

基于Ru(bpy)3~(2+)/二丁基乙醇胺电化学发光猝灭的新型毛细管电泳电化学发光检测装置的研制及应用研究

电化学发光(ECL)检测技术是近年来发展迅速的一种新型毛细管电泳(CE)分析检测方法,已经在生命科学、临床检验及食品安全等领域得到了广泛的应用~([1-3]).传统的CE-ECL检测技术均是以Ru(bpy)3~(2+)的共反应物为检测对象,但由于能强烈增强Ru(bpy)3~(2+)电化学发光的共反应试剂有限,使该方法在应用上受到很大的限制.     

甲醇-联吡啶钌(II)体系的电致化学发光研究

研究了碱性溶液中甲醇-联吡啶钌(II)[Ru(bpy)3^2^+]的电致化学发光行为。在玻碳电极上甲醇于+1.28V(vs.Ag/AgCl)处被氧化为甲氧基离子(CH3O.), 该自由基离子发生歧化反应, 生成激发态的甲醛(HCHO), 发出波长为545nm的光。另一方面当体系含有少量的Ru(bpy)3^2^+时会得到较强的发光信号, 发光波长为608nm, 该发光起因于在甲醇的氧化电位下, Ru(bpy)3^2^+被氧化成Ru(bpy)3^3^+, CH3O.与Ru(bpy)3^3^+反应, 生成激发态的Ru(bpy)3^2^+而发光。     

甲醇-联吡啶钌(II)体系的电致化学发光研究

研究了碱性溶液中甲醇-联吡啶钌(II)[Ru(bpy)3^2^+]的电致化学发光行为。在玻碳电极上甲醇于+1.28V(vs.Ag/AgCl)处被氧化为甲氧基离子(CH3O.), 该自由基离子发生歧化反应, 生成激发态的甲醛(HCHO), 发出波长为545nm的光。另一方面当体系含有少量的Ru(bpy)3^2^+时会得到较强的发光信号, 发光波长为608nm, 该发光起因于在甲醇的氧化电位下, Ru(bpy)3^2^+被氧化成Ru(bpy)3^3^+, CH3O.与Ru(bpy)3^3^+反应, 生成激发态的Ru(bpy)3^2^+而发光。     

固定化联吡啶钌电化学发光免疫分析研究进展

综述了固定化联吡啶钌[Ru(bpy)23+]电化学发光免疫传感技术的发展状况,介绍了近年来在电化学发光免疫传感领域出现的新型固相载体材料和固定方法,及其与其他分析技术联用方面的发展,并对其发展趋势进行了展望.指出电化学发光免疫分析技术在生物分子检测、药物分析及临床诊断中显示出强大的生命力.Ru(bpy)23+的电化学发光已引起广泛的关注.固定化Ru(bpy)23+电化学发光免疫分析体系具有线性范围宽、灵敏度高、装置简单、可控性强等优点,被广泛应用于分子生物学、化学、药学等领域.     

Ru(bpy)_3~(2+)固相电致化学发光研究进展

联吡啶钌(Ru(bpy)2+3)是应用最广泛的电致化学发光(ECL)活性物。将可电化学再生的Ru(bpy)2+3及其类衍生物固定于电极表面,获得固相ECL传感器是ECL研究的重要方向之一。本文综述了Ru(bpy)2+3及其衍生物固相ECL近年来的研究进展,简要介绍不同固定化技术及其应用情况。     

玻碳电极上Ru(bpy)23+的吸附及其电致化学发光的研究

通过电化学循环伏安法和电致化学发光方法,研究了Ru(bpy)23+在玻碳电极上的吸附,研究结果表明,Ru(bpy)23+的浓度和与玻碳材料接触的时间,直接影响了Ru(bpy)23+在玻碳上的吸附.还考察了吸附的Ru(bpy)23+在玻碳电极上被氧化后脱附的情况.     

十二烷基苯磺酸钠-盐酸苯海索-Ru(bpy)2+3体系的电化学发光行为研究及应用

在十二烷基苯磺酸钠(SDBS)存在下,考察了盐酸苯海索(BH)-Ru(bpy)32+体系的电化学及其发光行为。结果表明,BH对Ru(bpy)32+体系的电化学发光具有增敏效应;在SDBS存在下,BH对Ru(bpy)32+体系电化学发光的增敏效应显著增强,发光强度提高约16倍。据此建立了一种高效、简便的BH电化学发光新方法。在最佳实验条件下,BH的浓度在4.0×10-7～1.0×10-4 mol/L范围内与相对发光强度呈线性关系(r=0.995 5),检出限(S/N=3)为1.11×10-9 mol/L;连续平行测定1.0×10-5 mol/L BH溶液10次,发光强度的RSD为3.2%。样品的回收率为96%～108%,RSD为4.3%。该方法样品前处理简单,具有较高的选择性和灵敏度,用于实际样品中BH的测定,结果满意。     

几种醇类的固态电致化学发光-高效液相色谱检测

使用水／油反相微乳法合成包埋联吡啶钌（Ru（bpy）3^2＋）的纳米硅球（RuSiNPs）,利用Nation材料固定RuSiNPs于玻碳电极上,构筑了RuSiNPs／Nafion复合膜修饰传感电极,进行了醇类的电致化学发光一高效液相色谱（ECL-HPLC）分离检测．利用循环伏安等方法考察了RuSiNPs／Nafion复合膜电极的电化学和ECL行为,结果表明包埋在硅球里的Ru（bpy）32＋较好地保持了原有的光学和电化学性质．研究了实验条件对其ECL的影响,通过HPLC条件的优化建立了利用RuSiNPs／Nafion固态ECL进行醇类样品的分离检测方法,所提出方法对甲醇、乙醇、丙醇和丁醇的检测下限分别为6．7×10^5,8．2×10^5,3．9×10^-4和4．2×10^-4mmol／L．方法被初步应用于一些啤酒样品中醇的检测．     

Direct tris(2,2'-bipyridyl)ruthenium (II) electrochemiluminescence detection of polyamines separated by capillary electrophoresis

Capillary electrophoresis (CE) with tris(2,2'-bipyridyl) ruthenium (II) (Ru(bpy)3(2+)) electrochemiluminescence (ECL) detection technique was developed for the analysis of four polyamines (putrescine (Put), cadaverine (Cad), spermidine (Spd), and spermine (Spm)) analysis. The four polyamines contain different amine groups, which have different ECL activity. There are several parameters which influence the resolution and ECL peak intensities, including the buffer pH and concentrations, separation voltage, sample injection, electrode materials, and Ru(bpy)3(2+) concentrations. Polyamines are separated by capillary zone electrophoresis in an uncoated fused-silica capillary (50 cmx25 micro m (ID) filled with acidic phosphate buffer (200 mmol/L phosphate, pH 2.0) - 1mol/L phosphoric acid (9:1 v/v) and a separation voltage of 5 kV (25 micro A), with end-column Ru(bpy)3(2+) ECL detection. A 5 mmol/L Ru(bpy)3(2+) solution plus 200 mmol/L phosphate buffer (pH 11.0) is added into the reagent reservoir. The calibration curve is linear over a concentration range of two or three orders of magnitude for the polyamines. The analysis time is less than 25 min. Detection limits for Put and Cad are 1.9x10(-7) mol/L and 7.6x10(-9) mol/L for Spd and Spm, respectively. Intraday and interday relative standard deviations of ECL peak intensities are less than 8%. The main advantages of this CE-ECL detection technique for polyamines analysis presented herein are the omission of chemical derivatization of the analytes and the high selectivity.     

Drug-human serum albumin binding studied by capillary electrophoresis with electrochemiluminescence detection

A new technique for investigating drug-protein binding was developed employing capillary electrophoresis (CE) coupled with tris(2,2'-bipyridyl) ruthenium(II) [Ru(bpy)(3) (2+)] electrochemiluminescence (ECL) (CE-ECL) detection after equilibrium dialysis. Three basic drugs, namely pridinol, procyclidine and its analogue trihexyphenidyl, were successfully separated by capillary zone electrophoresis with end-column Ru(bpy)(3) (2+) ECL detection. The relative drug binding to human serum albumin (HSA) for each single drug as well as for the three drugs binding simultaneously was calculated. It was found that the three antiparkinsonian drugs compete for the same binding site on HSA. This work demonstrated that Ru(bpy)(3) (2+) CE-ECL can be a suitable technique for studying drug-protein binding.     

Simultaneous electrochemical and electrochemiluminescence detection for microchip and conventional capillary electrophoresis

A simultaneous electrochemical (EC) and electrochemiluminescence (ECL) detection scheme was introduced to both microchip and conventional capillary electrophoresis (CE). In this dual detection scheme, tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+)) was used as an ECL reagent as well as a catalyst (in the formation of Ru(bpy)3(3+)) for the EC detection. In the Ru(bpy)3(2+)-ECL process, Ru(bpy)3(3+) was generated and then reacted with analytes resulting in an ECL emission and a great current enhancement in EC detection due to the catalysis of Ru(bpy)3(3+). The current response and ECL signals were monitored simultaneously. In the experiments, dopamine and three kinds of pharmaceuticals, anisodamine, ofloxacin, and lidocaine, were selected to validate this dual detection strategy. Typically, for the EC detection of dopamine with the presence of Ru(bpy)3(2+), a approximately 5 times higher signal-to-noise ratio (S/N) can be achieved than that without Ru(bpy)3(2+), during the simultaneous EC and ECL detection of a mixture of dopamine and lidocaine using CE separation. The results indicated that this dual EC and ECL detection strategy could provide a simple and convenient detection method for analysis of more kinds of analytes in CE separation than the single EC or ECL detection alone, and more information of analytes could be achieved in analytical applications simultaneously.     

Determination of Amino Acids by Ru(bpy)_3~(2+) Cathodic Electrochemiluminescence with High Sensitivity

The unique cathodic electrochemiluminescence(ECL) emission of Ru(bpy)32+(bpy=2,2′-bipyridine) was observed via Nafion film at Au electrode[Au/Nafion/Ru(bpy)32+] at about 0.20 V(vs. Ag/AgCl) and applied to the determination of several amino acids without prior derivatization with high sensitivity. The cathodic electrochemilumi-nescence(ECL) exhibits the detection limits and linear ranges of several amino acids comparable to or better than those of capillary electrophoresis with conventional ECL detection method(at 1.10—1.20 V vs. Ag/AgCl) based on precolumn derivatization. The results suggest that the cathodic ECL is promising for the detection of amino acids in bioanalysis.     

金属离子对联吡啶钌电致化学发光影响的研究

在玻碳电极上, 联吡啶钌[Ru(bpy)₃^2＋]于＋1.50 V (vs. Ag/AgCl)左右被氧化为Ru(bpy)₃^3＋, 该氧化态离子与碱性水溶液中(pH 8.2)的OH•反应生成激发态的[Ru(bpy)₃^2＋*]而发光. 研究比较了15种金属离子对Ru(bpy)₃^2＋碱性水溶液电致化学发光的影响, 并对这些影响进行了初步的解释.     

Capillary electrophoresis with electrochemiluminescence detection of procyclidine in human urine pretreated by ion-exchange cartridge

This paper describe a Ru(bpy)₃²⁺ based electrochemiluminescence (ECL) method to detect procyclidine in human urine following separation by capillary electrophoresis (CE). An ECL detection cell was designed for post-column addition of Ru(bpy)₃²⁺. Parameters affecting separation and detection were optimized, leading to a detection limit of 1×10⁻⁹ mol/l in an on-capillary stacking mode. For application in urine, a cartridge packed with slightly acidic cation-exchange resin was used to eliminate the matrix effects of urine and improve the detection sensitivity. Extraction recovery was nearly 90%.     

毛细管电泳电致化学发光法测定牛奶样中的土霉素残留量

以铕离子(Ⅲ)掺杂类普鲁士蓝(Eu-PB)化学修饰铂电极为工作电极,基于铜(Ⅱ)-土霉素配合物对三联吡啶钌(Ⅱ)电致化学发光强度的增敏作用,建立了用毛细管电泳电致化学发光法测定土霉素的新方法。实验对毛细管电泳分离条件和电化学发光检测条件进行了优化。在最佳实验条件下,电致化学发光峰面积与铜(Ⅱ)-土霉素配合物的浓度在0.138～46.1μg/mL范围内呈良好的线性关系,检出限为57.0ng/mL(3σ)。本法用于牛奶样中土霉素残留量的测定,加标回收率为95.5%(n=5)。     

一系列Ru(II)配合物电致化学发光性质的比较研究

比较研究了以C₂O₄^2－为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)₂L¹]^2＋, [Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋, [Ru(phen)₂L¹]^2＋和[Ru(phen)₂L²]^2＋(其中bpy＝2,2′-联吡啶, phen＝1,10-邻菲啰啉, L¹＝4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L²＝3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L³＝3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋和[Ru(phen)₂L²]^2＋的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)₃]^2＋相差不大.