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1.

Conducting polymers are considered as reactive gels which can sense the working ambient through their unique electrochemical reaction. Copolymers of aniline with o-toluidine for three different monomer compositions were synthesized chemically and were characterized using FTIR and UV-Vis spectroscopy, SEM, TGA, and cyclic voltammetry. The electrochemical reactive sensing characteristics with respect to the electrical and chemical working conditions of the copolymers were verified and compared through Chronopotentiometric responses in aqueous solutions of HCl by changing the reaction variables: applied current and chemical environment (electrolyte concentration) at a fixed constant charge. The consumed electrical energy during the electrochemical reaction of the copolymers varies linearly with the driving current and follows a logarithmic dependence on the electrolyte concentration. The consumed electrical energy during the reaction was found to act as the sensing parameter. At the same experimental condition, the sensitivity was associated with the conductivity of the copolymers. The highly conducting composition gives the highest sensitivity. These experimental results were fitted with the theoretical equation.

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2.

A new electrochemical biosensor is developed for the detection of diazinon. For this purpose, a glassy carbon electrode is modified with MWCNTs and poly-l-lysine to immobilize a double-strain DNA (ds-DNA) on the surface of the electrode. In the first step, the interaction of diazinon with ds-DNA is transduced by electrochemical impedance spectroscopy and UV–Vis spectroscopy to monitor the intercalation of diazinon with DNA helix. This interaction leads to reduced interfacial charge-transfer resistance (Rct). The difference in the Rct before and after the interaction is considered as a suitable signal for diazinon detection. The proposed biosensor has a low detection limit (0.3 nmol L−1), a wide linear dynamic range (0.001‒100 µmol L−1), and high selectivity for the determination of diazinon. Finally, the performance of the biosensor for detecting of diazinon is verified in real samples such as river water, agricultural wastewater, lettuce juice, and tomato juice.

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3.

Oxidative stress is considered as an imbalance of reactive species over antioxidants, leading to diseases and cell death. Various methods have been developed to determine the antioxidant potential of natural or synthetic compounds based on the ability to scavenge free radicals. However, most of them lack biological relevance. Here, a gold-based self-assembled monolayer (SAM) was compared with a gold-supported lipid bilayer as models for the mammalian cell membrane to evaluate the free radical scavenging activity of different antioxidants. The oxidative damage induced by reactive species was verified by cyclic and differential pulse voltammetry and measured by the increase of electrochemical peak current of a redox probe. Trolox, caffeic acid (CA), epigallocatechin gallate (EGCG), ascorbic acid (AA), and ferulic acid (FA) were used as model antioxidants. The change in the decrease of the electrochemical signal reflecting oxidative membrane damage confirms the expected protective role. Both model systems showed similar efficacies of each antioxidant, the achieved order of radical scavenging potential is as follows: Trolox > CA > EGCG > AA > FA. The results showed that the electrochemical assay with SAM-modified electrodes is a stable and powerful tool to estimate qualitatively the antioxidative activity of a compound with respect to cell membrane protection against biologically relevant reactive species.

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4.
Abstract

The dual electrochemical detectors for ordinary and micro high-performance liquid chromatography were briefly reviewed.

The electrochemical behaviors of biogenic amine metabolites were studied by cyclic semi-differential and semi-integral voltammetry with a glassy carbon working electrode. It was found that the electrochemical reactions of many biogenic amine metabolites are quasi-reversible. The dual electrochemical detector based on thin-layer electrolytic cell with two working electrodes (anode and cathode) in series configuration was tested for selective detection of biogenic amine metabolites on their electrochemical quasi-reversibility. The detector was successfully utilized for the simultaneous determination of 3, 4-dihydroxyphenylacetic acid, homovanillic acid and 5-hydroxyindole-3-acetic acid in human urine directly injected by micro high-performance liquid chromatography.  相似文献   

5.

Several methods of enhancing the signal-to-noise ratio for instrumentation designed to measure electrochemical noise are practically tested. The experiments are carried out using model RC-circuits and lielectrolyte electrochemical cells. Strong limitations in the tested objects’ impedance values are found due to the input current noise of the instrumentation, especially during the parallel connection of several channels. The advantages of a two-channel scheme for automatically compensating the instrument’s self noise are demonstrated. Different methods of lowering the dispersion of the frequency dependences of the spectral power density of electrochemical noise are compared. It is shown that averaging over segments with an overlap is the most effective method but averaging over frequencies can lead to large distortions when investigating electrochemical systems.

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6.
《Analytical letters》2012,45(10):647-658
Abstract

The electrochemical behavior of the system Eu(III)/Eu(II) in aqueous formamide solutions was studied by current reversal chronopotentiometry at a mercury pool electrode, in 1 M NaClO4 The results indicate that double layer effects must be considered rather that ion solvation effects when explaining the influence of formamide on the Eu(III)/Eu(II) electrode reaction.  相似文献   

7.
《Analytical letters》2012,45(12):2039-2051
Abstract

A systematic study of a new series of 4-methyl-1,4-dihydropyridine derivatives by HPLC by both photodiode array and electrochemical detectors is reported.

The optimum mobile phase was acetonitrile 0.05 M phosphate buffer pH 3 (55/45, v/v) at a flow-rate of 1.5 mL/min.

Compounds I–VIII were determined with UV detection at 250 nm and by electrochemical detection at + 1200 mV.

Retention times varied between 3.0 and 14.0 minutes in the optimal experimental conditions.

Good linear relationships between the peak areas and concentration were found, with limits of quantification ranging between 1 x 10?8 M and 1 x 10?6 M. Repeatability studies showed average variation coefficients lower than 1% for a photodiode array detector. No significant differences between the detectors in sensitivity and selectivity were found.

Also, we used different degradation trials to test the selectivity of the methods. Results of these experiments revealed that the developed methods exhibited a good selectivity.  相似文献   

8.
At low current intensities with tetraethylammonium perchlorate as supporting electrolyte a stationary cationic polymerization of isobutyl vinyl ether in an acetonitrile-diisopropyl ether solvent is obtained at the platinum anode. The electrochemical and kinetic characteristics of the system are determined. An influence of water is found. The molecular weight of the polymer is mainly given by chain transfer to the monomer.

Mit 1 Abbildung

Gegenwärtige Adresse: Semperit AG, A-2514 Traiskirchen.  相似文献   

9.
《Analytical letters》2012,45(10):729-735
Abstract

A novel “electrochemical ionic distribution coefficient”, i is defined based on Guggenheim's electrochemical potential concept. i correlates the activities of a given ion in different solvents. The definition of i is entirely consistent with the practice to interrelate chemical equilibrium constants in various solvents via the classical ionic distribution coefficient i.  相似文献   

10.
Abstract

Determination of urinary uric acid has been attempted by reversed-phase high-performance liquid chromatography with electrochemical detection. We have found that the electrochemical detection method is suitable for monitoring eluate from reversed-phase column and also that the minimum detectable quantity of uric acid using en electrochemical detector is about 10 pg. Complete separation of uric acid was achieved in about 8 min under the present chromatographic conditions.  相似文献   

11.

This paper reports on the preparation and electrochemical performance of chitin- and chitin-cellulose-based hydrogel electrolytes. The materials were prepared by a casting solution technique using ionic liquid-based solvents. The method of chitin dissolution in ionic liquid with the assistance of dimethyl sulfoxide co-solvent was investigated. The obtained membranes were soaked with 1-M lithium sulfate aqueous solution. The prepared materials were preliminarily characterized in terms of structural and physicochemical properties. Further, the most promising biopolymer membranes were assembled with activated carbon cloth electrodes in symmetric electrochemical capacitor cells. The electrochemical performances of these devices were studied in a 2-electrode system by commonly known electrochemical techniques, such as cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The devices operated at a maximum voltage of 0.8 V. All the investigated materials have shown high efficiency in terms of specific capacitance, power density, and cyclability. The studied capacitors exhibited specific capacitance values in the range of 92–98 F g−1, with excellent capacitance retention (ca. 97–98%) after 20,000 galvanostatic charge and discharge cycles. Taking into account the above information and the eco-friendly nature of the biopolymer, it appears that the prepared chitin- and chitin-cellulose-based hydrogel electrolytes can be promising components for green electrochemical capacitors.

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12.
Abstract

Liquid chromatography with electrochemical detection (LC/EC) has proven itself to be a very useful technique for the determination of electrochemically oxidizable or reducible compounds in complex matrices. Practical aspects of the application of LC/EC to pharmaceuticals in biological samples are discussed. These have been gleaned from several years experience with the determination of over a dozen compounds. The aspects discussed are a comparison of EC and UV detection which facilitates a choice between the two, and common problems including electrode coating, late eluters, detector temperature dependence and baseline instability. Various possible solutions to these problems are considered.  相似文献   

13.
Zheng  Dongyun  Liu  Xiaojun  Zhu  Shanying  Cao  Huimin  Chen  Yaguang  Hu  Shengshui 《Mikrochimica acta》2015,182(15):2403-2410

We describe an electrochemical sensor for nitric oxide that was obtained by modifying the surface of a nanofiber carbon paste microelectrode with a film composed of hexadecyl trimethylammonium bromide and nafion. The modified microelectrode displays excellent catalytic activity in the electrochemical oxidation of nitric oxide. The mechanism was studied by scanning electron microscopy and cyclic voltammetry. Under optimal conditions, the oxidation peak current at a working voltage of 0.75 V (vs. SCE) is related to the concentration of nitric oxide in the 2 nM to 0.2 mM range, and the detection limit is as low as 2 nM (at an S/N ratio of 3). The sensor was successfully applied to the determination of nitric oxide released from mouse hepatocytes.

NO electrochemical sensor based on CTAB-Nafion/CNFPME was fabricated through a simple method and applied to detect NO released from mouse hepatocytes successfully.

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14.
Abstract

The reversed phase chromatography of salbutamol in an aqueous phosphate buffer with quaternary and tertiary amine modifiers is described. The object was to control the retention and improve the asymmetry for use with electrochemical detection.  相似文献   

15.
《Analytical letters》2012,45(13):2309-2331
Abstract

A report on the status of the electrochemical DNA probes for the detection of a DNA sequence for environmental and clinical studies is presented. The literature on the electrochemistry of DNA in the last ten years is reviewed. Results obtained in this laboratory using an electroactive hybridization indicator for constructing an electrochemical DNA probe are reported.  相似文献   

16.

Here we are presenting complete electrochemical studies on redox activities of 1,2-dinitrobenzene (DNB) in the presence of antioxidants–quercetin, morin, rutin, ascorbic acid and β-carotene. Bimolecular rate constants (k2), antioxidant activities (Ka) and diffusion coefficients (Do) were evaluated from changes in voltammeric responses and electrochemical parameters in the presence of antioxidant’s concentrations. Theoretical charge calculations by PM3 parameterization were done which further justified our experimental electrochemical work and proposed scavenging mechanism. Present findings were also compared in details with our previously reported studies on 1,3- and 1,4-dinitrobenzene systems for their interactions with antioxidants.

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17.
Abstract

The compatibility of gradient elution and reversed phase ion-pair partition systems combined with electrochemical and fluorometric detection has been investigated. The phase system consisting of buffers with perchlorate counter-ions as mobile phases and tri-n-butylphosphate as stationary phase allows the use of pH and counter-ion gradients. It appeared that (i) use of gradients is time saving and favourable with respect to detection limits and (ii) dual electrode detection may offer a solution to the problem of gradient-induced baseline shifting in electrochemical Electrochemical detectors are rather sensitive towards changes in the mobile phase. Applying the differential coulometric detection principle the gradient induced baseline shift is reduced and consequently the quantification of a number of compounds is facilitated, although noise levels are slightly increased.

Future research will be devoted to noise investigations in order to minimize detection limits.  相似文献   

18.
Gao  Yan-Sha  Zhu  Xiao-Fei  Yang  Tao-Tao  Xu  Jing-Kun  Lu  Li-Min  Zhang  Kai-Xin 《Mikrochimica acta》2015,182(11):2027-2035

The authors describe an electrochemical immunoassay for α-fetoprotein (α-FP) using a glassy carbon electrode (GCE) modified with a nanocomposite made from gold nanoparticles, graphene oxide and multi-walled carbon nanotubes (AuNPs/GO-MWCNTs) and acting as a signal amplification matrix. The nanocomposite was synthesized in a one-pot redox reaction between GO and HAuCl4 without using an additional reductant. The stepwise assembly of the immunoelectrode was characterized by means of cyclic voltammetry and electrochemical impedance spectroscopy. The interaction of antigen and antibody on the surface of the electrode creates a barrier for electrons and causes retarded electron transfer, this resulting in decreased signals in differential pulse voltammetry of hexacyanoferrate which is added as an electrochemical probe. Using this strategy and by working at a potential of 0.2 V (vs. SCE), a wide analytical range (0.01 - 100 ng∙mL‾1) is covered. The correlation coefficient is 0.9929, and the limit of detection is as low as 3 pg∙mL‾1 at a signal-to-noise ratio of 3. This electrochemical immunoassay combines the specificity of an immunological detection scheme with the sensitivity of an electrode modified with AuNPs and GO-MWCNTs.

Schematic illustration of the fabrication procedure of the immunosensor

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19.

The purpose of this study was to evaluate the effects of press pressure and sintering temperature on the microstructure and electrochemical performance of silver oxide-graphene oxide composite as a novel electrode produced by the powder metallurgy (PM) route. Scanning electron microscopy method used to investigate the microstructure of electrodes and energy dispersive X-ray spectroscopy analysis method was used for point analysis. Potentiodynamic polarization and electrochemical impedance spectroscopy methods were used to research the effects of sintering temperature and press pressure on the electrochemical behaviour in the 1.4 wt % KOH solution and electrical discharge test was used for evaluate the ultimate electrical capacity of silver oxide-zinc batteries with electrolyte of the 1.4 wt % KOH solution.

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20.

Nickel-metal hydride (Ni-MH) batteries were widely used due to their various advantages, but its further application and development have been seriously hindered by the low electrochemical discharge capacity of conventional hydrogen storage alloy electrode. The hydrogenated amorphous silicon (a-Si:H) thin film electrode for Ni-MH battery has been proven to have a dramatic electrochemical capacity. We prepared a-Si:H thin films by a two-step process of rf-sputtering followed by hydrogenation, and investigated the effect of hydrogenation on the structure and electrochemical properties of which as an anode. The maximum discharge capacity of a-Si:H thin film electrode after hydrogenation increases from initial 180 mAh·g−1to 1827 mAh·g−1, which is over tenfold that of as-deposited hydrogen-less a-Si thin film electrode. Then, the preliminary relationships between hydrogen content and electrochemical performance of a-Si:H thin film electrode were analyzed, and several negative factors of electrochemical performance for a-Si:H thin film electrode were proposed.

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