在抗坏血酸存在下用L-赖氨酸修饰玻碳电极测定多巴胺

采用电化学氧化法制备了L-广赖氮酸单分子层修饰玻碳电极，研究了多巴胺（DA）和抗坏血酸（AA）在该电极上的电化学行为。结果表明，L-广赖氨酸单分子层修饰玻碳电极不仅能改善多巴胺和抗坏血酸的电化学行为，而且能将多巴胺和抗坏血酸二者在裸电极上的完全重叠的单氧化峰分开成为两个完全独立的氧化峰，循环伏安（CV）图上峰间距为507mV，差分脉冲伏安（DPV）图上峰间距为460mV，由此可实现在AA的共存下对样品中的DA进行选择性测定。     

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.     

Gold nanoparticles on a thiol-functionalized silica network for ascorbic acid electrochemical detection in presence of dopamine and uric acid

A simple preparation methodology able to stabilize gold nanoparticles and to obtain an electrode which detects ascorbic acid, uric acid, and dopamine by different techniques is presented. A 3-mercaptopropyl-functionalized silica network was synthesized using the sol–gel method. Gold nanoparticles (nAu) were immobilized on the material at synthesis by adding a sol of these previously prepared particles to the reaction mixture. The electrochemical behavior of the SiO₂/MPTS/Au carbon paste electrode was studied using cyclic voltammetry in the presence of a hexacyanoferrate probe molecule. The presence of nAu in the functionalized silica network changes the electrochemical characteristics of the material, favoring the electron transfer process of this complex ion. The SiO₂/MPTS/Au electrode was proven to be an efficient tool in the simultaneous determination of ascorbic acid (H₂AA), dopamine (DA), and uric acid (UA) using square wave voltammetry techniques. With the nAu on the electrode, an increase in the peak current related to the redox process of the H₂AA, DA, and UA was observed. The separations of the anodic peak potentials between DA/H₂AA and UA/H₂AA were 310 and 442?mV, respectively. The results obtained show that the SiO₂/MPTS/Au electrode can be used in the simultaneous determination of H₂AA, DA, and UA.     

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.     

Highly sensitive electrochemical impedance spectroscopic detection of DNA hybridization based on Aunano-CNT/PANnano films

A polyaniline nanofibers (PAN_nano)/carbon paste electrode (CPE) was prepared via dopping PAN_nano in the carbon paste. The nanogold (Au_nano) and carbon nanotubes (CNT) composite nanoparticles were bound on the surface of the PAN_nano/CPE. The immobilization and hybridization of the DNA probe on the Au_nano-CNT/PAN_nano films were investigated with differential pulse voltammetry (DPV) and cyclic voltammetry (CV) using methylene blue (MB) as indicator, and electrochemical impedance spectroscopy (EIS) using [Fe(CN)₆]^3−/4− as redox probe. The voltammetric peak currents of MB increased dramatically owing to the immobilization of the probe DNA on the Au_nano-CNT/PAN_nano films, and then decreased obviously owing to the hybridization of the DNA probe with the complementary single-stranded DNA (cDNA). The electron transfer resistance (R_et) of the electrode surface increased after the immobilization of the probe DNA on the Au_nano-CNT/PAN_nano films and rose further after the hybridization of the probe DNA. The remarkable difference between the R_et value at the DNA-immobilized electrode and that at the hybridized electrode could be used for the label-free EIS detection of the target DNA. The loading of the DNA probe on Au_nano-CNT/PAN_nano films was greatly enhanced and the sensitivity for the target DNA detection was markedly improved. The sequence-specific DNA of phosphinothricin acetyltransferase (PAT) gene and the polymerase chain reaction (PCR) amplification of nopaline synthase (NOS) gene from transgenically modified beans were determined with this label-free EIS DNA detection method. The dynamic range for detecting the PAT gene sequence was from 1.0 × 10⁻¹² mol/L to 1.0 × 10⁻⁶ mol/L with a detection limit of 5.6 × 10⁻¹³ mol/L.     

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.     

Polystyrene sulphonate wrapped multiwalled carbon nanotubes modified graphite electrode for simultaneous determination of ascorbic acid, dopamine and uric acid

Graphite electrode is modified by casting multi-walled carbon nanotubes (MWCNTs) wrapped with polystyrene sulphonate (PSS) onto the surface of the bare graphite electrode. The modified electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The behavior of the modified electrode towards the oxidation of ascorbic acid (AA), dopamine (DA) and uric acid (UA) has been determined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry (CA). The modified electrode showed better electrocatalytic activity towards AA, DA and UA compared to bare graphite electrode. The electrochemical oxidation signals of AA, DA and UA are well separated into three distinct peaks with peak potential difference of 222, 128 and 350 mV between AA-DA, DA-UA and AA-UA respectively in CV studies and corresponding peak potential separation in DPV are 228, 120 and 348 mV. This modified electrode was successfully used for simultaneous determination of AA, DA and UA in ternary mixture.     

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.     

Platinum nanoparticles–decorated graphene-modified glassy carbon electrode toward the electrochemical determination of ascorbic acid,dopamine, and paracetamol

In the present study, we report the synthesis and characterization of platinum nanoparticles decorated graphene (GPtNPs) nanocomposite toward the electrochemical determination of ascorbic acid (AA), dopamine (DA), and paracetamol (PCT). GPtNPs demonstrated synergistic catalytic activity with enhanced currents in all of the measurements when compared with graphene-modified glassy carbon electrode (G-GCE) and bare GCE. The nanocomposite exhibited low overpotential for AA oxidation and good peak-to-peak separation of 218.0, 218.0, and 436.0 mV for AA–DA, DA–PCT, and AA–PCT, respectively. Cyclic voltammetry (CV) and chronoamperometry (CA) determination of AA, DA, and PCT showed wide linearity ranges. CV determination of AA exhibited linearity range from 300 μM to 20.89 mM and from 22.02 to 39.87 mM. DA determination using CV exhibited linearity range from 5 to 104 μM and from 114 to 684 μM, whereas CA determination of PCT showed a linearity range from 20 μM to 6.43 mM. Differential pulse voltammetry determinations of AA, DA, and PCT exhibited low detection limits of 300, 5, and 5 μM, respectively.     

Electrocatalytic response of dopamine at a dl-homocysteine self-assembled gold electrode

The gold electrode self-assembled with the homocysteine monolayer (Hcy/Au) is demonstrated to catalyze the electrochemical response of dopamine (DA) by cyclic voltammetry. A pair of well-defined redox waves was obtained and the calculated standard rate constant (k_s) is 2.1×10⁻² cm/s at the self-assembled electrode. The reduction peak of DA can be used to determine the concentration of DA in presence of ascorbic acid (AA) owing to the Hcy/Au also catalyzing the electrochemical oxidation of AA.     

柠檬酸修饰电极对抗坏血酸、多巴胺和尿酸的同时检测

研究柠檬酸(CA)修饰玻碳电极(CA/GC)在抗坏血酸(AA)、多巴胺(DA)和尿酸(UA)混合体系中的循环伏安(CV)行为.结果表明,AA、DA和UA在CA/GC电极上氧化峰电流增大,且三者氧化峰电位明显分离(ΔEp(DA,AA)=170 mV,ΔEp(DA,UA)=130 mV,ΔEp(AA,UA)=300 mV).据此,可同时检测AA、DA和UA.在优化的实验条件下,AA、DA和UA的氧化峰电流与其浓度分别在2.0×10-6～1.5×10-3mol.L-1,6.0×10-7～1.0×10-3mol.L-1和6.0×10-7～1.0×10-3mol.L-1范围内呈线性关系.该电极重现性好,可用于盐酸多巴胺针剂DA、VC片剂AA及人体尿液UA的测定.     

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.     

Simultaneous determination of ascorbic acid,dopamine and uric acid based on tryptophan functionalized graphene

A new type of tryptophan-functionalized graphene nanocomposite (Trp-GR) was synthesized by utilizing a facile ultrasonic method via π–π conjugate action between graphene (GR) and tryptophan (Trp) molecule. The material as prepared had well dispersivity in water and better conductivity than pure GR. The surface morphology of Trp-GR was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. The electrochemical behaviors of ascorbic acid (AA), dopamine (DA), and uric acid (UA) were investigated by cyclic voltammetry (CV) on the surface of Trp-GR. The separation of the oxidation peak potentials for AA–DA, DA–UA and UA–AA was about 182 mV, 125 mV and 307 mV, which allowed simultaneously determining AA, DA, and UA. Differential pulse voltammetery (DPV) was used for the determination of AA, DA, and UA in their mixture. Under optimum conditions, the linear response ranges for the determination of AA, DA, and UA were 0.2–12.9 mM, 0.5–110 μM, and 10–1000 μM, with the detection limits (S/N = 3) of 10.09 μM, 0.29 μM and 1.24 μM, respectively. Furthermore, the modified electrode was investigated for real sample analysis.     

Selective determination of dopamine with a cibacron blue/poly-1,5-diaminonaphthalene composite film

A selective detection method for dopamine (DA) was developed by incorporating cibacron blue (F3GA) into poly-1,5-diaminonaphthalene (PDAN) layer. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) were employed to characterize the modified surfaces. The modified electrode was effective in selectively facilitating the electron transfer of DA and blocking the interferences of negatively charged species attributed to the sulfonate groups in the F3GA/PDAN composite film. This method enabled the determination of DA in the presence of various interfering species, including ascorbic acid (AA), in a phosphate buffer solution (pH 7.4). The modified electrode demonstrated good performance in the detection of DA in a concentration range of 5.0-100 μM, with a detection limit (k = 3) of 0.1 ± 0.01 μM. The application was conducted for the determination of DA in a human urine sample and the sensor was proven to be rapid, has excellent selectivity, and stable amperometric response.     

Alumina Polished Glassy Carbon Electrode as a Simple Electrode for Lower Potential Electrochemical Detection of Dopamine in its Sub‐micromolar Level

The electrochemical behaviour of dopamine (DA) at a cleaned and alumina polished glassy carbon electrode (GCE) was studied using cyclic voltammetry (CV). The CV studies revealed that alumina polished GCE (AGCE) shows an enhanced oxidation peak current response with 217 mV negative potential shift towards DA than that of cleaned GCE. The differential pulse voltammetry result shows that the AGCE detects the DA in the linear concentration ranges from 0.15 to 25.25 µmol L^?1. The limit of detection was calculated as 0.046 µmol L^?1 with a sensitivity of 3.74 µA µmol L^?1 cm^?2 for the determination of DA. The fabricated AGCE shows a satisfactory selectivity, practicality along with appreciable repeatability and reproducibility.     

Simultaneous electrochemical sensing of ascorbic acid,dopamine and uric acid at anodized nanocrystalline graphite-like pyrolytic carbon film electrode

Nanocrystalline graphite-like pyrolytic carbon film (PCF) electrode fabricated by a non-catalytic chemical vapor deposition (CVD) process was used for the simultaneous electrochemical sensing of ascorbic acid (AA), dopamine (DA), and uric acid (UA). The electrode was studied with respect to changes in electrocatalytic activity caused by a simple and fast electrochemical pretreatment. The anodized electrode exhibited excellent performance compared to many chemically modified electrodes in terms of detection limit, linear dynamic range, and sensitivity. Differential pulse voltammetry (DPV) was used for the simultaneous determination of ternary mixtures of DA, AA, and UA. Under optimum conditions, the detection limits were 2.9 μM for AA, 0.04 μM for DA, and 0.03 μM for UA with sensitivities of 0.078, 5.345, and 6.192 A M⁻¹, respectively. The peak separation was 219 mV between AA and DA and 150 mV between DA and UA. No electrode fouling was observed and good reproducibility was obtained in all the experiments. The sensor was successfully applied for the assay of DA in an injectable drug and UA in human urine by using standard addition method.     

Fabrication and characterisation of high performance polypyrrole modified microarray sensor for ascorbic acid determination

In this study, gold microelectrode array (Au/MEA) with electrode of 12 μm diameter was fabricated by photolithography technique. Subsequently, polypyrrole (Ppy) modified gold microarrays sensor (Ppy/Au/MEA) was prepared by cyclic voltammetry technique. The deposition potential range and number of cycles were optimised in order to get optimum thickness of Ppy film. Scanning Electron Microscope and Atomic Force Microscope investigations reveal that Ppy coating formed at 3 cycles is porous with thickness of 1.5 μm which exhibiting high catalytic current for ascorbic acid (AA) in square wave technique (SWV). In contrast to earlier sensors designs, these Ppy/Au/MEA sensors exhibits lower detection limit (LOD) of 10 nm towards AA at physiological conditions. It also exhibits enhanced sensitivity (2.5 mA cm⁻² mM⁻¹) and long range of linear detection limit from 10 nm to 2.8 mM. In the same way, polypyrrole modified macro Au (Ppy/Au/MA) biosensor was also fabricated and its electro catalytic property towards AA was compared with that of Ppy/Au/MEA. The Ppy/Au/MA exhibits sensitivity of only 0.27 mA cm⁻² mM⁻¹, LOD of 5 μM and linear range of 10 μM to 2.2 mM. Hence, our investigations indicate that the Ppy/Au/MEA could serve as highly sensitive sensor for AA than any of the earlier designs. So, the Ppy/Au/MEA electrode was utilised for determination AA in a wide variety of real samples.     

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.     

Simultaneous voltammetric determination of ascorbic acid and dopamine at the surface of electrodes modified with self-assembled gold nanoparticle films

Gold nanoparticles (GNs) could be efficiently immobilized on binary mixed self-assembled monolayers (SAMs) on a gold surface composed of 1,6-hexanedithiol and 1-octanethiol (nano-Au/SAMs gold electrode). This GN chemically modified electrode was used for electrochemical determination of ascorbic acid (AA) and dopamine (DA) in aqueous media. The result showed that the GN-modified electrode could clearly resolve the oxidation peaks of AA and DA, with a peak-to-peak separation (∆E _p) of 110 mV enabling determination of AA and DA in the presence of each other. The linear analytical curves were obtained in the ranges of 0.3–1.4 mM for AA and 0.2–1.2 mM for DA concentrations using differential pulse voltammetry. The detection limits (3σ) were 9.0 × 10⁻⁵ M for AA and 9.0 × 10⁻⁵ M for DA.     

Multi-walled carbon nanotube paste electrode for selective voltammetric detection of isoniazid

A multi-walled carbon nanotube paste electrode (MWCPE) is prepared as an electrochemical sensor with high sensitivity and selectivity in responding to isoniazid. The electrochemical oxidation of isoniazid is investigated in buffered solution by cyclic and differential pulse voltammetry. The electrode is shown to be very effective for the detection of isoniazid in the presence of other biological reductant compounds. The electrochemical oxidation of cysteine, due to the high overvoltage, is completely stopped at the surface of MWCPE. The electrode exhibits a very good resolution between the voltammetric peak of isoniazid and the peaks of ascorbic acid (AA) and dopamine (DA). A resolution of more than 450 mV between the anodic peak potentials makes the MWCPE suitable for simultaneous detection of isoniazid in the presence of AA or DA in clinical and pharmaceutical preparations. Differential pulse voltammetry (DPV) is applied as a sensitive method for the determination of isoniazid. The linear range in these determinations is 1 × 10⁻⁶–1 × 10⁻³ M for isoniazid and the detection limit is 5 × 10⁻⁷ M. The electrode was applied to the simultaneous determinations in isoniazid and AA mixtures and also, isoniazid and DA mixture over a wide concentration range. The slope variation for the calibration curves of isoniazid (RSD) was less than 4.5% (based on ten measurements over a period of three months).