Electrochemically Degraded Dopamine Film for the Determination of Dopamine

A dopamine (DA) polymer was deposited electrochemically on to a glassy carbon (GC) surface until the electrode surface was passivated. The DA film on the GC surface was re‐formed for high sensitivity and reproducibility by electrochemical degradation. The re‐formed electrode was sensitive and selective in the determination of DA in the presence of ascorbic acid. The linear range obtained by square‐wave voltammetry was between 0.1 and 2.1 μM (R=0.996, n=6) with a sensitivity of 1.2 μA μM^?1 and a detection limit (S/N=3) of 0.04 μM. The electropolymerized DA film was stable and the re‐formed electrode was reproducible for DA determination.     

Determination of Rutin in Drinks Using an Electrode Modified with Carbon Nanotubes-Prussian Blue

A new sensor was developed using a screen-printed carbon electrode modified with single-walled carbon nanotubes (SWCNTs) and Prussian blue (PB) coated with chitosan. The modified electrode allowed the oxidation and reduction of rutin at 0.25 and 0.096 V, respectively, with a ΔE of 0.154 V. Furthermore, the peak currents increase nearly 100% compared with the electrode without modification. The process was more reversible compared with the electrode modified with only SWCNTs or PB. Cyclic voltammetry was used to characterize the modified electrode surface. The quantification of rutin was more sensitive with adsorptive stripping voltammetry than with anodic stripping voltammetry. Adsorption potential, adsorption time and pH were optimized based on the oxidation of rutin: E_ads =–0.10 V, t_ads = 60 s, pH 3.0. The detection limit (3σ/b) was 0.01 μM and the relative standard derivation was 3%. The new sensor was used in the quantification of rutin in black tea, coffee and synthetic drink of tea with satisfactory results.     

Highly Sensitive and Selective Determination of Dopamine Based on Graphite Nanosheet‐Nafion Composite Film Modified Electrode

A graphite nanosheet (GNS)‐Nafion modified glassy carbon (GC) electrode was prepared and used for highly sensitive and selective determination of dopamine (DA). The GNS‐Nafion/GC electrode displayed excellent electrocatalytic activities towards DA and ascorbic acid (AA). The selective determination of DA was carried out successfully in the presence of AA by differential pulse voltammetry. High sensitivity (3.695 μA μM^?1) and low detection limit (0.02 μM, S/N=3) for the DA detection were obtained. These good properties can be attributed to a large amount of edge plane defects presented on GNSs and the charge‐exclusion and concentration features of Nafion.     

Chitosan Incorporating Cetyltrimethylammonium Bromide Modified Glassy Carbon Electrode for Simultaneous Determination of Ascorbic Acid and Dopamine

Simultaneous determination of a neurotransmitter, dopamine (DA), and ascorbic acid (AA) is achieved at neutral pH on a chitosan incorporating cetyltrimethylammonium bromide (CTAB) modified glassy carbon (GC) electrode. Differential pulse voltammetry (DPV) technique was used to investigate the electrochemical response of DA and AA at a glassy carbon electrode modified with chitosan incorporating CTAB. An optimum 6.0 mmol L^?1 of CTAB together with 0.5 wt% of chitosan was used to improve the resolution and the determination sensitivity. In 0.1 mol L^?1 aqueous phosphate buffer solution of pH 6.8, the chitosan‐CTAB modified electrode showed a good electrocatalytic response towards DA and AA. The anodic peak potential of DA shifted positively, while that of AA shifted negatively. Thus, the difference of the anodic peaks of DA and AA reached 0.23 V, which was enough to separate the two anodic peaks very well. The presented method herein could be applied to the direct simultaneous determination of DA and AA without prior treatment. The anodic peak currents (I_pa) of DPV are proportional to DA in the concentration range of 8 μM to 1000 μM, to that of AA 10 μM to 2000 μM, with correlation coefficients of 0.9930 and 0.9945, respectively. The linear range is much wider than previously reported.     

Simultaneous Determination of Ranitidine and Metronidazole at Glassy Carbon Electrode Modified with Single Wall Carbon Nanotubes

Single‐walled carbon nanotubes(SWCNTs) were dispersed into DMSO, and a SWCNTs‐film coated glassy carbon electrode was achieved via evaporating the solvent. The results indicated that CNT modified glassy carbon electrode exhibited efficiently electrocatalytic reduction for ranitidine and metronidazole with relatively high sensitivity, stability and life time. Under conditions of cyclic voltammetry, the potential for reduction of selected analytes is lowered by approximately 150 mV and current is enhanced significantly (7 times) in comparison to the bare glassy carbon electrode. The electrocatalytic behavior is further exploited as a sensitive detection scheme for these analytes determinations by hydrodynamic amperometry. Under optimized condition in amperometric method the concentration calibration range, detection limit and sensitivity were about, 0.1–200 μM, detection limit (S/N=3) 6.3×10^?8 mol L^?1 and sensitivity 40 nA/μM for metronidazole and 0.3–270 μM 7.73×10^?8 mol L^?1 and 25 nA/μM for ranitidine. In addition, the ability of the modified electrode for simultaneous determination of ranitidine and metronidazole was evaluated. The proposed method was successfully applied to ranitidine and metronidazole determination in tablets. The analytical performance of this sensor has been evaluated for detection of these analytes in serum as a real sample.     

Electrochemical Characterization of Pyrocatechol Sulfonephthalein-Modified Glassy Carbon Electrode and Separation of Electrocatalytic Responses for Ascorbic Acid and Dopamine Oxidation

A pyrocatechol sulfonephthalein- (PS-) modified glassy carbon (PS/GC) electrode has been prepared by adsorption of PS on a glassy carbon electrode surface. Cyclic voltammograms of the PS/GC electrode indicate the presence of a couple of well-defined redox peaks, and the formal potential shifts in the negative direction with increasing solution pH. The relation between formal potential,E^0′, and solution pH can be fit to the equationE^0′(mV) = −51.4 pH + 538.7. The PS/GC electrode shows high electrocatalytic activity toward ascorbic acid oxidation, with an overpotential ca. 380 mV less than that of the bare electrode and a drastic enhancement of the anodic currents. The electrocatalytic reaction rate constant (k), which was decreased with increasing concentration of H₂A, was determined using rotating disk electrode measurements. The values ofkwas also affected by the solution pH. The electrode can also separate the electrochemical responses of ascorbic acid and dopamine. The separation between the anodic peak potentials of ascorbic acid and dopamine is more than 50 mV by the differential pulse voltammetry.     

2,2‐Bis(3‐Amino‐4‐hydroxyphenyl)hexafluoropropane Modified Glassy Carbon Electrodes as Selective and Sensitive Voltammetric Sensors. Selective Detection of Dopamine and Uric Acid

2,2‐bis(3‐Amino‐4‐hydroxyphenyl)hexafluoropropane (BAHHFP) was electro‐polymerized oxidatively on glassy carbon by cyclic voltammetry. The activity of the modified electrode towards ascorbic acid (AA), uric acid (UA) and dopamine (DA) was characterized with cyclic voltammetry and differential puls voltammetry (DPV). The findings showed that the electrode modification drastically suppresses the response of AA and shifts it towards more negative potentials. Simultaneously an enhancement of reaction reversibility is seen for DA and UA. Unusual, selective preconcentration features are observed for DA when the polymer‐modified electrode is polarized at negative potential. In a ternary mixture containing the three analytes studied, three baseline resolved peaks are observed in DPV mode. At physiological pH 7.4, after 5 min preconcentration at ?300 mV, peaks positions were ?0.073, 0.131 and 0.280 V (vs. Ag/AgCl) for AA, DA and UA, respectively. Relative selectivities DA/AA and UA/AA were over 4000 : 1 and 700 : 1, respectively. DA response was linear in the range 0.05–3 μM with sensitivity of 138 μA μM^?1 cm^?2 and detection limit (3σ) of 5 nM. Sensitive quantification of UA was possible in acidic solution (pH 1.8). Under such conditions a very sharp peak appeared at 630 mV (DPV). The response was linear in the range 0.5–100 μM with sensitivity of 4.67 μA μM^?1 cm^?2 and detection limit (3σ) of 0.1 μM. Practical utility was illustrated by selective determination of UA in human urine.     

Lignosulfonate‐Modified Electrode for Electrocatalytic Reduction of Acidic Nitrite

Sodium lignosulfonate (LS) undergoes oxidative electropolymerization on a glassy carbon (GC) electrode from sulfuric acid solution to form a chemically modified electrode exhibiting anionic character and redox activity. Cyclic voltammetry reveals the existence of two redox systems at E°′ values of +0.29 and +0.53 V, respectively. Peak currents are proportional to the scan rate as expected for surface confined systems. The GC|poly‐LS electrode shows electrocatalytic activity toward the reduction of acidic nitrite. When operating in a constant potential amperometric mode (at 0.0 V, vs. Ag/AgCl), a linear relationship between nitrite concentration and reduction current is observed over the range of 1 to 250 μM. The detection limit reaches 0.3 μM (S/N=3). The electrode may be practically applied for nitrite determination in human saliva.     

Electropolymerized film of functionalized thiadiazole on glassy carbon electrode for the simultaneous determination of ascorbic acid, dopamine and uric acid

The present study reports the simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) in 0.20 M phosphate buffer solution (pH 5.0) using electropolymerized ultrathin film of 5-amino-2-mercapto-1,3,4-thiadiazole (AMT) on glassy carbon (GC) electrode. The bare GC electrode does not separate the voltammetric signals of AA, DA and UA. However, electropolymerized AMT (p-AMT) modified GC electrode not only resolved the voltammetric signals of AA, DA and UA but also dramatically enhanced their oxidation peak currents when compared to bare GC electrode. The enhanced oxidation currents for AA, DA and UA at p-AMT modified electrode are due to the electrostatic interactions between them and the polymer film. Using amperometric method, we achieved the lowest detection of 75 nM AA, 40 nM DA and 60 nM UA at p-AMT modified electrode. The amperometric current was linearly increased from 200 nM to 0.80 mM for each AA, DA and UA and the lowest detection limit was found to be 0.92, 0.07 and 0.57 nM, respectively (S/N = 3). The practical application of the modified electrode was demonstrated by the determination of DA in dopamine hydrochloride injection.     

Selective Electrochemical Determination of Dopamine with Molecularly Imprinted Poly(Carbazole‐co‐Aniline) Electrode Decorated with Gold Nanoparticles

Dopamine (DA) is a significant neurotransmitter in the central nervous system, coexisting with uric acid (UA) and ascorbic acid (AA). UA and AA are easily oxidizable compounds having potentials close to that of DA for electrochemical analysis, resulting in overlapping voltammetric response. In this work, a novel molecularly imprinted (MI) electrochemical sensor was proposed for selective determination of DA (in the presence of up to 80‐fold excess of UA and AA), relying on gold nanoparticles (Au_nano)‐decorated glassy carbon (GC) electrode coated with poly(carbazole (Cz)‐co‐aniline (ANI)) copolymer film incorporating DA as template (DA imprinted‐GC/P(Cz‐co‐ANI)‐Au_nano electrode, DA‐MIP‐Au_nano electrode). The DA recognizing sensor electrode showed great electroactivity for analyte oxidation in 0.2 mol L^?1 pH 7 phosphate buffer. Square wave voltammetry (SWV) was performed within 10^?4–10^?5 mol L^?1 of DA, of which the oxidation peak potential was observed at 0.16 V. The limit of detection (LOD) and limit of quantification (LOQ) were 2.0×10^?6 and 6.7×10^?6 mol L^?1, respectively. Binary and ternary synthetic mixtures of DA‐UA, DA‐AA and DA‐UA‐AA yielded excellent recoveries for DA. Additionally, DA was quantitatively recovered from a real sample of bovine serum spiked with DA, and determined in concentrated dopamine injection solution. The developed SWV method was statistically validated against a literature potentiodynamic method using a caffeic acid modified‐GC electrode.     

聚多巴胺/多壁碳纳米管/玻璃碳电极上多巴胺的电分析

基于多巴胺（DA）在多壁碳纳米管（MWCNTs）修饰玻璃碳（GC）电极上的电聚合,制得聚多巴胺(PDA)/MWCNTs/GC电极,并对该修饰电极进行了电化学阻抗谱 (EIS)和循环伏安法(CV)表征。 在该修饰电极上,DA呈现良好的电化学行为。在pH=7.4磷酸缓冲溶液中其氧化电流显著高于在裸电极上的响应,且能有效地抑制2.0 mmol/L抗坏血酸(AA)或K4Fe(CN)6的直接电化学响应,表明MWCNTs可增敏信号,且阳离子选择透过性PDA膜可抑制阴离子的电化学干扰。 采用CV实验检测DA,DA氧化的半微分伏安峰高(ipa-sd)与多巴胺浓度在0.08～1.76 μmol/L范围内呈线性关系,在无抗坏血酸和有0.5 mmol/L抗坏血酸共存时的线性回归方程分别为ipa-sd(μA/s1/2)=0.107+0.405c(μmol/L)（r2=0.986）和ipa-sd(μA/s1/2)=0.628+0.649c(μmol/L)(r2=0.992),检测限均为8.0×10-8 mol/L(S/N=3)。 该法用于盐酸多巴胺注射液中多巴胺的快速测定,结果满意。     

Comparison of Boron‐Doped Diamond and Glassy Carbon Electrodes for Determination of Procaine Hydrochloride

The electrochemical oxidation of procaine hydrochloride (PC?HCL, 2‐diethylaminoethyl 4‐aminobenzoate hydrochloride) was investigated at as‐deposited boron‐doped diamond (ad‐BDD) electrode, anodically oxidized BDD (ao‐BDD) electrode and glassy carbon (GC) electrode using cyclic voltammetry (CV). Well‐defined cyclic voltammograms were obtained for PC?HCL oxidation with high signal‐to‐background (S/B) ratio, low tendency for adsorption, good reproducibility and long‐term stability at ad‐BDD electrode, demonstrating its superior electrochemical behavior and significant advantages in contrast to ao‐BDD and GC electrode. At 100 μM PC?HCL, the voltammetric S/B ratio was nearly one order of magnitude higher at an ad‐BDD electrode than that at a GC electrode. In a separate set of experiments for oxidation of 100 μM PC?HCL, 96%, 92% and 84% of the initial oxidation peak current was retained at the ad‐BDD, ao‐BDD and GC electrode, respectively, by stirring the solution after the tenth cycle. The current response was linearly proportional to the square root of the scan rate within the range 10–1000 mV s^?1 in 10 μM PC?HCL solutions, indicating that the oxidation process was diffusion‐controlled with negligible adsorption at an ad‐BDD surface. The good linearity was observed for a concentration range from 5 to 200 μM with a linear equation of y=0.03517x+0.65346 (r=0.999), and the detection limit was 0.5 μM for oxidation of PC?HCL at the ad‐BDD electrode. The ad‐BDD electrode could maintain 100% of its original activity after intermittent use for 3 months.     

Glassy Carbon Electrode Modified with Layering of Carbon Black/Poly(Allylamine Hydrochloride) Composite for Multianalyte Determination

An electrochemical sensor using glassy carbon electrode modified with carbon black within a poly(allylamine hydrochloride) film is proposed in this work. The novel sensor was characterized by scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry using the redox probe Fe(CN)6^3−/4−. The sensor was applied for the simultaneous determination of dopamine (DA), paracetamol (PAR), amlodipine (AML), and rosuvastatin (RSV). The quantification of all four analytes was carried out by linear sweep voltammetry and presented a linear concentration range for all analytes from 1.0 to 90 μmol L⁻¹, with limit of detection of 0.55, 1.3, 5.7, and 3.0 μmol L⁻¹ for DA, PAR, AML, and RSV, respectively. This sensor was successfully applied in the simultaneous determination of these analytes in environmental, pharmaceutical, and biological samples.     

Selective Detection of Dopamine and Its Metabolite,DOPAC, in the Presence of Ascorbic Acid Using Diamond Electrode Modified by the Polymer Film

The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM^?1, respectively. The modified electrode exhibits a stable and sensitive response to DA.     

Simultaneous Determination of Dopamine and Ascorbic Acid Using the Nano‐Gold Self‐Assembled Glassy Carbon Electrode

Electrochemical behavior of dopamine (DA) was investigated at the gold nanoparticles self‐assembled glassy carbon electrode (GNP/LC/GCE), which was fabricated by self‐assembling gold nanoparticles on the surface of L ‐cysteine (LC) modified glassy carbon electrode (GCE) via successive cyclic voltammetry (CV). A pair of well‐defined redox peaks of DA on the GNP/LC/GCE was obtained at E_pa=0.197 V and E_pc=0.146 V, respectively. And the peak separation between DA and AA is about 0.2 V, which is enough for simultaneous determination of DA and AA. The peak currents of DA and AA were proportional with their concentrations in the range of 6.0×10^?8–8.5×10^?5 mol L^?1 and 1.0×10^?6–2.5×10^?3 mol L^?1, with the detection limit of 2.0×10^?8 mol L^?1 and 3.0×10^?7 mol L^?1 (S/N=3), respectively. The modified electrode exhibits an excellent reproducibility, sensibility and stability for simultaneous determination of DA and AA in human serum with satisfactory result.     

Fabrication of Chitosan‐Multiwall Carbon Nanotube Nanocomposite Containing Ferri/Ferrocyanide: Application for Simultaneous Detection of D‐Penicillamine and Tryptophan

We report a simple and effective strategy for fabrication of the nanocomposite containing chitosan (CS) and multiwall carbon nanotube (MWNT) coated on a glassy carbon electrode (GCE). The characterization of the modified electrode (CS‐MWNT/GC) was carried out using scanning electron microscopy (SEM) and UV–vis absorption spectroscopy. The electrochemical behavior of CS‐MWNT/GC electrode was investigated and compared with the electrochemical behavior of chitosan modified GC (CS/GC), multiwalled carbon nanotube modified GC (MWNT/GC) and unmodified GC using cyclic voltammetry (CV) and electron impedance spectroscopy (EIS). The chitosan films are electrochemically inactive; similar background charging currents are observed at bare GC. The chitosan films are permeable to anionic Fe(CN)₆^3?/4? (FC) redox couple. Electrochemical parameters, including apparent diffusion coefficient for the Fe(CN)₆^3?/4? redox probe at FC/CS‐MWNT/GC electrode is comparable to values reported for cast chitosan films. This modified electrode also showed electrocatalytic effect for the simultaneous determination of D‐penicillamine (D‐PA) and tryptophan (Trp). The detection limit of 0.9 μM and 4.0 μM for D‐PA and Trp, respectively, makes this nanocomposite very suitable for determination of them with good sensitivity.     

肉桂酸修饰电极同时测定多巴胺和抗坏血酸的研究

用电化学聚合方法制备肉桂酸(CA)修饰的玻碳电极(PCA/GC),研究多巴胺(DA)和抗坏血酸(AA)在修饰电极上的电化学行为.结果表明,在DA和AA共存体系中,DA、AA在PCA/GC电极上氧化峰电流增大且氧化峰电位相差200 mV,据此可同时检测DA和AA.在pH 7.0磷酸盐缓冲液中,DA和AA的氧化峰电流与其浓...     

Electrocatalytic Oxidation of Dopamine by Ferrocene in Lipid Film Cast on a Glassy Carbon Electrode

ＩｎｔｒｏｄｕｃｔｉｏｎＤＡｉｓｏｎｅｏｆｅｓｓｅｎｔｉａｌｐａｒｔｉｃｉｐａｎｔｓｉｎｔｈｅｎｅｕｒｏ ｔｒａｎｓｍｉｓｓｉｏｎｐｒｏｃｅｓｓｉｎｍａｍｍａｌｉａｎｃｅｎｔｒａｌｎｅｒｖｏｕｓｓｙｓ ｔｅｍ .ＡｌｏｓｓｏｆＤＡ ｃｏｎｔａｉｎｉｎｇｎｅｕｒｏｎｓｍａｙｒｅｓｕｌｔｉｎｓｏｍｅｓｅｒｉｏｕｓｄｉｓｅａｓｅｓｕｃｈａｓＰａｒｋｉｎｓｏｎｉｓｍ .1Ｓｉｎｃｅｉｔｓｄｉｓｃｏｖ ｅｒｙｉｎｔｈｅ 195 0ｓ ,ＤＡｈａｓｂｅｅｎｏｆｉｎｔｅｒｅｓｔｔｏｎｅｕｒｏｓｃｉｅｎ ｔｉｓｔｓａｎｄｃｈｅｍ…     

聚钙羧酸修饰玻碳电极差分脉冲伏安法同时测定多巴胺和尿酸

采用电化学方法将钙羧酸(CCA)聚合修饰在玻碳电极(GCE)表面制备了聚钙羧酸指示剂修饰玻碳电极(PCCA/GCE),并用循环伏安法和交流阻抗法研究了电极的电化学性能。结果表明:在pH 6.0的磷酸盐缓冲溶液中,多巴胺(DA)和尿酸(UA)在聚钙羧酸修饰电极上的氧化峰得以分开,峰电位差为0.14V,据此提出了聚钙羧酸修饰电极差分脉冲伏安法同时测定多巴胺和尿酸的方法。DA和UA的浓度分别在5.0～43.8μmol.L-1和5.0～50.0μmol.L-1范围内与其氧化峰电流呈线性关系,检出限(3S/N)分别为0.2μmol.L-1和0.5μmol.L-1。方法可用于多巴胺注射液样品中DA和UA的测定,测定值的相对标准偏差(n=5)依次为2.43%和2.35%。     

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...