An alternative field switching ion gate for ESI-ion mobility spectrometry

In electrospray ionization (ESI)-ion mobility spectrometry, continuously generated ions must be desolvated in a first tube before short ion pulses are introduced into a second (drift) tube. Both tubes are separated by an ion-gate. The resolving power of the resulting drift time spectrum is strongly influenced by the design of the ion gate. In the case of the Bradbury-Nielsen gates typically used, an orthogonal field between oppositely charged, parallel wires blocks ions from entering the drift tube. However, the blocking field also distorts the entering ion cloud. One alternative, which eliminates these effects and therefore enables a potentially higher resolving power, is already known for spectrometers with small ionization volumes, where ions are formed between two electrodes and subsequently transferred into the drift tube by a high voltage pulse. Based on this setup, we introduce an alternative ion gate design for liquid samples, named field switching ion gate (FSIG). The continuous flow of ions generated by ESI is desolvated in the first tube and introduced into the space between two electrodes (repeller and transfer electrodes). A third (blocking) electrode prevents the movement of ions into the drift tube in the closed state. Ions are transferred during the open state by pulsing the voltages of the repeller and blocking electrodes. First results demonstrate an increase of the resolving power by 100% without intensity losses and further changes in the spectrometer setup. The parameters of the FSIG, such as electrode voltages and pulse width, are characterized allowing the optimization of the spectrometer’s resolving power.     

Continuous flow analysis of lead (II) and mercury (II) with substituted diazacrown ionophore membrane electrodes

A novel flow cell for use with ion-selective membrane electrodes is reported in which the carrier stream is drawn through a tube that suppresses the pump noise. PVC membrane electrodes based on 7,16-dithenoyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTODC), and 7,16-di-(2-thiopheneacetyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTAODC) for lead (II), and 7,16-dithenyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DTDC) and 7,16-di-(2-methylquinolyl)-1,4,10,13-tertraoxa-7,16-diazacyclootadecane (DQDC), for mercury (II) were prepared and evaluated. The linear ranges were pPb: 5.5-3.0 (DTODC) and 6.0-2.0 (DTAODC); pHg: 5.5-3.0 (DTDC) and 4.5-2.5 (DQDC). With flow rate of 3 ml min(-1) the repeatability of measurements was less than 5% RSD (n = 3). The system was applied to the determination of lead (II) and mercury (II) in spiked natural water samples.     

An AC electroosmotic micropump for circular chromatographic applications

Flow rates of up to 50 microm s(-1) have been successfully achieved in a closed-loop channel using an AC electroosmotic pump. The AC electroosmotic pump is made of an interdigitated array of unequal width electrodes located at the bottom of a channel, with an AC voltage applied between the small and the large electrodes. The flow rate was found to increase linearly with the applied voltage and to decrease linearly with the applied frequency. The pump is expected to be suitable for circular chromatography for the following reasons: the driving forces are distributed over the channel length and the pumping direction is set by the direction of the interdigitated electrodes. Pumping in a closed-loop channel can be achieved by arranging the electrode pattern in a circle. In addition the inherent working principle of AC electroosmotic pumping enables the independent optimisation of the channel height or the flow velocity.     

A channel Brownian pump powered by an unbiased external force

A Brownian pump of particles in an asymmetric finite tube is investigated in the presence of an unbiased external force. The pumping system is bounded by two particle reservoirs. It is found that the particles can be pumped through the tube from a reservoir at low concentration to one at the same or higher concentration. There exists an optimized value of temperature (or the amplitude of the external force) at which the pumping capacity takes its maximum value. The pumping capacity decreases with increasing radius at the bottleneck of the tube.     

聚苯胺的电化学现场ESR-电导同步测量

本论文工作通过设计新型的电解池 ,首次实现了导电聚合物的电化学现场ESR_电导同步测量 .从获得的聚苯胺ESR信号及膜电阻随电极电势变化的精细图象看出 ,极化子晶格的形成与消亡决定了聚苯胺的导电行为 .从不同电势下聚苯胺的ESR饱和行为也得到Curie自旋与Pauli自旋相互转化的新证据 .     

Low-voltage electroosmosis pump for stand-alone microfluidics devices

Two types of low-voltage electroosmosis pumps were developed using microfabrication technology for usage in handy or stand-alone applications of the micrototal analysis systems (micro-TAS) and the lab-on-a-chip. This was done by making a thin (< 1 microm) region in the flow path and by only applying voltages near this thin region using electrodes inserted into the flow path. The inserted electrodes must be free from bubble formation and be gas-tight in order to avoid pressure leakage. For these electrodes, Ag/AgCl or a gel salt bridge was used. For patterning the gel on the chip, a hydrophilic photopolymerization gel and a photolithographic technique were optimized for producing a gel with higher electric conductivity and higher mechanical strength. For high flow rate application, wide (33.2 mm) and thin (400 nm) pumping channels were compacted into a 1 mm x 6 mm area by folding. This pump achieves an 800 Pa static pressure and a flow of 415 nL/min at 10 V. For high-pressure application, a pump was designed with the thin and thick regions in series and positive and negative electrodes were inserted between them alternatively. This pump could increase the pumping pressure without increasing the supply voltage. A pump with 10-stage connections generated a pressure of 25 kPa at 10 V.     

Use of laser-excited atomic fluorescence spectrometry with a novel diffusive graphite tube electrothermal atomizer for the direct determination of silver in sea water and in solid reference materials

Laser-excited atomic fluorescence spectrometry is used with a novel diffusive graphite tube electrothermal atomizer for the determination of silver in sea water and three National Institute of Science and Technology (NIST) soil reference materials (SRM 2709, 2710 and 2711). The samples are contained in a small graphite boat which is attached to one of two graphite electrodes. The boat is inserted into the center of a graphite tube which is then sealed by the electrodes and heated. The vaporized sample diffuses through the heated graphite walls and is excited by a laser beam which passes a few mm above the tube. The seawater matrix causes a two-fold suppression in the silver fluorescence signal compared with a pure aqueous standard of the same concentration. The depression is constant over a concentration range of 6 orders of magnitude. When aqueous standards were used for the determination of Ag in the solid samples, no significant difference between the measured values and the certified values were found. A limit of detection of 40 fg (4 ppt) was obtained for pure aqueous solutions and 90 fg (9 ppt) in a 1:1 diluted seawater matrix. A concentration of silver of 14 ng L⁻¹ was determined in a sample of coastal Atlantic water.     

Electrochemical cell with solid oxide electrolyte and oxygen pump thereof

The paper presents the scientific basis and technical implementation of a method for obtaining oxygen by extraction from air using an electrochemical cell based on a solid oxide cell (SOC) with anion-conducting solid electrolyte. A nanopowder of a weak aggregate of the YSZ solid electrolyte and LSM fine powder was used to manufacture SOC. The electrolyte-electrode SOC structure was formed as a tube by joint pressing of functional layers and the further co-sintering at the temperature of 1200°C. The characteristics of an electrochemical cell of the oxygen pump based on a thin-wall tube of the YSZ supporting electrolyte (150 μm) with symmetrical electrodes based on LSM (∼20 μm) are studied. A prototype of a compact oxygen generator (oxygen pump) is developed and manufactured with an electrochemical part based on three serially connected SOCs. The connection is implemented in the form of metallic couplings of the Crofer 22 APU steel. The method of reaction magnetron sputtering was used to protect current leads from corrosion by applying a coating based on a Mn _x Co_{3 − x} O₄ spinel. The efficiency of a demonstration prototype at 800°C was 9 l/h at the power consumption of 50 W. The current density through SOC was 1.1 A/cm². The prototype was designed to contain no noble metal components. It is shown that the engineering approach applied allows manufacturing effective nanostructural SOCs and devices on their basis.     

Thin-layer hydrodynamic biamperometric end-point detection: application to the coulometric titration of arsenic(III) with bromine

A sandwich-type thin-layer cell has been applied to hydrodynamic biamperometric end-point detection in coulometric titrations. The detector cell, constructed from two pieces of teflon, has platinum indicator electrodes and is placed in a flow loop attached to the coulometric titration cell. The thin-layer cavity has a volume of 6.5 μl and a thickness of 51μm, which are obtained using teflon tape as a spacer. A peristaltic pump maintains a continual flow through the loop. The titration cell is a closed vessel completely filled with the solution to be titrated. Operational amplifier circuits control the potential difference applied across the two thin-layer electrodes, and to measure the current developed in the thin-layer cell. Noise arising from the pulsed nature of the flow is reduced by a factor of 25 by using an electronic filter. The titration of arsenic(III) with electrogenerated bromine was used to study the performance of the system. Concentrations from 24 ppb to 1.6 ppm can be determined with relative inaccuracies of +4 and +0.1%, respectively.     

AC electroosmotic pump with bubble-free palladium electrodes and rectifying polymer membrane valves

We present the design, test and theoretical analysis of a novel micropump. The purpose is to make a pump with large flow rate (approximately 10 microL min-1) and high pressure capacity (approximately 1 bar) powered by a low voltage DeltaV<30 V. The pump is operated in AC mode with an electroosmotic actuator in connection with a full wave rectifying valve system. Individual valves are based on a flexible membrane with a slit. Bubble-free palladium electrodes are implemented in order to increase the range of applications and reduce maintenance.     

Concentric glucose/O2 biofuel cell

A concentric glucose/O₂ biofuel cell has been developed. The device is constituted of two carbon tubular electrodes, one in the other, and combines glucose electrooxidation at the anode and oxygen electroreduction at the cathode. The anodic catalyst is glucose oxidase co-immobilized with the mediator 8-hydroxyquinoline-5-sulfonic acid hydrate, and the cathodic catalyst is bilirubin oxidase co-immobilized with the mediator 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt. Both enzymes and mediators are entrapped at the surface of the tubular electrodes by an electrogenerated polypyrrole polymer. The originality of the concentric configuration is to compartmentalize the anode and cathode electrodes and to supply dissolved oxygen separate from the electrolyte in order to avoid secondary reactions. The dissolved oxygen circulates through the inside of the cathode tube and diffuses from the inner to the external surface of the tube to react directly with the immobilized bilirubin oxidase. The assembled biofuel cell is studied at 37 °C in phosphate buffer pH 7.4. We show the influence of the thickness of the polypyrrole polymer on the electrochemical activity of the biocathodes. We also demonstrate the effect of the chemical reticulation of the enzymes by glutaraldehyde within the polymer on the performances of the bioelectrodes. The maximum power density delivered by the assembled glucose/O₂ biofuel cell reaches 42 μW cm⁻², evaluated from the geometric area of the electrodes, at a cell voltage of 0.30 V with 10 mM glucose. The results demonstrate that the concentric design of the BFC based on compartmented electrodes is a promising architecture for further development of micro electronic devices.     

Preparation and characterization of superporous agarose-reticulated vitreous carbon electrodes as platforms for electrochemical bioassays

Three-dimensional flow-through electrodes were fabricated using superporous agarose (SPA) and reticulated vitreous carbon (RVC) composite materials that were suitable as a platform for sandwich assays. These SPA-RVC composite electrodes were fabricated by fitting a SPA-RVC composite cylinder inside a graphite tube and subsequently fixing the graphite tube onto a polypropylene micropipette tip. The electrode design allows for ease in reagent/washing steps involved in sandwich assay protocols and could easily be made portable. The electrode materials were characterized with respect to pore-size distribution, total free volume, ligament and bulk densities of the RVC, and physical structural characteristics. Coulometric detection of redox molecules such as K(3)Fe(CN)(6) and 4-aminophenol was possible using SPA-RVC electrodes by the trapping of these redox molecules inside the SPA-RVC electrodes. Avidin affinity molecules were covalently immobilized onto the SPA matrix inside the RVC electrodes by periodate-activation followed by reductive amination. The amount of avidin immobilized inside the SPA-RVC electrodes was (5+/-0.06)x10(-11) mol, which was determined by saturating the avidin sites with biotinylated fluorescein (b-fluo) and subsequently determining the amount of immobilized b-fluo via a standard addition method using fluorescence spectroscopy. Non-specific binding of labeled enzymes such as biotinylated alkaline phosphatase (b-ALP) onto the SPA-RVC electrodes without avidin capture sites was determined to be less than 1% compared to the specific binding of b-ALP on avidinylated SPA-RVC electrodes.     

Carbon fibre electrodes in flow potentiometric stripping analysis

The construction of carbon fibre flow electrodes suitable for use in connection with potentiometric and constant-current stripping is described, and the fibre electrodes are compared with a glassy carbon disc thin layer cell. The signal-to-background ratio is approximately 1.6 times higher for an 8–10 μm carbon fibre compared to the glassy carbon disc electrode. If an Ag/AgCl tube is used as both counter and reference electrode, the signal-to-noise ratio of the fibre electrode is approximately five times better than for a glassy carbon disc electrode with a calomel reference; the latter electrode design, however, gives slightly better precision. The dead volume and internal potential drop of the fibre electrodes are more than one order of magnitude smaller than for the glassy carbon disc electrode. Because of the simplicity of the manufacturing process and low material cost, the fibre cells can be used as disposable electrodes and the polishing process necessary in connection with glassy carbon disc electrodes can be omitted.     

Hydrogel-based flexible micro-reference electrodes for use in alkaline and neutral pH solutions

Two types of nonbreakable, flexible micro-reference electrodes filled with gel-electrolytes were prepared for use in solutions with alkaline and neutral pH. The electrodes are intended for electrochemical measurements, in which chloride-free conditions are important. Due to the flexible, bendable construction of the electrodes, electrochemical experiments at locations difficult to access with common reference electrodes are enabled. Hg|HgO-type electrodes were prepared from amalgamated Au wires, followed by oxidation of the amalgam, which is mounted in a PTFE tube filled with 0.1M NaOH solution immobilized in a PAA-g-PEO gel. The potential of this type of electrode was found to be 0.162?±?0.002 V (SHE) at room temperature. Cu|CuSO₄ electrodes, consisting of a Cu wire immersed in a saturated CuSO₄ solution jellied with gelatin, showed a stable open-circuit potential of 0.312?±?0.001 V (SHE). Further characterization of the electrodes was performed in terms of electrochemical impedance spectroscopy and micro-polarization measurements. As an alternative to the flexible electrodes, rigid electrodes in glass enclosure were fabricated in analogy to the flexible-type electrodes.     

A simple lecture demonstration of flow injection analysis

Summary The difficulties of explaining the basic concepts of dispersion in flow injection analysis are discussed with particular reference to comparisons with segmented flow analysis and high performance liquid chromatography. The problems with diagrammatic illustration of the laminar flow processes and subsequent dispersion of an injected sample zone are explained. A simple demonstration based on a flow cell for a slide projector consisting of a peristaltic pump tube sandwiched between two slightly modified slide mounts is described.

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Einfache Vorlesungsdemonstration der Fließinjektionsanalyse

     

A new type of d.c. arc as spectrochemical light source

A new type of d.c. arc light source for spectrochemical purposes has been developed. The horizontal arc burning in a graphite tube is placed in an inhomogeneous magnetic field. The limits of detection of In and Pb have been determined. The temperature distribution between the electrodes and the tube wall has been measured.     

单级高压微流量电渗泵的研究

设计了一种高压微流量电渗泵。泵体主要由高压电源、电渗柱、毛细通道、导电空心电极以及气泡去除器、压力传感器等构成。单级电渗泵可以给出0～20MPa范围的输出压力和nL～μL级输出流量。输出压强和输出流量取决于电压、填充柱阻力和流体性质。     

Plasma Polymerization Inside Tubes in Hexamethyldisiloxanes and Ethyne Glow Discharges: Effects of Deposition Atmosphere on Wetting and Ageing in Solvents

The coating deposition inside tubes becomes increasingly important for fluidic applications, in which inner surfaces are chemically and mechanically strained by the flowing liquid and by scratching of particles. The developed process for tube coating, presented in this work, is based on the discharge in the precursor gas atmosphere between two mesh electrodes at the ends of the tube. The gas mixture is introduced on one end and pumped through the electrode on the other end. Igniting plasma inside the tube, the tube walls are the barrier to the atmosphere. Especially pulsed DC discharges for plasma polymerization in this alignment lead to good coating results, which is shown in this work focusing on deposition in pure and mixed hexamethyldisiloxane, ethyne, and oxygen atmospheres. Chemical binding, wetting, and ageing are strongly influenced by the choice of the gas mixtures. Sufficient oxygen partial pressure in the deposition atmosphere leads to hydrophilic behavior of the SiO₂-like polymer-like carbon coatings, all other applied atmospheres to generally hydrophobic behavior of pure and Si-doped plasma polymers, respectively.     

Electrical,Thermal and Optical Diagnostics of an Atmospheric Plasma Jet System

Plasma diagnostics of atmospheric plasmas is a key tool in helping to understand processing performance issues. This paper presents an electrical, optical and thermographic imaging study of the PlasmaStream atmospheric plasma jet system. The system was found to exhibit three operating modes; one constricted/localized plasma and two extended volume plasmas. At low power and helium flows the plasma is localized at the electrodes and has the electrical properties of a corona/filamentary discharge with electrical chaotic temporal structure. With increasing discharge power and helium flow the plasma expands into the volume of the tube, becoming regular and homogeneous in appearance. Emission spectra show evidence of atomic oxygen, nitric oxide and the hydroxyl radical production. Plasma activated gas temperature deduced from the rotational temperature of nitrogen molecules was found to be of order of 400 K: whereas thermographic imaging of the quartz tube yielded surface temperatures between 319 and 347 K.