Capillary electrophoresis coupled with electrochemiluminescence detection using porous etched joint

A new setup to couple capillary electrophoresis (CE) with electrochemiluminescence (ECL) detection is described in which the electrical connection of CE is achieved through a porous section at a distance of 7 mm from the CE capillary outlet. Because the porous capillary wall allowed the CE current to pass through and there was no electric field gradient beyond that section, the influence of CE high-voltage field on the ECL procedure was eliminated. The porous section formed by etching the capillary with hydrofluoric acid after only one side of the circumference of 2-3 mm of polyimide coating of the capillary was removed, while keeping the polyimide coating on the other part to protect the capillary from HF etching makes the capillary joint much more robust since only a part of the circumference of it is etched. A standard three-electrode configuration was used in experiments with Pt wire as a counter electrode, Ag/AgCl as a reference electrode, and a 300-mum diameter Pt disk as a working electrode. Compared with CE-ECL conventional decoupler designs, the present setup with a porous joint has no added dead volume created.

Miniaturized tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescence detection cell for capillary electrophoresis and flow injection analysis

The design and performance of a miniaturized chip-type tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] electrochemiluminescence (ECL) detection cell suitable for both capillary electrophoresis (CE) and flow injection (FI) analysis are described. The cell was fabricated from two pieces of glass (20 x 15 x 1.7 mm), and the 0.5-mm-diameter platinum disk was used as working electrode held at +1.15 V (vs silver wire quasi-reference), the stainless steel guide tubing as counter electrode, and the silver wire as quasi-reference electrode. The performance traits of the cell in both CE and FI modes were evaluated using tripropylamine, proline, and oxalate and compared favorably to those reported for CE and FI detection cells. The advantages of versatility, sensitivity, and accuracy make the device attractive for the routine analysis of amine-containing species or oxalate by CE and FI with Ru(bPY)(3)(2divided by) ECL detection.

Fabrication of nanometer-sized electrodes and tips for scanning electrochemical microscopy

A novel method for fabrication of nanometer-sized electrodes and tips suitable for scanning electrochemical microscopy (SECM) is reported. A fine etched Pt wire is coated with polyimide, which was produced by polymerization on the Pt surface initiated by heat. This method can prepare electrodes with effective radii varying from a few to hundreds of nanometers. Scanning electron microscopy, cyclic voltammetry, and SECM were used to characterize these electrodes. Well-defined steady-state voltammograms could be obtained in aqueous or in 1,2-dichloroethane solutions. Ibis method produced the nanoelectrodes with exposed Pit on the apex, and they can also be employed as the nanotips for SECM investigations. Different sizes of Pt nanotips made by this method were employed to evaluate the kinetics of the redox reaction of Ru(NH3)6(3+) on the surface of a large Pt electrode by SECM, and the standard rate constant kappa (o) of this system was calculated from the best fit of the SECM approach curve. This result is similar to the values obtained by analysis of the obtained voltammetric data.

A one-pot procedure to prepare ethynylferrocene and iodoethynylferrocene

Ethynylferrocene and iodoethynylferrocene were prepared in high yield as 88-90% through a one-pot procedure. 1, 1'-diiodoferrocenylene was in-situ prepared from reaction of CHI3 PPh3, t-BuOK and ferrocenecarboxaldehyde, further reaction with t-BuOK or n-BuLi gave the title compounds.

The fabrication and performance of an Ag/AgCl reference electrode in human serum

A simple set of electric circuits was used to assemble a pulse generator. With pulse potentials and under galvanostatical control, a clean silver wire was anodized electrochemically for 0.2-0.5 min in 1.0 moll(-1) HCl with a pulse current density of 20 mA cm(-2), and the pulse wave parameters of t(a)/t(c) = 1 and a cycle of 4 s forming an Ag/AgCl reference electrode. Even though the AgCl layer was consumed during the working period when the Ag/AgCl electrode was used as a cathode, the AgCl layer could be in situ recovered electrochemically in serum used when a reversed potential was applied to the electrode system immediately after the measuring program was finished. The current response curve of the anode indicated that an AgCl layer in high density was basically accomplished during the first 6 pulse cycles in human serum. In order to keep a stable and uniform AgCl layer on the reference electrode after each measuring cycle, the ratio of the recovery time (t(r)) to the working time (t(w)) was measured and the smallest value was obtained at 0.03. The open-circuit potential of the Ag/AgCl electrode with respect to a SCE in 0.1 moll(-1) KCl was monitored over a period of 14 days and the mean value was 40.09 mV vs SCE with a standard deviation of 2.55 mV. The potential of the Ag/AgCl reference electrode did remain constant when the measurements were repeated more than 600 times in undiluted human serum with a standard deviation of 1.89 mV. This study indicated that the Ag/AgCl reference electrode could been rapidly fabricated with a pulse potential and could be used as a reference electrode with long-term stable properties in human serum samples.

A STUDY ABOUT PH CHEMICALLY MODIFIED ELECTRODES BASED ON AMINO-DERIVATIVES OF NAPHTHALENE

The electrochemical polymerization of amino-derivatives of naphthalene has been studied on the platinum wire electrodes. The effects of acidity of the modifying media and the potential scan rate on the cyclic voltammograms are verified. As potentiometric pH sensors, the electrodes prepared from 1-naphthylamine and 2,3-diaminonaphthalene showed performance characteristics superior to some other electrodes tested. The electrode modified with 1-naphthylamine in the optimum medium showed a nearly Nernstian response of 4.20-13.70 pH and a slope of -54.8 mV/pH, while the linear range of the electrode prepared by 2,3-diaminonaphthalene was 4.00-13.60 pH, with a slope of -52.4 mV/pH.

THE REVERSIBLE ELECTRON-TRANSFER REACTION OF MYOGLOBIN AT BRILLIANT CRESYL BLUE MODIFIED PLATINUM GAUZE ELECTRODE

The electrochemical behavior of myoglobin at a Brilliant Cresyl Blue (BCB) modified platinum gauze electrode and spiral pt wire in the BCB solution in optically transparent thin layer cell base been investigated by using cyclic potential-absorbance method and double potential step chronoabsorptometry. The results reveal a reversible electron transfer resection of myoglobin. Exhaustive reductive and oxidative electrolyses are achieved at the modified platinum surface in 20 and 100s respectively. The formal h...

一种3自由度并联柔索驱动机器人的变刚度特性研究

以一种3自由度并联驱动机器人为研究对象,研究这种机器人的变刚度特性。从操作臂的静力学出发,对并联柔索驱动机器人的刚度进行了分析得到刚度公式。从得到的公式可以看出,操作臂的刚度不仅与各分支的刚度有关,与操作臂位姿有关,还与张紧柔索的张紧力有关。在机器人各分支上串联刚度较低的弹簧后做刚度实验,试验结果验证了对刚度理论分析所得的结论。

一种3自由度并联柔索驱动机器人的精度研究

研究了一种3自由度并联柔索驱动机器人精度分析和精度综合的问题.分析了影响机器人位姿精度的主要因素,推导建立了关节误差及柔索误差模型.提出了一种精度综合算法,并基于给定的机器人关节允差,综合分析出装配误差及柔索误差的最大取值.通过仿真验证了误差模型的正确性.样机试验表明,利用柔索误差模型可以提高机器人的运动精度.

3自由度并联柔索驱动变刚度操作臂的刚度控制

利用柔索的弹性及驱动冗余性构造了一种3自由度并联柔索驱动变刚度操作臂,在静力学与刚度分析的基础上,进行刚度控制研究。首先,将柔索驱动力映射到关节空间,并分析等效关节力与柔索张力和外力的关系, 提出该操作臂的三维力矢量闭合原理。根据微分变换原理进行刚度分析,得到关节刚度矩阵及操作手刚度矩阵, 并进行数值算例分析,结果表明:刚度与柔索的张力有关,调节柔索张力可以改变系统刚度。最后,采用位置与张力混合控制的策略,对该变刚度操作臂进行了刚度控制,并进行了仿真验证。

一种3自由度并联柔索驱动柔性操作臂的建模与控制

以一种3自由度并联柔索驱动机器人为研究对象,研究这种并联柔性系统的控制规律。考虑到运动描述的唯一性及易测性,取约束关节的位置作为广义关节变量,用以描述操作臂的运动状态。在此基础上分析了操作臂的运动学和静力学关系,建立了并联柔性系统的动力学模型。然后,以轨迹控制为目标,分别基于刚性模型和柔性模型设计控制器,并对系统的性能进行分析和仿真。结果表明:基于刚性模型控制器的性能较差,而基于柔性模型的奇异摄动方法则可以获得较好的控制效果。

一种6自由度柔索并联机器人的动力学研究

采用串联约束 /并联驱动的原理 ,通过加入约束机构 ,设计一种新型柔索驱动并联机器人。然而由于约束机构的引入 ,机器人的动力学分析变得更为复杂。在对机器人进行运动学分析的基础上 ,利用牛顿 欧拉法建立机器人动力学方程。仿真结果证明了该方法的有效性

约束机构在柔索并联机器人设计中的应用

柔索并联机构是一类新型的机构 ,具有一些优于其他机构的特点 ,但因柔索特性的限制 ,可实现的运动形式较少。本文通过增加约束机构对运动平台运动进行限制 ,扩大了柔索并联机构的应用范围。文章提出约束机构的概念 ,讨论了约束机构的种类 ,并进行奇异位形的分析。

并联柔索驱动操作臂静刚度的理论分析

文章对并联柔索驱动机器人(PWDRs)的静态刚度问题进行了理论分析。首先，基于微分变换原理，提出并证明了关于柔索矩阵微小变化变分形式的命题，在此基础上推导了操作臂完整刚度的解析公式，它包括与结构参数有关的刚度及与柔索张力有关的刚度两部分。然后，对这一理论结果进行了数值仿真。研究结果表明：操作臂刚度不仅依赖于机构几何尺寸、柔索与电机刚度及操作臂位置与姿态等结构参数，还与柔索的张力有关、因此，可以通过改变柔索张力来调节PWDRs操作臂的刚度．实现机构变刚度。

柔索驱动三自由度球面并联机构运动学与静力学研究

柔索驱动并联机器人采用柔索代替连杆作为机器人的驱动元件 ,它结合了并联结构和柔索驱动的优点 .文章提出了一种新型带有约束机构的并联柔索驱动机器人 ,采用四根柔索驱动 .由于约束机构的引入 ,机器人可实现在空间的三维转动 .介绍柔索驱动并联机器人的机构构型 ,给出了位姿逆解 ,建立了静力平衡方程和运动学方程 ,讨论了柔索拉力的确定方法 .研究结果证明在加入了约束机构后 ,柔索机器人可以实现更多的运动形式 ,这就为更广泛的应用柔索驱动成为可能