A selective determination of levodopa in the presence of ascorbic acid and uric acid using a glassy carbon electrode modified with reduced graphene oxide

A selective determination of levodopa (LD) in the presence of ascorbic acid (AA) and uric acid (UA) has been investigated at a glassy carbon electrode modified with reduced graphene oxide (rGO). The graphene oxide was synthesized chemically by Hummers method and characterized by energy-filtered transmission electron microscopy (EF-TEM). The reduced graphene oxide modified glassy carbon electrode (rGO/GCE) showed excellent electrochemical performance in the simultaneous electrochemical detection of LD, AA, and UA due to the unique properties of graphene, such as large surface area, facile electronic transport and high electrocatalytic activity. The redox characteristics of rGO/GCE were investigated with cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Well-resolved oxidation peak potentials, corresponding to the oxidation of AA, LD, and UA, were observed from their mixture solution at 0.098, 0.285, and 0.423 V, respectively. The rGO/GCE showed that LD can be detected without the interference of AA and UA. Under the optimized conditions, the oxidation peak current of LD is linear with the concentration of LD from 2.0 to 100 μM with the detection limit of 1.13 μM (S/N = 3). The present electrode system was also successfully applied to direct determination of LD in commercially available tablets and urine samples.     

Electrochemical synthesis and characterization of a novel thiazole-based copolymer and its application in biosensor

A novel copolymer based on 2-aminothiazole (AT) and 2-amino-4-thiazoleacetic acid (ATA) is electrochemically synthesized and then characterized using UV–visible absorption spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and electrochemical techniques. The results confirmed that the obtained polymer was a copolymer rather than a blend or a composite of the respective homopolymers and could improve the electrochemical response of both positively and negatively charged analytes. Therefore, the copolythiazole film was applied to determine ascorbic acid (AA), dopamine (DA) and uric acid (UA). It is found that the peak separating degrees and peak currents of AA, DA and UA at copolythiazole modified electrode were much better than those at bare GCE. Under the optimum conditions, the linear calibration curves were obtained in the range of 10–2000 μM for AA, 1–150 μM for DA, 1–180 μM for UA. The detection limits of AA, DA and UA were 2, 0.04 and 0.4 μM, respectively (S/N = 3). The practical application of the modified electrode was demonstrated by the determination of UA in urine sample.     

聚ABSA修饰电极对多巴胺、抗坏血酸、尿酸的同时测定

采用电聚合的方法制备了聚对氨基苯磺酸修饰电极（pABSA/GCE）,并采用循环伏安法和线性扫描方法分别对多巴胺（DA）,抗坏血酸（AA）,尿酸（UA）以及三者的混合液进行了测定,研究了该修饰电极的电化学行为。结果表明,pABSA/GCE对AA,DA,UA有良好的电催化作用。在混合液的测定中,三者可以很好的分离,AA-DA、DA-UA、AA-UA的峰电位差分别为265 mV,146 mV和411 mV。该pABSA/GCE修饰电极既用于混合液中AA、DA和UA的分别测定也可以用于三者的同时测定,电极重现性和稳定性良好。     

Separation and concentration effect of f-MWCNTs on electrocatalytic responses of ascorbic acid, dopamine and uric acid at f-MWCNTs incorporated with poly (neutral red) composite films

A novel conductive composite film containing functionalized multi-walled carbon nanotubes (f-MWCNTs) with poly (neutral red) (PNR) was synthesized on glassy carbon electrodes (GC) by potentiostatic method. The composite film exhibited promising electrocatalytic oxidation of mixture of biochemical compounds such as ascorbic acid (AA), dopamine (DA) and uric acid (UA) in pH 4.0 aqueous solutions. It was also produced on gold electrodes by using electrochemical quartz crystal microbalance technique, which revealed that the functional properties of composite film were enhanced because of the presence of both f-MWCNTs and PNR. The surface morphology of the polymer and composite film deposited on transparent semiconductor tin oxide electrodes were studied using scanning electron microscopy and atomic force microscopy. These two techniques showed that the PNR was fibrous and incorporated on f-MWCNTs. The electrocatalytic responses of neurotransmitters at composite films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). These experiments revealed that the difference in f-MWCNTs loading present in the composite film affected the electrocatalysis in such a way, that higher the loading showed an enhanced electrocatalytic activity. From further electrocatalysis studies, well separated voltammetric peaks were obtained at the composite film modified GC for AA, DA and UA with the peak separation of 0.17 V between AA-DA and 0.15 V between DA-UA. The sensitivity of the composite film towards AA, DA and UA in DPV technique was found to be 0.028, 0.146 and 0.084 μA μM⁻¹, respectively.     

Simultaneous determination of ascorbic acid, dopamine and uric acid by use of a MWCNT modified carbon-ceramic electrode and differential pulse voltammetry

Multi walled carbon nanotube modified carbon-ceramic electrode (MWCNT/CCE) was employed for the simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). The MWCNT/CCE displayed very good electrochemical catalytic activities with respect to CCE. The oxidation over-potentials of AA, DA and UA decreased dramatically, and their oxidation peak currents increased significantly at MWCNT/CCE compared to those obtained at the bare CCE. Differential pulse voltammetry was used for the simultaneous determination of AA, DA and UA in their ternary mixture. The peak separation between AA and DA, and DA and UA was large up to 205 and 160 mV, respectively. The calibration curves for AA, DA and UA were obtained in the range of 15.00-800.00, 0.50-100.00, and 0.55-90.00 μM, respectively. The detection limits (S/N = 3) were 7.71, 0.31, and 0.42 μM for AA, DA and UA, respectively.The present method was applied to the determination of AA, DA and UA in human serum and some commercial pharmaceutical samples, using standard adding method and the results were quite promising.     

Selective detection of dopamine using a functionalised polyaniline composite electrode

The behaviour of a poly (aniline boronic acid) (PABA) modified glassy carbon electrode (GCE) for the detection of dopamine (DA) in the presence of excess of ascorbic acid (AA) using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques is investigated. On bare GCE, both DA and AA are oxidized at ~0.16 V, whereas on PABA modified GCE they are oxidized at 0.2 and 0.054 V, respectively. Though PABA favours DA oxidation through ester formation with boronic acid motif, the AA oxidation is also promoted by polyaniline backbone through the involvement of AA in the redox of polyaniline. Since both DA and AA undergo oxidation at closely spaced potentials at a PABA electrode, Nafion®-incorporation into the PABA film was examined for selective determination of DA in the presence of AA. The selectivity was due to accumulation of DA on the electrode surface through ester formation with the boronic acid group and suppression of AA oxidative current through charge discrimination by Nafion.     

Simultaneous determination of dopamine and uric acid on nafion/sodium dodecylbenzenesulfonate composite film modified glassy carbon electrode

A novel electrochemical sensor has been constructed by using a glassy carbon electrode (GCE) coated with nafion/sodium dodecylbenzenesulfonate (SDBS). Differential pulse voltammetry (DPV) was used to study the electrochemical behaviors of dopamine (DA) and uric acid (UA). An optimum of 5 mM SDBS together with 0.05 wt% of nafion was used to improve the resolution and the determination sensitivity successfully. In 0.1 M phosphate buffer solution (pH 6.5), the modified electrode exhibited high electrocatalytical activity toward the oxidation of DA and UA with obvious reduction of overpotential. Compared with bare GCE, the modified electrode resolved the voltammetric response of DA and UA into two well-defined voltammetric peaks by DPV, which can be used for simultaneous determination of these species in mixture. The peak currents obtained from DPV were linearly related to the concentrations of DA and UA in the ranges of 4.0 × 10⁻⁷–8.0 × 10⁻⁵ M and 4.0 × 10⁻⁶–8.0 × 10⁻⁴ M, respectively. The detection limit of DA and UA (signal-to-noise ration was 3) were 5.0 × 10⁻⁸ and 4.0 × 10⁻⁷ M, respectively.     

A mesoporous carbon nanofiber-modified pyrolytic graphite electrode used for the simultaneous determination of dopamine,uric acid,and ascorbic acid

A mesoporous carbon nanofiber-modified pyrolytic graphite electrode (MCNF/PGE) has been prepared and applied to the simultaneous electrochemical determination of dopamine (DA), uric acid (UA) and ascorbic acid (AA). The oxidation overpotentials of these biomolecules decrease significantly, the overlapping of these peaks in bare PGE is well resolved, and their anodic peak currents increase dramatically in MCNF/PGE due to the large amount of edge-plane-like defects, large surface area and especially the mesoporous structure of MCNFs. Using this method, anodic currents of DA, UA and AA are linear with their concentration in the range of 0.05–30 μM, 0.5–120 μM and 0.1–10 mM, respectively, with detection limits of 0.02, 0.2 and 50 μM. The good sensitivity and reproducibility of the proposed electrode make it be used as a good electrochemical sensor for the simultaneous determination of DA, UA and AA in real sample analysis.     

Layer‐by‐layer self‐assembled multilayer films of single‐walled carbon nanotubes and tin disulfide nanoparticles with chitosan for the fabrication of biosensors

In this study, multilayer films containing chitosan, tin disulfide (SnS₂) nanoparticles, and single‐walled carbon nanotubes were prepared on glassy carbon electrodes with the use of a layer‐by‐layer assembly technique. The resulting films were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy, and ultraviolet–visible absorption spectroscopy. The results of CV and EIS indicates that the peak currents and charge‐transfer resistance all had linear responses to the number of assembled layers. The multilayer‐film‐modified electrode showed excellent electrocatalytic properties for some species, such as dopamine hydrochloride (DA), ascorbic acid (AA), and uric acid (UA). The well‐separated voltammetric signals of DA, UA, and AA could be obtained on the assembled multilayer‐film‐modified electrode, and the peak‐to‐peak potential separations were 171, 136, and 307 mV for DA–UA, DA–AA, and UA–AA on CV, respectively. These facts showed that the multilayer‐film‐modified electrode could be used as a new sensor for the simultaneous detection of DA and UA in the presence of AA in a real sample. In addition, the multilayer films were stable, selective, and reproducible. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrocatalytic oxidation and simultaneous determination of uric acid and ascorbic acid on the gold nanoparticles-modified glassy carbon electrode

A new gold nanoparticles-modified electrode (GNP/LC/GCE) was fabricated by self-assembling gold nanoparticles to the surface of the l-cysteine-modified glassy carbon electrode. The modified electrode showed an excellent character for electrocatalytic oxidization of uric acid (UA) and ascorbic acid (AA) with a 0.306 V separation of both peaks, while the bare GC electrode only gave an overlapped and broad oxidation peak. The anodic currents of UA and AA on the modified electrode were 6- and 2.5-fold to that of the bare GCE, respectively. Using differential pulse voltammetry (DPV), a highly selective and simultaneous determination of UA and AA has been explored at the modified electrode. DPV peak currents of UA and AA increased linearly with their concentration at the range of 6.0 × 10⁻⁷ to 8.5 × 10⁻⁴ mol L⁻¹ and 8.0 × 10⁻⁶ to 5.5 × 10⁻³ mol L⁻¹, respectively. The proposed method was applied for the detection of UA and AA in human urine with satisfactory result.     

Enhanced electrochemical response in oxidative differential pulse voltammetry of dopamine in the presence of ascorbic acid at carboxyl-terminated boron-doped diamond electrodes

The differential pulse voltammetric (DPV) peak for dopamine (DA) oxidation was found to be highly amplified by the addition of ascorbic acid (AA) when carboxyl-terminated boron-doped diamond (BDD) electrodes were used as the working electrode. The DP voltammogram for a solution containing DA and AA obtained using a 4-pentenoic acid-modified BDD (4PA-BDD) electrode showed well-separated oxidation peaks for DA and AA at 0.4 and 0.6 V vs. Ag/AgCl, respectively. In addition, as the DA concentration increased at constant AA concentration, a simultaneous increase in the DA peak current density and decrease in the AA peak current density were observed. The slope of the calibration curve for the [DA] range of 1-10 μM in the presence of AA (500 μM) was seven times larger than that obtained in the absence of AA. Such an enhancement was found to be more efficient at 4PA-BDD than at oxidized-BDD, partly due to simple electrostatic effects and partly due to suppression of the polymerization of DA oxidation products by the terminal carboxyl groups. The enhanced detection method using a carboxyl-terminated BDD electrode should be an effective analytical tool, especially for determining low concentrations of DA in the presence of high concentrations of AA.     

Electrochemical characterization of poly(eriochrome black T) modified glassy carbon electrode and its application to simultaneous determination of dopamine, ascorbic acid and uric acid

A polymerized film of eriochrome black T (EBT) was prepared on the surface of a glassy carbon (GC) electrode in alkaline solution by cyclic voltammetry (CV). The redox response of the poly(EBT) film at the GC electrode appeared in a couple of redox peak in 0.1 M hydrochloride and the pH dependent peak potential was −55.1 mV/pH which was close to the Nernst behavior. The poly(EBT) film-coated GC electrode exhibited excellent electrocatalytic activity towards the oxidations of dopamine (DA), ascorbic acid (AA) and uric acid (UA) in 0.05 mM phosphate buffer solution (pH 4.0) and lowered the overpotential for oxidation of DA. The polymer film modified GC electrode conspicuously enhanced the redox currents of DA, AA and UA, and could sensitively and separately determine DA at its low concentration (0.1 μM) in the presence of 4000 and 700 times higher concentrations of AA and UA, respectively. The separations of anodic peak potentials of DA-AA and UA-DA reached 210 mV and 170 mV, respectively, by cyclic voltammetry. Using differential pulse voltammetry, the calibration curves for DA, AA and UA were obtained over the range of 0.1-200 μM, 0.15-1 mM and 10-130 μM, respectively. With good selectivity and sensitivity, the present method provides a simple method for selective detection of DA, AA and UA in biological samples.     

Monolayer covalent modification of 5-hydroxytryptophan on glassy carbon electrodes for simultaneous determination of uric acid and ascorbic acid

5-Hydroxytryptophan (5-HTP) was covalently grafted on the surface of glassy carbon electrodes (GCEs) using cyclic voltammetric method in a phosphate buffer solution. The prepared electrode, denoded as 5-HTP/GCE, was characterized by X-ray photoelectron spectroscopy, cyclic voltammetry and differential pulse voltammetry (DPV). Tryptophan grafted GCE (TRP/GCE) and 5-hydroxytryptamine grafted GCE (5-HTP/GCE) were also prepared by the same method for comparison. It was found that the electrocatalytic activities toward the oxidation of uric acid (UA) and ascorbic acid (AA) was in the order of 5-HT/GCE > 5-HTP/GCE > TRP/GCE for UA oxidation and 5-HT/GCE = 5-HTP/GCE > TRP/GCE for AA oxidation. However, the CV current sensitivity was estimated as 4:2:1 for 5-HTP/GCE:5-HT/GCE:TRP/GCE. The DPV peaks for UA and AA oxidation appeared at 0.07 V and 0.34 V versus SCE, respectively, allowing simultaneous determination in mixtures. A linearly response in the range of: 5.0 × 10⁻⁷ to 1.1 × 10⁻⁵ M with the detection limit (s/n = 3) of 2.8 × 10⁻⁷ M for UA determination, and a linear response in the range of: 5.0 × 10⁻⁶ to 1.0 × 10⁻⁴ M with the detection limit of 4.2 × 10⁻⁶ M for AA determination were obtained. This electrode was used for UA and AA determinations in human urine samples satisfactorily.     

Controllable synthesis of nitrogen-doped graphene and its effect on the simultaneous electrochemical determination of ascorbic acid,dopamine, and uric acid

A simple, low-cost method for fabricating nitrogen-doped graphene (NG) is demonstrated by combining the ultrafast thermal exfoliation and covalent transformation from the melamine (MA)–graphene oxide (GO) mixture. NGs prepared at 300, 600, and 900 °C were systematically characterized by X-ray photoelectron spectroscopy (XPS), in which pyridinic-N, pyrrolic-N and graphitic-N are the main nitrogen-doped structures in various ratios. These NGs possess large specific surface area and porous microstructures, confirmed by the N₂ adsorption–desorption isotherms. The NG-modified screen-printed carbon electrodes (SPCEs) were fabricated to detect ascorbic acid (AA), dopamine (DA) and uric acid (UA) simultaneously by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). Due to the large specific surface area, mesoporous structures and nitrogen-doped sites, these NGs show highly electrochemical sensitivity for AA, DA and UA. Notably, the pyrrolic-N structure makes the negative shift in the oxidation peak potential of these biomolecules, showing the better catalytic activity than pyridinic-N and graphitic-N structures. The large surface area of NGs provides more nitrogen-doped sites to oxidize bio-compounds and enhances the corresponding currents. The good sensitivity of NG-modified SPCEs makes them become effective sensors for determining AA, DA and UA simultaneously. The discrimination to peak potential and current among these NGs can be observed.     

The influence of organization of LbL films containing a silsesquioxane polymer on the electrochemical response of dopamine

This paper describes the construction, evaluation, and application of an electrochemical sensor for the determination of dopamine (DA) in the presence of ascorbic acid (AA) and uric acid (UA). Satisfactory results were achieved for the simultaneous determination of DA and UA, it was verified that it is possible to detect AA in the presence of DA, but high concentrations of AA interfere in detection of DA. The sensor was constructed using the layer-by-layer (LbL) technique with the modification of the surface of indium tin oxide coated glass (ITO) substrate with nanostructured films comprising a 3-n-propylpyridinium silsesquioxane polymer (SiPy⁺Cl^?) and nickel(II) tetrasulfophthalocyanine (NiTsPc). Using the square wave voltammetry technique (SWV), the LbL modified electrodes produced at different pHs (pH 2 and 8) were used to determine DA in the presence UA, and the electrochemical responses of the electrodes were compared. It was observed that the electrodes with the highest concentration of monomeric species showed the highest current intensity and the lowest peak potential for the DA and UA analytes in analysis of DA and UA, individually and simultaneously, with peak potential separation of 460 mV versus Ag/AgCl. Applying SWV, a linear dynamic range of 10–99 μmol L^?1 and 100–900 μmol L^?1 with detection limit of 16.8 μmol L^?1 and 58.3 μmol L^?1 was obtained for DA and UA, respectively. The method has good selectivity and sensitivity, and it was successfully applied to the simultaneous determination of DA and UA in spiked human urine sample.     

Development of an amperometric sensor for simultaneous determination of uric acid and ascorbic acid using 2-[bis(2-aminoethyl)amino]ethanol, 4,4′-bipyridine bridged dicopper(II) complex

Binuclear copper complex (2-[bis(2-aminoethyl)amino]ethanol, 4,4′-bipyridine bridged dicopper(II) complex) was grafted onto the surface of a glassy carbon electrode (GCE) using the cyclic voltammetric method in a phosphate buffer solution (PBS). The modified electrode resulted in efficient electrocatalytic activity for anodic oxidation of uric acid (UA) and ascorbic acid (AA) via a substantial decrease in anodic over-potentials for both compounds. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) using this modified electrode result in two well-resolved anodic waves for the oxidation of UA and AA in mixed solution, making possible the simultaneous determination of both compounds. Linear analytical curves were obtained in the ranges 5.0–300.0 μM and 5.0–160.0 μM for UA and AA concentrations through DPV methods, respectively. The detection limits were 2.0 μM of UA and AA. This electrode was used for UA and AA determinations in urine samples with satisfactory results.     

Electrochemical detection of acetaminophen on the functionalized MWCNTs modified electrode using layer-by-layer technique

A selective electrochemical method is fabricated via layer-by-layer (LBL) method using both positively and negatively charged multi walled carbon nanotubes (MWCNTs) on poly (diallyldimetheylammonium chloride) (PDDA)/poly styrene sulfonate (PSS) modified graphite electrode, for the determination of acetaminophen (ACT) in the presence of dopamine (DA) and high concentration of ascorbic acid (AA). The modified electrode was characterized by cyclic voltammetry (CV) electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Experimental conditions such as pH, accumulation potential and time, effect of potential sweep rates and interferents were studied. In CV well defined peaks for AA, ACT and DA are obtained at 24, 186 and 374 mV, respectively. The separations of peaks were 210, 188 and 398 mV between AA and DA, DA and ACT and AA and ACT, respectively. The diffusion coefficient was calculated by chronocoulometric. Chronoamperometric studies showed the linear relationship between oxidation peak current and concentration of ACT in the range 25–400 μM (R = 0.9991). The detection limit was 5 × 10⁻⁷ mol/L. The proposed method gave satisfactory results in the determination of ACT in pharmaceutical and human serum samples.     

Electrochemical preparation of poly(bromothymol blue) film and its analytical application

The poly(bromothymol blue) film was prepared using a simple cyclic voltammetry method. Field emission scanning electron microscopy and electrochemical methods were employed to characterize this film. When the film was electropolymerized on an electrode, it showed excellent catalytic activity toward the oxidation of dopamine (DA) in pH 4.0 phosphate buffer solution. In addition, the overlapped voltammetric responses of dopamine and ascorbic acid were resolved into two well-defined peaks by the film-modified electrode with a large peak separation of 0.17 V. A calibration curve for DA was obtained by the amperometric method in the range of 3.0–195.0 μM with a correlation coefficient of 0.9997. The film-modified electrode has been successfully used to measure the concentration of DA in injections and human serum samples.     

Simultaneous voltammetric determination of dopamine and adenosine using a single walled carbon nanotube – Modified glassy carbon electrode

The simultaneous voltammetric determination of adenosine (ADS) and dopamine (DA) using a single wall carbon nanotube (SWCNT) modified glassy carbon electrode (GCE) is reported. This has physiological importance in controlling Parkinson’s disease. In phosphate buffer medium of pH 7.2, the concentration vs. peak current plots were linear in the range 1–100 μM for ADS and DA. A comparison of the voltammetric response of DA at acid-treated (purified and super-purified) and untreated SWCNT modified GCE indicates that the oxidation peak current of DA decreases considerably at the treated SWCNT modified GCE. This indicates that metallic impurities in nanotubes play a large role in enhancing the electrochemical current. The detection limit (3σ) and sensitivity observed for ADS and DA were 34.7 μM, 7 μM and 9.5 nA μM⁻¹, 77.9 nA μM⁻¹, respectively.     

Selective determination of dopamine in the presence of ascorbic acid using ferrocenyl-tethered PAMAM dendrimers modified glassy carbon electrode

Determination of dopamine (DA) in the absence and presence of ascorbic acid (AA) by ferrocenyl-tethered PAMAM G3 dendrimers (Fc-D) modified glassy carbon electrode (GCE) was reported. The modified electrode was characterized with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Factors influencing the detection processes were optimized and kinetic parameters were calculated. The sensor exhibited excellent catalytic activities for the oxidation–reduction reactions of DA and eliminated the interference of AA. Under optimal condition, the linear range of 1 × 10⁻⁵–1.5 × 10⁻³ mol L⁻¹ and the detection limit of 4.7 × 10⁻⁶ mol L⁻¹ was obtained. This study provides a new idea for the determination of DA in the presence of AA.