Voltammetric Determination of Dopamine in the Presence of Ascorbic Acid Using Polycarminic Acid Film Coated Carbon Fiber Cylinder Microelectrode

Dopamine ((3,4-dihydroxyphenyl) ethylamine, DA) is an important neurotransmitter in the mammalian central nervous system (CNS). Recently, investigations on the measurement of DA have attracted much attention. Ascorbic acid (AA), however, usually coexists together with DA in mammalian body and their oxidative potential are very close. Therefore, the measurement of DA in vivo is always interfered with AA. In this paper, we reported the polycarminic acid (PCA) film coated carbon fiber cylinder microelectrodes. This film tends to exclude the interference of big anions such as AA but selectively responds to big cations such as DA.     

Modified microelectrodes and multivariate calibration for flow injection amperometric simultaneous determination of ascorbic acid, dopamine, epinephrine and dipyrone

Flow injection amperometric quantification of ascorbic acid (AA), dopamine (DA), epinephrine (EP) and dipyrone (DI) in mixtures (in the microgram g-1 range) was successfully performed by using an array of microelectrodes with units modified by the electrodeposition of different noble metals, together with multivariate calibration analysis. The four groups of microelectrodes utilized included a pure gold electrode and electrodes modified by electrodeposition of platinum, palladium or a mixture of platinum + palladium. The array of microelectrodes was inserted in a flow cell and the amperometric data acquisition was performed with a four-channel potentiostat. The analysis of the resulting signals was carried out by a multivariate calibration method, using a group of 16 standard mixtures selected by a two-level factorial design. The analysis of synthetic samples and pharmaceutical compounds containing AA and DI led to very similar values to those obtained by the classical iodimetric analysis. The average absolute errors (in microgram g-1) calculated for each analyte were 0.3, 0.2, 0.4 and 0.4 for AA, DA, EP and DI, respectively.     

Modified platinum electrode with phytic acid and single-walled carbon nanotube: Application to the selective determination of dopamine in the presence of ascorbic and uric acids

A platinum (Pt) electrode modified by single-walled carbon nanotubes (SWNTs) and phytic acid (PA) was investigated by voltammetric methods in buffer solution. The PA-SWNTs/Pt-modified electrode demonstrated substantial enhancements in electrochemical sensitivity and selectivity towards dopamine (DA) in the presence of L-ascorbic acid (AA) and uric acid (UA). The PA-SWNTs films promoted the electron transfer reaction of DA, while the PA film, acting as a negatively charged linker, combined with the positively charged DA to induced DA accumulation in the film at pH under 7.4. However, the PA film restrained the electrochemical response of the negatively charged AA due to the electrostatic repulsion. The anodic peak potentials of DA, AA and UA could be separated by electrochemical techniques, and the interferences from AA and UA were effectively eliminated in the DA determination. Linear calibration plots were obtained in the DA concentration range of 0.2-10 μM and the detection limit of the DA oxidation current was determined to be 0.08 μM at a signal-to-noise ratio of 3. The results indicated that the modified electrode can be used to determine DA without interference from AA and UA, while ensuring good sensitivity, selectivity, and reproducibility.     

Ultrathin Cell‐Membrane‐Mimic Phosphorylcholine Polymer Film Coating Enables Large Improvements for In Vivo Electrochemical Detection

Resisting biomolecule adsorption onto the surface of brain‐implanted microelectrodes is a key issue for in vivo monitoring of neurochemicals. Herein, we demonstrate that an ultrathin cell‐membrane‐mimic film of ethylenedioxythiophene tailored with zwitterionic phosphorylcholine (EDOT‐PC) electropolymerized onto the surface of a carbon fiber microelectrode (CFE) not only resists protein adsorption but also maintains the sensitivity and time response for in vivo monitoring of dopamine (DA). As a consequence, the as‐prepared PEDOT‐PC/CFEs could be used as a new reliable platform for tracking DA in vivo and would help understand the physiological and pathological functions of DA.     

Electrocatalytic activity of three-dimensional monolayer of 3-mercaptopropionic acid assembled on gold nanoparticle arrays

3-Mercaptopropionic acid (MPA) was assembled on gold nanoparticle arrays to form three-dimensional monolayer. The electrochemical behavior of small biomolecules such as NADH, ascorbic acid (AA), uric acid (UA) and dopamine (DA) on the as-prepared three-dimensional monolayer was studied. The cyclic voltammetric results indicated that three-dimensional MPA monolayer promoted the electron transfer between NADH and electrode, which was similar to two-dimensional MPA monolayer assembled on planar gold electrode. However, to the electrooxidation of AA, although two-dimensional MPA monolayer exhibited a blocking effect, three-dimensional MPA monolayer showed an obvious promotion. The catalytic activity of three-dimensional MPA monolayer towards UA and DA was also observed, which was attributed to its three-dimensional structure that might effectively prevent the poison of the electrode surface by the oxidation products.     

The Influence of the Cathodic Pretreatment on the Electrochemical Detection of Dopamine by Poly(1‐aminoanthracene) Modified Electrode

In this study we demonstrated the influence of the cathodic pretreatment of poly(1‐aminoanthracene) (PAA) electropolymerized on a platinum electrode for determination of dopamine (DA). The DA electrochemical response was obtained after a cathodic pretreatment of the PAA electrode which consisted of applying a potential of ?0.7 V (vs. Ag/AgCl) for 3 s before each measurement. The pretreatment of the electrode changed the PAA electrocatalytic properties so that the electrode began to present electrochemical response to DA without interference of ascorbic acid (AA). The anodic peak currents determined by differential pulse voltammetry using pretreated PAA showed a linear dependence on the DA concentration from 0.56 to 100 µM with a detection limit of 0.13 µM and a correlation coefficient of 0.9986. The electrode exhibits a relative standard deviation of 1.2 % for ten successive measurements of a 0.5 mM DA solution. The analysis by scanning electron microscopy and atomic force microscopy show a homogeneous and nanostructured film with globular structures with diameter of about 20 nm. The analytical results obtained for DA determination at a pretreated PAA electrode in pharmaceutical formulation sample were in good agreement with those obtained by a comparative procedure at a 95 % confidence level. PAA electrode after the pretreatment showed electrochemical responses to DA with excellent selectivity, sensitivity, and high stability without interference of AA.     

Determination of dopamine with improved sensitivity by exploiting an accumulation effect at a nano-gold electrode modified with poly(sulfosalicylic acid)

We describe a glassy carbon electrode modified with nano-gold and a film of poly(sulfosalicylic acid) that was obtained by electropolymerization of sulfosalicylic acid. The electrochemical characteristics of the electrode were investigated by using (a) the anionic hexacyanoferrate, and (b) the cationic ruthenium-trisbipyridyl systems as redox probes. The electrode displayed selective and enhanced electroanalytical response towards dopamine (DA), obviously because DA (which is cationic) is accumulated at the electrode, while anions such as ascorbic acid (AA) do not and in fact are being repelled. A 2000-fold molar excess of AA is tolerated after a 120-s accumulation time followed by stripping detection at pH?6.5. Response is linear with the concentration of DA in the range from 0.05 to 5???M, and the detection limit is 7 nM (at an S/N of 3) even in the presence of 100 ??M concentrations of AA.

聚伊文思蓝修饰电极对多巴胺和抗坏血酸的电分离及同时测定

研究多巴胺(DA)和抗坏血酸(AA)在聚伊文思蓝(Evans Blue)修饰电极上的伏安行为,建立差示脉冲伏安测定法.在pH4.5磷酸盐缓冲液中,聚伊文思蓝修饰电极对DA和AA有显著的增敏和电分离作用.DA和AA氧化峰电流与浓度分别在1.0×10-6~3.0×10-5mol/L和5.0×10-6~1.05×10-4mol/L范围内呈良好的线性关系,检测限分别为2.5×10-7mol/L和3.0×10-7mol/L.当DA与AA共存时,由该修饰电极检测的二者氧化峰电位差达184 mV,故可同时测定DA和AA,并有效消除其它组分对DA测定的干扰,已用于实际样品中DA和AA含量的测定,结果令人满意.     

Preparation and characterization of PtAu hybrid film modified electrodes and their use in simultaneous determination of dopamine, ascorbic acid and uric acid

A novel biosensor was fabricated by electrochemical deposition of platinum and gold nanoparticles (nanoAu) with l-Cysteine on glassy carbon electrode. It was found that the nanoAu particle size distribution range was (50-80 nm), and the platinum particle size range was (200-300 nm). The hybrid film could be produced on gold and transparent indium tin oxide electrodes for different kind of studies such as electrochemical quartz crystal microbalance (EQCM), scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) and electrochemical studies. The PtAu hybrid film was applied to the electro catalytic oxidation of dopamine (DA), ascorbic acid (AA) and uric acid (UA) at pH 4.0 using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The modified electrode was quite effective not only to detect DA, AA and UA individually but also in simultaneous determination of these species in a mixture. The overlapping anodic peaks of DA, AA and UA were resolved into three well-defined voltammetric peaks in CV and DPV. The catalytic peak currents obtained from CV and DPV increased linearly with concentration. The relative standard deviation (% R.S.D., n = 10) for AA, DA and UA were less than 2.0% and DA, AA and UA can be determined in the ranges of 0.103-1.65, 0.024-0.384 and 0.021-0.336 mM, respectively. In addition, the modified electrode also shows good sensitivity, and stability. Satisfactory results were achieved for the determination of DA, AA and UA in dopamine injection solution, vitamin C tablets and human urine samples.     

电化学活化碳纤维微电极和脑神经递质及抗坏血酸在体测定

本文采用一种简单电化学方法,即恒电流法处理自制碳纤维电极,在脑神经递质测定中显示了很高的灵敏度和分辨能力.活化后的电极对多巴胺的检测限达5×10^-8mol.dm^-3,对多巴胺和抗坏血酸的伏安峰分离达170mV.作者使用该电极,采用半微分伏安法测定了活体大鼠脑内抗坏血酸,3,4-二羟苯乙酸和5-羟吲哚乙酸的浓度分别为1.7×10^-4,2.1×10^-5和 3.3×10^-6mol·dm^-3.本文对电极的制作,活化条件,伏安峰判别,在体药物实验和电极活化机理等进行了研究和探讨.     

A microchip-based flow injection-amperometry system with mercaptopropionic acid modified electroless gold microelectrode for the selective determination of dopamine

A novel chip-based flow injection analysis (FIA) system has been developed for automatic, rapid and selective determination of dopamine (DA) in the presence of ascorbic acid (AA). The system is composed of a polycarbonate (PC) microfluidic chip with an electrochemical detector (ED), a gravity pump, and an automatic sample loading and injection unit. The selectivity of the ED was improved by modification of the gold working microelectrode, which was fabricated on the PC chip by UV-directed electroless gold plating, with a self-assembled monolayer (SAM) of 3-mercaptopropionic acid (MPA). Postplating treatment methods for cleaning the surface of electroless gold microelectrodes were investigated to ensure the formation of high quality SAMs. The effects of detection potential, flow rate, and sampling volume on the performance of the chip-based FIA system were studied. Under optimum conditions, a detection limit of 74 nmol L⁻¹ for DA was achieved at the sample throughput rate of 180 h⁻¹. A RSD of 0.9% for peak heights was observed for 19 runs of a 100 μmol L⁻¹ DA solution. Interference-free determination of DA could be conducted if the concentration ratio of AA–DA was no more than 10.     

Direct Determination of Trace Dopamine in an Ascorbic Acid Solution at a Bare Glassy Carbon Electrode Using Differential Pulse Voltammetry

It is difficult to monitor dopamine (DA) accurately with a bare glassy carbon electrode because of the interference of ascorbic acid (AA). In this paper, a method for the determination of DA in an AA solution using differential pulse voltammetry was established. Because AA loses its electrochemical activity after being oxidized, hydrogen peroxide was used to oxidize AA, and the interference of AA was completely eliminated. As a result, trace DA could be directly determined in the AA solution with a bare glassy carbon electrode. When trace DA was determined in a 1.0 mmol L^?1 AA solution, there was a wide linear range from 3.0×10^?8 mol L^?1 to 1.0×10^?5 mol L^?1. The application of this method was demonstrated by the selective measurement of DA in an injection without pretreatment.     

Poly (3-(3-pyridyl) acrylic acid) modified glassy carbon electrode for simultaneous determination of dopamine, ascorbic acid and uric acid

Trans-3-(3-pyridyl) acrylic acid (PAA) was deposited on glassy carbon electrode (GCE) by electropolymerization in pH 7.0 phosphate buffer solution (PBS). The poly (3-(3-pyridyl) acrylic acid) (PPAA) film modified glassy carbon electrode shows an excellent electrochemical response for dopamine (DA), ascorbic acid (AA) and uric acid (UA). The cyclic voltammetry oxidation peaks for DA and AA, DA and UA, AA and UA are separated by 150 mV, 130 mV and 280 mV, respectively. This permits the simultaneous determination of AA, DA and UA. The interference of AA with the determination of DA could be eliminated because of the electrostatic interaction between DA cations and the negatively charged PPAA film at pH 7.0. The anodic peak currents of DA, AA and UA increase linearly with concentration in the range of 1-40 micromol L(-1), 10-400 micromol L(-1) and 1.6-80 micromol L(-1), respectively, with a correlation coefficient (r) always higher than 0.998. The detection limit is 0.06 micromol L(-1), 0.8 micromol L(-1) and 1.1 micromol L(-1) for DA, AA and UA, respectively.     

Detection of Uric Acid in the Presence of Dopamine and High Concentration of Ascorbic Acid Using PDDA Modified Graphite Electrode

The properties of graphite electrode (Gr) modified with poly(diallyl dimethyl ammonium chloride) (PDDA) for the detection of uric acid (UA) in the presence of dopamine (DA) and high concentration of ascorbic acid (AA) have been investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The polymer modified graphite electrode was prepared by a very simple method just by immersing the graphite electrode in PDDA solution for 20 minutes. The PDDA/Gr modified electrode displayed excellent electrocatalytic activity towards the oxidation of UA, DA and AA compared to that at the bare graphite electrode. The electrochemical oxidation signals of UA, DA and AA are well resolved into three distinct peaks with peak potential separations of 220 mV, 168 mV and 387 mV between AA‐DA, DA‐UA and AA‐UA respectively in cyclic voltammetry studies and the corresponding peak potential separations are 230 mV, 130 mV and 354 mV respectively in differential pulse voltammetry. The lowest detection limits obtained for UA, DA and AA were 1×10^?7 M, 2×10^?7 M and 800×10^?9 M respectively. The PDDA/Gr electrode efficiently eliminated the interference of DA and a high concentration of AA in the determination of UA with good selectivity, sensitivity and reproducibility. The modified electrode was also successfully applied for simultaneous determination of UA, DA and AA in their ternary mixture.     

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

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

同时测定多巴胺和肾上腺素的大环镍膜修饰电极

研究了大环镍膜修饰电极对多巴胺和肾上腺素的电化学响应特性；结果表明，该修饰电极对多巴胺和肾上腺素的电极反应具有良好的催化活性，多巴胺和肾上腺素在修饰电极上的氧化电位比在裸铂电极上分别负移了230mV和70mV，使二者的阳极峰得到很好的分离，且灵敏度大为提高；将该修饰电极用于多巴胺和肾上腺素的同时检测，获得满意结果，生物体中的主要干扰物质抗坏血酸和NO2^-等均不干扰测定。     

Micro-flow in vivo analysis of L-glutamate with an on-line enzyme amplifier based on substrate recycling.

A micro-flow enzyme system with a microdialysis probe is proposed for the amperometric detection of trace amounts of neurotransmitter L-glutamate released from rat brain cells. The L-glutamate oxidase (EC 1.4.3.11)/glutamate dehydrogenase (EC 1.4.1.4) coimmobilized reactor was used to enhance the sensitivity of L-glutamate as an on-line amplifier based on substrate recycling. A poly(1,2-diaminobenzene) film-coated platinum electrode was also used to selectively detect only the hydrogen peroxide generated into a upstream enzyme reactor, without interference from oxidizable species, such as L-ascorbate, the adsorption of low molecular-weight proteins in a dialysate, and NADPH added to the carrier solution to initiate substrate recycling. By the present in vivo system, L-glutamate was selectively assayed with about a 600-fold increase in sensitivity compared with the unamplified responses. The detection limit was 0.08 mumol dm-3. This method was applied to an in vivo assay of L-glutamate in the extracellular space of rat brain; also, monitoring of the L-glutamate level changed after a continuous stimulation of KCl to demonstrate the reliability of the system.     

On-line microfluidic sensor integrated with a micro array electrode and enzyme-modified pre-reactor for the real-time monitoring of blood catecholamine

We developed an on-line microfluidic sensing device with an interdigitated array (IDA) electrode and a micro pre-reactor for the real-time monitoring of blood catecholamine (CA) and succeeded in the highly sensitive detection of dopamine (DA) in the presence of L-ascorbic acid (AA). Our device exhibits the lowest detection limit (110 ± 10 pM (S/N=3)), of reported catecholamine sensors. The improvement in sensitivity results from the high redox cycling of DA and the increase in the mass transfer rate per unit time onto the IDA electrode achieved by the flow measurement. The pre-reactor was integrated upstream in the micro flow channel to eliminate AA. A large number of rectangular shaped micropillars, which were modified with ascorbate oxidase, were formed in the pre-reactor to increase the surface area. The flow was disturbed by the two dimensional micropillar arrangement. This structure enables us to increase the elimination efficiency for AA. As a result, we achieved both the continuous and highly selective detection of 1 nM DA with complete elimination of 10 μM AA in the sample solution without employing any selective membrane such as Nafion, whose use reduces sensitivity due to the low diffusion coefficient of DA inside the membrane.     

Simultaneous determination of dopamine and ascorbic acid on poly (3,4-ethylenedioxythiophene) modified glassy carbon electrode

Detection of dopamine (DA) in the presence of excess of ascorbic acid (AA) has been demonstrated using a conducting polymer matrix, poly (3,4-ethylenedioxythiophene) (PEDOT) film in neutral buffer (PBS 7.4) solution. The PEDOT film was deposited on a glassy carbon electrode by electropolymerization of EDOT from acetonitrile solution. Atomic force microscopy studies revealed that the electrodeposited film was found to be approximately 100 nm thick with a roughness factor of 2.6 nm. Voltammetric studies have shown catalytic oxidation of DA and AA on PEDOT modified electrode and can afford a peak potential separation of ∼0.2 V. It is speculated that the cationic PEDOT film interacts with the negatively charged ascorbate anion through favorable electrostatic interaction, which results in pre-concentration at a less anodic value. The positively charged DA tends to interact with the hydrophobic regions of PEDOT film through hydrophobic–hydrophobic interaction thus resulting in favorable adsorption on the polymer matrix. Further enhancement in sensitivity to micro molar level oxidation current for DA/AA oxidation was achieved by square wave voltammetry (SWV) which can detect DA at its low concentration of 1 μM in the presence of 1000 times higher concentration of AA (1 mM). Thus the PEDOT modified electrode exhibited a stable and sensitive response to DA in the presence of AA interference.     

Electrochemical determination of dopamine using a poly(2-picolinic acid) modified glassy carbon electrode

A poly(2-picolinic acid) chemically modified electrode (CME) for the determination of dopamine (DA) by cyclic voltammetry is described. Compared with a bare glassy carbon electrode, the CME exhibits a 200 mV shift of the oxidation potential of DA in the cathodic direction and a marked enhancement of the current response. In pH 7.0 buffer solution, a linear calibration graph is obtained over the range from 2.5 x 10(-7) to 1.0 x 10(-5) mol dm-3 with a correlation coefficient of 0.998. The detection limit is 3.0 x 10(-8) mol dm-3. The modified electrode eliminated efficiently the interference from ascorbic acid (AA) when present in a 150-fold concentration ratio. It also showed excellent stability and reproducibility.