Electrochemical synthesis of polyaniline nano-networks on p-aminobenzene sulfonic acid functionalized glassy carbon electrode Its use for the simultaneous determination of ascorbic acid and uric acid

A composite film of polyaniline (PAN) nano-networks/p-aminobenzene sulfonic acid (ABSA) modified glassy carbon electrode (GCE) has been fabricated via an electrochemical oxidation procedure and applied to the electro-catalytic oxidation of uric acid (UA) and ascorbic acid (AA). The ABSA monolayer at GCE surface has been characterized by X-ray photo-electron spectroscopy (XPS) and electrochemical techniques. Atomic force microscopy (AFM), field emission scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), UV-visible absorption spectra (UV-vis) and cyclic voltammetry (CV) have been used to investigate the PAN-ABSA composite film, which demonstrates the formation of the composite film and the maintenance of the electroactivity of PAN in neutral and even in alkaline media. Due to its different catalytic effects towards the electro-oxidation of UA and AA, the modified GCE can resolve the overlapped voltammetric response of UA and AA into two well-defined voltammetric peaks with both CV and differential pulse voltammetry (DPV), which can be used for the selective and simultaneous determination of these species in a mixture. The catalytic peak currents are linearly dependent on the concentrations of UA and AA in the range of 50-250 and 35-175mumoll(-1) with correlation coefficients of 0.997 and 0.998, respectively. The detection limits for UA and AA are 12 and 7.5mumoll(-1), respectively. Besides the good stability and reproducibility of PAN-ABSA/GCE due to the covalent attachment of ABSA at GCE surface, the modified electrode also exhibits good sensitivity and selectivity.     

Simultaneous voltammetric detection of dopamine and uric acid at their physiological level in the presence of ascorbic acid using poly(acrylic acid)-multiwalled carbon-nanotube composite-covered glassy-carbon electrode

The use of poly(acrylic acid) (PAA)-multiwalled carbon-nanotubes (MWNTs) composite-coated glassy-carbon disk electrode (GCE) (PAA-MWNTs/GCE) for the simultaneous determination of physiological level dopamine (DA) and uric acid (UA) in the presence of an excess of ascorbic acid (AA) in a pH 7.4 phosphate-buffered solution was proposed. PAA-MWNTs composite was prepared by mixing of MWNTs powder into 1 mg/ml PAA aqueous solution under sonication. GCE surface was modified with PAA-MWNTs film by casting. AA demonstrates no voltammetric peak at PAA-MWNTs/GCE. The PAA-MWNTs composite is of a high surface area and of affinity for DA and UA adsorption. DA exhibits greatly improved electron-transfer rate and is electro-catalyzed at PAA-MWNTs/GCE. Moreover, the electro-catalytic oxidation of UA at PAA-MWNTs/GCE is observed, which makes it possible to detect lower level UA. Therefore, the enhanced electrocatalytic currents for DA and UA were observed. The anodic peak currents at approximately 0.18 V and 0.35 V increase with the increasing concentrations of DA and UA, respectively, which correspond to the voltammetric peaks of DA and UA, respectively. The linear ranges are 40 nM to 3 microM DA and 0.3 microM to 10 microM UA in the presence of 0.3 mM AA. The lowest detection limits (S/N=3) were 20 nM DA and 110 nM UA.     

The electrochemical modification of clenbuterol for biosensors of dopamine, norepinephrine, adrenalin, ascorbic acid and uric acid at paraffin-impregnated graphite electrode

The electrochemical modification of clenbuterol (CLB) was studied at paraffin-impregnated graphite electrode (WGE) in two potential ranges of 0.0-1.6V and -1.2 to 1.2V. Various methods including X-ray photoelectron spectroscopy (XPS), UV-spectroelectrochemistry, infrared (IR) spectra and electrochemical techniques have been used to characterizing the modification. Clenbuterol can be modified at the electrode surface by carbon-nitrogen linkage or carbon-carbon linkage in 0.0-1.6V or -1.2 to 1.2V, respectively. The electrochemical behaviors of dopamine (DA), norepinephrine (NE), adrenalin (EP), ascorbic acid (AA) and uric acid (UA) were studied at clenbuterol-modified paraffin-impregnated graphite electrode (CLB/WGE), and it was found that all these compounds could be detected successfully.     

Simultaneous determination of catecholamines, uric acid and ascorbic acid at physiological levels using poly(N-methylpyrrole)/Pd-nanoclusters sensor

An interesting electrochemical sensor has been constructed by the electrodeposition of palladium nanoclusters (Pd_nano) on poly(N-methylpyrrole) (PMPy) film-coated platinum (Pt) electrode. Cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy were used to characterize the properties of the modified electrode. It was demonstrated that the electroactivity of the modified electrode depends strongly on the electrosynthesis conditions of the PMPy film and Pd_nano. Moreover, the modified electrode exhibits strong electrocatalytic activity toward the oxidation of a mixture of dopamine (DA), ascorbic acid (AA), and uric acid (UA) with obvious reduction of overpotentials. The simultaneous analysis of this mixture at conventional (Pt, gold [Au], and glassy carbon) electrodes usually struggles. However, three well-resolved oxidation peaks for AA, DA, and UA with large peak separations allow this modified electrode to individually or simultaneously analyze AA, DA, and UA by using differential pulse voltammetry (DPV) with good stability, sensitivity, and selectivity. This sensor is also ideal for the simultaneous analysis of AA, UA and either of epinephrine (E), norepinephrine (NE) or l-DOPA. Additionally, the sensor shows strong electrocatalytic activity towards acetaminophen (ACOP) and other organic compounds. The calibration curves for AA, DA, and UA were obtained in the ranges of 0.05 to 1 mM, 0.1 to 10 μM, and 0.5 to 20 μM, respectively. The detection limits (signal/noise [S/N] = 3) were 7 μM, 12 nM, and 27 nM for AA, DA, and UA, respectively. The practical application of the modified electrode was demonstrated by measuring the concentrations of AA, DA, and UA in injection sample, human serum, and human urine samples, respectively, with satisfactory results. The reliability and stability of the modified electrode gave a good possibility for applying the technique to routine analysis of AA, DA, and UA in clinical tests.     

Simultaneous voltammetric measurement of ascorbic acid, epinephrine and uric acid at a glassy carbon electrode modified with caffeic acid

A stable electroactive thin film of poly(caffeic acid) has been deposited on the surface of a glassy carbon electrode by potentiostatic technique in an aqueous solution containing caffeic acid. Poly(caffeic acid) was used as a modified electrode for the detection of ascorbic acid (AA), epinephrine (EP), uric acid (UA) and their mixture by cyclic voltammetry. This modified electrode exhibits potent and persistent electron-mediating behavior followed by well-separated oxidation peaks towards AA, EP and UA with activation overpotential. For the ternary mixture containing AA, EP and UA, the three compounds can well separate from each other at the scan rate of 20 mVs(-1) with a potential difference of 156, 132 and 288 mV between AA and EP, EP and UA and AA and UA, respectively, which was large enough to determine AA, EP and UA individually and simultaneously. The catalytic peak current obtained, was linearly dependent on the AA, EP and UA concentrations in the range of 2.0 x 10(-5) to 1.0 x 10(-3) mol l(-1), 2.0 x 10(-6) to 8.0 x 10(-5) mol l(-1) and 5.0 x 10(-6) to 3.0 x 10(-4) mol l(-1), and the detection limits for AA, EP and UA were 7.0 x 10(-6), 2.0 x 10(-7) and 6.0 x 10(-7) mol l(-1), respectively. The modified electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of EP in practical injection samples and that of EP, UA and AA simultaneously with satisfactory results.     

Hollow nitrogen-doped carbon microspheres pyrolyzed from self-polymerized dopamine and its application in simultaneous electrochemical determination of uric acid, ascorbic acid and dopamine

Hollow nitrogen-doped carbon microspheres (HNCMS) as a novel carbon material have been prepared and the catalytic activities of HNCMS-modified glassy carbon (GC) electrode towards the electro-oxidation of uric acid (UA), ascorbic acid (AA) and dopamine (DA) have also been investigated. Comparing with the bare GC and carbon nanotubes (CNTs) modified GC (CNTs/GC) electrodes, the HNCMS modified GC (HNCMS/GC) electrode has higher catalytic activities towards the oxidation of UA, AA and DA. Moreover, the peak separations between AA and DA, and DA and UA at the HNCMS/GC electrode are up to 212 and 136 mV, respectively, which are superior to those at the CNTs/GC electrode (168 and 114 mV). Thus the simultaneous determination of UA, AA and DA was carried out successfully. In the co-existence system of UA, AA and DA, the linear response range for UA, AA and DA are 5-30 μM, 100-1000 μM and 3-75 μM, respectively and the detection limits (S/N = 3) are 0.04 μM, 0.91 μM and 0.02 μM, respectively. Meanwhile, the HNCMS/GC electrode can be applied to measure uric acid in human urine, and may be useful for measuring abnormally high concentration of AA or DA. The attractive features of HNCMS provide potential applications in the simultaneous determination of UA, AA and DA.     

The simultaneous electrochemical detection of ascorbic acid, dopamine, and uric acid using graphene/size-selected Pt nanocomposites

In this study, a graphene/Pt-modified glassy carbon (GC) electrode was created to simultaneously characterize ascorbic acid (AA), dopamine (DA), and uric acid (UA) levels via cyclic voltammetry (CV) and differential pulse voltammetry (DPV). During the preparation of the nanocomposite, size-selected Pt nanoparticles with a mean diameter of 1.7 nm were self-assembled onto the graphene surface. In the simultaneous detection of the three aforementioned analytes using CV, the electrochemical potential differences among the three detected peaks were 185 mV (AA to DA), 144 mV (DA to UA), and 329 mV (AA and UA), respectively. In comparison to the CV results of bare GC and graphene-modified GC electrodes, the large electrochemical potential difference that is achieved via the use of the graphene/Pt nanocomposites is essential to the distinguishing of these three analytes. An optimized adsorption of size-selected Pt colloidal nanoparticles onto the graphene surface results in a graphene/Pt nanocomposite that can provide a good platform for the routine analysis of AA, DA, and UA.     

Uric acid determination in the presence of ascorbic acid using self-assembled submonolayer of dimercaptothiadiazole-modified gold electrodes

This article reports the determination of uric acid (UA) in the presence of ascorbic acid (AA) using a self-assembled submonolayer of heteroaromatic dithiol, 2,5-dimercapto-1,3,4-thiadiazole (DMcT), on gold (Au) electrode. Submonolayer to multilayers of DMcT can be prepared on Au electrode by varying the soaking time of Au electrode in 1mM aqueous solution of DMcT. The formation of submonolayer, monolayer, and multilayers of DMcT on Au electrode was confirmed from its reductive desorption measurements and electrochemical blocking behavior toward ferricyanide. Interestingly, submonolayer of DMcT separates the voltammetric signal of UA from AA by 210 mV, whereas monolayer and multilayers of DMcT fail to separate them. The voltammetric signals of AA and UA are highly stable and reproducible at submonolayer of DMcT. Fast electron transfer, weak hydrogen bonding interactions with AA and UA, and prevention of fouling effect caused by oxidized product of AA can be achieved at submonolayer of DMcT, and thus it successfully separates the voltammetric signals of AA and UA. The practical application of the current system is demonstrated by measuring the concentration of UA in human urine samples without any treatment.     

Simultaneous electrochemical determination of dopamine, uric acid and ascorbic acid using palladium nanoparticle-loaded carbon nanofibers modified electrode

Palladium nanoparticle-loaded carbon nanofibers (Pd/CNFs) were prepared by electrospinning and subsequent thermal treatment processes. Pd/CNFs modified carbon paste electrode (Pd/CNF-CPE) displayed excellent electrochemical catalytic activities towards dopamine (DA), uric acid (UA) and ascorbic acid (AA). The oxidation overpotentials of DA, UA and AA were decreased significantly compared with those obtained at the bare CPE. Differential pulse voltammetry was used for the simultaneous determination of DA, UA and AA in their ternary mixture. The peak separation between UA and DA, DA and AA was 148 mV and 244 mV, respectively. The calibration curves for DA, UA and AA were obtained in the range of 0.5-160 microM, 2-200 microM, and 0.05-4mM, respectively. The lowest detection limits (S/N=3) were 0.2 microM, 0.7 microM and 15 microM for DA, UA and AA, respectively. With good selectively and sensitivity, the present method was applied to the determination of DA in injectable medicine and UA in urine sample.     

Simultaneous determination of dopamine, ascorbic acid, and uric acid using carbon ionic liquid electrode

A recently constructed carbon composite electrode using room temperature ionic liquid as pasting binder was employed as a novel electrode for sensitive, simultaneous determination of dopamine (DA), ascorbic acid (AA), and uric acid (UA). The apparent reversibility and kinetics of the electrochemical reaction for DA, AA, and UA found were improved significantly compared to those obtained using a conventional carbon paste electrode. The results show that carbon ionic liquid electrode (CILE) reduces the overpotential of DA, AA, and UA oxidation, without showing any fouling effect due to the deposition of their oxidized products. In the case of DA, the oxidation and reduction peak potentials appear at 210 and 135mV (vs Ag/AgCl, KCl, 3.0M), respectively, and the CILE shows a significantly better reversibility for dopamine. The oxidation peak due to the oxidation of AA occurs at about 60mV. For UA, a sharp oxidation peak at 340mV and a small reduction peak at 250mV are obtained at CILE. Differential pulse voltammetry was used for the simultaneous determination of ternary mixtures of DA, AA, and UA. Relative standard deviation for DA, AA, and UA determinations were less than 3.0% and DA, AA, and UA can be determined in the ranges of 2.0x10(-6)-1.5x10(-3), 5.0x10(-5)-7.4x10(-3), and 2.0x10(-6)-2.2x10(-4)M, respectively. The method was applied to the determination of DA, AA, and UA in human blood serum and urine samples.     

Selective detection of uric acid in the presence of ascorbic acid at physiological pH by using a beta-cyclodextrin modified copolymer of sulfanilic acid and N-acetylaniline

A beta-cyclodextrin (CD) modified copolymer membrane of sulfanilic acid (p-ASA) and N-acetylaniline (SPNAANI) on glassy carbon electrode (GCE) was prepared and used to determine uric acid (UA) in the presence of a large excess of ascorbic acid (AA) by differential pulse voltammetry (DPV). The properties of the copolymer were characterized by X-ray photoelectron spectra (XPS) and Raman spectroscopy. The oxidation peaks of AA and UA were well separated at the composite membrane modified electrode in phosphate buffer solution (PBS, pH 7.4). A linear relationship between the peak current and the concentration of UA was obtained in the range from 1.0 x 10(-5) to 3.5 x 10(-4)mol L(-1), and the detection limit was 2.7 x 10(-6)mol L(-1) at a signal-to-noise ratio of 3. Two hundred and fifty-fold excess of AA did not interfere with the determination of UA. The application of the prepared electrode was demonstrated by measuring UA in human serum samples without any pretreatment, and the results were comparatively in agreement with the spectrometric clinical assay method.     

Selective electrochemical sensor for folic acid at physiological pH using ultrathin electropolymerized film of functionalized thiadiazole modified glassy carbon electrode

This paper demonstrated the selective determination of folic acid (FA) in the presence of important physiological interferents, ascorbic acid (AA) and uric acid (UA) at physiological pH using electropolymerized film of 5-amino-2-mercapto-1,3,4-thiadiazole (p-AMT) modified glassy carbon (GC) electrode. Bare GC electrode fails to determine the concentration of FA in the presence of AA and UA due to the surface fouling caused by the oxidized products of AA and FA. However, the p-AMT film modified electrode not only separates the voltammetric signals of AA, UA and FA with potential differences of 170 and 410 mV between AA–UA and UA–FA, respectively but also shows higher oxidation current for these analytes. The p-AMT film modified electrode displays an excellent selectivity towards the determination of FA even in the presence of 200-fold AA and 100-fold UA. Using amperometric method, we achieved the lowest detection of 75 nM UA and 100 nM each AA and FA. The amperometric current response was increased linearly with increasing FA concentration in the range of 1.0 × 10⁻⁷–8.0 × 10⁻⁴ M and the detection limit was found to be 2.3 × 10⁻¹⁰ M (S/N = 3). The practical application of the present modified electrode was successfully demonstrated by determining the concentration of FA in human blood serum samples.     

Electrochemical determination of uric acid at ordered mesoporous carbon functionalized with ferrocenecarboxylic acid-modified electrode

Ordered mesoporous carbon (OMC) functionalized with ferrocenecarboxylic acid (Fc) was used to modify the glassy carbon (GC) electrode. The characterization of OMC–Fc shows that, after anchoring ferrocene on the mesoporous, ordered mesostructure of the material (OMC–Fc) remains intact and Fc is electrochemically accessible. The obtained OMC–Fc-modified electrode was used to investigate the electrochemical behavior of uric acid (UA). UA oxidation is catalyzed by this electrode in aqueous buffer solution (pH 7.3) with a decrease of 200 mV in overpotential compared to GC electrode. The detection and determination of UA in the presence of ascorbic acid (AA), the main interferent, were achieved. The voltammetric signals due to UA and AA were well separated with a potential difference of 308 mV, a separation that can allow the simultaneous determination of UA and AA. With amperometric method, at a constant potential of 375 mV, the catalytic current of UA versus its concentration shows a good linearity in the range 60–390 μM (R = 0.998) with a detection limit of 1.8 μM (S/N = 3). These results are not influenced by the presence of AA in the sample solution. With good stability and reproducibility, the present OMC–Fc-modified electrode was applied in the determination of UA content in urine sample and satisfactory results were obtained.     

Simultaneous determination of ascorbic acid and dopamine in the presence of uric acid on ruthenium oxide modified electrode

RuOx x nH2O film was electrochemically synthesized conveniently using cyclic voltammetric technique. The film formation was ascertained by the Electrochemical quartz crystal microbalance (EQCM) method and 45 ng of deposit per cycle was obtained. Stoichiometric ratio of the ruthenium and ruthenium oxide have been studied with different pH of phosphate buffer. The stability of the modified electrode in the presence of different cations and anions with different concentrations and pH were examined. Electrochemical studies have shown that the ascorbic acid (AA) and dopamine (DA) catalytic oxidation on ruthenium oxide modified electrode (RME) with a span of 300 mV separation even in the presence of uric acid (UA) with a large decrease in their respective over potential compared with bare glassy carbon electrode (GC). Accidentally, the reversible redox properties of the AA have been expediently studied on the RME using cyclic voltammetry and this peculiarity was interrogated through rotating ring disc electrode (RRDE) experiments. RRDE experiment results are conformed to the CV studies result and thus reversible redox property of AA have been reiterated. Amperometric detection under stirred condition up to approximately 0.8mM of AA and DA was carried out at free of electrode fouling. Interestingly, the regeneration of used RME electrode even after many consequent analysis, 100% was obtained.     

Zinc oxide/redox mediator composite films-based sensor for electrochemical detection of important biomolecules

Electrochemical oxidation of serotonin (SN) onto zinc oxide (ZnO)-coated glassy carbon electrode (GCE) results in the generation of redox mediators (RMs) that are strongly adsorbed on electrode surface. The electrochemical properties of zinc oxide-electrogenerated redox mediator (ZnO/RM) (inorganic/organic) hybrid film-coated electrode has been studied using cyclic voltammetry (CV). The scanning electron microscope (SEM), atomic force microscope (AFM), and electrochemical techniques proved the immobilization of ZnO/RM core/shell microparticles on the electrode surface. The GCE modified with ZnO/RM hybrid film showed two reversible redox peaks in acidic solution, and the redox peaks were found to be pH dependent with slopes of −62 and −60 mV/pH, which are very close to the Nernst behavior. The GCE/ZnO/RM-modified electrode exhibited excellent electrocatalytic activity toward the oxidations of ascorbic acid (AA), dopamine (DA), and uric acid (UA) in 0.1 M phosphate buffer solution (PBS, pH 7.0). Indeed, ZnO/RM-coated GCE separated the anodic oxidation waves of DA, AA, and UA with well-defined peak separations in their mixture solution. Consequently, the GCE/ZnO/RMs were used for simultaneous detection of DA, AA, and UA in their mixture solution. Using CV, calibration curves for DA, AA, and UA were obtained over the range of 6.0 × 10⁻⁶ to 9.6 × 10⁻⁴ M, 1.5 × 10⁻⁵ to 2.4 × 10⁻⁴ M, and 5.0 × 10⁻⁵ to 8 × 10⁻⁴ M with correlation coefficients of 0.992, 0.991, and 0.989, respectively. Moreover, ZnO/RM-modified GCE had good stability and antifouling properties.     

Overoxidized polypyrrole film directed single-walled carbon nanotubes immobilization on glassy carbon electrode and its sensing applications

In this paper, the films of overoxidized polypyrrole (PPyox) directed single-walled carbon nanotubes (SWNTs) have been electrochemically coated onto glassy carbon electrode (GCE). Electroactive monomer pyrrole was added into the solution containing sodium dodecyl sulfate (SDS) and SWNTs. Then, electropolymerization was proceeded at the surface of GCE, and a novel kind of conducting polymer/carbon nanotubes (CNTs) composite film with the orientation of CNTs were obtained correspondingly. Finally, this obtained polypyrrole (PPy)/SWNTs film modified GCE was oxidized at a potential of +1.8 V. It can be found that this proposed PPyox/SWNTs composite film modified GCE exhibited excellent electrocatalytic properties for some species such as nitrite, ascorbic acid (AA), dopamine (DA) and uric acid (UA), and could be used as a new sensor for practical applications. Compared with previous CNTs modified electrodes, SWNTs were oriented towards the outside of modified layer by PPyox and SDS, which made the film easily conductive. Moreover, this proposed film modified electrode was more stable, selective and applicable.     

Selective determination of inosine in the presence of uric acid and hypoxanthine using modified electrode

This article describes the selective determination of inosine (INO) in the presence of important physiological interferents, uric acid (UA) and hypoxanthine (HXN), by differential pulse voltammetry at physiological pH (7.2) using the electropolymerized film of 3-amino-5-mercapto-1,2,4-triazole (p-AMTa) modified glassy carbon (GC) electrode. The electropolymerization of AMTa was carried out by the potentiodynamic method in 0.1M H(2)SO(4). An atomic force microscopy image shows that the p-AMTa film contains a spherical-like structure. Bare GC electrode fails to resolve the voltammetric signal of INO in the presence of UA and HXN due to the surface fouling caused by the oxidized products of UA and HXN. However, p-AMTa film modified GC electrode (p-AMTa electrode) not only separates the voltammetric signals of UA, HXN, and INO, with potential differences of 730 mV between UA and HXN and 310 mV between HXN and INO, but also shows enhanced oxidation current for them. The selective determination of INO in the presence of UA and HXN at physiological pH was achieved for the first time. Using the amperometric method, we achieved the lowest detection of 50 nM for INO. The practical application of the current modified electrode was demonstrated by determining the concentration of INO in human blood serum and urine samples.     

Simultaneous and sensitive determination of a quaternary mixture of AA, DA, UA and Trp using a modified GCE by iron ion-doped natrolite zeolite-multiwall carbon nanotube

The evaluation of a novel modified glassy carbon electrode modified with iron ion-doped natrolite zeolite-multiwalled carbon nanotube for the simultaneous and sensitive determination of ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp) has been described. The measurements were carried out using cyclic voltammetry in buffer solution with pH 1. This modified electrode exhibits potent and persistent electroxidation behavior followed by well-separated oxidation peaks towards AA, DA, UA and Trp with increasing of the oxidation current. For the quaternary mixture containing AA, DA, UA and Trp, the 4 compounds can well separate from each other at the scan rate of 100 mVs(-1) with a potential difference of 270 mV, 150 mV and 260 mV for the oxidation peak potentials of AA-DA, DA-UA and UA-Trp, respectively, which was large enough to simultaneous determine AA, DA, UA and Trp. The catalytic peak current obtained, was linearly dependent on the AA, DA, UA and Trp concentrations in the range of 7.77-833 μM, 7.35-833 μM, 0.23-83.3 μM and 0.074-34.5 μM and the detection limits for AA, DA, UA and Trp were 1.11, 1.05, 0.033 and 0.011 μM, respectively. The analytical performance of this sensor has been evaluated for simultaneous detection of AA, DA, UA and Trp in human serum and urine samples.     

Highly selective and sensitive determination of dopamine using a Nafion/carbon nanotubes coated poly(3-methylthiophene) modified electrode

A poly(3-methylthiophene) modified glassy carbon electrode coated with Nafion/single-walled carbon nanotubes film was fabricated and used for highly selective and sensitive determination of dopamine. The hybrid film surface of the modified electrode was characterized by scanning electrochemical microscopy (SECM) and the results indicated that the carbon nanotubes were dispersed uniformly on the conductive polymer. The experimental results suggest that the hybrid film modified electrode combining the advantages of poly(3-methylthiophene), carbon nanotubes with Nafion exhibits dramatic electrocatalytic effect on the oxidation of dopamine (DA) and results in a marked enhancement of the current response. In 0.1M phosphate buffer solution (PBS) of pH 7.0, the differential pulse voltammetric (DPV) peak heights are linear with DA concentration in three intervals, viz. 0.020-0.10 microM, 0.10-1.0 microM and 1.0-6.0 microM, with correlation coefficients of 0.9993, 0.9996 and 0.9993, respectively. The detection limit of 5.0 nM DA could be estimated (S/N=3). Moreover, the interferences of ascorbic acid (AA) and uric acid (UC) are effectively diminished. This hybrid film modified electrode can be applied to the determination of DA contents in dopamine hydrochloride injection and human serum. These attractive features provide a potential application for either in vitro measurement of DA in the presence of excess AA and UA or as detectors in flow injection analysis (FIA) and high performance liquid chromatography (HPLC).     

Determination of nanomolar uric and ascorbic acids using enlarged gold nanoparticles modified electrode

Individual and simultaneous determination of 50 nM uric acid (UA) and ascorbic acid (AA) using enlarged, citrate-stabilized gold nanoparticles (AuNPs) self-assembled to 2,5-dimercapto-1,3,4-thiadiazole (DMT) monolayer modified Au (Au/DMT) electrode by an amperometric method is described for the first time. Self-assembly of AuNPs on the electrode surface was confirmed by atomic force microscopy (AFM), attenuated total reflectance FT-IR and diffuse reflectance spectral measurements. The electron transfer reaction (ETR) of [Fe(CN)₆]^3−/4− was blocked at Au/DMT electrode, whereas it was restored with a peak separation of 200 mV after the attachment of AuNPs on the Au/DMT (Au/DMT/AuNPs) electrode, which was confirmed from the ETR of the [Fe(CN)₆]^3−/4− redox couple. When the self-assembled AuNPs were enlarged by hydroxylamine seeding, the ETR of [Fe(CN)₆]^3−/4− was improved significantly with a peak separation of 100 mV. Tapping mode AFM showed that the average size of the enlarged-AuNPs (E-AuNPs) was 50-70 nm. The E-AuNPs modified electrode catalyzes the oxidation of AA and UA, separates their voltammetric signals by 200 mV, and has excellent sensitivity towards AA and UA with a detection limit of 50 nM. The practical application of the modified electrode was demonstrated by measuring the concentration of UA in blood serum and urine.