Direct electrochemistry with enhanced electrocatalytic activity of hemoglobin in hybrid modified electrodes composed of graphene and multi-walled carbon nanotubes

A graphene (GR) and multi-walled carbon nanotubes (MWCNT) hybrid was prepared and modified on a 1-hexylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE). Hemoglobin (Hb) was immobilized on GR-MWCNT/CILE surface with Nafion as the film forming material and the modified electrode was denoted as Nafion/Hb-GR-MWCNT/CILE. Spectroscopic results revealed that Hb molecules retained its native structure in the GR-MWCNT hybird. Electrochemical behaviors of Hb were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks obtained, which indicated that direct electron transfer of Hb was realized in the hybrid modified electrode. The result could be attributed to the synergistic effects of GR-MWCNT hybrid with enlarged surface area and improved conductivity through the formation of a three-dimensional network. Electrochemical parameters of the immobilized Hb on the electrode surface were further calculated with the results of the electron transfer number (n) as 1.03, the charge transfer coefficient (a) as 0.58 and the electron-transfer rate constant (k_s) as 0.97 s⁻¹. The Hb modified electrode showed good electrocatalytic ability toward the reduction of different substrates such as trichloroacetic acid in the concentration range from 0.05 to 38.0 mmol L⁻¹ with a detection limit of 0.0153 mmol L⁻¹ (3σ), H₂O₂ in the concentration range from 0.1 to 516.0 mmol L⁻¹ with a detection limit of 34.9 nmol/L (3σ) and NaNO₂ in the concentration range from 0.5 to 650.0 mmol L⁻¹ with a detection limit of 0.282 μmol L⁻¹ (3σ). So the proposed electrode had the potential application in the third-generation electrochemical biosensors without mediator.     

Sensitive voltammetric determination of rutin at an ionic liquid modified carbon paste electrode

An ionic liquid modified carbon paste electrode (IL/CPE) had been fabricated by using hydrophilic ionic liquid 1-amyl-3-methylimidazolium bromide ([AMIM]Br) as a modifier. The IL/CPE was characterized by scanning electron microscope and voltammetry. Electrochemical behavior of rutin at the IL/CPE had been investigated in pH 3.29 Britton-Robinson (B-R) buffer solution by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results suggested that the modified electrode exhibited an electrocatalytic activity toward the redox of rutin. The electron transfer coefficient (α) and the standard rate constant (k_s) of rutin at the modified electrode were calculated. Under the selected conditions, the reduction peak current was linearly dependent on the concentration of rutin in the range of 4.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol L⁻¹ (r = 0.9998), with a detection limit of 1.0 × 10⁻⁸ mol L⁻¹ (S/N = 3). The relative standard deviation (R.S.D.) for six times successful determination of 8.0 × 10⁻⁷ mol L⁻¹ rutin was 1.2%. The proposed method was applied to determine rutin in tablet and urine sample. In addition, the IL/CPE exhibited a distinct advantage of simple preparation, surface renewal, good reproducibility and good stability.     

Development of a sensitive and selective Riboflavin sensor based on carbon ionic liquid electrode

The electrochemical properties of Riboflavin adsorbed on carbon ionic liquid electrode (CILE) were studied by cyclic voltammetry. A film with a surface coverage of up to 3.3 × 10⁻⁹ mol cm⁻² was formed after 10 min exposure time. Electron transfer coefficient and rate constant of electron transfer across the modified electrode were found to be 0.43 and 3.03 s⁻¹, respectively. Differential pulse voltammetry was used for the determination of Riboflavin. Two linear working ranges of 0.8-110 nM and 0.11-1.0 μM were obtained with correlation coefficients of 0.998 and 0.996, respectively. The experimental detection limit was obtained as 0.1 nM. The relative standard deviation for five replicate analyses was 4.7%. Other soluble vitamins had no significant interferences and the electrode was used for the determination of Riboflavin in pharmaceutical products, nutrition and beverages.     

Electrochemical behaviors of guanosine on carbon ionic liquid electrode and its determination

The electrochemical behaviors of guanosine on the ionic liquid of N-butylpyridinium hexafluorophosphate (BPPF₆) modified carbon paste electrode (CPE) was studied in this paper and further used for guanosine detection. Guanosine showed an adsorption irreversible oxidation process on the carbon ionic liquid electrode (CILE) with the oxidation peak potential located at 1.12 V (vs. SCE) in a pH 4.5 Britton-Robinson (B-R) buffer solution. Compared with that on the traditional carbon paste electrode, small shift of the oxidation peak potentials appeared but with a great increment of the oxidation peak current on the CILE, which was due to the presence of ionic liquid in the modified electrode adsorbed the guanosine on the surface and promoted the electrochemical response. The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n), and the electrode reaction standard rate constant (k_s) were calculated as 0.74, 1.9 and 1.26 × 10⁻⁴ s⁻¹, respectively. Under the optimal conditions the oxidation peak current showed a good linear relationship with the guanosine concentration in the range from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol/L by cyclic voltammetry with the detection limit of 2.61 × 10⁻⁷ mol/L (3σ). The common coexisting substances showed no interferences to the guanosine oxidation. The CILE showed good ability to distinguish the electrochemical response of guanosine and guanine in the mixture solution. The urine samples were further detected by the proposed method with satisfactory results.     

Amorphous carbon nitride as an alternative electrode material in electroanalysis: Simultaneous determination of dopamine and ascorbic acid

Boron-doped diamond (BDD) films are excellent electrode materials, whose electrochemical activity for some analytes can be tuned by controlling their surface termination, most commonly either to predominantly hydrogen or oxygen. This tuning can be accomplished by e.g. suitable cathodic or anodic electrochemical pretreatments. Recently, it has been shown that amorphous carbon nitride (a-CN_x) films may present electrochemical characteristics similar to those of BDD, including the influence of surface termination on their electrochemical activity toward some analytes. In this work, we report for the first time a complete electroanalytical method using an a-CN_x electrode. Thus, an a-CN_x film deposited on a stainless steel foil by DC magnetron sputtering is proposed as an alternative electrode for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) in synthetic biological samples by square-wave voltammetry. The obtained results are compared with those attained using a BDD electrode. For both electrodes, a same anodic pretreatment in 0.1 mol L⁻¹ KOH was necessary to attain an adequate and equivalent separation of the DA and AA oxidation potential peaks of about 330 mV. The detection limits obtained for the simultaneous determination of these analytes using the a-CN_x electrode were 0.0656 μmol L⁻¹ for DA and 1.05 μmol L⁻¹ for AA, whereas with the BDD electrode these values were 0.283 μmol L⁻¹ and 0.968 μmol L⁻¹, respectively. Furthermore, the results obtained in the analysis of the analytes in synthetic biological samples were satisfactory, attesting the potential application of the a-CN_x electrode in electroanalysis.     

Electrocatalytic oxidation behavior of guanosine at graphene, chitosan and Fe3O4 nanoparticles modified glassy carbon electrode and its determination

A graphene, chitosan and Fe₃O₄ nanoparticles (nano-Fe₃O₄) modified glassy carbon electrode (graphene-chitosan/nano-Fe₃O₄/GCE) was fabricated. The modified electrode was characterized by scanning electron microscope and electrochemical impedance spectroscopy. The electrochemical oxidation behavior of guanosine was investigated in pH 7.0 phosphate buffer solution by cyclic voltammetry and differential pulse voltammetry. The experimental results indicated that the modified electrode exhibited an electrocatalytic and adsorptive activities towards the oxidation of guanosine. The transfer electron number (n), transfer proton number (m) and electrochemically effective surface area (A) were calculated. Under the optimized conditions, the oxidation peak current was proportional to guanosine concentration in the range of 2.0 × 10⁻⁶ to 3.5 × 10⁻⁴ mol L⁻¹ with the correlation coefficient of 0.9939 and the detection limit of 7.5 × 10⁻⁷ mol L⁻¹ (S/N = 3). Moreover, the modified electrode showed good ability to discriminate the electrochemical oxidation response of guanosine, guanine and adenosine. The proposed method was further applied to determine guanosine in spiked urine samples and traditional Chinese medicines with satisfactory results.     

Selective response of dopamine in the presence of ascorbic acid on carbon paste electrode modified with titanium phosphated silica gel

Titanium phosphate grafted on the surface of silica gel (devoted briefly as Si-TiPH) was synthesized and used as bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The Si-TiPH bulk modified carbon paste electrode was used for the selective determination of dopamine (DA) in the presence of ascorbic acid (AA). The modified electrode offers an excellent and stable response for the determination of DA in the presence of AA. The differential pulse voltammetry peak current was found to be linear with the DA concentration in the range 2 × 10⁻⁷ to 1 × 10⁻⁶ and 2 × 10⁻⁶ to 6 × 10⁻⁵ mol L⁻¹. The detection limit of the proposed method in the presence of 2.0 × 10⁻⁵ M of AA was found to be 4.3 × 10⁻⁸ mol L⁻¹ for DA determination. The proposed method was successfully applied for the determination of DA in injections.     

Differential pulse voltammetric simultaneous determination of noradrenalin and acetaminophen using a hematoxylin biosensor

A highly efficient noradrenalin (NA) biosensor was fabricated on the basis of hematoxylin electrodeposited on a glassy carbon electrode, GCE. The cyclic voltammetric responses of the hematoxylin biosensor at various scan rates, which were obtained in a 0.25 mmol L⁻¹ NA solution, showed the characteristic shape typical of an EC_cat process. The kinetic parameters such as electron transfer coefficient, α, the catalytic electron transfer rate constant, k′, and the standard catalytic electron transfer rate constant, k⁰, for oxidation of NA at the hematoxylin biosensor surface were estimated using cyclic and RDE voltammetry. The peaks of differential pulse voltammetric (DPV) for NA and acetaminophen (AC) oxidation at the hematoxylin biosensor surface were clearly separated from each other when they co-exited in the physiological pH (pH 7.0). It was, therefore, possible to simultaneously determine NA and AC in the samples at a hematoxylin biosensor. Linear calibration curves were obtained for 5.0 × 10⁻¹ to 65.40 μmol L⁻¹ and 65.40-274.20 μmol L⁻¹ of NA, and for 12.00-59.10 μmol L⁻¹ and 59.10-261.70 μmol L⁻¹ of AC. The sensitivities of the biosensor to NA in the absence and presence of AC were found virtually the same, which indicates the fact that the electrocatalytic oxidation processes of NA are independent of AC and, therefore, simultaneous or independent measurements of the two analytes (NA and AC) are possible without any interference. The results of 16 successive measurements show an average voltammetric peak current of 1.13 ± 0.03 μA for an electrolyte solution containing 5.00 μmol L⁻¹ NA. The hematoxylin biosensor has been satisfactorily used for the determination of NA and AC in pharmaceutical formulations. The results obtained, using the biosensor, are in very good agreement with those declared in the label of pharmaceutical inhalation products.     

Sensitive voltammetric determination of baicalein at DNA Langmuir-Blodgett film modified glassy carbon electrode

The present paper describes to modify a double stranded DNA-octadecylamine (ODA) Langmuir-Blodgett film on a glassy carbon electrode (GCE) surface to develop a voltammetric sensor for the detection of trace amounts of baicalein. The electrode was characterized by atomic force microscopy (AFM) and cyclic voltammetry (CV). Electrochemical behaviour of baicalein at the modified electrode had been investigated in pH 2.87 Britton-Robinson buffer solutions by CV and square wave voltammetry (SWV). Compared with bare GCE, the electrode presented an electrocatalytic redox for baicalein. Under the optimum conditions, the modified electrode showed a linear voltammetric response for the baicalein within a concentration range of 1.0 × 10⁻⁸-2.0 × 10⁻⁶ mol L⁻¹, and a value of 6.0 × 10⁻⁹ mol L⁻¹ was calculated for the detection limit. And the modified electrode exhibited an excellent immunity from epinephrine, dopamine, glucose and ascorbic acid interference. The method was also applied successfully to detect baicalein in the medicinal tablets and spiked human blood serum samples with satisfactory results.     

Electrochemical behavior of dopamine at a 3,3′-dithiodipropionic acid self-assembled monolayers

Monolayers of 3,3′-dithiodipropionic acid (DTDPA) were prepared on a polycrystalline gold electrode through a self-assembly procedure to produce a gold 3,3′-dithiodipropionic acid self-assembled monolayer (AuDTDPA) modified electrode. The characterization of the AuDTDPA electrode was investigated by cyclic voltammetry and ac impedance using the [Fe(CN)₆]^3−/4− redox couple. The electrochemical behavior of DA on the modified electrode AuDTDPA was studied by cyclic and square-wave voltammetries, using phosphate buffer as supporting electrolyte. The oxidation peak current for DA increases linearly with concentration in the range of 0.35 × 10⁻⁵ to 3.4 × 10⁻⁵ mol L⁻¹. The performance of the AuDTDPA modified electrode was evaluated for the electroanalytical determination of dopamine (DA) in a pharmaceutical formulation. The AuDTDPA modified electrode showed a stable behavior and the presence of surface-COOH groups avoided the passivation of the electrode surface during the dopamine oxidation.     

Exploiting micellar environment for simultaneous electrochemical determination of ascorbic acid and dopamine

A simple and reliable method for simultaneous electrochemical determination of ascorbic acid (AA) and dopamine (DA) is presented in this work. It was based on the use of the cationic surfactant cetylpyridinium chloride (CPC) that enables the separation of the oxidation peaks potential of AA and DA. Cyclic voltammetry (CV) as well as pulse differential voltammetry (PDV) were used in order to verify the voltammetric behaviour in micellar media. In the cationic surfactant CPC, a remarkable electrostatic interaction is established with negatively charged AA, as a consequence, the oxidation peak potential shifted toward less positive potential and the peak current increased. On the other hand, the positively charged DA is repelled from the electrode surface and the oxidation peak potential shifts toward more positive potential in comparison to the bare electrode. Therefore, the common overlapped oxidation peaks of AA and DA can be circumventing by using CPC. Parameter that affects the E_pa and I_pa such as CPC concentration and pH were studied. Under optimised conditions, the method presented a linear response to AA and DA in the concentration range from 5 to 75 μmol L⁻¹ and 10 to 100 μmol L⁻¹, respectively. The proposed method was successfully applied to the simultaneous determination of AA and DA in dopamine hydrochloride injection (DHI) samples spiked with AA.     

Simultaneous determination of N-acetyl-p-aminophenol and p-aminophenol with poly(3,4-ethylenedioxythiophene) modified glassy carbon electrode

A sensitive and selective method was developed for the determination of N-acetyl-p-aminophenol (APAP) and p-aminophenol (PAP) using poly(3,4-ethylenedioxythiophene) (PEDOT)-modified glassy carbon electrode (GCE). Cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical reaction of APAP and PAP at the modified electrode. Both APAP and PAP showed quasireversible redox reactions with formal potentials of 367 mV and 101 mV (vs. Ag/AgCl), respectively, in phosphate buffer solution of pH 7.0. The significant peak potential difference (266 mV) between APAP and PAP enabled the simultaneous determination both species based on differential pulse voltammetry. The voltammetric responses gave linear ranges of 1.0 × 10⁻⁶-1.0 × 10⁻⁴ mol L⁻¹ and 4.0 × 10⁻⁶-3.2 × 10⁻⁴ mol L⁻¹, with detection limits of 4.0 × 10⁻⁷ mol L⁻¹ and 1.2 × 10⁻⁶ mol L⁻¹ for APAP and PAP, respectively. The method was successfully applied for the determination of APAP and PAP in pharmaceutical formulations and biological samples.     

Voltammetric performance and application of a sensor for sodium ions constructed with layered birnessite-type manganese oxide

The preparation and electrochemical characterization of a carbon paste electrode modified with layered birnessite-type manganese oxide for use as a sodium sensor is described. The effects of powder synthesis process (sol-gel and redox precipitation) for birnessite on the electrochemical activity of the sensor was investigated by cyclic voltammetry. The carbon paste electrode modified with birnessite-type manganese oxide that was synthesized by the sol-gel method showed a best electrochemical for sodium ions. The detection is based on the measurement of anodic current generated by oxidation of Mn(III) to Mn(IV) at the surface of the electrode and consequently the sodium ions extraction into the birnessite structure. The best voltammetric response was obtained for an electrode composition of 15% (w/w) birnessite oxide in the paste, a TRIS buffer solution of pH 8.0 and a scan rate of 50 mV s⁻¹. A sensitive linear voltammetric response for sodium ions was obtained in the concentration range of 7.89 × 10⁻⁵ to 3.49 × 10⁻⁴ mol L⁻¹ with a slope of 37.5 μA L mmol⁻¹ and a detection limit (3σ/slope) of 3.43 × 10⁻⁵ mol L⁻¹ using cyclic voltammetry. Under the working conditions, the proposed method was successfully applied to determination of sodium ions in urine samples.     

Direct electrochemistry and electrocatalysis of hemoglobin on gold nanoparticle decorated carbon ionic liquid electrode

In this paper a carbon ionic liquid electrode (CILE) was fabricated by using ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM]EtOSO₃) as modifier and further gold nanoparticles were in situ electrodeposited on the surface of CILE. The fabricated Au/CILE was used as a new platform for the immobilization of hemoglobin (Hb) with the help of a Nafion film. Electrochemical experimental results indicated that direct electron transfer of Hb was realized on the surface of Au/CILE with a pair of well-defined quasi-reversible redox peaks appeared. The formal peak potential (E⁰′) was obtained as −0.210 V (vs. SCE) in pH 7.0 phosphate buffer solution (PBS), which was the characteristic of Hb heme Fe(III)/Fe(II) redox couple. The fabricated Nafion/Hb/Au/CILE showed excellent electrocatalytic activity to the reduction of trichloroacetic acid (TCA) and the reduction peak current was in proportional to TCA concentration in the range from 0.2 to 18.0 mmol/L with the detection limit as 0.16 mmol/L (S/N = 3). The proposed electrode showed good stability and reproducibility, and it had the potential application as a new third-generation electrochemical biosensor.     

Electrochemical determination of L-phenylalanine at polyaniline modified carbon electrode based on β-cyclodextrin incorporated carbon nanotube composite material and imprinted sol-gel film

A sensitive and selective electrochemical sensor based on a polyaniline modified carbon electrode for the determination of l-phenylalanine has been proposed by utilizing β-cyclodextrin (β-CD) incorporated multi-walled carbon nanotube (MWNT) and imprinted sol-gel film. The electrochemical behavior of the sensor towards l-phenylalanine was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric i-t curve. The surface morphologies of layer-by-layer assembly electrodes were displayed by scanning electron microscope (SEM). The response mechanism of the imprinted sensor for l-phenylalanine was based on the inclusion interaction of β-CD and molecular recognition capacity of the imprinted film for l-phenylalanine. A linear calibration plot was obtained covering the concentration range from 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 1.0 × 10⁻⁹ mol L⁻¹. With excellent sensitivity, selectivity, stability, reproducibility and recovery, the electrochemical imprinted sensor was used to detect l-phenylalanine in blood plasma samples successfully.     

Characterization of a carbon paste electrode modified with tripolyphosphate-modified kaolinite clay for the detection of lead

We report about the use of carbon paste electrode modified with kaolinite for analytical detection of trace lead(II) in domestic water by differential pulse voltammetry. Kaolinite clay was modified with tripolyphosphate (TPP) by impregnation method. The results show that TPP in kaolinite clay plays an important role in the accumulation process of Pb(II) on the modified electrode surface. The electroanalytical procedure for determination of Pb(II) comprised two steps: chemical accumulation of the analyte under open-circuit conditions, followed by electrochemical detection of the pre-concentrated species using differential pulse voltammetry. The analytical performance of this system has been explored by studying the effects of preconcentration time, carbon paste composition, pH, supporting electrolyte concentration, as well as interferences due to other ions. The calculated detection limit based on the variability of a blank solution (3s_b criterion) for 10 measurements was 8.4 × 10⁻⁸ mol L⁻¹, and the sensitivity determined from the slope of the calibration graph was 0.910 mol L⁻¹. The reproducibility (RSD) for five replicate measurements at 1.0 mg L⁻¹ lead level was 1.6%. The results indicate that this electrode is sensitive and effective for the determination of Pb²⁺.     

A new method for electrocatalytic oxidation of ascorbic acid at the Cu(II) zeolite-modified electrode

A new method is developed for the catalytic oxidation of ascorbic acid at graphite zeolite-modified electrode, doped with copper(II) (Cu²⁺A/ZCME). Copper(II) exchanged in zeolite type A acts as catalyst to oxidize ascorbic acid. The modified electrode lowered the overpotential of the reaction by ∼400 mV. First, the electrochemical behavior of copper(II), incorporated in the zeolite type A modified electrode, was studied. The results illustrate that diffusion can control the copper(II)/copper(0) redox process at the Cu²⁺A/ZCME. Then, the behavior of electrocatalytic oxidation reaction for ascorbic acid was researched. The electrode was employed to study electrocatalytic oxidation of ascorbic acid, using cyclic voltammetry and chronoamperometry as diagnostic techniques. The diffusion coefficient of ascorbic acid was equal to 1.028 × 10⁻⁵ cm² s⁻¹. A linear calibration graph was obtained over the ascorbic acid with a concentration range of 0.003-6.00 mmol L⁻¹. The detection limit (DL) of ascorbic acid was estimated as 2.76 × 10⁻⁷ mol L⁻¹. The relative standard deviations of 10 replicate measurements (performed on a single electrode at several ascorbic acid concentrations between 3.0 and 200 μmol L⁻¹) were measured between 1.0 and 2.4%.     

Enhanced sensing of ascorbic acid, dopamine and serotonin at solid carbon paste electrode with a nonionic polymer film

A nonionic poly(2-amino-5-mercapto-thiadiazole) film was electrodeposited on a solid carbon paste electrode via a potential scanning procedure, and used for amperometric sensing of ascorbic acid (AA), dopamine (DA) and serotonin (ST). The highly electrocatalytic activity of the sensor to the three analytes was demonstrated from the sensitive and well separated voltammetric signals. The polymer film did not show significant accumulation effect on all the three species, reducing the fouling and deactivation of the electrode surface as well as the mutual interference among the analytes. The sensor achieved amperometric sensitivities of 1.92 nA (nmol L⁻¹)⁻¹ cm⁻² to AA in the linear range of 0.025-1.95 μmol L⁻¹, 3.76 nA (nmol L⁻¹)⁻¹ cm⁻² to DA and 7.00 nA (nmol L⁻¹)⁻¹ cm⁻² to ST both in the linear range of 0.02-1.56 μmol L⁻¹. The lowest detection limits were found to be 1.5, 0.7 and 0.4 nmol L⁻¹ for AA, DA and ST, respectively. This sensor was successfully employed for the successive determination of AA, DA and ST in pharmaceutical samples. The good antifouling property and reproducibility of the proposed sensor can be attributed to the nonionic polymer film without electrostatic attraction to the ionized species in the solutions.     

Simultaneous voltammetric determination of paracetamol and caffeine in pharmaceutical formulations using a boron-doped diamond electrode

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 × 10⁻⁷ mol L⁻¹ to 8.3 × 10⁻⁵ mol L⁻¹ for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 × 10⁻⁷ mol L⁻¹ and 3.5 × 10⁻⁸ mol L⁻¹, respectively. The proposed method was successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level).     

Enhanced electrochemical performance at screen-printed carbon electrodes by a new pretreating procedure

A new method for the pretreatment of screen-printed carbon electrodes (SPCEs) by two successive steps was proposed. In step one, fresh SPCEs were soaked into NaOH with high concentration (e.g. 3 M) for tens to hundreds of minutes, and the resulted electrodes were called as SPCE-I. In step two, SPCE-I were pre-anodized in low concentration of NaOH, which were designated as SPCE-II. The pretreated electrodes showed remarkable enhancement in heterogeneous electron transfer rate constant (k⁰) increased from 1.6 × 10⁻⁴ cm s⁻¹ at the fresh SPCE to 1.1 × 10⁻² cm s⁻¹ at SPCE-I for Fe(CN)₆^3−/4− couple. The peak to peak separation (ΔE_p) in cyclic voltammetry was reduced from ca. 480 to 84 mV, indicating that the electrochemical reversibility was greatly promoted, possibly due to the removing of polymers/oil binder from the electrode surfaces. The electroactive area (A_ea) of the electrode was increased by a factor of 17 after pretreatment in step one. Further analysis by the electrochemical impedance method showed that the electron transfer resistance (R_ct) decreased from ca. 2100 to 1.4 Ω. These pretreated electrodes, especially SPCE-II, exhibited excellent electrocatalytic behavior for the redox of dopamine (DA). Interference from ascorbic acid (AA) in the detection of DA at SPCE-II could be effectively eliminated due to the anodic peak separation (190 mV) between DA and AA, which resulted from the functionalization of the electrode surface in the pretreatment of step two. Under optimum conditions, current responses to DA were linearly changed in two concentration intervals, one was from 3.0 × 10⁻⁷ to 9.8 × 10⁻⁶ M, and the other was from 9.8 × 10⁻⁶ to 3.3 × 10⁻⁴ M. The detection limit for DA was down to 1.0 × 10⁻⁷ M.