Pyrolyzed Photoresist Carbon Electrodes for Microchip Electrophoresis with Dual‐Electrode Amperometric Detection

The fabrication and evaluation of pyrolyzed photoresist films (PPF) for microchip capillary electrophoresis (CE) with dual‐electrode electrochemical (EC) detection is described. The sensitivity, linearity, and reproducibility were evaluated using catecholamines and related compounds, including dopamine (DA), 5‐hydroxyindole‐3‐acetic acid (5‐HIAA), ascorbic acid (AA), and catechol. Initial studies with DA show the response of the PPF electrodes to be linear between 25 and 500 μM (r²=0.999) with a limit of detection (LOD) of 5 μM (S/N=3) and sensitivity of 5.8 pA/μM. Selectivity was further enhanced by employing dual‐electrode detection in the series configuration for detection of species exhibiting chemically reversible redox reactions.     

Electrochemical reduced graphene oxide-poly(eriochrome black T)/gold nanoparticles modified glassy carbon electrode for simultaneous determination of ascorbic acid,dopamine and uric acid

This work reports on the preparation of electrochemically reduced graphene oxide (ERGO)-poly(eriochrome black T) (pEBT) assembled gold nanoparticles for the simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) in PBS pH 6.0. Characterisations of the composite were carried out by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry. As a result of the synergistic effect, the modified glassy carbon electrode (GCE) possessed an efficient electrochemical catalytic activity with a high selectivity and sensitivity in oxidising AA-DA and DA-UA as compared to the bare GCE. The peak separations of AA and DA, DA and UA were 183 mV and 150 mV, respectively. The linear response ranges for AA, DA and UA were 10–900 μM, 0.5–20 μM and 2–70 μM with detection limits of 0.53 μM, 0.009 μM and 0.046 μM (S/N = 3), respectively. The sensitivity of ERGO-pEBT/AuNPs was measured as 0.003 µA/μM, 0.164 µA/μM and 0.034 µA/μM for AA, DA, and UA, respectively. The modified electrochemical sensor was used in the determination of AA, DA, and UA in vitamin C tablets and urine sample with good recovery.     

Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid Based on Gold Nanoparticles‐PTCA‐Cys Composites Modified Electrodes

In this study, a nanocomposite of 3, 4, 9, 10‐perylenetetracarboxylic acid and L‐cysteine (PTCA‐Cys) with satisfactory water‐solubility and film‐forming ability was prepared and worked as substrate for modifying the glassy carbon electrode. Then, gold nanoparticles (AuNPs) were immobilized to achieve a PTCA‐Cys‐AuNPs modified electrode which provided more reaction positions on the sensor. Scanning electron microscopy, transmission electron microscopy, cyclic voltammetry and different pulse voltammetry were employed to characterize the assembly process of the sensor. The constructed sensor displayed desirable sensitivity, selectivity and stability towards the simultaneous detection of ascorbic acid (AA), dopamine (DA) and uric acid (UA). Under the optimal experimental conditions, the oxidation peaks of AA, DA and UA appeared at 64, 240 and 376 mV, respectively. The corresponding linear response ranges were 3.2–435, 0.04–100 and 0.80–297 μM, and the detection limits were 1.1, 0.010 and 0.27 μM (S/N=3), respectively.     

Sensitive and Facile Determination of Catechol and Hydroquinone Simultaneously Under Coexistence of Resorcinol with a Zn/Al Layered Double Hydroxide Film Modified Glassy Carbon Electrode

A stable dihydroxybenzene sensor was fabricated by electrochemical deposition of Zn/Al layered double hydroxide film on glassy carbon electrode (LDHf/GCE). The sensitive and facile electrochemical method for the simultaneous determination of catechol (CA) and hydroquinone (HQ) under coexistence of resorcinol (RE) has been achieved at the LDHf/GCE in phosphate buffer solution (pH 6.5). Under the optimized conditions, the differential pulse voltammetry response of the modified electrode to CA (or HQ) shows a linear concentration range of 0.6 μM to 6.0 mM (or 3.2 μM to 2.4 mM) with a correlation coefficient of 0.9987 (or 0.9992) and the calculated limit of detection is 0.1 μM (or 1.0 μM) at a signal‐to‐noise ratio of 3. In the presence of 50 μM isomer, the linear concentration ranges for CA and HQ are 3.0 μM to 1.5 mM and 12.0 μM to 0.8 mM, respectively. The detection limits are 1.2 μM and 9.0 μM. Further, the proposed method has been performed to successfully detect dihydroxybenzene isomers in analysis of real samples, such as water and tea.     

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.     

Fluoride Sensing by Catechol‐Based π‐Electron Systems

We have developed new catechol‐based sensors that can detect fluoride via fluorescence or optical absorption even in the presence of other halides. The level and sensitivity of detection of the sensing molecules is dependent on the chromophore length, which is controlled by the number of thiophene units (one to three) within the chromophore. The sensor with three thiophene units, (E)‐2‐(2,2′‐terthiophen‐5‐yl)‐3‐(3,4‐dihydroxyphenyl)acrylonitrile, gives the best response to fluoride. By using fluorescence measurements fluoride is detectable over the concentration range 1.7 μM to 200 μM . Importantly, when adsorbed onto a solid support the fluorescent catechol dye can be used to detect the presence of fluoride in aqueous solution.     

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.     

A Facile Fabrication of Poly-ethionine Film on Glassy Carbon Electrode for Simultaneous and Sensitive Detection of Dopamine and Paracetamol

An electrochemical sensor based on poly-ethionine (Poly-ET) film modified glassy carbon electrode was developed for sensitive and simultaneous sensing of dopamine (DA) and paracetamol (PA). The electropolymerization of ethionine monomer was carried out to modify the electrode. The modified electrode was characterized by using scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The Poly-ET/GCE exhibited excellent electrocatalysis towards the sensing of DA and PA. Poly-ET/GCE showed a linear increase of current response with increase concentration of DA and PA ranging from 0.1 μM–60 μM and 0.1 μM–180 μM, respectively. The LODs were found to be 7 nM and 18 nM (S/N=3) for DA and PA, respectively. This electrochemical sensor was successfully utilized for the detection of DA and PA in pharmaceutical samples.     

Platinum Nanoparticles/Poly(isoleucine) Modified Glassy Carbon Electrode for the Simultaneous Determination of Hydroquinone and Catechol

A new electrochemical sensor based on Poly(Isoleucine) modified glassy carbon electrode decorated with platinum nanoparticles (Pt/Poly(Isoleucine)/GCE) was developed for sensitive individual and simultaneous determination of hydroquinone (HQ) and catechol (CC). Scanning electron microscopy (SEM), Electrochemical impedance spectroscopy (EIS), Cyclic voltammetry (CV) and Differential pulse voltammetry (DPV) were performed in order to characterize the Pt/Poly(Isoleucine)/GCE nanocomposite. For simultaneous determination of HQ and CC, Pt/Poly(Isoleucine)/GCE showed wide linear range between the 0.01–100.0 μM. The detection limits were 0.006 μM for HQ and 0.005 μM for CC. The Pt/Poly(Isoleucine)/GC electrode exhibited good sensitivity and reliability in the simultaneous electroanalysis of two isomers in PBS of pH 7.5. The modified electrode was used to detect the isomers in naturel samples.     

A selective supramolecular photochemical sensor for dopamine

Dopamine (DA) is an important biomarker for diseases and biological disorders. Existing techniques for DA detection suffer from drawbacks including low sensitivity and selectivity as well as interfering signals from non-target molecules. A simple and selective photochemical sensor for the determination of DA in a supramolecular manner is presented. This approach utilises the complexation properties of a highly fluorescent water-soluble complex of perylene bis(diimide) dye with the macrocyclic host cucurbit[8]uril. The method can be used for the determination of DA in aqueous media, with detection limits below 2 × 10^? 5 M, even in the presence of known interferents including ascorbic acid and the catecholamines epinephrine and norepinepherine.     

Selective enrichment of catecholamines using iron oxide nanoparticles followed by CE with UV detection

This study examines the use of unmodified magnetite nanoparticles (Fe₃O₄ NPs) for selective extraction and enrichment of the catecholamines dopamine (DA), noradrenaline (NE), and adrenaline (E), prior to analysis using capillary electrophoresis with UV detection. Coordination between Fe³⁺ on‐the‐surface Fe₃O₄ NPs and the catechol moiety of catecholamines enables Fe₃O₄ NPs to capture catecholamines from an aqueous solution. We obtained maximum loading of catecholamines on the NP surface by adjusting the pH of the solution to 7.0. In addition, catecholamine loading on the Fe₃O₄ NPs increased in conjunction with NP concentrations. H₃PO₄ was found to be efficient for the removal of adsorbed catecholamines on the NP surface. Adding 1.2% poly(diallyldimethylammonium chloride) to the background electrolyte resulted in a baseline separation of the liberated catecholamines within 20 min. Under optimal extraction and separation conditions, the limit of detections at a S/N ratio of 3 for E, NE, and DA were 9, 8, and 10 nM, respectively. Significantly, the combination of a phenylboronate‐containing spin column and the proposed method was successfully applied to the determination of NE and DA in human urine and NE in Portulaca oleracea L. leaves.     

Selective amine recognition: development of a chemosensor for dopamine and norepinephrine

[reaction: see text] A boronic acid-containing coumarin aldehyde was designed and synthesized. The sensor binds to catecholamines such as dopamine and norepinephrine by forming an iminium ion with the amine as well as a boronate ester with the catechol. An internal hydrogen bond produces a colorimetric response to these analytes with good selectivity for catecholamines over simple amines. The fluorescence of the sensor is quenched by the catechol.     

A novel palygorskite-modified carbon paste amperometric sensor for catechol determination

A palygorskite-modified carbon paste electrode (CPE) was constructed using graphite powder mixed with palygorskite particles. Compared with the unmodified CPE, the resulting palygorskite-modified CPE remarkably increases the peak currents of catechol, and greatly lowers the peak potential separation. Therefore, the palygorskite exhibits catalytic activity to catechol and significantly improves the determining sensitivity. The electrocatalytic activity of palygorskite is attributed to its high adsorption capability and the –OH groups on its surface, which plays an important role in the electron transfer between the modified CPE and the catechol in the solution. The sensor shows a linear response range between 5 and 100 μM catechol with a correlation coefficient of 0.998. The detection limit was calculated as 0.57 μM (s/n = 3).     

Enhanced Electrocatalytic Activity of Ni‐CNT Nanocomposites for Simultaneous Determination of Epinephrine and Dopamine

A promising electrochemical sensor based nickel‐carbon nanotube (Ni‐CNT) modified on glassy carbon (GC) electrode had been developed and the properties of the modified electrode were characterized by multispectroscopic analysis. The fabricated sensor (GC/Ni‐CNT) electrode was utilized to determine the catecholamines such as epinephrine and dopamine simultaneously. Differential pulse voltammetry and amperometry were used to verify the electrochemical behavior of the studied compounds. The GC/Ni‐CNT based amperometric sensor showed a wide linear range and low detection limit with high analytical sensitivity of 8.31 and 6.61 μA μM^?1 for EP and DA, respectively which demonstrates better characteristics compared to other electrodes reported in the literature. Further, no significant change in amperometric current response was observed in presence of biological interference species such as glucose, cysteine, citric acid, uric acid and ascorbic acid in the detection of EP and DA. The utility of this GC/Ni‐CNT electrode was well established for the determination of EP and DA in human urine samples.     

An end-channel amperometric detector for microchip capillary electrophoresis

An end-channel amperometric detector with a guide tube for working electrode was designed and integrated on a home-made glass microchip. The guide tube was directly patterned and fabricated at the end of the detection reservoir, which made the fixation and alignment of working electrode relatively easy. The fabrication was carried out in a two-step etching process. A 30 μm carbon fiber microdisk electrode and Pt cathode were also integrated onto the amperometric detector. The characteristics and primary performance of the home-made microchip capillary electrophoresis (MCCE) were investigated with neurotransmitters. The baseline separation of dopamine (DA), catechol (CA) and epinephrine (EP) was achieved within 80 s. Separation parameters such as injection time, buffer components, pH of the buffer were studied. Relative standard deviations of not more than 6.0% were obtained for both peak currents and migration times. Under the selected separation conditions, the response for DA was linear from 5 to 200 μM and from 20 to 800 μM for CA. The limits of detection of DA and CA were 0.51 and 2.9 μM, respectively (S/N=3).     

Immobilization of CoII-(N,N′-bis(salicylidene)-2-aminobenzylamine) on Poly(pyrrole-co-o-anisidine)/Chitosan Composite Films: Application to Electrocatalytic Oxidation of Catechol

In this study, poly (pyrrole-co-o-anisidine)/chitosan composite (Cs) films were prepared by cyclic voltammetry technique on platinum electrode using different pyrrole and o-anisidine mole ratios. Immobilization process was accomplished in Co^II-(N,N′-bis(salicylidene)-2-aminobenzylamine)(CoL) dissolved 0.15 M acetonitrile-LiClO₄ solution by cyclic voltammetry technique at 0.2–2.0 V potential range. Three electrode methods were applied in all electrochemical studies. After immobilization process, the characterizations of the electro catalytic surfaces (Cs−CoL−Pt) were carried out by cyclic voltammetry and SEM images. The SEM images clearly indicated that the [CoL] complex is immobilized onto composite films. The electrocatalytic activity of the modified electrodes on the catechol was investigated using buffer solutions of different pH values. The results of catalytic studies revealed that, pH=10 buffer solution was the optimal solution and 1 : 1 Cs−CoL−Pt electrode was the best electrode for catechol oxidation. In square wave voltammetry measurements using this electrode, two linear working ranges were determined. The linear response ranges for catechol determination were found as 3.0 μM–6.0 μM and 16 μM–80 μM for the first and the second linear working ranges, respectively, with 1.1 μM detection limit.     

Hydrophobicity‐aided potentiometric detection of catecholamines,beta‐agonists,and beta‐blockers in a mixed‐solvent capillary electrophoresis system

A series of cationic drug‐like substances with distinct basicity, hydrogen‐bonding ability, and hydrophobicity, including three catecholamines, two beta‐agonists, and thirteen beta‐blockers, was successfully detected in a capillary electrophoresis system using an end‐capillary coupled potentiometric sensor consisting of a PVC‐based liquid membrane deposited directly on a 100 μm diameter copper rod. The electrophoretic separation was performed on a 72 cm×75 μm id uncoated fused‐silica capillary with an acidic background electrolyte containing phosphoric acid in a water–acetonitrile mixture, pH* 2.8. Samples were injected electrokinetically at 5.0 kV for 10 s and a running voltage of 19.5 kV was applied. Excluding the bufuralol/practolol pair, baseline separation of all substances was achieved in the developed CE system within 9 minutes. A linear relationship (R² 0.8752) between the sensitivity of the applied potentiometric detector and the parameter log P characterising the hydrophobicity of the analytes was demonstrated. The best observable limits of detection (LODs) were obtained for the highly hydrophobic substances, i. e. bufuralol (8.10×10^–8 M injected concentration, S/N = 3), propranolol, alprenolol, and clenbuterol (ca. 1.10×10^–7 M). In the case of hydrophilic catecholamines and carbuterol their LODs with potentiometric detection were lowered by a factor of almost one thousand, reaching a value of 6.6×10^–5 M.     

Development of a disposable miniature l-lysine sensor

A hybrid l-lysine sensor consisting of an immobilized l-lysine decarboxylase and a miniature bacterial CO₂ sensor was fabricated using semiconductor techniques. The bacteria was immobilized in a calcium alginate gel in a miniature oxygen electrode cell together with the electrolyte. The enzyme was immobilized in a bovine serum albumin matrix on a gas-permeable membrane. The cell was formed on a silicon substrate by anisotropic etching and had a two-gold-electrode configuration. The response time of the l-lysine sensor was 1–3 min. The optimum pH was 6.0 and the optimum temperature was 33°C. The response to l-lysine concentration was linear from 25 to 400 μM. Reproducible responses were obtained by adding more than 1 μM pyridoxal-5′-phosphate. The sensor had excellent selectivity for l-lysine and a stable response for more than 25 repetitive operations.     

Rational Design of Highly Efficient One-pot Synthesis of Ternary PtNiCo/FTO Nanocatalyst for Hydroquinone and Catechol Sensing

In this work, we present a simple and efficient method for preparation of widely dispersed PtNiCo nanocatalyst on FTO without the use of any heavy complex structure. The proposed nanocatalyst enhances the chemical interaction of PtNiCo/FTO and increases its catalytic activity, which was used for electrochemical sensing of catechol and hydroquinone. The surface morphology was characterized by TEM, HRTEM, and XRD. The size of the PtNiCo/FTO octahedrons nanocatalyst was about 0.35–4 nm. Gradual increase of concentration exhibited linearity in oxidation peak response up to 1100 μM with a low detection limit of 0.79 μM for HQ and 1.05 μM for CC. The sensitivity is 1035 μAmM⁻¹ cm⁻² for catechol and 1197 μAmM⁻¹ cm⁻² for hydroquinone. The prepared nanomaterial/sensor applied to real water samples with good reproducibility (98–99 %).     

Synthesis of Ferrosoferric Oxide‐graphene Oxide Nanocomposite by Isoelectric Point Method for the Detection of Catechol

Ferrosoferric oxide functionalized graphene oxide nanocomposite with layer by layer structure was synthesized by isoelectric point method in this work. The prepared material was characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, transmission electron microscopy and Raman spectroscopy. Then the material was used to modify a glassy carbon electrode to fabricate an electrochemical sensor for the detection of catechol. The electrochemical sensor exhibited excellent electrochemical performance towards the detection of catechol with a linear response in the range of 5–205 μM and a detection limit of 2.32 μM. Furthermore, the electrochemical sensor showed excellent selectivity, stability and repeatability. These results revealed ferrosoferric oxide functionalized graphene oxide nanocomposite has potential applications in the fabrication of electrochemical sensors.