Amperometric Determination of Ascorbic Acid at an Electrodeposited Redox Polymer Film Modified Gold Electrode

A sensitive and selective electrochemical method for the determination of ascorbic acid was developed. It was shown that a hydrated osmium complex‐containing redox polymer film can be electrodeposited at the gold electrode and it exhibits excellent electrocatalytic activity towards the oxidation of ascorbic acid. In contrast to a bare gold electrode, the oxidation current of ascorbic acid increased greatly and the oxidation peak potential shifted negatively to about 0.01 V (vs. SCE) at the modified electrode. Amperometric measurements were performed at an applied potential of 0.01 V and a linear response was obtained in the range of 2–400 μM with a limit of detection (LOD) of 0.6 μM (S/N=3). The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of uric acid and dopamine. The proposed procedure was successfully applied to the determination of ascorbic acid in human urine samples.     

Chitosan-coated electrodes for bimodal sensing: selective post-electrode film reaction for spectroelectrochemical analysis

Electrochemical methods are well suited for chemical detection in hand-held devices because they are simple, fast, and sensitive. However, electrochemical detection methods generally suffer from limitations in selectivity. We report a novel approach that enables electrochemically initiated reactions to generate optical signals that can be used to enhance the discriminating power for the electrochemical analysis of antioxidant food phenols. This spectroelectrochemical approach employs transparent electrodes coated with a film of the aminopolysaccharide chitosan. The phenolic analytes diffuse through the chitosan film to the electrode where they are anodically oxidized into electrophilic intermediates that undergo postelectrode reactions with the chitosan film. The postelectrode reaction was analyzed by FTIR and XPS, and this reaction was observed to impart optical properties (color and UV-visible absorbance) to the otherwise colorless and transparent chitosan film. We demonstrate that the optical signal generated from the postelectrode film reaction is selective for oxidized phenols, compared to that for unoxidized phenols or the nonphenolic antioxidant ascorbic acid. Furthermore, we demonstrate that the optical signal (film absorbance) can be correlated to the electrical signal (charge transferred). Finally, we use simple mixtures to demonstrate that the coupling of information from independent optical and electrical measurement modes can assist in the qualitative analysis of antioxidant phenols. Potentially, the postelectrode film reaction may provide a selective and reagentless alternative to conventional colorimetric methods for detecting antioxidant phenols. In a broader perspective, this work suggests the potential for coupling independent detection modes (optical and electrical) to enhance the information content of sensor measurements.     

3-D nanoporous gold thin film for the simultaneous electrochemical determination of dopamine and ascorbic acid

In this study, we demonstrated a novel fabrication method of three dimensional nanoporous gold thin film (NPGF) onto gold (Au) substrate using electrochemical deposition method. Scanning electron microscope (SEM) investigation reveals the formation of highly-ordered pores, approximately 30 nm in diameter and 150 nm thick. The NPGF-modified electrode shows a linear range (0.1–40 μM) for dopamine detection in the presence of ascorbic acid. The electrochemical measurements of mixtures of dopamine, ascorbic acid, and uric acid in human serum sample for real sample applications was also investigated based on differential pulse voltammetry (DPV) technique. These high sensitivity and selectivity features of the proposed NPGF biosensor offer great promise for real sample biosensor application.     

Simultaneous determination of dopamine, ascorbic acid and uric acid at poly (Evans Blue) modified glassy carbon electrode

A sensitive and selective electrochemical method for the determination of dopamine using an Evans Blue polymer film modified on glassy carbon electrode was developed. The Evans blue polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of dopamine in phosphate buffer solution (pH 4.5). The linear range of 1.0 x 10(-6)-3.0 x 10(-5) M and detection limit of 2.5 x 10(-7) M were observed in pH 4.5 phosphate buffer solutions. The interference studies showed that the modified electrode exhibits excellent selectivity in the presence of large excess of ascorbic acid and uric acid. The separation of the oxidation peak potentials for dopamine-ascorbic acid and dopamine-uric acid were about 182 mV and 180 mV, respectively. The differences are large enough to determine AA, DA and UA individually and simultaneously. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid in physiological samples.     

Poly(4-amino-1-1'-azobenzene-3, 4'-disulfonic acid) coated electrode for selective detection of dopamine from its interferences

Here, we described a new method for electrochemically selective detection of dopamine (DA). In this report, for the first time, electrochemical polymerization of 4-amino-1-1'-azobenzene-3,4'-disulfonic acid (acid yellow 9 dye (AY)) was carried out onto the surface of glassy carbon (GC) electrode and indium tin oxide coated electrode (ITO) from acidic solution containing AY monomers. A polymerized film of acid yellow on the surface of a glassy carbon electrode was characterized by cyclic voltammetry (CV). The redox response of the poly(AY) film on the GC electrode showed a couple of redox peak in 0.1M sulfuric acid solution and the pH dependent peak potential was -58mV/pH which was close to the Nernst behavior. The poly(AY) film-coated GC electrode (GC/PAY) exhibited excellent electrocatalytic activity towards the oxidations of dopamine (DA) in 0.1M phosphate buffer solution (PBS, pH 7.0) and increased the anodic peak current three time higher than bare GC electrode. GC/PAY did not reduce the considerable overpotential for oxidation of DA when compare to bare GC electrode. However, in contrast to other polymer modified electrode, due to the strong negatively charged back bone of poly(AY) highly repelled the important interference of DA, such as ascorbic acid (AA), uric acid (UA) and reduced form of nicotinamide adenine dinucleotide (NADH) in 0.1M PBS (pH 7.0) and did not showed any response for oxidation of these interferences. This behavior makes the GC/PAY for selective detection of DA in the presence of higher concentrations AA, UA and NADH. Using differential pulse voltammetry the calibration curves for DA were obtained over the range of 1-100muM with good selectivity and sensitivity. The proposed method provides a simple method for selective detection of DA from its interferences.     

A novel carbon/chitosan paste electrode for electrochemical detection of normetanephrine in the urine

Normetanephrine is a marker for pheochromocytoma, a rare catecholamine-secreting and neuroendocrine tumor, that arises from sympathetic and parasympathetic paraganglia. In this work, a novel carbon/chitosan electrode paste was used for sensitive voltammetric determination of normetanephrine and dopamine in the presence of ascorbic acid and uric acid. The modified electrode has shown an increase in the effective area of up to 68%, well-separated oxidation peaks, and an excellent electrocatalytic activity. The electrochemical response characteristics were investigated by cyclic and differential pulse voltammetry. Interestingly, high sensitivity and selectivity in the linear range of normetanephrine, dopamine, ascorbic acid, and uric acid concentrations were observed. The present method was applied in the urine sample and satisfactory results were obtained showing that this electrode is very suitable in pharmaceutical and clinical preparations.     

Dopamine Detection Using the Selective and Spontaneous Formation of Electrocatalytic Poly(dopamine) Films on Indium?Tin Oxide Electrodes

In this study, we report the simple and sensitive electrochemical detection of dopamine in the presence of excess ascorbic acid. The detection is based on the spontaneous formation of electrocatalytic poly(dopamine) films on bare indium? tin oxide (ITO) electrodes. The poly(dopamine) films are formed by immersing ITO electrodes in a solution of dopamine and ascorbic acid for 10 min. Afterwards, the electrocatalytic oxidation of hydrazine is measured using modified electrodes. The electrooxidation current of hydrazine increases with increasing dopamine concentration. This method allows a detection limit of 1 nM for dopamine in the presence of 100 µM of ascorbic acid.     

Improvement of the Selectivity of Amperometric Biosensors by Using a Permselective Electropolymerized Film

Abstract

Dichlorophenolindophenol (DCPIP) was electrochemically deposited onto the surface of glassy carbon and platinum electrodes to form a permselective film. Cyclic voltammetry of the DCPIP coated electrode exhibited a reversible oxidation/reduction current at +0.14 V, behavior similar to monomeric DCPIP. However, such an electrode did not mediate glucose oxidase in the presence of β-D-glucose. For operation at +0.7 V vs Ag/AgCl, the DCPIP electrodeposited film behaved like a permselective membrane and virtually eliminated oxidative interference currents resulting from 0.2 mM acetaminophen, uric acid and glutathione. For ascorbic acid, interfering current due to 0.2 mM ascorbate was decreased by 80%. Improvement of the selectivity due to ascorbic acid was achieved using an electrodeposited film prepared from a mixture of DCPIP with diaminobenzene or resorcinol.     

Synthesis of magnetic molecularly imprinted polymer particles for selective adsorption and separation of dibenzothiophene

We are presenting an electrochemical sensor for the simultaneous determination of dopamine (DA) and uric acid (UA) in the presence of even high concentrations of ascorbic acid (AA). It based on a glassy carbon electrode modified with an electroactive film of polymerized dibromofluorescein. The electrochemical behaviors of DA and UA were studied by cyclic voltammetry using the modified electrode. It exhibits excellent electrocatalytic activity towards the oxidation of the two analytes. Most notably, the oxidation potentials differ by 180 and 200?mV between AA-DA and DA-UA, respectively. Thus, excellent selectivity towards the oxidation of DA and UA in the presence of even high concentrations of AA is accomplished. Under the optimum conditions, the anodic peak currents are linearly related to the concentrations of DA and UA in the range from 0.2 to 200?μmol?L^-1 and from 1.0 to 250?μmol?L^-1, respectively. The detection limits for DA and UA are 0.03?μmol?L^-1 and 0.2?μmol?L^-1, respectively (at an S/N of 3). The method has good selectivity and sensitivity and was successfully applied to the simultaneous determination of DA and UA in spiked human serum.

Amperometric sensor for ascorbic acid based on a glassy carbon electrode modified with gold-silver bimetallic nanotubes in a chitosan matrix

We report on an amperometric sensor for ascorbic acid (AA) that is based on highly dense gold-silver nanotubes in a chitosan film on a glassy carbon electrode. The nanotubes were synthesized by a poly(vinyl pyrrolidone)-mediated polyol method employing a replacement reaction with silver nanowires as templates, and were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. Under the optimal conditions, the sensor exhibits good electrocatalytic activity towards the oxidation of AA, and this enables the determination of AA in the 5 μM to 2 mM concentration range, with a detection limit at 2 μM (at an S/N of 3). The response time is 2 s. The sensor displays good reproducibility, selectivity, sensitivity, and long-term stability.

Attachment of DNA to the carbon fiber microelectrode via gold nanoparticles for simultaneous determination of dopamine and serotonin.

A novel biochemical sensor was fabricated on a carbon fiber microelectrode, which consisted of an inner layer of electrodeposited gold nanoparticles, as a nano-array electrode, and an outer layer of electrodeposited calf thymus ds-DNA at +1.5 V vs. SCE. This modified electrode was characterized by X-ray photoelectron spectroscopy, scanning electron microscope, atomic force microscopy, cyclic voltammetry and differential pulse voltammetry (DPV). It was found that this electrochemical sensor exhibits a strong catalytic activity toward the oxidation of dopamine (DA), serotonin (5-HT) and ascorbic acid (AA), as a result of resolving the anodic voltammetric peaks of DA, 5-HT and AA into three well-defined peaks. Simutaneous DPV determination of DA and 5-HT can be achieved in the presence of 2000-fold AA. The modified electrode shows good sensitivity, selectivity and stability.     

多壁碳纳米管-Nafion化学修饰电极在高浓度抗坏血酸和尿酸体系中选择性测定多巴胺

多巴胺是人体内一种重要的神经传递物质 ,它参与许多生命过程[1] .因此 ,测定体内多巴胺的浓度十分重要 .多巴胺的电化学分析方法已有不少报道 [2 ,3 ] .然而 ,共存的抗坏血酸和尿酸的电化学性质与多巴胺相似 ,对多巴胺的测定会产生严重干扰 .因此建立一种选择性测定多巴胺的高灵敏度的分析方法就显得尤为重要 .碳纳米管是一种新型的纳米材料 [4 ] ,它的出现引起了广泛的研究兴趣 [5,6] .由于其性质稳定 ,不溶于水及一般的有机溶剂 ,因此限制了其在电分析方面的应用 .本文将多壁碳纳米管分散在 Nafion的无水乙醇中 ,得到了一种均匀的多壁碳…     

Highly selective dopamine quantification using a glassy carbon electrode modified with a melanin-type polymer

A highly selective dopamine quantification at a new polymer-modified electrode in the presence of large excess of ascorbic acid and 3,4-dihydroxyphenyl acetic acid (dopac) is described. The electrochemical detection was performed at a glassy carbon electrode modified with a melanin-type polymer obtained by polymerization of 3.0×10⁻³ M -dopa in 0.050 M phosphate buffer solution pH 7.40 by applying 1.00 V for 60 min. The polymeric film exhibits attractive permselectivity excluding anionic species such as potassium ferricyanide, ascorbic acid, dopac and uric acid. Cationic species such as epinephrine, norepinephrine and dopamine and neutral ones such as catechol and hydrogen peroxide can be oxidized at the polymer-modified electrode. The use of ascorbic acid in the measurement solution allows the amplification of dopamine oxidation signal due to the reduction of the electrochemically generated dopaminequinone. By using 1.0×10⁻³ M ascorbic acid, the detection limit for dopamine is 5.0 nM. The interference for the maximum physiological concentrations of ascorbic acid and dopac in nervous centers, i.e. 500 μM ascorbic acid and 50 μM dopac is 8.1 and 1.4%, respectively.     

A glassy carbon electrode modified with the nickel(II)-bis(1,10-phenanthroline) complex and multi-walled carbon nanotubes, and its use as a sensor for ascorbic acid

A glassy carbon electrode (GCE) was modified with the nickel(II)-bis(1,10-phenanthroline) complex and with multi-walled carbon nanotubes (MWCNTs). The nickel complex was electrodeposited on the MWCNTs by cyclic voltammetry. The modified GCE displays excellent electrocatalytic activity to the oxidation of ascorbic acid (AA). The effects of fraction of MWCNTs, film thickness and pH values were optimized. Response to AA is linear in the 10 to 630 μM concentration range, and the detection limit is 4 μM (at a signal-to-noise ratio of 3:1). The modified electrode was applied to determine AA in vitamin C tablets and in spiked fruit juice.

Interference‐Free Electrochemical Detection of Nanomolar Dopamine Using Doped Polypyrrole and Silver Nanoparticles

This paper presents a new approach to detect dopamine in nanomolar range using an electrochemical sensor utilizing a composite made of chitosan‐stabilized silver nanoparticles and p‐toluene sulfonic acid‐doped ultrathin polypyrrole film. Studies included cyclic voltammogram, amperometry, differential pulse voltammetry and also investigation by electrochemical impedance spectroscopy. A detection limit of 0.58 nM was achieved in the linear range 1×10^?9 M to 1.2×10^?7 M. High sensitivity towards DA, good reproducibility and long‐term stability have been demonstrated without interference from ascorbic acid, uric acid, epinephrine, L ‐dopa, glucose. The sensing system was successfully applied for quantitative determination of dopamine in commercially available human blood serum.     

Amperometric Detection of Catecholamine Neurotransmitters Using Electrocatalytic Substrate Recycling at a Laccase Electrode

An enzyme electrode based on the coimmobilization of an osmium redox polymer and laccase on glassy carbon electrodes has been applied to ultra sensitive amperometric detection of the catecholamine neurotransmitters dopamine, epinephrine and norepinephrine, resulting in nanomolar detection limits, as low as 4 nM for dopamine. The sensitivity of the electrode is due to signal amplification via oxidation of the catecholamine by the immobilized laccase, which is regenerated by concomitant reduction of oxygen to water, coupled to the electrocatalytic re‐reduction of the oxidized catecholamine by the osmium redox complex: electrocatalytic substrate recycling. In addition because the sensor can be operated in reductive mode at ?0.2 V (vs. Ag/AgCl), noise and interferences are diminished. Combined with its high sensitivity this enzyme electrode also exhibited excellent selectivity allowing the detection of catecholamines in the presence of ascorbic acid. However, differentiation between the current responses achieved for the three catecholamines is not possible. The effective mode of constant recycling, resulting in amplification of the current response, of the laccase enzyme electrode sensor combined with the inherent advantages of using electrochemical techniques holds great promise for the future of catecholamine detection and monitoring.     

Glucose biosensor based on glucose oxidase immobilized on a nanofilm composed of mesoporous hydroxyapatite, titanium dioxide, and modified with multi-walled carbon nanotubes

We report on a highly sensitive glucose biosensor that was fabricated from a composite made from mesoporous hydroxyapatite and mesoporous titanium dioxide which then were ultrasonically mixed with multi-walled carbon nanotubes to form a rough nanocomposite film. This film served as a platform to immobilize glucose oxidase onto a glassy carbon electrode. The morphological and electrochemical properties of the film were examined by scanning electron microscopy and electrochemical impedance spectroscopy. Cyclic voltammetry and chronoamperometry were used to characterize the electrochemical performances of the biosensor which exhibited excellent electrocatalytic activity to the oxidation of glucose. At an operating potential of 0.3?V and pH 6.8, the sensor displays a sensitivity of 57.0?μA?mM^?1?cm^?2, a response time of <5?s, a linear dynamic range from 0.01 to 15.2?mM, a correlation coefficient of 0.9985, and a detection limit of 2?μM at an SNR of 3. No interferences are found for uric acid, ascorbic acid, dopamine and most carbohydrates. The sensor is stable and was successfully applied to the determination of glucose in real samples.

聚血红素修饰电极对儿茶酚类化合物和抗坏血酸氧化的电催化作用研究

电催化是化学修饰电极研究的中心课题之一,血红素是一种重要的铁卟啉化合物,其中的铁原子能够以两种价态存在．我们采用循环伏安法将血红素修饰于电极表面,得到了氧化还原体（ｒｅｄｏｘ）型化学修饰电极,并用于儿茶酚类化合物和抗坏血酸的电催化氧化研究．采用伏安法...     

ZrO2-Graphene-Chitosan nanocomposite modified carbon paste sensor for sensitive and selective determination of dopamine

A sensitive and stable electrochemical sensor was developed by modification of carbon paste electrode with ZrO₂/graphene/chitosan nanocomposite. The modified sensor served as a potential electrocatalytic platform for dopamine. Electrochemical impedance spectroscopy studies indicated reduction of charge transfer resistance at the modified electrode surface thereby facilitating the electron transfer process which resulted in higher current response to dopamine. The electrochemical behavior of dopamine at the modified electrode was studied using cyclic and square wave voltammetry. The maximum current response for the electro-oxidation of dopamine was observed at pH 7.4 and the process was realized to be diffusion controlled. The modified sensor demonstrated linearity in the range 1000–5000 nM, with high sensitivity (22 nA/nM), detection limit of 11.3 nM and selectivity for dopamine in the presence of ascorbic and uric acid which are found to co-exist with dopamine in physiological media. The method was employed for quantification of dopamine in a pharmaceutical formulation.     

DNA hybridization electrochemical biosensor using a functionalized polythiophene

A simple and label-free electrochemical sensor for recognition of the DNA sensor event was prepared by electrochemical polymerization of 4-hydroxyphenyl thiophene-3-carboxylate. Poly(4-hydroxyphenyl thiophene-3-carboxylate) (PHPT) was synthesized electrochemically onto glassy carbon electrode and characterized by cyclic voltammetry, FTIR and AFM measurements. An ODN-probe was physisorbed onto PHPT film and tested on hybridization with complementary ODN segments. A biological recognition can be monitored by comparison with electrochemical signal (cyclic voltammogram) of single and double strand state oligonucleotide. The oxidation current of double strand state oligonucleotide is lower than that of single strand, that is corresponding to the decrease of electroactivity of PHPT with the increase of stiffness of polymer structure. Physisorbed ODN-probe and its hybridization were observed morphologically onto ITO electrodes using AFM. The sensitivity of the electrochemical sensor is 0.02 μA/nmol, detection limit is 1.49 nmol and it has good selectivity.