Square-wave Adsorptive Stripping Voltammetry Research Articles

Environmentally friendly screen-printed electrodes for the selective detection of 4-bromo-2,5-dimethoxyphenethylamine (2C-B) in forensic analysis.

In response to the growing need for sustainable analytical methods, this study explores the repurposing of screen-printed electrodes (SPEs) that would otherwise be discarded. This involves recoating the working electrode surface with a graphite (Gr) and chitosan (CTS) dispersion, creating a reusable SPE (SPE-Gr/CTS). Demonstrating its utility, SPE-Gr/CTS was employed for the detection of 4-bromo-2,5-dimethoxyphenethylamine (2C-B), a phenylethylamine commonly used for recreational proposes. Identifying 2C-B in fluid oral and seized samples is of great interest for forensic and toxicological applications. The 2C-B detection using SPE-Gr/CTS was optimized in Britton-Robinson buffer solution (0.1 mol L-1) at pH 2.0, employing square-wave adsorptive stripping voltammetry. The electrochemical behavior of 2C-B on SPE-Gr/CTS exhibited one irreversible oxidation and a reversible redox process. The proposed method presented a dynamic linear range for 2C-B determination (0.05 to 7.5 μmol L-1) with a low LOD (0.015 μmol L-1). Moreover, the stability of 2C-B electrochemical responses on SPE-Gr/CTS was confirmed using the same or different electrodes (N = 3), with a relative standard deviation of less than 5.0%. Interference studies with seventeen other illicit drugs and adulterants demonstrated that the proposed method is selective for 2C-B detection even in the presence of these substances. Real seized and oral fluid samples containing 2C-B were analyzed using this method, and the results were confirmed by LC-MS. The proposed device demonstrates to be an environmentally friendly and selective sensor for 2C-B detection in forensic analysis, offering a rapid and straightforward screening method for seized and biological samples. In addition, a portable and sensitive determination of 2C-B in forensic samples is presented with minimal sample consumption (50 μL).

Glycine-modified Pencil Graphite Electrode as a Sensor for Caffeine Determination: A Voltammetric Study

Background: Caffeine (CAF) is a widely used chemical in foods and pharmaceuticals that is consumed by a lot of people every day. Overconsumption of caffeine can lead to some undesirable symptoms. However, CAF is considered a crucial nervous system stimulant. Aims: This study aimed to find an accurate and effective route for determining caffeine using voltammetric techniques. Objective: In this work, for the first time, a glycine (Gly) modified pencil graphite electrode (Gly/PGE) was used for the determination of caffeine (CAF) by Square Wave Adsorptive Stripping Voltammetry (SWAdSV) technique. Methods: The modification procedure of PGE by Gly was accomplished by performing the cyclic voltammetry (CV) technique for 10 cycles at a potential range of 0.8 to 1.8 V. Moreover, the characterization of Gly/PGE was done by applying the CV technique in aqueous and non-aqueous media and electrochemical impedance spectroscopy (EIS) in addition to the SEM technique. The movement type of CAF toward Gly/PGE was proven to be a diffusion-controlled process by conducting some measurements at different scan rates. The supporting electrolyte for the determination of CAF was studied, where 100 mM of sulfuric acid (H2SO4) provided the best result. Optimization of accumulation time, pulse size, and wave frequency were implemented and found to be 60 s accumulation time, 50 mV pulse size, and 25 Hz wave frequency. The stability of Gly/PGE was studied in different mediums, such as air, ultrapure water, and acetonitrile (CH3CN). Results: The determination of CAF under optimum conditions was within the linear concentration range of 0.1–75 μM, with a correlation coefficient of R2 = 0.9990. The limit of detection (LOD) and limit of quantification (LOQ) were 0.070 and 0.231 μM, respectively. Conclusion: An effective voltammetric methodology was suggested to determine CAF. This methodology has great promise to be applied in different matrices to determine CAF.

Ultrasensitive tadalafil detection with eco-friendly CeO2/Al-pillared clay incorporated pencil graphite paste electrode

In this study, we have constructed a novel voltammetric sensor based on montmorillonite clay (MMT) incorporated with CeO2 nanoparticles using a composite graphite paste electrode as a cross linker (MMT-CeO2NPs/GPG-PE) for the trace determination of tadalafil (TAD) drug. The characterization of CeO2 nanoparticles has been conducted using various analytical techniques, including X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. The morphology of the composite of CPG and MMT-CeO2NPs/CPG was elucidated through scanning electron microscopy (SEM). The newly developed sensor (MMT-CeO2NPs/CPG-PE) exhibited remarkable efficiency towards TAD oxidation using adsorptive stripping square-wave voltammetry (AdS-SWV) in Mcllvaine buffer solution (pH 8.0). A highly selective and sensitive method for TAD detection has been successfully applied based on MMT-CeO2NPs/CPG-PE, showing two different linear concentration ranges of 0.005−0.1 and 0.1–9.9 µM. The LOD and LOQ were determined to be 1.97 × 10−10 and 6.57 × 10−10 M, respectively, with a sensitivity of 3916 µA µM−1 cm−2. Interestingly, the sensing electrode exhibited excellent reproducibility, reusability, and stability even after 30 days. Moreover, the newly developed nano-sensor (MMT-CeO2NPs/CPG-PE) has been effectively utilized for the accurate detection of TAD in pharmaceutical formulations and spiked human blood serum and urine samples, demonstrating no interference from other substances.

Rapid determination of uracil in biological fluids at mercury thin film electrode for early detection of potential 5-fluorouracil toxicity due to dihydropyrimidine dehydrogenase deficiency

Determination of plasma uracil was reported as a method for evaluation of Dihydropyrimidine dehydrogenase (DPD) activity that is highly demanded to ensure the safe administration of 5-fluorouracil (5-FU)-based therapies to cancer patients. This work reports the development of a simple electroanalytical method based on adsorptive stripping square wave voltammetry (AdSWV) at mercury film-coated glassy carbon electrode (MF/GCE) for the highly sensitive determination of uracil in biological fluids that can be used for diagnosis of decreased DPD activity. Due to the formation of the HgII–Uracil complex at the electrode surface, the accuracy of the measurement was not affected by the complicated matrices in biological fluids including human serum, plasma, and urine. The high sensitivity of the developed method results in a low limit of detection (≈1.3 nM) in human plasma samples, falling below the practical cut-off level of 15 ng mL−1 (≈0.14 μM). This threshold concentration is crucial for predicting 5-FU toxicity, as reported in buffer, and ≤1.15% in biological samples), and accuracy (recovery percentage close to 100%).

Silica graphite as an ink additive for stencil printed electrodes: A novel approach for electroanalytical determination of sulfanilamide

Silica-graphite composites present a high surface area, mechanical and chemical stability, and high functionality to be applied in electrochemical sensing. Indeed, those materials have been successfully employed to build composite electrodes such as carbon paste electrodes for a wide range of applications. Despite excellent performance, this kind of electrodes have been replaced by stencil printed electrodes (SPEs), emerging as a scalable alternative for manufacture offering sensors disposables, low-cost, customizable, and miniaturized. Based on this, herein a novel silica-graphite (SiG) composite is described as an ink additive aiming scalable production of SPEs with high functionality and surface area. The SPE as well as SiG were characterized by electrochemical impedance spectroscopy, scanning electron microscopy, thermogravimetric analysis, and contact angle. After an accumulation step, SiG-SPE pretreated has shown a significant improvement on oxidation of sulfanilamide compared with unmodified SPE. Electrochemical surface activation and pre-concentration conditions were investigated to enhance sensitivity and selectivity. Under optimized conditions, silica-graphite stencil printed electrode (SiG-SPE) was employed for the electrochemical determination of sulfanilamide by using square wave-adsorptive stripping voltammetry (SWAdSV). It was possible to achieve a linear dynamic range (LDR) from 2 to 20 mmol L−1 with a limit of detection (LOD) and quantification (LOQ) of 0.34 and 1.13 mmol L−1, respectively. The stability of the sensors was evaluated over five weeks, and a decrease of around 5.5 % in response was observed compared to fresh electrodes. SiG-SPE also presented high selectivity and low matrix interference for sulfanilamide determination with a recovery range of 96.2–100.1 % for urine and 98.2–106.1 % for commercial fat milk. Those results suggest that SiG is a promising ink additive for the production of low-cost and high-performance sensors, showing enhanced analytical properties, mechanical resistance, and chemical stability.

Electrochemical Properties and Determination of Serotonin with Graphene/Coal Tar Pitch/Pencil Graphite Sensor Electrode using Square Wave Adsorptive Stripping Voltammetry Technique

In the present work, electrochemical and spectroelectrochemical behaviors of Serotonin (5-HT) were studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. Cyclic voltammetric experiments of 5-HT on graphene/coal tar pitch/pencil graphite electrode (GR/CTP/PGE) were carried out between 0.0 V and 1.8 V potential range at a scan rate of 100 mV s-1 with 20 cycles in non-aqueous media. Surface characterizations were performed using CV, EIS and scanning electron microscope (SEM). Effect of different pH values was investigated by square wave voltammetry (SWV) for determination of 5-HT. Optimization of accumulation time was determined using square wave adsorptive stripping voltammetry (SWAdSV) within potential range of -0.2 to +0.6 V. 5-HT standard solutions changing from 75 µM to 1.0 µM were prepared and the corresponding peak currents were measured. From the obtained data calibration equation was derived Ip = 0.0329C5-HT + 0.1511 with correlation coefficient (R2) 0.9958. LOD was 3.51x10-7 M and LOQ was 1.05x10-6 M.

Investigation of Electrochemical Properties and Behaviors of NBITEP Molecule; Availability of Sensor Electrode in Determination of Hg2+ with SWAdSV Technique

This Master's Thesis focuses on the synthesis and structural elucidation of 4-(2-((6-nitro-1h-benzo[d]imidazol-2-yl)thio)ethyl)phenol (NBITEP) molecule, along with its electrochemical behaviors. Electrochemical studies were carried out employing a glassy carbon (GC) electrode as the working electrode. The cyclic voltammetry (CV) technique was utilized for modification and characterization processes. Furthermore, the potential of the modified surface as a sensor electrode for Hg2+ ion detection was investigated using square wave adsorptive stripping voltammetry (SWAdSV). Detailed examinations were conducted in a phosphate buffer solution (PBS) medium specifically for Hg2+ ion detection, demonstrating the suitability of the reduced NBITEP modified GC electrode surface as a sensor electrode.

Cobalt(II) bis-(1,10-phenanthroline) complex electropolymerized glassy carbon electrode and its electrocatalytic sensing of diclofenac in pharmaceuticals and biological samples

Diclofenac (DCF) is a nonsteroidal anti-inflammatory drug (NSAID) that is used to treat acute and chronic inflammatory diseases. High consumption and indiscriminate use of DCF pose serious health issues, prompting the consideration of electroanalytical methods for detecting and controlling DCF levels in various samples. A sensitive and highly selective sensor was established for voltammetric determination of diclofenac (DCF) based on poly[cobalt(II) bis-(1,10-phenanthroline) complex] modified glassy carbon electrode (poly(Co(Phen)2)/GCE). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize the performance of a poly(Co(Phen)2)/GCE sensor, revealing a negative oxidation potential shift and higher DCF peaks of current. CV and adsorptive stripping square wave voltammetry (AdSSWV) were used to evaluate the electrochemical behavior of DCF at poly(Co(Phen)2)/GCE. Under the optimized experimental conditions, AdSSWV current signal of DCF at poly(Co(Phen)2)/GCE provided linearity over the range of 1–250 μM with a limit of detection (LOD) and limit of quantification (LOQ) of 6.40 ×10−2 and 2.13 ×10−1, and 5.60×10−2 and 2.27×10−1 µM for Ip I and Ip II, respectively. The sensor for determining DCF was tested in pharmaceuticals, milk, serum, and urine samples, demonstrating excellent selectivity despite potential interferences like atorvastatin (ATS), chloroquine (CQ), and sulfamethoxazole (SMX). The detected DCF amounts ranged between 92.3% and 106.6%. The established sensor demonstrated excellent performance in determining DCF in real samples, with spiked recoveries exceeding 95.6%, demonstrating low LOD, high sensitivity, selectivity, repeatability, and long-term stability. These results confirm that the established method displays outstanding applicability for electrochemical determination of DCF in numerous real samples.

Powerful Analytical Platform for Diazepam Determination in Pharmaceuticals and Alcoholic Drinks Based on Batch Injection Analysis Coupled with Adsorptive Stripping Voltammetry

The presented study focuses on the development and optimization of a powerful electroanalytical platform for the direct quantification of diazepam (DZP). This innovative approach integrates a batch injection analysis (BIA) system with a screen-printed electrode arrangement employing square-wave adsorptive stripping voltammetry (SWAdSV). The BIA-SWAdSV method underwent a comprehensive evaluation, wherein various experimental and instrumental parameters were systematically examined in detail. Beneficial analytical performance for detecting DZP was attained in Britton-Robinson buffer with pH 6.0, with an amplitude of 75 mV, a frequency of 10 Hz, a deposition potential of –1.2 V, a deposition time of 150 s, an injection volume of 75 μl, a dispensing rate of 7 μl s−1 and without stirring during the deposition step. Under these conditions, the proposed BIA-SWAdSV method demonstrated an adequately broad linear concentration range from 5 μM to 40 μM (R 2 = 0.997) with a micromolar limit of detection (2.0 μM) and a satisfactory precision (RSD = 5.0%). The practical applicability of the newly established and powerful analytical protocol was confirmed through the analysis of pharmaceuticals and a fortified samples of an alcoholic drink (rum) associated with potential criminal activities involving DZP abuse.

Fabrication of mesoporous carbon with a large surface area to achieve sensitive electrochemical sensing for nitazoxanide drug determination in human serum

Abstract Mesoporous carbon (MC) with a large surface area was developed to mix with the conventional carbon paste (CP) electrode. The developed MC/CP sensor had the highest sensitivity compared to many sensors made from other materials. A common drug, nitazoxanide (NTZ), was used as an application example. Using the MC/CP electrode and square wave-adsorptive stripping voltammetry (SW-AdSV), the concentration of NTZ in human serum was quantitatively estimated. We achieved a limit of quantification (LOQ) of 22 nM.

A simple electroanalytical methodology for determination of zaleplon by adsorptive stripping voltammetry in oral fluids

A glassy carbon electrode (GCE), modified with reduced graphene oxide (ErGO) (ErGO/GCE) was prepared for the determination of zaleplon, a common hypnotic pharmaceutical in synthetics and oral fluids. The modified electrode was evaluated using cyclic voltammetry, Raman spectroscopy, and scanning electrochemical microscopy (SECM). The electroanalytical studies were developed by square wave adsorptive stripping voltammetry (SW-AdSV) and parameters such as pH, accumulation potential, deposition time, and current response were optimized to determine zaleplon in Britton Robinson buffer. The validation was made using saliva-certified reference materials (Fusayama/Meyer Artificial Saliva and Artificial Saliva for Pharmaceutical Research showing good accuracy and reproducibility. The ErGO/GCE system showed a linear response between 10 and 130 µg/L at pH 10.0. The limit of detection was 5.30 μg L−1. The methodology was applied in the determination of zaleplon in saliva samples, obtaining excellent results (RSD < 10%), allowing the sensitive detection of zaleplon.

Utilizing epicatechin voltammetric oxidation signal for the estimation of total phenolic content in the tea samples via the unmodified boron-doped diamond electrode surface

In this work, the boron-doped diamond (BDD) electrode surface was employed for the first time in conjunction with the epicatechin (EC) oxidation signal to estimate the total phenolic content of tea samples by voltammetry. During cyclic voltammetry analysis of the EC, an easily identifiable, irreversible, and adsorption-controlled oxidation peak was observed at around +1.05 V (vs. Ag/AgCl) in HNO3 solution. Our experimental setup was fine-tuned by investigating the effect of electrode pretreatment, pH of the supporting electrolyte, accumulation factors, and instrumental parameters on the oxidation peak response of EC. When measuring EC in a 0.1 mol L−1 HNO3 solution at +1.0 V, square-wave adsorptive stripping voltammetry provided a highly linear response (at open-circuit accumulation for 30 s). The dynamic range was determined to be between 1.0 and 50.0 μg mL−1 (3.4510−6–1.7210−4 mol L−1), while the detection limit was found to be 0.28 μg mL−1 (9.6510−7 mol L−1). Selectivity studies were performed with other phenolic compounds found in tea such as epigallocatechin gallate, catechin, tannic acid, and gallic acid. Finally, by assessing the total phenolic content in the black and green tea samples, the suggested approach's applicability was shown by providing an estimate of the EC equivalents present in the samples.

The First Electroanalytical Study Of Umifenovir (Arbidol) Used As A Potential Antiviral Drug For The Treatment of SARS-CoV-2: A Voltammetric Quantification On The Boron-Doped Diamond Electrode By Using Anionic Surfactant Media

In this work, an electroanalytical procedure for sensing umifenovir (arbidol) by square wave adsorptive stripping voltammetry (SW-AdSV) was developed utilizing an anodically pretreated boron-doped diamond electrode. Measurements of umifenovir using cyclic voltammetry with phosphate buffer solution (PBS, 0.1 M, pH 2.5) revealed irreversible behaviour, adsorption-controlled as well as an ill-defined (+1.13 V, PA1) and a well-defined (+1.47 V, PA2) two oxidation peaks. Umifenovir oxidations depend critically on supporting electrolytes and pH. The second oxidation peak (PA2) current of the umifenovir was enhanced by adding sodium dodecyl sulfate (SDS, anionic surfactant) in the chosen supporting electrolyte. Umifenovir was quantified using its second oxidation peak (PA2) at about +1.39 V. Using the optimized condition, the oxidation peak current of PA2 showed a linear relationship for umifenovir determination in the concentration range from 0.005 to 1.0 μg ml−1 (9.73 × 10−9−1.95 × 10−6 M), with a detection limit of 0.0014 μg ml−1 (2.72 × 10−9 M) in PBS (PH 2.5) with SDS. Finally, the developed approach was successfully utilized to determine umifenovir in the pharmaceutical formulation and urine samples. To the best of our knowledge, this is the first electroanalytical approach for voltammetric sensing of umifenovir.

Glassy Carbon Modified with Cationic Surfactant (GCE/CTAB) as Electrode Material for Fast and Simple Analysis of the Arsenic Drug Roxarsone

For the fast and simple sensing of the arsenic drug roxarsone (ROX), the development of a glassy carbon electrode (GCE) modified with cationic surfactant (cetyltrimethylammonium bromide, CTAB) material is critical. The CTAB-modified glassy carbon electrode, in contrast to the unmodified one, showed excellent behavior for electrochemical reduction of ROX using cyclic voltammetry (CV) and square-wave adsorptive stripping voltammetry (SWAdSV) techniques. CV studies reveal an irreversible reduction process of NO2 to NH-OH in the ROX molecule in NaAc-HAc buffer (pH = 5.6). The electrode material was characterized using CV and electrochemical impedance spectroscopy. The experiments show that the surfactant-modified material has faster electron transfer and a higher active surface area, and permits a diffusion-adsorption-controlled process. After optimization, the SWAdSV procedure with GCE/CTAB has linear ranges of 0.001-0.02 and 0.02-20 µM, and a detection limit of 0.13 nM. Furthermore, the procedure successfully determined roxarsone in river water samples.

Voltammetric determination of anti-malarial drug amodiaquine at a boron-doped diamond electrode surface in an anionic surfactant media

In this study, the electrochemical determination of the amodiaquine (ADQ) drug was evaluated using an electrochemically pretreated boron-doped diamond (BDD) electrode due to the enhanced surface activity. The cyclic voltammogram results of ADQ were given as single reversible and diffusion-controlled peaks at +0.48 V for the oxidation peak and +0.05 V for the reduction peak (vs. Ag/AgCl) in Britton-Robinson (BR) buffer at pH 8.0. The peak potential and current signals of ADQ were evaluated at the surface of the BDD electrode using instrumental parameters to develop a simple method for ADQ detection. Also, the effect of an anionic surfactant, sodium dodecyl sulfate (SDS), on the adsorption applicability of the BDD electrode significantly increased the stripping voltammetric determination of ADQ. Under the optimal conditions chosen and employing square-wave adsorptive stripping voltammetry at the BDD electrode, ADQ was determined at + 0.34 V (vs. Ag/AgCl) at the open-circuit condition in BR buffer at pH 8.0 in the presence of 2·10–4 mol l–1 SDS. Furthermore, analytical parameters showed the linear relationship for ADQ determination in the concentration range of 0.1–20.0 μg ml–1 (2.2·10–7 – 4.3·10–5 mol l–1), with a detection limit of 0.03 μg ml–1 (6.5·10–8 mol l–1). The proposed approach can be applied to determine ADQ in water samples.

Fast and Simple Preparation of a Sensor Based on Electrochemically Reduced Graphene Oxide (rGO) for the Determination of Zopiclone in Pharmaceutical Dosage by Square Wave Adsorptive Stripping Voltammetry (SWAdSV)

AbstractThe interactions of zopiclone with electrochemically reduced graphene oxide (rGO) modified electrode were examined. A comparison of GC/rGO and glassy carbon electrode (GC) by electrochemical impedance spectroscopy and scanning electrochemical microscopy (SECM) shows that the modified surface is much less conductive than GC. The role of rGO is to act as a site of specific adsorption of the analyte. Molecular dynamics showed that the monoanionic form of zopiclone presents more interactions with defects of rGO. The analytical methodology allowed obtaining a linearity of 10–130 μg L−1, with a limit of detection of 2.14 μg L−1 using SWAdSV at pH 10.0.

An l-cysteic acid-modified screen-printed carbon electrode for methyl parathion determination

This work demonstrates the development and validation of a non-enzymatic sensor consisting of an l-cysteic acid-modified screen-printed carbon electrode (LCA-SPCE) sensor for the determination of the hazardous organophosphorus pesticide methyl parathion (MP) using square-wave adsorptive stripping voltammetry (SWAdSV). The surface of LCA-SPCE was investigated using time of flight secondary ion mass spectrometry to confirm successful preparation of the LCA surface layer. In order to obtain the highest electrochemical response, the accumulation time and pH of the 0.1 M phosphate buffer solution (PBS) supporting electrolyte were optimized. Then, SWAdSV method validation was performed in 0.1 M PBS at pH 6.00, an accumulation potential at the open circuit potential, and an accumulation time of 120 s. Since an intensive background was observed from the measurement of blank solution on the LCA-SPCE, a background subtraction procedure was employed. Partial method validation of the LCA-SPCE sensor was performed by determining the limit of detection (LOD), the limit of quantification (LOQ), the linear concentration range, accuracy, and precision. The developed method has a very low LOD and LOQ of 2.5 µg/L and 5.0 µg/L, respectively, and a linear concentration range of 5.0–84.3 µg/L (R2 = 0.9948). The average recovery and relative standard deviation were 109.6 % and 7.1 %, respectively (n = 6). This work also demonstrates the advantageous use of the multiple standard addition methodology compared to the calibration curve for analysing MP by means of an LCA-SPCE. Furthermore, electrochemical impedance spectroscopy was performed to show the differences between the bare-SPCE and LCA-SPCE. Finally, the application of the developed and validated LCA-SPCE sensor for the determination of MP was successfully employed for a real water sample (tap water), which showed the high accuracy and precision of the method. In addition, the interference and matrix effects were also studied.

On spot detection of nickel and cobalt from exhausted batteries by a smart electrochemical sensor

This work presents the realization and the application of an user-friendly electrochemical platform based on screen-printed electrodes for the simultaneous determination of nickel and cobalt ions in real samples by means of square wave adsorptive stripping voltammetry (SWAdSV). The sensor was realized by electrodepositing in situ a bismuth film onto graphite screen-printed electrodes (GSPEs). The sensor surface was fully characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).The experimental conditions for the determination of nickel and cobalt in the form of dimethylglyoximate complexes were studied and optimized. Linear calibration curves for Ni(II) and Co(II), determined individually and together, in the range 10–40 μg/L for nickel and 10–60 μg/L for cobalt, respectively, were obtained. The limits of detection for nickel and cobalt determination were 2.5 μg/L and 2.4 μg/L, respectively. The performance of the sensor in terms of reproducibility and selectivity was also studied. The applicability of the developed platform was assessed by determining nickel and cobalt in samples deriving from an industrial process of recycling exhausted batteries and in soil samples.

Electrochemical study and forensic electroanalysis of fungicide benzovindiflupyr using disposable graphite pencil electrode

Nowadays, the use of pesticides in world agriculture is fundamental. However, it leads to an increase in the illegal sale and smuggling of these products in various parts of the world, mainly in Brazil. Therefore, the development of new analytical methods for screening and analysis of these kind of substances is a relevant issue. We present in this work, for the first time, an electrochemical study and a novel electroanalytical method for determination of fungicide benzovindiflupyr (BENZO). According to our knowledge, the electrochemical behavior of BENZO, as well as its voltammetric determination, have never been reported before. The sensors used here consisted of disposable pencil graphite electrodes (PGEs). On this electrode surface and at optimal pH, BENZO behaved according to a quasi-reversible system and showed two voltammetric peaks, one anodic at Ep = +0.59 V and another cathodic at Ep = +0.43 V. The analytical studies utilized BENZO anodic sweep and square-wave adsorptive stripping voltammetry (SWAdSV). All experimental and instrumental parameters were fully investigated and optimized. Under the best conditions, a calibration plot was obtained in the concentration range from 0.10 to 12.5 μmol L−1. The limits of detection (LOD) and quantification (LOQ) achieved were 0.023 and 0.076 μmol L−1, respectively. An electrochemical mechanism for BENZO oxidation was also proposed. The method developed here was successfully employed for the qualitative and quantitative forensic analysis of BENZO in smuggled products, showing good accuracy (recoveries ca. 104%) and precision (relative standard deviation < 5%). These data attest the potential for use of this method in forensic area.

Square wave-adsorptive stripping voltammetric technique development and validation for the determination of budesonide in pharmaceuticals and biological fluids using graphite working electrode

The cyclic voltammetry method was preliminarily used to study the reversibility nature of the electrochemical behaviour of budesonide (BDN) compound. The square wave-adsorptive stripping voltammetry (SW-AdSV) technique was applied to evaluate an electrochemical reduction of BDN in the phosphate buffer pH 2.5. The ultra-trace graphite working electrode was used to accumulate BDN onto its surface. An SW-AdSV reduction peak was observed in the potential of −0.98 V using Ag/AgCl reference electrode and Pt auxiliary electrode. Different parameters ,such as pH, buffer solutions, accumulations time and potential, frequency, amplitude and scan were investigated, and convection rates parameters were studied to acquire a high reduction response. The repeatability, stability, recovery, calibration curve and limit of detection and quantification parameters were studied to evaluate the analytical performance of the SW-AdSV technique. Repeatability and stability were monitored for 20 µM of BDN to give a 0.29% relative standard deviation (RSD%) that was achieved for five measurements and a very stable current for 120 min. The linearity was evaluated by studying the calibration curve over the range of 2 –25 µM (n = 8), given a linear relation between BDN concentrations and SW-AdSV signals. The limits of detection (LOD) and quantification (LOQ) were calculated to become 40 nM (0.017 ppm) and 0.134 µM (0.0577 ppm), respectively. The developed and validated method was successfully applied to the electrochemical study of BDN in pharmaceuticals and biological fluids.