Fabrication of a template-synthesized gold nanorod-modified electrode for the detection of dopamine in the presence of ascorbic acid

Gold nanorods (GNRs) with suitable aspect ratio were synthesized with a template technique and then dispersed in a saturated sodium citrate solution by ultrasonication to form a GNR suspension. A GNR-modified electrode was fabricated using the GNR suspension. The oxidation of dopamine at the GNR/GC electrode exhibited surprisingly high electrocatalytic activity and adsorption-controlled characteristics. Square-wave voltammetry was used to detect dopamine. At the GNR/GC electrode, the linear concentration range of DA is from 1 × 10⁻⁸ M to 1 × 10⁻⁷ M and the detection limit (s/n = 3) is as low as 5.5 × 10⁻⁹ M. The current sensitivity is 3.280 μA/μM, and 1000-fold ascorbic acid (AA) cannot interfere with the determination of DA. All these performances are greatly superior to those of the bare GC electrode.     

A rapid technique for determination of nitrate and nitric acid by acid reduction and diazotization at elevated temperature

A rapid technique for determination of nitrate by acid reduction and diazotization at elevated temperature has been standardized. The technique is based on quantitative diazotization of sulfanilamide by nitrate on incubation in boiling water bath for 3, 5 or 10 min in presence of high concentration of HCl, ca. 64.5%. The diazotized sulfanilamide is coupled at room temperature to N-1-(naphthyl)-ethylenediamine dihydrochloride, and the chromophore evaluated spectrophotometrically at 540 nm. The technique provides linear estimate of nitrate over the test range of 0.5 through 10 μg N mL⁻¹ sample with all test incubation time periods using alkali nitrate and nitric acid as sources of nitrate anion. Urea treatment enables selective determination of nitrate in presence of nitrite with overall 99 ± 1% recovery, and without affecting nitrate determination (P > 0.1) or its regression coefficient. The technique has obvious advantages over metal-reduction technique. It is simple, rapid, selective in presence of nitrite, and an inexpensive method for routine determination of nitrate with detection range 0.5–10 μg N mL⁻¹ sample. Besides, the technique provides opportunity to detect nitric acid as low as 35 μM even in presence of other acids.     

Voltammetric determination of quercetin at a multi-walled carbon nanotubes paste electrode

Quercetin can effectively accumulate at multi-walled carbon nanotubes-paraffin oil paste electrodes (CNTPE) and cause a sensitive anodic peak at around 0.32 V (vs. SCE) in a 0.10 M phosphate buffer solution (pH = 4.0). Under optimized conditions, the anodic peak current is linear to quercetin concentration in the ranges of 2.0 × 10^− 9−1.0 × 10^− 7 M and 1.0 × 10^− 7−2.0 × 10^− 5 M, and the regression equations are i_p (μA) = 0.0017 + 0.928c (μM, r = 0.999) and i_p (μA) = 0.183 + 0.0731c (μM, r = 0.995), respectively. This paste electrode can be regenerated by repetitively cycling in a blank solution for about 2 min. A 1.0 × 10^− 6 M quercetin solution is measured for 10 times using the same electrode regenerated after every determination, and the relative standard deviation of the peak current is 1.7%. The method has been applied to the determination of quercetin in hydrolysate product of rutin and the recovery is 99.2–102.6%. In comparison with graphite paste electrode, carbon nanotubes-nujol paste electrode and carbon nanotubes casting film modified glassy carbon electrode, the CNTPE gives higher ratio of signal to background current and better defined voltammetric peak.     

Electrocatalytic Oxidation of Nitric Oxide on an Electrode Modified with Fullerene Films

Fullerene was immobilized on the surface of a glassy carbon electrode and reduced by an electrochemical method to form a partially reduced fullerene film. The films on the electrode showed stable electrocatalytic activity towards the oxidation of nitric oxide (NO). The catalytic current was proportional to the concentration of nitric oxide. Based on this property, a method for the detection of nitric oxide in aqueous solution is proposed. The detection conditions, such as supporting electrolyte, scan rate and thickness of the film were optimized. Under the optimized conditions, the catalytic currents increase linearly with the concentration of NO in the range of 3×10^–71.0×10^–4M, and the detection limit is 7.4×10^–8M. In addition, the modified electrode is very selective with respect to interferences including ascorbic acid, dopamine, and nitrite when further modified by a Nafion film on the surface of the electrode. The experimental results indicate that the partially reduced fullerene can act as an NO sensor featuring fast response and high stability.     

Dual electrochemical microsensor for simultaneous measurements of nitric oxide and oxygen: Fabrication and characterization

A planar-type amperometric dual microsensor was developed for the simultaneous measurement of the nitric oxide (NO) and oxygen (O₂) concentrations. The sensor (overall diameter = 500 μm) consisted of a dual working electrode (WE) containing two platinized platinum microdisks (25 μm diameter, WE1, WE2, distance between two disks > 330 μm) and a Ag/AgCl wire reference electrode covered with an expanded poly(tetrafluoroethylene) gas-permeable membrane. The differentiation and concurrent measurements of NO and O₂ were obtained successfully using two sensing WEs with different applied potentials (+0.75 V for WE1 and −0.4 V for WE2). Cross-talk between WE1 and WE2 was eliminated with an optimized internal solution composition. Linear dynamic range, selectivity, sensitivity, detection limit (<5 nM for NO; <500 nM for O₂), and stability (>50 h) were evaluated.     

Development of an amperometric biosensor based on covalent immobilization of tyrosinase on a boron-doped diamond electrode

An amperometric enzyme electrode based on direct covalent immobilization of tyrosinase on a boron-doped diamond (BDD) electrode has been developed for the detection of phenolic compounds. Combined chemical and electrochemical modifications of the BDD film with 4-nitrobenzenediazonium tetrafluoroborate, an aminophenyl-modified BDD (AP–BDD) surface was produced, and then the tyrosinase was covalently immobilized on the BDD surface via carbodiimide coupling. The response dependences of the enzyme electrode (Tyr–AP–BDD electrode) on pH of solution, applied potential, oxygen level and phenolic compounds diffusion were studied. The Tyr–AP–BDD electrode shows a linear response range of 1–200, 1–200 and 1–250 μM and sensitivity of 232.5, 636.7 and 385.8 mA M⁻¹ cm⁻² for phenol, p-cresol and 4-chlorophenol, respectively. 90 percent of the enzyme activity of the Tyr–AP–BDD electrode is retained for 5 weeks storing in 0.1 M PBS (pH 6.5) at 4 °C.     

Direct electrochemistry of glucose oxidase based on its direct immobilization on carbon ionic liquid electrode and glucose sensing

Direct electrochemistry of glucose oxidase (GOx) has been achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1-butyl pyridinium hexafluophosphate ([BuPy][PF₆]) as binder for the first time. A pair of reversible peaks is exhibited on GOx/CILE by cyclic voltammetry. The peak-to-peak potential separation (ΔE_P) of immobilized GOx is 0.056 V in 0.067 M phosphate buffer solution (pH 6.98) with scan rate of 0.1 V/s. The average surface coverage and the apparent Michaelis–Menten constant are 6.69 × 10⁻¹¹ mol·cm⁻² and 2.47 μM. GOx/CILE shows excellent electrocatalytic activity towards glucose determination in the range of 0.1–800 μM with detection limit of 0.03 μM (S/N = 3). The biosensor has been successfully applied to the determination of glucose in human plasma with the average recoveries between 95.0% and 102.5% for three times determination. The direct electrochemistry of GOx on CILE is achieved without the help of any supporting film or any electron mediator. GOx/CILE is inexpensive, stable, repeatable and easy to be fabricated.     

Sensitive electrochemical detection of arsenic (III) using gold nanoparticle modified carbon nanotubes via anodic stripping voltammetry

Gold nanoparticles were deposited electrolessly on multiwalled carbon nanotubes (CNTs) via in situ reduction of HAuCl₄ by NaBH₄. The resulting gold covered nanotubes were immobilised onto the surface of a glassy carbon electrode via evaporation of a suspension in chloroform. Anodic stripping voltammetry was performed with the modified electrode in As(III) solutions. A limit of detection (LOD based on 3σ) of 0.1 μg L⁻¹ was obtained but more importantly a sensitivity of 1985 μA μM⁻¹ was obtained with square wave voltammetry (SWV) in an optimised system with a deposition time of 120 s. These values, particularly the high sensitivity compare favourably with previously reported methods in the area of electrochemical arsenic detection.     

Indirect voltammetric determination of caffeine content in coffee using 1,4-benzoquinone modified carbon paste electrode

In this paper a simple and highly sensitive electroanalytical method for the determination of caffeine content using 1,4-benzoquinone modified carbon paste electrode is presented. The method is based on suppression of 1,4-benzoquinone peak current on addition of caffeine. Square-wave and cyclic voltammetric techniques were utilised for the investigation. The 1,4-benzoquinone modified electrode exhibited a well-defined peak with reproducible peak current values for repetitive measurements; and showed a decrease in peak current value with an increase in caffeine content. The result revealed two linear range regions between 0 mmol L⁻¹ and 0.5 mmol L⁻¹ and 0.5 mmol L⁻¹ and 8.0 mmol L⁻¹, with detection limits of 0.3 μmol L⁻¹ and 5.1 μmol L⁻¹, respectively. The method was then successfully applied to the determination of caffeine content in coffee samples. The effects of pH, electrode composition, step potential, pulse amplitude and square-wave frequency on the voltammetric responses were also investigated.     

Functionalization of platinum nanoparticles for electrochemical detection of nitrite

In this work, a novel electrochemical method for nitrite detection by using functionalized platinum nanoparticles (PtNPs) is proposed. Firstly, a gold electrode is immobilized with 4-(2-aminoethyl)benzenamine. Then, PtNPs are modified with 5-[1, 2]dithiolan-3-yl-pentanoic acid [2-(naphthalene-1-ylamino)-ethyl]amide (DPAN). Consequently, in the presence of nitrite ions, Griess reaction occurs between 4-(2-aminoethyl)benzenamine on the electrode and DPAN on PtNPs, thus PtNPs are localized onto the electrode surface. So, PtNPs-electrocatalyzed reduction of H₂O₂ can be achieved to correlate the electrochemical signal with the concentration of nitrite ions. The linear concentration range can be as wide as 10–1,000 μM, while the detection limit is as low as 5 μM. The proposed method has been also successfully applied to the detection of nitrite with the local lake water, and the result is well consistent with that obtained by UV-visible spectrophotometric method. So, this method has potential use for monitoring nitrite in drinking water supplies in the future.     

Fabrication and characterization of enhanced hydrazine electrochemical sensor based on gold nanoparticles decorated on the vanadium oxide,ruthenium oxide nanomaterials,and carbon nanotubes composites

This work describes the synthesis of mixed oxide film of vanadium and ruthenium by pulsed deposition technique on multiwall carbon nanotubes and the decoration of gold nanoparticles on the mixed film. A ternary electrocatalyst has been developed for the electrochemical oxidation of hydrazine by combining two metal oxide mixtures with Au nanoparticles. Surface morphology and chemical composition of the electrode have been examined with SEM, EDX, HRTEM, EIS, and XRD. The peak current of hydrazine increased 9 times at the AuNPs/(VOx-RuOx)/CNT/GCE compared to the bare GCE, and the peak potential shifted to negative 848 mV. Linear sweep voltammetry (LSV) and amperometric techniques revealed that the AuNPs/(VOx-RuOx)/CNT/GCE displays linear concentration range 2.5–10000 µM (LSV) and the concentration range 0.03–100 µM (amperometry). The limit of detection (LOD) is 0.5 μM and 0.1 μM at (S/N = 3) for LSV and amperometric technique, respectively. The results obtained show a good RSD% of 2.1%–3.2% and reasonable recovery of 97%–108% of hydrazine detection.     

Highly sensitive and selective measurements of cobalt by catalytic adsorptive cathodic stripping voltammetry

A very sensitive and selective catalytic adsorptive cathodic stripping procedure for trace measurements of cobalt is presented. The method is based on adsorptive accumulation of the cobalt-MTB (methyl thymol blue) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species by voltammetric scan using differential pulse modulation. The reduction current is enhanced catalytically by nitrite. The optimum conditions for the analysis of cobalt include pH 9.0 (ammonia buffer), 2.0 μM methyl thymol blue, 0.8 M sodium nitrite and an accumulation potential of −0.5 V (versus Ag/AgCl). The peak current is proportional to the concentration of cobalt over the entire concentration range tested (0.02–500 ng ml⁻¹) with a detection limit of 0.005 ng ml⁻¹ for an accumulation time of 60 s. The method was applied to determination of cobalt in a mineral water sample and some analytical grade salts with satisfactory results.     

Cysteine combined with carbon black as support for electrodeposition of poly (1,8-Diaminonaphthalene): Application as sensing material for efficient determination of nitrite ions

Poly 1,8-Diaminonaphtahlene/cysteine (poly 1,8-DAN/Cys) combined with carbon black (CB) nanoparticles are proposed as an excellent sensor for the detection of nitrite ions. To design the electrocatalyst, a simple approach consisting on drop-casting method was applied to disperse carbon black on the surface of glassy carbon electrode, followed by the immobilization of cysteine on the surface of CB nanoparticles. The electrochemical polymerization of 1,8-Diaminonaphthalene was conducted in acidic medium by using cyclic voltammetry. The prepared hybrid material was denoted poly 1,8-DAN /Cys/CB. Several methods were used to characterize the structural and electrochemical behavior of the reported hybrid material including Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), amperometry and differential pulse voltammetry (DPV). The prepared electrode displayed an outstanding electroactivity towards nitrite ions reflected by an enhancement in the intensity of the current and a decrease of the charge transfer resistance. Poly 1,8-DAN/Cys/CB displayed an excellent sensing performance towards the detection of nitrite with a very low detection limit of 0.25 µM. Two linear ranges of 1–40 µM and 20–210 µM when using amperometry and differential pulse voltammetry (DPV) were obtained respectively. This work highlights the simple preparation of a polymeric film rich in amine and thiol groups for nitrite detection.     

Characterization of a micro spiral flow cell for chemiluminescence detection

A 5.5 μl spiral micro-flow cell, mounted in front of a photomultiplier, is made from Teflon capillary (75 cm×100 μm ID) with two inlets for the CL reagent and carrier buffer and a waste outlet. It allows the rapid mixing of CL reagent and analyte and simultaneous detection of the emitted light. Using a flow rate of 25 μl/min for a 0.4 mM luminol-8 μM hemin solution (pH 11.6) and 50 μl/min of carrier buffer (pH 11.6), the slight exponential calibration curve for the flow injection–chemiluminescence (FI–CL) determination of H₂O₂ is 2.5–10 μM and the detection limit is 1.5 μM. The detection limit achieved by using a spiral flow cell is 24 times lower than that obtained from a conventional FI system with a low dead volume tee mixer and a 12 μl flow cell in a HPLC fluorometer with the source lamp off. This luminol CL detection method is successfully applied to the enzymatic determination of -lactate by FI. The lactate sample is mixed with polyethylene glycol (PEG)-stabilized lactate oxidase (LO) enzyme and then injected into the buffered (pH 7.5) carrier stream for CL detection of the H₂O₂ product. Using the optimal conditions of reaction temperature set to 37.5 °C and flow rates of 45 μl/min for the CL reagent and 60 μl/min for the carrier buffer, the calibration range for lactate is 5–50 μM and the detection limit is 2.9 μM. This method is applied to the determination of -lactate in beer.     

Electrochemical analysis of -penicillamine using a boron-doped diamond thin film electrode applied to flow injection system

The electroanalysis of -penicillamine in 0.1 phosphate buffer (pH 7) was studied at a boron-doped diamond thin film (BDD) electrode using cyclic voltammetry as a function of concentration of analyte and pH of analyte solution. Comparison experiments were performing using a glassy carbon (GC) electrode. The BDD electrode exhibited a well-resolved and irreversible oxidation voltammogram, but the GC electrode provided only an ill-defined response. The BDD electrode provided a linear dynamic range from 0.5 to 10 mM and a detection limit of 25 μM (S/B≥3) in voltammetric measurement. It was also found that the peak potentials were decreased when the pH of the analyte solution was increased. In addition, penicillamine has been studied by hydrodynamic voltammetry and flow injection analysis with amperometric detection using the BDD electrode. The flow injection analysis results at the diamond electrode indicated a linear dynamic range from 0.5 to 50 μM and a detection limit of 10 nM (S/N≈4). The proposed method was applied to determine -penicillamine in dosage form (capsules), the results obtained in the recovery study (255±2.50 mg per tablet) were comparable to those labeled (250 mg per tablet).     

Photoacoustic gas detection using a cantilever microphone and III–V mid-IR LEDs

The cantilever enhanced photoacoustic trace gas detection in the mid-infrared 3–7 μm wavelength range has been combined with light emitting diode (LED) technology. Mid-IR LED output power was modulated by pulse driving current with frequency high enough to avoid acceleration and acoustical noise. Methane (CH₄), propane (C₃H₈), carbon dioxide (CO₂) and sulphur dioxide (SO₂) gases have been used for preliminary evaluation of the method sensitivity. The lowest detection limit of 6 ppm was observed for propane employing a LED with a center wavelength 3.3 μm and with 1 s sample integration time.     

Electrocatalytic reduction of nitrite at polypyrrole nanowire-platinum nanocluster modified glassy carbon electrode

Pt nanoclusters were deposited in polypyrrole (PPy) nanowires by cyclic voltammetry method, fabricating a PPy-Pt nanocomposite on glassy carbon electrode (PPy-Pt/GCE). The electrocatalytic reduction of nitrite at PPy-Pt/GCE has been investigated using 0.5 M H₂SO₄ solution. The sensor exhibited excellent electrocatalytic activity toward nitrite reduction. In acidic medium, the cyclic voltammetry at 20 mV s^− 1 gave a nitrite reduction peak at − 0.124 V with 0.566 μA μM^− 1 current sensitivity in the range of 5.0 × 10^− 7-1.0 × 10^− 3 M. The detection limit was 1.5 × 10^− 7 M (s/n = 3). The proposed method was successfully applied in the detection of nitrite in real water samples and obtained satisfactory results. The PPy-Pt composite modified electrode had good storage stability, reproducibility and anti-interference ability.     

Fabrication of polyaniline/carbon nanotube composite modified electrode and its electrocatalytic property to the reduction of nitrite

A polyaniline (PANI)/carbon nanotubes (CNTs) composite modified electrode was fabricated by galvanostatic electropolymerization of aniline on multi-walled carbon nanotubes (MWNTs)-modified gold electrode. The electrode thus prepared exhibits enhanced electrocatalytic behavior to the reduction of nitrite and facilitates the detection of nitrite at an applied potential of 0.0 V. Although the amperometric responses toward nitrite at MWNTs/gold and PANI/gold electrodes have also been observed in the experiments, these responses are far less than that obtained at PANI/MWNTs/gold electrode. The effects of electropolymerization time, MWNTs concentration and pH value of the detection solution on the current response of the composite modified electrode toward sodium nitrite, were investigated and discussed. A linear range from 5.0 × 10⁻⁶ to 1.5 × 10⁻² M for the detection of sodium nitrite has been observed at the PANI/MWNTs modified electrode with a sensitivity of 719.2 mA M⁻¹ cm⁻² and a detection limit of 1.0 μM based on a signal-to-noise ratio of 3.     

Glucose biosensing based on the highly efficient immobilization of glucose oxidase on a Prussian blue modified nanostructured Au surface

We report on a novel glucose biosensor based on the immobilization of glucose oxidase (GOx) on a Prussian blue modified nanoporous gold surface. The amperometric glucose biosensor fabricated in this study exhibits a fast response and the very low detection limit of 2.5 μM glucose. The sensitivity of the biosensor was found to be very high, 177 μA/mM; the apparent Michaelis–Menten constant is calculated to be 2.1 mM. In addition, the biosensor has good reproducibility and remains stable over 60 days. The anti-interference ability of the biosensor was also assessed, showing little interference from possible interferents such as ascorbic acid (AA), acetaminophen (AP) and uric acid (UA).     

Amperometric glucose biosensor based on a gold nanorods/cellulose acetate composite film as immobilization matrix

We report on the utilization of gold nanorods to create a highly responsive glucose biosensor. The feasibility of an amperometric glucose biosensor based on immobilization of glucose oxidase (GOx) in gold nanorod is investigated. GOx is simply mixed with gold nanorods and cross-linked with a cellulose acetate (CA) medium by glutaraldehyde. The adsorption of GOx on the gold nanorods is confirmed by X-ray photoelectron spectroscopy (XPS) measurements. Circular dichroism (CD) and UV-spectrum results show that the activity of GOx was preserved after conjugating with gold nanorods. The current response of modified electrode is 10 times higher than that of without gold nanorods. Under optimal conditions, the biosensor shows high sensitivity (8.4 μA cm⁻² mM⁻¹), low detection limit (2 × 10⁻⁵ M), good storage stability and high affinity to glucose (). A linear calibration plot is obtained in the wide concentration range from 3 × 10⁻⁵ to 2.2 × 10⁻³ M.