Simultaneous Differential Pulse Voltammetric Determination of Ascorbic Acid and Caffeine in Pharmaceutical Formulations Using a Boron‐Doped Diamond Electrode

A cathodically pretreated boron‐doped diamond electrode was used for the simultaneous anodic determination of ascorbic acid (AA) and caffeine (CAF) by differential pulse voltammetry. Linear calibration curves (r=0.999) were obtained from 1.9×10^?5 to 2.1×10^?4 mol L^?1 for AA and from 9.7×10^?6 to 1.1×10^?4 mol L^?1 for CAF, with detection limits of 19 μmol L^?1 and 7.0 μmol L^?1, respectively. This method was successfully applied for the determination of AA and CAF in pharmaceutical formulations, with results equal to those obtained using a HPLC reference method.     

Simultaneous Determination of Acetaminophen and Ascorbic Acid at an Unmodified Boron‐Doped Diamond Electrode by Differential Pulse Voltammetry in Buffered Media

A boron‐doped diamond electrode (BDDE) was used for the simultaneous anodic determination of L ‐ascorbic acid (AA) and acetaminophen (AC) in aqueous buffered media by differential pulse voltammetry (DPV). Linear calibration plots of anodic current peaks versus concentration were obtained for both analytes in the concentration range 0.01–0.1 mM with very high correlation coefficients. RSD of 2–3% and high sensitivities were obtained from DPV data in single and dicomponent systems. The potential applicability of the DPV technique associated with standard addition was illustrated by simultaneous determination of AA and AC in real sample solutions made up from pharmaceutical products.     

Electrochemical Behavior and Electroanalytical Determination of Indole‐3‐Acetic Acid Phytohormone on a Boron‐Doped Diamond Electrode

In this work, a boron‐doped diamond (BDD) electrode was used for the electroanalytical determination of indole‐3‐acetic acid (IAA) phytohormone by square‐wave voltammetry. IAA yielded a well‐defined voltammetric response at +0.93 V (vs. Ag/AgCl) in Britton–Robinson buffer, pH 2.0. The process could be used to determine IAA in the concentration range of 5.0 to 50.0 µM (n=8, r=0.997), with a detection limit of 1.22 µM. The relative standard deviation of ten measurements was 2.09 % for 20.0 µM IAA. As an example, the practical applicability of BDD electrode was tested with the measurement of IAA in some plant seeds.     

Simultaneous Differential Pulse Voltammetric Determination of Sulfamethoxazole and Trimethoprim on a Boron‐Doped Diamond Electrode

The performance of hydrogen‐ (HT) and oxygen‐terminated (OT) boron‐doped diamond (BDD) electrodes (electrochemically pretreated) on the simultaneous differential pulse voltammetric determination of sulfamethoxazole and trimethoprim in pharmaceutical products is presented. Under the optimum analytical experimental conditions, the HT‐BDD electrode presented two well‐defined oxidation peaks at 920 and 1100 mV vs. Ag/AgCl for sulfamethoxazole and trimethoprim, respectively. On the other hand, when the OT‐BDD electrode was used, the sulfamethoxazole oxidation current peak was decreased twenty fold. The calculated LOD values for sulfamethoxazole and trimethoprim using the HT‐BDD electrode were 3.65 μg L^?1 and 3.92 μg L^?1, respectively. The results obtained in the simultaneous determination of sulfamethoxazole and trimethoprim in three different commercial formulations were similar to those obtained using a standard HPLC method at 95% confidence level.     

Electrochemical Oxidation of Ibuprofen and Its Voltammetric Determination at a Boron‐Doped Diamond Electrode

The electrochemical oxidation of ibuprofen at a boron‐doped diamond electrode (BDDE) and its voltammetric determination is reported for the first time. A well‐defined oxidation peak was observed at around 1.6 V in 0.1 mol L^?1 H₂SO₄ solution with 10 % (v/v) ethanol at the BDDE surface activated by either cathodic or anodic pretreatments. A differential‐pulse voltammetric method for the determination of ibuprofen in pharmaceutical formulations was optimized with a detection limit of 5 µmol L^?1 and compared with the British Pharmacopeia method.     

Voltammetric Assay of Naproxen in Pharmaceutical Formulations Using Boron‐Doped Diamond Electrode

The electrooxidation of naproxen was studied, for the first time, using boron‐doped diamond (BDD) electrode by cyclic and differential pulse voltammetry (CV and DPV) in nonaqueous solvent supporting electrolyte system. The results were also compared with glassy carbon electrode (GC) under the same conditions. Naproxen undergoes one electron transfer resulting in the formation of cation radical for the first electrooxidation step, which follows other chemical and electrochemical steps such as deprotonation, removal of another electron and the attack of nucleophile (ECEC mechanism). BDD electrode provided higher signal to background ratio, well resolved and highly reproducible cyclic voltammograms than the GC electrode. With a scan rate of 50 mV s^?1 and pulse height of 50 ms, respectively, the DPV technique was able to determine the naproxen concentrations in the range of 0.5 to 50 μM with a detection limit of 30 nM. The influence of interference compounds namely 2‐acetyl‐6‐methoxy naphthalene (AMN) on naproxen oxidation can also be followed successfully. Moreover, the percentage of AMN present in the standard chemical form of a mixture containing naproxen can be found accurately. Rapidity, precise and good selectivity were also found for the determination of naproxen in pharmaceutical formulations.     

Voltammetric Behavior of Nitrofurazone at Highly Boron Doped Diamond Electrode

The electrochemical behavior of nitrofurazone (NFZ) at a highly boron doped diamond (BDD) electrode was studied in Britton‐Robinson (BR) buffer using cyclic voltammetry. NFZ was directly reduced to the amine derivative (RNH₂) in the pH range of 2.0 to 4.0 in a process involving six (6.0±0.4) electrons and six protons. In the range of pH 7.0 to 12 and, predominantly aqueous medium, the reduction step split into its two components: the reduction of NFZ to the radical anion (RNO₂^.?) and reduction of RNO₂^.? to hydroxylamine derivative (RNHOH) in processes involving one and three (3.1±0.1) electrons, respectively. On the anodic scan of the voltammograms and at pH 8.0, the oxidation of the hydroxylamine to the nitroso derivative (RNO), was observed in a process involving 2 (1.7±0.2) electrons and 2 protons. In addition and unreported in the literature on any electrode material, was the detection of a new oxidation peak at pH>8.0, which was observed regardless of whether NFZ had been previously reduced or not. The calculation of n, number of electrons, involved in each electrochemical step was satisfactorily accomplished using the Randles‐?evcik equation.     

Electroanalytical Determination of Carbaryl in Natural Waters on Boron Doped Diamond Electrode

The anodic voltammetric behavior of carbaryl on a boron‐doped diamond electrode in aqueous solution is reported. The results, obtained by square‐wave voltammetry at 0.1 mol L^?1 Na₂SO₄ and pH 6.0, allow the development of a method to determine carbaryl, without any previous step of extraction, clean‐up, preconcentration or derivatization, in the range 2.5–30.0×10^?6 mol L^?1, with a detection limit of 8.2±0.2 μg L^?1 in pure water. The analytical sensitivity of this electrochemical method diminished slightly, from 3.07 mA mmol^?1 L to 2.90 mA mmol^?1L, when the electrolyte was prepared with water samples collected from two polluted points in an urban creek. In these conditions, the recovery efficiencies obtained were around 104%. The effect of other pesticides (fenthion and 4‐nitrophenol) was evaluated and found to exert a negligible influence on carbaryl determination. The square‐wave voltammetric data obtained for carbaryl were typical of an irreversible electrode process with mass transport control. The combination of square‐wave voltammetry and diamond electrodes is an interesting and desirable alternative for analytical determinations.     

Anodic Stripping Voltammetry of Heavy Metals at Nanocrystalline Boron‐Doped Diamond Electrode

Boron‐doped Diamond (BDD) electrode has become one of the important tools for heavy metal detection. By studying some analytical parameters of DPASV method, like deposition time and potential in different electrolyte concentrations (acetate buffer), the conditions for detecting very low metal ion levels (Zn, Cd, Pb, and Cu) could be chosen. Diluted electrolyte (0.01 M buffer) was one of the factors favoring low detection and quantification limits, but its quantification range is short in comparison to more concentrated media. For ?1.7 V deposition potential, the detection of single metal at ppb levels was reached in 60 s deposition time. Understanding different metal‐metal interactions shows the limits to the simultaneous determination of heavy metals at BDD. Quantification was possible for the simultaneous determination of Zn, Cd and Pb despite the overlapping of Zn and Cd peaks. The performance of the BDD was compared with that of another C‐based solid electrode: the glassy carbon electrode (without mercury plating). A lower base line current, wider potential range, higher sensitivity (3 to 5 times higher than GC) and longevity of the material were noticed for the BDD.     

Electroanalytical Determination of N‐Nitrosamines in Aqueous Solution Using a Boron‐Doped Diamond Electrode

The electrochemical methods cyclic and square‐wave voltammetry were applied to develop an electroanalytical procedure for the determination of N‐nitrosamines (N‐nitrosopyrrolidine, N‐nitrosopiperidine and N‐nitrosodiethylamine) in aqueous solutions. Cyclic voltammetry was used to evaluate the electrochemical behaviors of N‐nitrosamines on boron‐doped diamond electrodes. It was observed an irreversible electrooxidation peak located in approximately 1.8 V (vs. Ag/AgCl) for both N‐nitrosamines. The optimal electrochemical response was obtained using the following square‐wave voltammetry parameters: f=250 Hz, E_sw=50 mV and E_s=2 mV using a Britton–Robinson buffer solution as electrolyte (pH 2). The detection and quantification limits determined for total N‐nitrosamines were 6.0×10^?8 and 2.0×10^?7 mol L^?1, respectively.     

Anodic Oxidation Behaviors of Formaldehyde at Boron‐Doped Diamond Electrodes

The electrochemical behaviors of formaldehyde (FA) at boron‐doped diamond (BDD) electrodes are investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and linear scanning voltammetry (LSV) techniques. The CV results show that the oxidation reaction of FA is influenced by the hydroxyl concentration in the solution, and the peak current response with the FA concentration is linear at the range from 10 to 100 mM. The differential capacitance from EIS results indicate that the FA molecules adsorb at the BDD electrode surface at low potential (from 1.0 to 1.4 V). The kinetic studies have been examined with the various concentrations of FA, pH, and temperature. The activation energy of FA oxidation is also calculated. The results of kinetic study indicate that the adsorption of FA molecules at the BDD electrode is the rate‐determining step at low potential (from 1.0 to 1.40 V).     

Determination of Sodium Diethyldithiocarbamate in Water by Anodic Voltammetry Using a Boron‐Doped Diamond Electrode

An electrochemical study was made of the anodic behavior of sodium diethyldithiocarbamate (DEDTC) using a boron‐doped diamond electrode (BDDE) in sodium sulfate supporting electrolyte. This paper presents a new alternative for the electroanalytical determination of DEDTC in protic media, using cyclic voltammetry or chronoamperometry. Linear plots of current vs. concentration correlated with anodic stepwise oxidation were obtained in delimited potential ranges with very good correlation coefficients.     

Simple and Feasible Simultaneous Determination of Three Phenolic Pollutants on Boron‐Doped Diamond Film Electrode

A simple, rapid and feasible method is developed for direct and simultaneous determination of phenol (Ph), hydroquinone (HQ) and 4‐nitrophenol (4‐NP) on unmodified boron‐doped diamond (BDD) electrode. Results showed that the oxidative peaks of these three phenolic compounds can be completely separated on BDD electrode in acidic conditions by using electrochemical cyclic voltammetry technique. The peak potential separations are all higher than 0.35 V. Moreover, BDD electrode is extremely easy to be refreshed to obtain current values with good reproducibility, even if it is passivated by phenolic compounds with different adsorption characteristics. All the above features are on account of the outstanding electrochemical characteristics of BDD electrode, and lead to the advantage and feasibility for simultaneous determination of three phenolic compounds without any other separation operation. For each tested phenolic compound, the concentration range with linearity is in two or three orders of magnitude in the presence of other coexisting phenolic compounds with the concentrations more than 1000 times higher than that of the tested component. The present method is also shown to be promising for the determination of phenolic contaminants in the real wastewater samples.     

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

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

Differential Pulse Voltammetric Determination of Paraquat Using a Bismuth‐Film Electrode

A bismuth‐film electrode (BiFE) ex situ electrochemically deposited onto a copper substrate has been presented for paraquat determination. The bismuth film was electrochemically deposited at an applied potential of ?0.18 V vs. Ag/AgCl (3.0 M KCl) for 200 s. The analytical curve was linear in the paraquat concentration range from 6.6×10^?7 M to 4.8×10^?5 M with a limit of detection of 9.3×10^?8 M. The method presented satisfactory results at a confidence level of 95% and the performance was evaluated in water samples.     

Selective Electroanalytical Assay for Cysteine at a Boron Doped Diamond Electrode

The electrochemical oxidation of the cysteine‐quinone adduct has been examined as a means of providing an electroanalytical cysteine specific detection protocol. The appliance of square‐wave voltammetry allowed 0.5 μM as a limit of detection. The effects of various biologically relevant interferences including other thiols were studied and found to present no change in the voltammetric profile. The practical applicability and efficiency of the methodology was probed through the determination of cysteine concentration in growth tissue medium.     

Voltammetric Determination of Carcinogenic Derivatives of Pyrene Using a Boron-Doped Diamond Film Electrode

Based on the study of voltammetric behavior of carcinogenic 1-nitropyrene (1-NP), 1-aminopyrene (1-AP), and 1-hydroxypyrene (1-HP), optimum conditions have been found for the determination of these analytes by differential pulse voltammetry (DPV) at a boron-doped diamond film electrode. The optimum medium was methanol-Britton–Robinson buffer (BR buffer) pH 3.0 (70:30) for 1-NP and 1-AP, and methanol-BR buffer pH 5.0 (70:30) for 1-HP. Concentration dependences of the DPV response were measured in the range 1 · 10^?6–1 · 10^?4 mol dm^?3 (R = ?0.9998) with the limit of detection (LOD) 3 · 10^?7 mol dm^?3 for 1-NP, 1 · 10^?7–1 · 10^?5 mol dm^?3 (R = 0.9971) with LOD 6 · 10^?8 mol dm^?3 for 1-AP, and 1 · 10^?7–1 · 10^?5 mol dm^?3 (R = 0.9934) with LOD 1 · 10^?7 mol dm^?3 for 1-HP. Simultaneous determination of 1-NP and 1-AP in a mixture was tested in the methanol-BR buffer pH 3.0 (70:30) medium as well. The content of 1-AP in the concentration range from 1 · 10^?6 to 1 · 10^?4 mol dm^?3 had no effect on the sensitivity of the determination of 1-NP, and vice versa. Due to the close peak potentials of 1-AP and 1-HP, the direct determination of their mixture using voltammetric methods is impossible.     

Electrochemical Determination of Vitamin D3 in Pharmaceutical Products by Using Boron Doped Diamond Electrode

A sensitive square‐wave voltammetry method was developed to determine cholecalciferol (vitamin D₃) in pharmaceutical products at boron‐doped diamond electrode as a working electrode. Vitamin D₃ provided a well‐defined voltammetric peak at around +1.00 V (vs. Ag/AgCl, 3.5 mol dm^?3) in 0.02 mol dm^?3 Britton‐Robinson buffer pH 5.0 prepared in 50 % ethanol. The influence of various factors such as type and pH of the supporting electrolyte, scan rate and square‐wave parameters were studied and optimized. Under optimum conditions, the oxidation peak current increased linearly with the concentration of vitamin D₃ over the range of 2 to 200 μmol dm^?3. The calculated limit of detection and limit of quantitation were 0.17 μmol dm^?3 and 0.51 μmol dm^?3, respectively. The boron‐doped diamond electrode exhibited specific recognition capability for cholecalciferol amongst possible interferences, and the determination of vitamin D₃ was possible in samples such as commercial pharmaceutical products without complicated sample pretreatments.     

Non‐Invasive Salivary Electrochemical Quantification of Paraquat Poisoning Using Boron Doped Diamond Electrode

The present work describes the first electrochemical method for quantifying paraquat herbicide poisoning in human saliva samples. Paraquat shows two couples of well‐defined peaks in aqueous solution using a boron doped diamond (BDD) electrode. By using square wave voltammetry (SWV) technique under optimum experimental conditions, a linear analytical curve was obtained for paraquat concentrations ranging from 0.800 to 167 µmol L^?1, with a detection limit of 70 nmol L^?1. This method was applied to quantify paraquat spikes in human saliva samples and in two different water samples (tap and river). The recovery values obtained ranged from 83.0 to 104 % and 99.1 to 105 %, respectively, which highlight the accuracy of the proposed method.     

Sensitive Detection of Capsaicin by Adsorptive Stripping Voltammetry at a Boron‐Doped Diamond Electrode in the Presence of Sodium Dodecylsulfate

In the present paper, a sensitive electroanalytical methodology for the determination of capsaicin using adsorptive stripping voltammetry (AdSV) at a boron‐doped diamond (BDD) electrode is presented. The voltammetric results indicate that in the presence of sodium dodecylsulfate (SDS) the BDD electrode remarkably enhances the oxidation of capsaicin which leads to an improvement of the peak current with a shift of the peak potential to less negative values. A linear working range of 0.05 to 6.0 µg mL^?1 (0.16–20 µM) with a detection limit of 0.012 µg mL^?1 (0.034 µM) has been obtained using BDD electrode by AdSV.