Square Wave Voltammetry Research Articles

Tailoring glassy carbon electrode surface with FeBiO3 for electrochemical detection of dinitrophenol isomers

ABSTRACT This study presents a simultaneous, rapid, and highly sensitive electrochemical detection of 2,4- and 2,5-dinitrophenol isomers using an iron bismuth oxide (FeBiO3)-modified glassy carbon electrode (GCE). The FeBiO3-modified GCE exhibited superior electrochemical performance over bare GCE, Bi2O3-modified GCE, and Fe2O3-modified GCE, as demonstrated by electrochemical impedance spectroscopy (EIS) with the potassium ferricyanide (Fe(CN6)3-/4-) standard. The synthesised electrocatalyst FeBiO3 exhibited strong absorption both in the visible and UV regions of the spectrum, attributed to band gap transitions and charge transfer transitions linked to its Bi2O3 and Fe2O3 components. The morphology and the structure of the FeBiO3 were characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD), while Fourier transform infrared spectroscopy (FTIR) was employed to analyse the functional groups attached to the surface of FeBiO3. Cyclic voltammetry (CV) clearly demonstrated an increased current and improved peak resolution for the reduction of 2,4- and 2,5-dinitrophenols at the FeBiO3/GCE, compared to the bare GCE. The mechanism shows that the reduction of 2,4- and 2,5-dinitrophenols occurs through interactions with the surface oxygen functional groups of FeBiO3, resulting in the stepwise reduction of their NO2 groups to hydroxyamino compounds and then to nitrosophenols. Using square wave voltammetry (SWV), the reduction peak currents were significantly improved, enhancing detection sensitivity beyond that reported in previous works. A linear range from 1 µM to 1 mm for the dinitrophenol isomers was established, with detection limits of 0.07 µM for 2,4-dinitrophenol and 0.09 µM for 2,5-dinitrophenol. The FeBiO3/GCE electrode showed interferences with mono-nitrophenols and mono-/di-chlorophenols in solution but maintained excellent long-term stability and reproducibility, allowing it to effectively detect dinitrophenol isomers in drinking water, tap water, and wastewater samples.

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).

TiO2 aerogel − A sensing electrode matrix for the sensitive detection of diclofenac sodium

This study developed a new composite matrix containing TiO2 aerogel having mesoporous structure (TiO2AG), bioengineered flagellin (bioF) and chitosan (Ch) deposited on a glassy carbon electrode (GCE), for the detection of diclofenac sodium (DS) in aqueous solutions. It is worth mentioning that TiO2AG mesoporous material was used for the first time as a sensitive matrix for DS detection. The morpho-structural properties of the new electrode materials were assessed by X-ray diffraction (XRD), N2 adsorption–desorption measurements, and scanning electron microscopy (SEM) in conjunction with energy-dispersive X-ray spectroscopy. The electrochemical properties of the new bioF + TiO2AG + Ch/GCE modified electrode were determined by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV) techniques. The developed modified electrode exhibits a significant electrocatalytic activity for DS electrooxidation process reflected in the acquired performances (detection limit of 17 nM, sensitivity of 0.41 A/M, linear range from 0.15 to 2.5 µM), and presents excellent reproducibility, repeatability, and stability. The practical use of the new developed electrode was estimated by quantifying DS in pharmaceutical formulations (recovery mean of 100.66 % for DS, with a relative standard deviation of 0.39 %) and wastewater samples (relative error of 3.15 % and a relative standard deviation of 0.393 when compared to the LC-MS standard technique).

10-[(4-Cyanobenzylidene)]-Anthracen-9(10H)-One: syntheses, characterization and application in UV light detection

In this work, the compound 10-[(4-cyanobenzylidene)]-anthracen-9(10H)-one (1) has been synthesized from the corresponding anthrone and 4-cyanobenzaldehyde. It has been characterized by nuclear magnetic resonance (NMR), infrared spectroscopy (IR), high-resolution mass spectroscopy (HRMS) and single-crystal X-ray diffraction (XRD) analysis. Moreover, square wave voltammetry (SWV) was performed to determine the HOMO and LUMO potential levels of the anthrone derivative 1, which indicates that sensitization of TiO2-based electrodes is thermodynamically feasible. Therefore, this characteristic of compound 1 allowed its incorporation in a Grätzel-type solar cell. Photocurrent density measurements under UV irradiation are proportional to the light source intensity, and the operational parameters of the photoelectrochemical cell are relatively stable over time. In fact, the sensitivity of the generated photocurrent normalized by the supplied irradiance for TiO2-1 (7.73 µA/mW) as a photoanode is higher than that of TiO2 alone (5.14 µA/mW), indicating the improvement that 1 provides to TiO2 with respect to UV light detection. The higher photocurrent and the improved stability due to the implementation of 1 are very promising for possible applications as a sensitizer for UV light intensity sensors in dye-sensitized solar cells (DSSC).

Development of a 1D-WO3 and CuO nanocomposite modified electrode for enhanced detection of 2,4-dichlorophenol

A common chlorinated phenol known as 2,4-dichlorophenol (2,4-DCP) was investigated electrochemically using cyclic voltammetry (CV) and square wave voltammetry (SWV). The electrochemical investigation was carried out at 1D nanostructured tungsten dioxide (WO3) and copper (II) oxide (CuO) nanocomposite-modified carbon paste electrode (CPE). The electrode's sensitivity was improved by the WO3/CuO nanocomposite, enabling investigators to more precisely measure the 2,4-DCP's electrochemical characteristics. The hydrothermal method was utilized to synthesize the WO3 NPs. The XRD, AFM, SEM, and EDS techniques were used to characterize the nanocomposite and WO3 NPs. Numerous parameters have been studied, including pH, concentration variation, scan rate variation, and accumulation time. Samples of soil, fruits, and vegetables were examined using the fabricated WO3/CuO/CPE. In the concentration range of 7.0 × 10−8 M to 2.6 × 10−7 M, a linear relationship was established along with the lower limit of detection of 0.17 × 10−8 M and the limit of quantification of 0.57 × 10−7 M. The 0.2 M phosphate buffer (PB) of pH 10.4 increased the peak current, which contributed to the WO3/CuO/CPE sensor's sensing performance and was highly sensitive with respect to 2,4-DCP detection. Anodic peak current was observed for the WO3/CuO/CPE is at -7.45 µA whereas for unmodified CPE is at -1.31 µA. According to the findings, the nanostructured WO3 and CuO nanocomposite showed exceptional sensitivity in identifying the electrochemical characteristics and reactions of 2,4-DCP.

Coffee Biomass-Based Carbon Material for the Electrochemical Determination of Antidepressant in Synthetic Urine

Escitalopram (ESC) is commonly prescribed as an antidepressant to enhance serotonin levels in the brain, effectively addressing conditions such as depression and anxiety. The COVID-19 pandemic, along with ongoing mental health crises, has exacerbated the prevalence of these disorders, largely due to factors such as social isolation, fear of the virus, and financial difficulties. This study presents the enhancement of a glassy carbon electrode (GC) through the incorporation of hydrochar (HDC) derived from spent coffee grounds and copper nanoparticles (CuNPs) for the detection of ESC in synthetic urine. Characterization of the nanocomposite was conducted using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and cyclic voltammetry (CV). The analytical parameters were systematically optimized, and a sensing platform was utilized for the quantification of ESC via square-wave voltammetry (SWV). The established linear range was found to be between 1.0 µmol L−1 and 50.0 µmol L−1, with a limit of detection (LOD) of 0.23 µmol L−1. Finally, an electrochemical sensor was employed to measure ESC levels in synthetic urine, yielding recovery rates ranging from 91.7% to 94.3%. Consequently, the HDC-CuNPs composite emerged as a promising, sustainable, and cost-effective alternative for electroanalytical applications.

Construction of a waste-derived graphite electrode integrated IL/Ni-MOF flowers/Co3O4 NDs for specific enrichment and signal amplification to detect aspartame

A novel and cost-efficient electrochemical sensor was designed by immobilizing IL/Ni-MOF/Co3O4 nanodiamonds on the graphite (GE) electrode, marking the first application for the detection of aspartame. The graphite electrode was extracted and recycled from discharged batteries to serve as a working electrode. The nanocomposite features unique Co3O4 nanodiamonds, generated using Coriandrum sativum seed extract, alongside Ni-metal organic framework (MOF), which were synthesized through a solvothermal method. The conductivity and stability of the electrochemical sensor were enhanced through the incorporation of the ionic liquid (IL) ([BMIM][MeSO4]. The phytochemical profile of Coriandrum sativum seed extract, analyzed by GC-MS, identified key compounds involved in the synthesis of Co3O4 nanodiamonds. A comprehensive characterization of the nanocomposite was performed using UV-Vis, FTIR, DLS, Zeta potential, XRD, XPS, FE-SEM, TEM, optical profilometry, and AFM to confirm the structural and elemental modifications. Electrochemical characterization of the bare and modified electrodes was conducted through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The GE/IL/Ni-MOF/Co3O4 nanodiamonds modified electrode displayed enhanced electroanalytical performance for aspartame detection, characterized by signal amplification at +7.0V. Quantitative analysis by Differential Pulse Voltammetry (DPV) and Square Wave Voltammetry (SWV) revealed a linear detection range of 3-15µM for aspartame. A comparison of SWV and DPV revealed superior analytical performance for SWV, with limits of detection (LOD) and limit of quantification (LOQ) values of 1.02µM and 3.1µM (R2 = 0.993) compared to 1.81µM and 5.5µM (R2 = 0.986) for DPV. This study reveals the excellent adsorption capabilities of Ni-MOF and Co3O4 nanodiamonds (Co3O4 NDs), attributed to their high porosity and large surface area, paving the way for the development of affordable sensing devices for artificial sweeteners.

Voltametric detection of methylene blue dye in water at green and chemically synthesized Ag/MWCNT modified electrode

Abstract A well-known textile dye, methylene blue (MB) was electrochemically detected by using glassy carbon electrode (GCE), modified with green and chemically synthesized silver nanoparticles (AgNPs) decorating the surface of functionalized multiwalled carbon nanotubes (fMWCNT). The green and chemical methods were used to synthesize AgNPs, which decorated MWCNT forming MWCNT/Agchm and MWCNT/Aggrn nanocomposite. Comprehensive characterization of the nanomaterials was carried out using energy-dispersive x-ray spectroscopy (EDX) detector-equipped scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV–visible spectroscopy (UV), and x-ray diffraction (XRD). Using XRD, particle sizes were found to be 26.81, 10.05, 5.36, 19.26, and 17.48 nm for Agchm, Aggrn, MWCNT, Agchm/MWCNT, and Aggrn/MWCNT, respectively. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and square wave voltammetry (SWV) were employed for the investigation of the electrochemical properties and behaviour of MWCNT, Agchm, Aggrn, Agchm/MWCNT, and Aggrn/MWCNT electrodes, and higher electron transport capabilities and improved electrochemical activity towards MB on Agchm/MWCNT electrode were demonstrated by the results. Electroanalysis of methylene blue at the modified electrodes with square wave technique SWV was successful. At Agchm/MWCNT modified electrode, a low limit of detection (LOD) of 4.684 and limit of quantification (LOQ) of 14.194 pM, for MB, while at Aggrn/MWCNT modified electrode , an LOD and LOQ of 2.935 and 8.895 pM, were recorded respectively. In real sample analysis, the recovery percentage for Agchm/MWCNT ranged from 90 to 98% (n =3), and Aggrn/MWCNT showed a recovery percentage ranging from 97 to 103% (n = 3). Both electrodes’ remarkable recovery rate attest to their dependability and sensitivity in MB detection.

Proton conductive 2D MXene-derived potassium titanate nanoribbons fabricated electrochemical platform for trace detection of enrofloxacin

In recent years, due to exceptional properties like broad interlayered spacing and low working potential, MXene-derived titanate nanoribbons have been established as promising electrode materials. Herein, the electrocatalytic activity of MXene-derived potassium titanate nanoribbon was employed to develop a voltammetric sensor for the detection of enrofloxacin. The sensor's significance is to provide a sustainable solution to quantify the presence of enrofloxacin regarding food safety and environmental monitoring. Moreover, to achieve the United Nations' Sustainable Development Goals by preventing antimicrobial resistance to accomplish the One Health approach. Potassium titanate nanoribbons were synthesized using 2D Ti3C2 MXene as an active precursor material, while X-ray diffraction spectroscopy, field emission scanning electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction pattern, elemental mapping, and energy-dispersive X-ray spectroscopy were used to characterize the crystallinity, surface and layered morphology of synthesized nanoribbons. The Brunauer-Emmett-Teller (BET) technique was applied to calculate the specific surface area of the synthesized materials. The materials underwent electrochemical characterization using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). Later on, the nanoribbons were fabricated on the surface of a glassy carbon electrode, and the electro-oxidative behaviour of enrofloxacin was studied by CV, DPV, square wave voltammetry (SWV) in 0.1 M phosphate buffer (optimized pH 8). The developed sensor depicts a significantly lower limit of quantification of 0.007 μM (≈2.5 μg/L), and an upper limit of quantification of 18 μM (≈6.5 mg/L) along with a limit of detection (LOD) of 0.00279, 0.00803, 0.00881 μM obtained from CV, DPV, and SWV respectively. Furthermore, the developed electrodes show a reliable selectivity to be examined in real complex matrices, i.e. marine water, river water, agricultural soil, organic fertilizer, milk, honey, and poultry egg.

Monomeric and Dimeric Boron (III) Subphthalocyanines Functionalized with 4-Hydroxy-Benzoic Acid as Potential Photosensitizers and Photocatalysts in Sulfoxidation.

Axial modification of boron (III) subphthalocyanine bromides with 4-hydroxy-benzoic acid successfully led to the formation of the macrocycles with anchored 4-carboxyphenoxy group [RsPcPHBA] (R=tBu, H) in the axial position and to a new dimer [sPcPHBAsPc] as minor product. Tri-tert-butyl and unsubstituted subphthalocyanines bearing benzoate ([tBusPcBA], [sPcBA]), phenoxy-group ([tBusPcOPh], [sPcOPh])) in the axial position, have been also investigated as well as control sPcs. All compounds were characterized by NMR, IR, UV-Vis and mass spectrometry. The electrochemical properties were studied using cyclic voltammetry (CV) and square wave voltammetry (SWV). Singlet oxygen generation was systematically measured for all synthesized [RsPcX] by kinetic method of chemical trap decomposition (DPBF) and by determination of phosphorescence of singlet oxygen (at 1270 nm). Axially modified subphthalocyanines exhibit high quantum yields of singlet oxygen (1O2) generation (0.47-0.62). The observed exceptional photostability in oxygen-saturated ethanol or toluene solutions and high 1O2 quantum yields allows to use [tBusPcPHBA] as photocatalysts of selective oxidative transformations of organic sulfides to sulfoxides. Loading the catalyst to 9.7 ⋅ 10-2 mol % made it possible to achieve complete conversion of the substrate (TON up to 1700).

Pyridine functionalized nickel(II) N–heterocyclic carbene complexes as highly sensitive molecular sensors for the electrochemical sensing of date rape drugs

Molecular electrocatalysts featuring a nickel atom within a tailored N–heterocyclic carbene ligand environment are valuable for various electrocatalytic applications. This study presents the synthesis and characterisation of nickel organometallic electrocatalysts based on 1,2,4–triazol–5–ylidene with different steric profiles for the sensitive detection of date rape drugs (DRDs). Bis– N–heterocyclic carbene coordinated nickel(II) complexes were compared, and square wave voltammetry (SWV) showed that these catalysts detected xylazine in the concentration range of 1–100 µM with a limit of detection (LOD) of 0.621 nM. The developed electrocatalyst was also utilized for detecting scopolamine over a concentration range of 1–150 µM, with a LOD of 1.40 nM, as well as γ–butyrolactone in the range of 1–100 µM, with a LOD of 0.638 nM. The selectivity for these DRDs was analysed in the presence of other blood and urine components. The electrodes remained stable over 30 days with minimal performance variation, demonstrating the potential of these electrocatalysts for developing reliable on–site molecular sensors for DRD detection.

Molten‐Salt‐Assisted Synthesis of Carbon‐Doped BN Nanosheets for the Sensitive Detection of Paracetamol

AbstractHigh‐performance sensors are in constant demand for health care and environmental protection. In this study, a sensitive paracetamol (PCM) sensor was designed by modifying glassy carbon electrode (GCE) with carbon‐doped boron nitride (BCN/GCE) nanosheets. The BCN nanosheets were synthesized using a molten‐salt method, which ensured the uniformity of size distribution. X‐ray diffraction and transmission electron microscopy results suggested that the carbon‐doping hardly changed the crystal structure and morphology of hexagonal boron nitride (HBN). However, the carbon‐doping can reduce the bandgap, increase the specific surface area and improve the electrical conductivity, which is attributed to the formation of abundant point defects in the BN crystal. These point defects modulate electronic structure and surface activity, and further improve the electrocatalytic properties of BN. The BCN nanosheets exhibited outstanding electrocatalytic activity in the oxidation of paracetamol (PCM). With the help of square wave voltammetry (SWV) method, the BCN/GCE demonstrated linear current response towards PCM covering the concentrations of 0.05–70 μM and 70–200 μM with a detection limit (LOD) of 0.0086 μM. The developed method also showed excellent selectivity and high stability. In addition, the BCN/GCE sensor worked well when it was applied to quantify PCM in actual samples.

Synthesis of Thioglycolic Acid-Modified Molybdenum Disulfide Nanosheets for Electrochemical Sensing and Its Application in Molnupiravir Detection

In the modern world, population growth, industrialization, and lifestyle changes have led to a rise in existing and new diseases, increasing global drug consumption. Proper pharmaceutical dosage is vital since drugs are only effective within specific concentration ranges. Therefore, developing reliable analytical methods for drug analysis in pharmaceuticals and biological samples is essential. Electroanalytical methods are particularly advantageous due to their low cost, ease of use, and rapid response. This study introduces a highly sensitive electrochemical sensor based on thioglycolic acid (TA)-decorated metallic phase molybdenum disulfide (MP-MoS2) nanosheets for the selective detection of molnupiravir (MOL), an antiviral drug used in Covid-19 treatment. The TA@MP-MoS2 nanomaterial was characterized using FTIR, TEM, and EIS. Screen-printed carbon electrodes (SPCE) were modified with TA@MP-MoS2 nanosheets to evaluate their electro-chemical and catalytic behaviours towards MOL by cyclic voltammetry (CV) and square wave voltammetry (SWV). The sensor displayed a well-defined electro-oxidation signal for MOL at 0.534 V, with the linear responses in two concentration ranges: 0.50–3.40 μM and 3.40–9.55 μM, and a low detection limit of 22.6 nM. The proposed design that has promising results could be an alternative strategy to fabricate the sensitive sensor for the detection of antiviral agents in real samples.

Electrochemical aptasensor for sensitive detection of staphylococcal enterotoxin type A in milk and fruit juice.

Anaptamer-based electrochemical sensor for the sensitive detection of staphylococcal enterotoxin type A(SEA) is presented. The truncated aptamer AptSEA1.4 used in this work was screened using computational techniques, which reduced the cost of the SELEX screening process. The aptamer-SEA interactions were confirmed by employing circular dichroism (CD) and fluorescence spectroscopy. Afterwards, for developing an electrochemical aptasensor, a fabricated GNR/FTO aptasensor was prepared and characterized using scanning electron microscopy-energy-dispersive X-ray analysis (SEM-EDX), atomic force microscopy (AFM), cyclic voltammetry (CV), and square wave voltammetry (SWV). A detailed investigation of aptamer and SEA interaction in the presence of various experimental conditions was also conducted through SWV and electrochemical impedance spectroscopy (EIS). The aptamer exhibits a strong affinity for SEA, with a dissociation constant (Kd) of 19.93nM. The aptasensor is sensitive, with a lower limit of detection of 12.44pgmL-1. It has good stability, repeatability, and specificity and has displayed highly specific and sensitive detection SEA in spiked packaged mixed fruit juice and milk, with a recovery of 95-110%. The aptasensor has highpromise for detecting SEA in other food items.

Aptamer-Mediated Electrochemical Detection of SARS-CoV-2 Nucleocapsid Protein in Saliva.

Gold standard detection of SARS-CoV-2 by reverse transcription quantitative PCR (RT-qPCR) can achieve ultrasensitive viral detection down to a few RNA copies per sample. Yet, the lengthy detection and labor-intensive protocol limit its effectiveness in community screening. In view of this, a structural switching electrochemical aptamer-based biosensor (E-AB) targeting the SARS-CoV-2 nucleocapsid (N) protein was developed. Four N protein-targeting aptamers were characterized on an electrochemical cell configuration using square wave voltammetry (SWV). The sensor was investigated in an artificial saliva matrix optimizing the aptamer anchoring orientation, SWV interrogation frequency, and target incubation time. Rapid detection of the N protein was achieved within 5 min at a low nanomolar limit of detection (LOD) with high specificity. Specific N protein detection was also achieved in simulated positive saliva samples, demonstrating its feasibility for saliva-based rapid diagnosis. Further research will incorporate novel signal amplification strategies to improve sensitivity for early diagnosis.

Dual Electrochemical Methods for Determination of Anesthetic Procaine

Procaine belongs to a type of medicine in which excessive dosage form creates cardiac problems and many allergenic reactions. Thus, continuous monitoring of this drug and its metabolite is crucial for sustainable health management during treatment. In this study, electrochemical techniques such as square wave voltammetry (SWV) and differential pulse polarography (DPP) are utilized for assaying procaine amounts in standard and pharmaceutical formulations. In SWV, the reduction of diazotized procaine gives a reduction peak at −0.05 V which is directly proportional with procaine hydrochloride concentration, whereas in DPP, the interaction of the drug with lead cation at −0.4 V is followed by the decrease in peak current of the lead cation reduction peak, which is directly proportional with the concentration of the drug. Both methods indicate high accuracy, sensitivity and precision. Linear concentration ranges of both methods are 0.0999–5.996 × 10-7 M for SWV and 0.1999–5.996 × 10-7 M for DPP. The limit of detection (LOD) and limit of quantification (LOQ) are calculated for both SWV and DPP techniques, and found that LOD equals 1.984 × 10-9 M and LOQ equals 6.611 × 10-9 M for SWV, while for (DPP) LOD and LOQ were found to be 3.519 × 10-9 M and 1.173 × 10-8 M, respectively.

Green electrochemical sensor based on ZnO@α-Fe2O3 NPs modified carbon paste electrode for sensitive voltammetric determination of the FDA-approved Anti-COVID-19 medication baricitinib

In this study, we developed an electrochemical sensor for the sensitive voltammetric determination of Baricitinib (BCT), a recently FDA-approved medication for curing COVID-19. Voltammetric measurements were employed using a carbon paste electrode modified with zinc oxide and iron oxide nanoparticles (ZnO/α-Fe2O3-NPs/CPE). The composition of the fabricated electrode was optimized, and the best sensitivity was achieved by utilizing 5% of ZnO/α-Fe2O3-NPs, which maximized the electroactive surface area. The final optimized electrode was electrochemically and physicochemically characterized by exploiting the following techniques: X-ray diffraction (XRD) patterns, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). All experimental parameters, including the pH and scan rate, have been studied and optimized. The proposed sensor was successfully employed for BCT analysis by square wave voltammetry (SWV), and the attained linear dynamic range was (8.0 × 10−8 – 1.0 × 10−6 mol L−1), and the estimated limit of detection (LOD) and limit of quantitation (LOQ) were 1.799 × 10−8 mol L−1 and 5.453 × 10−8 mol L−1, respectively. The suggested electrochemical methodology was effectively utilized to determine BCT with satisfactory percentage recoveries in pharmaceutical preparation (99.69% ± 0.73) and human plasma samples. The developed approach underwent validation and was determined to be reproducible (RSD = 0.75%) and accurate (99.68% ± 0.76) following the ICH recommendations. The greenness of the established electrochemical protocol was assessed utilizing the Analytical Eco-Scale and Analytical GREEnness Metric Approach (AGREE).

Enhanced electrocatalytic activity of hafnium doped tungsten oxide (Hf-WO3) for ultrasensitive detection of nonsteroidal anti-inflammatory drug

Efficient hafnium-doped tungsten oxide nanoparticles (Hf-WO3) were developed by hydrothermal approach and characterization was carried out by X-ray diffraction pattern (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) techniques. Cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques were employed to assess the electrochemical response of the fabricated carbon paste electrodes (CPE) for the analysis of mefenamic acid (MA). The objective of this work is to develop and optimize parameters to enhance the selectivity and sensitivity of Hf-WO3 modified sensor for the trace-level detection of MA, addressing its critical importance in both pharmaceutical and environmental analysis. The Hf-WO3 predominantly showed a monoclinic phase with some hexagonal peaks, confirming its good crystallinity and 1-D structure, which enhances charge transport and catalytic sites. XPS analysis confirmed the formation of pure Hf-WO3 by showing distinct W and Hf peaks and verifying their valences: W in the +6 state and Hf in the +4 state. CV showed that the Hf-WO3/CPE greatly enhances the electrochemical oxidation of MA compared to unmodified and tungsten oxide-modified electrodes, with a six-fold increase in peak current and notable redox activity attributed to improved surface properties and charge transfer efficiency. Under optimum experimental conditions, the Hf-WO3/CPE exhibits a low limit of detection (LOD) of 3.94 nM with dynamic concentration linearity ranging from 0.01 to 100.0 μM with good sensitivity of 1.74 μAμM−1cm−2. Furthermore, the Hf-WO3/CPE was employed in real-time analysis of MA in spiked urine samples and pharmaceutical tablet samples, which showed satisfactory recovery results ⁓ 98 %. Moreover, the electrode showed good stability over multiple measurements, and these results demonstrate that Hf-WO3/CPE is a promising sensor for MA detection.

Bimetallic Fe/Co-MOF dispersed in a PVA/chitosan multi-matrix hydrogel as a flexible sensor for the detection of lactic acid in sweat samples.

Anovel bimetallic Fe/Co-metal-organic framework (MOF) hydrogel-based wearable sweat sensorwas developed. Morphological and structural analysis of the hydrogel shows uniformly sized spines and spindle-shaped particles of the Fe/Co-MOF, and it has a high surface area (132.306 m2g-1) and porosity (0.059 cm3g-1) as confirmed by Brunauer-Emmett-Teller (BET) studies. The integration of the bimetallic MOF into a polyvinyl alcohol/chitosan (PVA/CS)-mixed matrix resulted in a multiple network hydrogel. The optimisation study investigated the effects of different pH of the PBS electrolyte, scan rates, and accumulation time in voltammetry. The electrochemical methods such as cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS) provided information on the redox behaviour, electrochemical stability, and catalytic activity of the hydrogel. The sensor demonstrates a wide linear detection range from 0.05µM to 100mM, a superior sensitivity of 0.02mAmM-1cm-2, and a lower limit of detection of 0.01µM . Active sites distributed over the hydrogel surface, specifically Fe2+ and Co2+ within the MOF structure, catalyse the oxidation of L-lactic acid, resulting in electron transfer and the formation of pyruvic acid. Notably, the fabricated sensor exhibits high selectivity, effectively discriminating against interfering species such as uric acid, ascorbic acid, glucose, urea, dopamine, NaCl, and CaCl2. Real-time analysis conducted in a simulated sweat sample via the standard addition method resulted in good recovery percentages of a minimum of 98%. The work presented here is a versatile and simple platform for point-of-care testing, especially for athletes and military personnel.

Detection of the stimulant clobenzorex using voltammetry and screen-printed electrodes: A simple and fast screening method for application in seized samples and oral fluid of drivers

Clobenzorex (CBZ) is a stimulant drug, recognized for its anorectic potential, legally used in some countries for obesity treatment. However, CBZ is banned in much of the world and has been often used illegally by drivers needing to stay alert for extended periods. Therefore, the rapid identification of CBZ in forensic samples is of paramount importance for public health and safety. In this context, we introduce an innovative electroanalytical screening method for detecting CBZ in seized tablet samples and human oral fluid using voltammetry with a graphite screen-printed electrode (SPE-Gr). The electrochemical detection was optimized in phosphate buffer solution (0.1 mol L−1, pH 7.0) using square wave voltammetry (SWV). The SPE-Gr combined with SWV exhibited a good stability of the electrochemical responses for CBZ detection, with a relative standard deviation of less than 5% across different days (N = 5) and using different SPEs (N = 3). A linear detection range of 2.5–100.0 μmol/L (R2 = 0.992) was achieved, with a low limit of detection (LOD) of 0.32 μmol L−1. Interference studies with other illicit drugs and adulterants confirmed the selectivity of the proposed method for CBZ detection. In addition, the presence of CBZ in seized tablet samples and authentic oral fluids, collected from drivers, was detected and identified using the proposed method, which results were also confirmed by HPLC-MS. Consequently, integrating SPE-Gr with SWV offers a reliable, rapid, sensitive, selective, reproducible, and direct approach for the preliminary qualitative and quantitative analysis of CBZ in forensic contexts. Furthermore, the proposed method provides an efficient oral fluid test for CBZ screening in drivers under the influence of drugs.