基于电化学双共价键法构建可再生高灵敏的电化学发光适体传感器检测可卡因

基于点击化学和重氮盐法的双共价键固定化方法,制备了一种高灵敏、可重复使用的电化学发光(ECL)适体传感器. 该方法以可卡因为分析物,以可卡因适体为分子识别物质,以钌联吡啶衍生物为ECL信号物质. 采用电化学方法在玻碳电极表面重氮化叠氮苯胺,通过点击反应连接炔基功能化的钌联吡啶衍生物标记可卡因适体,获得适体传感器. 该传感器在共反应剂存在下,产生弱的电化学发光信号,可卡因存在下,电化学发光信号增加. 基于此,建立了“信号增强”型检测可卡因的电化学发光分析新方法. 电化学发光信号与可卡因浓度在0.1 nmol·L^-1 ~ 100 nmol·L^-1范围内呈良好的线性关系,检出限为60 pmol·L^-1. 该传感器具有良好的稳定性,可重复多次使用. 该双共价键法在构建ECL传感器方面具有很好的应用前景.     

化学发光消耗型锰传感器

化学和生物发光是由化学反应产生的一种光辐射,不需要任何光源。又由于它们具有高灵敏度、宽线性范围和相对比较便宜的仪器等优点,因而在化学和生物传感器领域引起了广泛的兴趣。已用于H_2O_2、乳酸和胆固醇等多种生物活性物质的测定,但未见有金属离子传感器的报道。本文发展了一种新型的全固态模式的消耗型锰离子化学发光传感器。该传感器将除待测物外的所有化学发光反应试剂全部固定在阴离子交换树脂Amberlyst A-27上,于化学发光反应之前,将一定量化学发光试剂从固定化试剂柱上洗脱,与样品中的锰离子产生化学发光。已成功地应用于水样中痕量锰离子的测定。每个固定化试剂柱可连续使用100次以上。 1 实验部分 1.1 仪器和试剂 化学发光传感器由流动系统和检测系统两部分组成。其中流动系统主要由蠕动泵、六通阀、固定化试剂柱和流通池组成。检测系统由光电信增管、负高压、放大器和记录仪组成(图1)。     

功能化金纳米修饰电极自组装及其在固定化酶生物传感器中应用

功能化金纳米修饰电极是化学修饰电极,不仅具有特定功能团性能,且能提供电化学信号,可用于与待测物的电子传递,电子捕获,判定某化学反应是否发生.功能化金纳米修饰电极检测待测物,具有灵敏度高、检测限低及长久使用的优势.我们就功能化金纳米修饰电极自组装制备、电化学表征方法及其在固定化酶生物传感器方面的应用研究,进行综述报道.     

马来酸麦角新碱化学发光传感器的研究

基于发光试剂通过电价键将铁氰化钾固定在阴离子交换树脂上 ,可直接对待测物马来酸麦角新碱进行传感 ,从而建立测定药物马来酸麦角新碱的传感器新方法。其线性范围为 5× 10 -3 ～ 1mg/L ,线性方程为ΔI =10 6 .4 5C +17.10 (R2 =0 .998) ,检出限达到 2 .6 μg/L。对 0 .0 1和 0 .1mg/L的马来酸麦角新碱进行10次测定 ,它们的相对标准偏差 (RSD)分别为 2 .1%、2 .4 %。此传感器的稳定性良好 ,可连续使用 2 0 0次以上。此法已成功地用于马来酸麦角新碱注射液含量的测定以及尿样中马来酸麦角新碱含量的检测     

共反应试剂增强电致化学发光信号生物传感器

在电致化学发光（ECL）生物传感器的构建中,利用共反应试剂促进发光基团的发光效率是一种常见、方便且非常有效的方法. 然而,如何更好地利用共反应试剂使其更加有效地与发光基团作用是提高该类生物传感器灵敏度的重要因素. 本文结合作者课题组部分工作综述了三种共反应试剂放大ECL信号的构建：共反应试剂内置于检测底液;共反应试剂共存于电极表面;酶促生成共反应试剂,并提出了今后ECL信号放大构建的展望.     

镝—钆—钛铁试剂体系荧光光度法测定镝

发现了钆对镝－钛铁试剂荧光体系的协同发光效应,研究了镝－钆－钛铁试剂协同发光体系的荧光光谱特性,确定了试验条件对体系荧光强度的影响。在镝－钛铁试剂荧光体系中引入适量钆,可使体系的荧光强度提高５０倍,用标准加入法测稀土样品中痕量镝可获得满意结果。     

基于适配体识别的凝血酶均相电化学发光检测方法(英文)

本文以钌联吡啶络合物标记的凝血酶适配体为电化学发光探针,建立了均相电化学发光测定凝血酶的新方法。实验发现待测物凝血酶的存在,使金电极上电化学发光探针的电化学发光强度急剧降低,这是由于电化学发光探针与凝血酶形成了大质量生物复合物,使其扩散系数增大和电化学发光效率降低所致。实验结果表明,电化学发光强度的降低与凝血酶浓度在0.5~7.5nmol/L范围内呈良好的线性关系。该方法的检测限为0.25nmol/L,对凝血酶测定的相对标准偏差为2.7%(c=5.0nmol/L,n=7)。该方法具有简单灵敏、选择性好和无需探针固定化和冲洗步骤等优点。     

基于荧光猝灭原理的光纤化学传感器定量分析模 型的建立与应用

根据光纤化学传感器的结构与信号传输特征,推导并建立了适合于定量描述基于荧光猝灭原理的光纤化学传感器对待测物响应的非线性数学模型。以此为基础,为更加简捷、直观地反映响应信号与待测物浓度的函数关系,建立可线性化的回归方程,准确预报待测物的浓度,提出了多模型回归技术建立此类光纤化学传感器定量分析模型的方法。为难定量分析模型的适用性,将该法应用于芘丁酸光纤化学传感器对甲硝唑、呋喃妥因和氧氟沙星等待测物响应的最佳数学模型的选择之中。结果表明,所选的数学模型对各待测物在一定范围内的浓度都能进行准确的预报。     

以聚丙烯酰胺凝胶为基质的光导纤维pH传感器

以凝胶为基质的新型固定化试剂制备了3种pH荧光传感器.在实验条件下,其信号响应时间低于10s,pH突跃范围为1.83～7.54和1.39～2.97.基本上无试剂脱落,在试剂本身化学稳定期限内,具有一定的使用寿命.     

联吡啶钌修饰电极固相电致化学发光

由于电致化学发光(ECL)的连续可测性、高灵敏度、稳定和方法简单,被广泛应用于分子生物学、药学、化学和环保等领域.而将可电化学再生的ECL试剂固定于电极表面,可获得ECL传感器,从而减少分析过程中试剂的消耗并简化实验装置.联吡啶钌及其衍生物在电极表面的固定化研究成为ECL研究的重要方向.本文综述了2004年以来联吡啶钌及其衍生物修饰电极的固相ECL的研究进展,并简要介绍了各种固定方法及其相关的应用情况.     

多吡啶钌(Ⅱ)配合物化学发光性质研究

详细研究了Ru(bpy)3^2+,Ru(bpy)2(dppx)^2+,Ru(bpy)2(dppz)^2+,Ru(phen)3^2+,Ru(phen)2(dppx)^2+和Ru(phen)2(dppz)^2+六个多吡啶钌(Ⅱ)配合物的化学发光性质,筛选出Ru(bpy)3^2+和Ru(phen)3^2+两种性能优良的化学发光试剂;并探讨了它们发光的可能机理和影响因素,为钌(Ⅱ)配合物在化学发光分析中的应用提供了可供参考的理论依据。     

Luminol-type chemiluminescence derivatization reagents for liquid chromatography and capillary electrophoresis

The present paper provides the principles for chemiluminescence of luminol-type compounds and their wide and powerful application to the detection system in liquid chromatography and capillary electrophoresis as derivatization reagents. The reagents can be classified into two types, chemiluminescence labeling and chemiluminogenic reagents. The former reagents are highly chemiluminescent themselves and used for tagging their intense chemiluminophores to analytes, whereas the latter are weakly chemiluminescent but generate intense chemiluminescence by reaction with analytes. The liquid chromatographic methods utilizing chemiluminescence derivatizing reactions with luminol-type reagents allow the analytes to be detected at pmol–sub-fmol levels. Furthermore, the chemiluminogenic reactions show high selectivity owing to their selective reaction against the analytes permitting facile and reproducible detection.     

Modification of the surface of integrated optical wave-guide sensors for immunosensor applications

Methods have been developed which enable attachment amino and epoxy groups to the surface of integrated optical wave-guide sensors for immunosensor applications. The SiO2-TiO2 surfaces were modified by use of the trifunctional silane reagents gamma-aminopropyltriethoxysilane (APTS) and gamma-glycidoxypropyltrimethoxysilane (GOPS) in organic and/or in inorganic phases. Silanization methods were optimized taking into consideration the concentration of silane reagent used and the temperature and time of reaction. To evaluate the layers formed, immobilization experiments were undertaken on the modified surfaces using the bovine serum albumin (BSA)-anti-BSA IgG antibody model molecule pair. The regenerability of the sensitized surfaces was also studied.     

Molecularly Imprinted Electrochemical Sensors

In this review, the applications of molecularly imprinted polymer (MIP) materials in the area of electrochemical sensors have been explored. The designs of the MIPs containing different polymers, their preparation and their immobilization on the transducer surface have been discussed. Further, the employment of various transducers containing the MIPs based on different electrochemical techniques for determining analytes has been assessed. In addition, the general protocols for getting the electrochemical signal based on the binding ability of analyte with the MIPs have been given. The review ends with describing scope and limitations of the above electrochemical based MIP sensors.     

New supramolecular interactions for electrochemical sensors development: different cucurbit[8]uril sensing platform designs

Three different strategies for cucurbit[8]uril immobilization on a glassy carbon electrode have been assayed. The electrochemical properties of the resulting modified electrodes in solutions containing neutral, positively and negatively charged potential cucurbit[8]uril guests were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The comparison of the electrochemical behaviour exhibited by the unmodified electrodes against various probes, with respect to that of each modified electrode, resulted in an appropriate method to choose among different strategies for the development of electrochemical sensors. These sensors are based on the incorporation of the cucurbit[8]uril molecular selection properties that depend on the chemical characteristics of the potential analytes. Furthermore, atomic force microscopy was employed for the characterization of the different surfaces developed.     

Sorbent extraction in flow injection analysis and its application to enhancement of atomic spectrometry

The extraction of metals as their chelates from aqueous samples can be simplified, miniaturized and automated by flow injection/sorbent extraction techniques. The chelate is formed in the flow stream, sorbed on C-18 bonded silica and then eluted for transfer to the atomic absorption spectrometer. The proposed method is shown to be useful for the preconcentration of copper and lead by means of their chelation with diethyldithiocarbamate or 8-quinolinol; complexation with 1-(2- pyridylazo)-2-naphthol or 4-(2-pyridylazo)resorcinol is also possible. This approach enables organic reagents to be used directly, without immobilization, in “open” flow-injection systems for preconcentration or separation of analytes.     

Biosensors designed for environmental and food quality control based on screen-printed graphite electrodes with different configurations

Graphite electrodes fabricated by screen-printing have been used as amperometric detectors in biosensors based on NAD(+)-dependent dehydrogenases, tyrosinase, or genetically modified acetylcholinesterases. The mono-enzyme sensors have been optimized as disposable or reusable devices for detection of a variety of substrates important in the food industry ( D-lactic acid, L-lactic acid, acetaldehyde) or in environmental pollution control (phenols and dithiocarbamate, carbamate and organophosphorus pesticides). The sensors were prepared in four configurations differing in enzyme confinement, enzyme immobilization and location of the immobilization agent in the biosensor assembly. Tests on real samples have been performed with the biosensors; D-lactic acid and acetaldehyde have been detected in wine and phenols in air.     

Improving the biocompatibility of in vivo sensors via nitric oxide release

The continuous, real-time monitoring of clinically important analytes (e.g., PO2, PCO2, pH, K+, Na+, glucose, and lactate) is of great importance to human health care. Despite considerable efforts spanning several decades, the use of in vivo sensors clinically remains limited due to inadequate biocompatibility. The discovery of nitric oxide (NO) as an effective inhibitor of platelet and bacterial adhesion has opened a new direction of research related to designing the next generation of in vivo sensors. In this Highlight article, recent progress in designing more biocompatible in vivo sensors is described, with a particular focus on preparing interfaces that resist biofouling via controlled NO release.     

Ru(bipy)~3^2^+/Ru(phen)~3^2^+-C~2O~4^2^——Ce~Ⅳ化学发光反 应动力学模型 的研究

根据Ru(bipy)~3^2^+/Ru(phen)~3^2^+-C~2O~4^2^--Ce~Ⅳ(bipy=2,2'-联吡啶,phen=1,10-邻菲咯啉)化学发光反应建立了该化学发光反应的动力学模型,根据模型计算出该反应的发光强度-反应时间曲线上升及下降阶段的反应速率常数、发光强度最大值及其出现的时间等。发光强度最大值及发光强度-反应时间曲线下的面积均可用于定量分析。     

Surface immobilization of catalytic beacons based on ratiometric fluorescent DNAzyme sensors: a systematic study

DNAzyme-based catalytic beacons have the potential for sensing a large number of relevant analytes. Thus, a systematic investigation of factors affecting their performance when immobilized into gold-coated nanocapillary array membranes (NCAMs) was undertaken. Enzyme immobilization times were varied to determine that as little as 15 min was sufficient for ratiometric detection of Pb2+-specific activity, while immobilization density saturated after 1.5 h. Immobilization of the DNAzymes into NCAMs with 600 nm pore size resulted in higher immobilization efficiency and higher enzymatic activity than that with 200 nm pore size. A poly-T linker length between the tethering thiol and first oligonucleotide, used to extend the DNAzyme above the backfilling mercaptohexanol (MCH) monolayer, had no effect on DNAzyme activity. The backfilling method of immobilization, involving backfilling followed by hybridization, was found most effective for DNAzyme activity compared to immobilization of hybridized DNAzyme complex (a 67% loss of activity) or concurrent enzyme and MCH immobilization (75% loss of activity). The backfilling MCH monolayer provided approximately 3.5 times increase in activity compared to DNAzyme assembled without MCH, and was over 5 times more active than shorter and longer backfilling molecules tested. The immobilized DNAzyme retained its optimized performance at 50 mM NaCl. Finally, the generalized immobilization and ratiometric procedure was employed for a uranyl-specific DNAzyme with 25 +/- 15 times increase in ratio observed. These findings form a firm basis on which practical applications of catalytic beacons can be realized, including sensors for both Pb2+ and UO22+ ions.