Search Results (11)

Xylazine (XYL), an FDA-approved veterinary tranquilizer, is being abused both as an opioid adulterant in a street-drug known as “Tranq-dope” and as a date rape drug. Given its now nearly ubiquitous use with fentanyl and fentanyl derivatives across the globe, XYL has become a primary target for researchers seeking to develop portable and cost-effective sensors for its detection. Electrochemical sensors based on the oxidation of XYL, while useful, have limitations due to certain interferents and inherent electrode fouling that render the approach less reliable, especially in certain sample matrices. In this work, modified electrode platforms incorporating layers of multi-walled carbon nanotubes for sensitivity along with semi-permeable polyurethane (PU) layers and host–guest chemistry using β-cyclodextrin for selectivity are deployed for XYL detection using complementary adsorptive cathodic stripping analysis. The modified electrode sensors are optimized to minimize high potentials and maintain fouling resistant capabilities and investigated to better understand the function of the PU layer. The use of adsorptive cathodic stripping differential pulse voltammetry indirectly indicates the presence and concentration of XYL within complex sample media (beverages and synthetic urine). When used in this manner, the modified electrodes exhibited an overall average sensitivity of ~35 (±9) nA/μM toward XYL with a limit of quantification of <10 ppm, while also offering adaptability for the analysis of XYL in different types of samples. By expanding the capability of these XYL sensors, this study represents another facet of tool development for use by medical professionals, first-responders, forensic investigators, and drug-users to limit exposure and help stem the dangerous and illegal use of XYL. Full article

The bioavailability of dissolved copper (Cu) in seawater is influenced by the presence of natural organic matter. Changes in physicochemical conditions, such as pH, temperature, and salinity, can significantly affect the solubility and speciation of copper, thereby impacting the complexation of Cu(II)-binding organic ligands. The concentration of dissolved Cu in the coastal water of Mersing, Malaysia, was detected by anodic stripping voltammetry (ASV). The natural organic copper(II)-binding ligands (CuL) and their conditional stability constants (log K′) were determined by using the competitive ligand exchange–adsorptive cathodic stripping voltammetry method (CLE–AdCSV) in our samples. The in situ parameters, such as pH, temperature, salinity, and dissolved oxygen (DO), were found to be significantly different between sampling periods and indicated the different physical chemical conditions between the sampling periods. However, we found a consistent concentration of dissolved Cu throughout the water column between sampling periods. This suggests that the presence of a strong class of natural organic ligands (L₁) in Mersing’s coastal water maintains the dissolved Cu(II) ions in the water column and prevents the scavenging and precipitation processes under the seasonal variations. Full article

In this study, a new and simple glassy carbon electrode modified with carbon nanohorns (SWCNH/GCE) was used for the determination of Cr(VI) in aqueous matrices via adsorptive cathodic stripping voltammetry (AdCSV). The modified electrode was characterized via field emission scanning electron microscopy and cyclic voltammetry, which revealed a homogeneous distribution of spherical agglomerates of SWCNH on the electrode surface. The modification increased the electrochemically active area from 0.10 cm² ± 0.01 (GCE) to 0.16 cm² ± 0.01 (SWCNH/GCE). The optimized analytical conditions were as follows: a supporting electrolyte (0.15 mol L⁻¹ HCl), an accumulation potential of 0.8 V versus Ag/AgCl, and an accumulation time of 240 s. Validation of the analytical methodology was performed, obtaining a linear range between 20 and 100 µg L⁻¹, a limit of detection of 3.5 µg L⁻¹, and a limit of quantification of 11.6 µg L⁻¹ with good accuracy and precision. The method was applied to the analysis of spiked tap water samples, and the results were compared using a flame atomic absorption spectrophotometer (FAAS) with no significant statistical differences. Full article

We aimed to monitor in situ nickel (Ni(II)) concentrations in aquatic systems in the nanomolar range. To achieve this, we investigated whether an analytical protocol for the direct quantification of cobalt (Co(II)) using adsorptive cathodic sweep voltammetry (Ad-CSV) on antifouling gel-integrated microelectrode arrays (GIME) we recently developed is also suitable for direct Ni(II) quantification. The proposed protocol consists of the reduction of the complex formed between Ni(II) (or Ni(II) and Co(II)) and nioxime adsorbed on the surface of the GIME-sensing element. The GIME enables to (i) avoid fouling, (ii) control the metal complex mass transport and, when interrogated by Ad-CSV, (iii) selectively determine the dynamic (kinetically labile Ni-nioxime) fraction that is potentially bioavailable. The nioxime concentration and pH were optimized. A temperature correction factor was determined. The limit of detection established for 90 s of accumulation time was 0.43 ± 0.06 in freshwater and 0.34 ± 0.02 nM in seawater. The sensor was integrated in a submersible probe in which the nioxime-containing buffer and the sample were mixed automatically. In situ field measurements at high resolution were successfully achieved in Lake Geneva during a diurnal cycle. The determination of the kinetically labile Ni-nioxime fraction allows one to estimate the potential ecotoxicological impact of Ni(II) in Lake Geneva. Additional Ni fractions were measured by ICP-MS and coupled to the in situ Ad-CSV data to determine the temporal Ni(II) speciation. Full article

Trace minerals play an essential role in methane production via anaerobic digestion (AD). It is important to monitor Ni(II) and Co(II) concentrations and the Ni/Co concentration ratio for the rapid diagnosis of the ecological status or activity of methanogens in AD. Electrochemical detection of Ni(II) and Co(II) was investigated by coating the Bi-chitosan nanocomposite on a glassy carbon electrode (GCE) via the electrodeposition technique. A square-wave adsorptive cathodic stripping voltammetry technique (SWAdCSV) was applied and optimized when dimethylglyoxime (DMG) was used as the chelating agent for Ni(II) and Co(II) measurements. The SWAdCSV results showed that the current peaks for Co(II) detection are 6.1 times greater than the current peaks for Ni(II) measurements, probably due to the different affinity of DMG molecules between Ni(II) and Co(II). DMG molecules demonstrated higher selectivity toward Co(II) cations compared to Ni(II). The modified Bi-chitosan GCE developed in this study showed a relatively wide range of the Ni(II) and Co(II) concentrations (2–100 µg L⁻¹) with a limit of detection of 3.6 µg L⁻¹ for Ni(II) and 2.4 µg L⁻¹ for Co(II), respectively. The developed sensor was applied to Ni(II) and Co(II) spiked natural water samples and showed good performance of detection with 12 consecutive measurements. Overall, the fabricated sensor showed excellent sensitivity toward Ni(II) and Co(II) in natural water samples. Full article

In this work, different electrodes were employed for the determination of Cr(VI) by the cathodic square-wave voltammetry (SWV) technique and the square-wave adsorptive stripping voltammetry (SWAdSV) technique in combination with diethylenetriaminepentaacetic acid. Using SWV, a comparison of the analytical performance of the bare glassy carbon electrode (GCE), ex situ electrodes (antimony-film—SbFE, copper-film—CuFE, and bismuth-film—BiFE), and the GCE modified with a new magnetic nanocomposite (MNC) material was performed. First, the MNC material was synthesized, i.e., MNPs@SiO₂@Lys, where MNPs stands for magnetic maghemite nanoparticles, coated with a thin amorphous silica (SiO₂) layer, which was additionally functionalized with derived lysine (Lys). The crystal structure of the prepared MNCs was confirmed by X-ray powder diffraction (XRD), while the morphology and nano-size of the MNCs were investigated by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM), where TEM was additionally used to observe the MNP core and silica layer thickness. The presence of functional groups of the MNCs was investigated by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and surface analysis was performed by X-ray photoelectron spectroscopy (XPS). The hydrophilicity of the modified electrodes was also tested by static contact angle measurements. Then, MNPs@SiO₂@Lys was applied onto the electrodes and used with the SWV and SWAdSV techniques. All electrodes tested with the SWV technique were effective for Cr(VI) trace determination. On the other hand, the SWAdSV technique was required for ultra-trace determination of Cr(VI). Using the SWAdSV technique, it was shown that a combination of ex situ BiFE with the deposited MNPs@SiO₂@Lys resulted in excellent analytical performance (LOQ = 0.1 µg/L, a linear concentration range of 0.2–2.0 µg/L, significantly higher sensitivity compared to the SWV technique, an RSD representing reproducibility of 9.0%, and an average recovery of 98.5%). The applicability of the latter system was also demonstrated for the analysis of a real sample. Full article

A simple and highly sensitive electrochemical sensor was developed for adsorptive cathodic stripping voltammetry of alprazolam. Based on an electrochemically pretreated glassy carbon electrode, the sensor demonstrated good adsorption and electrochemical reduction of alprazolam. The morphology of the glassy carbon electrode and the electrochemically pretreated glassy carbon electrode were characterized by scanning electron microscopy/energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical behaviors of alprazolam were determined by cyclic voltammetry, and the analytical measurements were studied by adsorptive cathodic stripping voltammetry. Optimized operational conditions included the concentration and deposition time of sulfuric acid in the electrochemical pretreatment, preconcentration potential, and preconcentration time. Under optimal conditions, the developed alprazolam sensor displayed a quantification limit of 0.1 mg L⁻¹, a detection limit of 0.03 mg L⁻¹, a sensitivity of 67 µA mg⁻¹ L cm⁻² and two linear ranges: 0.1 to 4 and 4 to 20 mg L⁻¹. Sensor selectivity was excellent, and repeatability (%RSD < 4.24%) and recovery (82.0 ± 0.2 to 109.0 ± 0.3%) were good. The results of determining alprazolam in beverages with the developed system were in good agreement with results from the gas chromatography–mass spectrometric method. Full article

The removal of selenium from superficial and waste water is a worldwide problem. The maximum limit according to the World Health Organization (WHO) for the selenium in the water is set at a concentration of 10 μg/L. Carbon based adsorbents have attracted much attention and recently demonstrated promising performance in removal of selenium. In this work, several materials (iron oxide based microparticles and graphene oxides materials) and their composites were prepared to remove Se(IV) from water. The graphene oxides were prepared according to the simplified Hummer’s method. In addition, the effect of pH, contact time and initial Se(IV) concentration was tested. An electrochemical method such as the differential pulse cathodic stripping voltammetry was used to determine the residual selenium concentration. From the experimental data, Langmuir adsorption model was used to calculate the maximum adsorption capacity. Graphene oxide particles modified by iron oxide based microparticles was the most promising material for the removal of Se(IV) from its aqueous solution at pH 2.0. Its adsorption efficiency reached more than 90% for a solution with given Se(IV) concentration, meanwhile its maximal recorded adsorption capacity was 18.69 mg/g. Full article

Progesterone is an important hormone responsible, among others, for maintaining pregnancy via inhibition of uterus muscles activity; thus, following its concentration levels in pregnant women is of immense importance in the endeavor to prevent premature birth. In this work, the nanostructured bismuth film electrode (nsBiFE) was studied for detection of progesterone in neutral medium. Due to the ability to accumulate progesterone at the nsBiFE, the adsorptive cathodic stripping voltammetry was beneficially exploited. The nsBiFE was prepared on the surface of a glassy carbon supporting electrode and several parameters influencing the detection of progesterone were investigated. The nsBiFE exhibited superior electroanalytical characteristics in comparison to other bismuth-based electrodes and unmodified glassy carbon electrode together with satisfactory response toward low concentrations of progesterone, which are consistent with clinically significant levels. Full article

The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni²⁺ in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV). The electrochemical platform is based on the adsorptive accumulation of Ni²⁺ ions directly onto a glassy carbon electrode (GCE) modified with dimethylglyoxime (DMG) as chelating agent and a Nafion-graphene (NGr) nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE) shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co²⁺ and Zn²⁺ demonstrates good selectivity and preferential binding towards the detection of Ni²⁺ in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (%) below 5% and a detection limit of 1.5 µg L⁻¹ for Ni²⁺ reduction at an accumulation time of 120 s., the prepared electrochemical sensor exhibited good detection and quantitation towards Ni²⁺ detection in tap water samples, well below 0.1 mg L⁻¹ set by the WHO and EPA standards. This comparable to the South African drinking water guidelines of 0.15 mg L⁻¹. Full article

Novel pyrolyzed photoresist carbon electrodes for electroanalytical applications have been produced by photolithographic technology followed by pyrolysis of the photoresist. A study of the determination of Ni(II) dimethylglyoximate (Ni-DMG) through adsorptive cathodic stripping voltammetry at an in situ bismuth-modified pyrolyzed photoresist electrode (Bi-PPCE) is reported. The experimental conditions for the deposition of a bismuth film on the PPCE were optimized. The Bi-PPCE allowed the analysis of trace concentrations of Ni(II), even in the presence of Co(II), which is the main interference in this analysis, with cathodic stripping square wave voltammograms characterized by well-separated stripping peaks. The calculated limits of detection (LOD) were 20 ng∙L⁻¹ for Ni(II) alone and 500 ng∙L⁻¹ in the presence of Co(II). The optimized method was finally applied to the analysis of certified spring water (NIST1640a). Full article