Electrochemical Methods Research Articles

Synthesis, structural characterization, thermal analysis and anticorrosion properties of novel AZO-based imidazo[1,2-a]pyridine derivatives: Experimental study and theoretical approaches

In this study, innovative AZO-based imidazo[1,2-a]pyridine derivatives were synthesized using simple and efficient synthetic approach enabling large-scale production. Thermal analysis highlights their suitability for potential applications requiring resistance to moderate temperatures. These compounds were investigated as corrosion inhibitors for MS in a 1 M HCl-medium. Corrosion inhibition studies, including weight loss, PotentioDynamic polarization and electrochemical impedance spectroscopy methods, revealed that AZOs exhibited maximum corrosion inhibition efficiencies reaching 96.13 % and 94.07 %, respectively, at a concentration of 10−3 M and a temperature of 298 K, with both compounds acting as mixed-type inhibitors. The study also delved into the influence of temperature and immersion time on inhibitory performance, revealing stable inhibition within the temperature range of 298–328 K. The calculated standard free energy of adsorption was −42.06 and −40.62 kJ/mol for AZO 1 and AZO 2, respectively, suggesting mixed-type adsorption, with adsorption behavior following the Langmuir isotherm. Morphological analysis through SEM and AFM, showed a reduction in surface roughness in the presence of the inhibitors, while water contact angle measurements indicated a significant increase in surface hydrophobicity. UV–visible and FT-IR analyses confirmed the interaction of AZOs with the MS surface, suggesting the formation of a protective layer composed of adsorbed AZO molecules. Furthermore, computational investigations employing DFT, Monte Carlo, and Molecular Dynamic simulation revealed the formation of coordinate bonds between the studied inhibitors and the metal surface, confirming adsorption on the metallic surface. These findings align well with experimental outcomes, and a possible corrosion inhibition mechanism process was discussed.

Electrochemical Synthesis of Metal Complexes Using Dissolving Anodes.

The use of dissolving metal electrodes for the direct electrochemical synthesis of metal complexes has been used widely in the last decade. A major benefit of the electrochemical approach is the minimal by-products resulting from the synthesis. As such, metal complexes can be produced on-demand and used directly in catalysis without the need for purification. Furthermore, the electrochemical method enables the production of metal complexes that cannot be synthesized using other methods, including those with base-sensitive ligands. General principles of the electrochemical method and recent advances in the field are discussed.

Self-Oxidated Hybrid Conductive Network Enables Efficient Electrochemical Lithium Extraction Under High-Altitude Environment.

The electrochemical deintercalation method has been considered as an effective way to address the demand for lithium resources due to its environmental friendliness, high selectivity, and high efficiency. However, the performance of electrochemical lithium extraction is closely dependent on the electrode material and needs to be compatible under plateau environments with high-altitude and low-temperature. Herein, an in situ self-oxidation method is conducted to construct a hybrid conductive network on the surface of LiFePO4 (LFP-HN). The introduction of a hybrid conductive network enhanced the interfacial electron/lithium-ion transfer. In addition, structural stability is strengthened through suppressing the intercalation of impurity cations. Consequently, the LFP-HN delivered extremely high lithium extraction capacity (27.42mg g-1), low energy consumption (4.91Wh mol-1), and superior purity (91.05%) in Baqiancuo real brine (4788 m, -10°C). What's more, LFP-HN-based large-scale prototypes are constructed and operated at Baqiancuo, which is calculated to extract 25kg Lithium Carbonate Equivalent per cycle (4.55h, 100 pairs of plates). Based on the excellent performance, the modification strategy developed in this work can be a promising solution for industrial lithium extraction under high-altitude environment.

Applications of vibrational phenomena to evaluate the effect of hydrogen solution on the elasticity and fatigue properties of industrial metal plates

Understanding resonance phenomena in materials is crucial in many fields, from controlling noise in small mobile devices to designing seismic-safe large structures or in energy harvesting. Resonance depends on material elasticity and its shape, influenced by temperature. While controlling elastic properties can control vibrations, seeking practical alternatives is essential. This research focuses on introducing hydrogen into industrial metal materials as a method to control resonance conditions, which is particularly relevant in the context of the upcoming hydrogen society. Controlled amounts of hydrogen were introduced to industrial metal plates (Ti, W) using electrochemical methods to investigate changes in their resonance characteristics. The results indicate that the introduction of hydrogen into Ti resulted in a maximum 20% reduction in Young's modulus, while W exhibited a 10% decrease. Additionally, the recovery of their modulus by hydrogen desorption was confirmed. This confirms that the control of hydrogen allows the manipulation of the modulus of elasticity at constant temperature, controlling the resonance without changing the dimensions. Furthermore, similar evaluations were performed on high hardness steel. The results showed fatigue failure due to vibration, increased Young's modulus with the introduction of hydrogen, and an observed trend toward decreased life to failure.

Water oxidation through electrocatalytic process using cobalt and nickel complexes of thiazole Schiff-base ligands

Ni(OAc)2.4H2O and CoCl2.6H2O reacted with thiazole ligands, HL and HL' (where HL= (E)-2-(((4-phenylthiazol-2-yl)imino)methyl)phenol and HL'= (Z)-2-(2-benzylidenehydrazinyl)-4-phenylthiazole, in ethanol to create new mononuclear Co(II) and Ni(II) complexes, CoL2, NiL2, CoL'2, and NiL'2 (1-4). X-ray diffraction analysis, spectroscopic, and electrochemical methods were used to study the complexes. A carbon paste electrode that had been modified by complexes 1-4 was used as the working electrode in a three-electrode setup to test the complexes' ability in water oxidation reaction at pH 13. The linear sweep voltammetry (LSV) curves showed that complexes 3 and 2 have much greater activity and only require the overpotential of 570 and 690 mV ʋs. RHE at a current density of 10 mA/cm2 with Tafel slopes of 86.92 and 94.19 mVdec−1 respectively in an alkaline solution. In addition, the amperometry tests exhibited brilliant stability for water oxidation by CPE-complex 3 and CPE-complex 2 under electrochemical conditions at pH 13. Although X-ray diffraction patterns did not display a crystalline structure, the scanning electron microscopy images displayed that cobalt oxide and nickel oxide in an alkaline condition are proper catalysts for water oxidation reaction on the surface of the modified electrode.

B-151 Development and Validation of Plasma Catecholamines by Mass Spectrometry

Abstract Background Our established method for measuring plasma catecholamines utilized a Shimadzu HPLC coupled to an ESA Coulochem III electrochemical detector. Chromatographic run times were long, resulting in slow turnaround times. Instrument maintenance was labor intensive, and the assay was prone to interferences. To overcome these limitations, we changed the method to liquid chromatography-tandem mass spectrometry (LC-MS/MS) measurements. Methods After the addition of a labeled internal standard for each analyte, samples are loaded onto 50 mg of activated alumina at pH 8.6, utilizing a Tris-HCl, sodium carbonate and EDTA buffer. After incubation the alumina is then washed with 50% acetonitrile followed by water. Elution off the alumina is performed with 2% acetic acid. Derivatization is then performed on the eluate utilizing acetaldehyde and a cyanoborohydride buffer. Following derivatization, the samples are analyzed for epinephrine, norepinephrine, and dopamine by LC-MS/MS using a Sciex 7500 coupled to a ThermoFisher Scientific TLX-4 equipped with Vanquish pumps. Chromatographic separation was obtained using a Phenomenex Kinetex 2.6 um BiPhenyl 50x3 mm analytical column. Results Runtimes were significantly shorter than with the previous method, and no interferences were observed. Assay validation consisted of: intra/inter assay precision, accuracy, recovery, linearity, carryover, limit of detection (LOD), and interferences. Three levels were assessed for intra assay precision and each of the analytes monitored yielded %CVs of less than 6%. Four levels were assessed for inter assay precision and each of the analytes monitored yielded %CVs of less than 10%. When using linear regression analysis to compare results with the previous clinical assay, the slope, y-intercept and R2 were the following; dopamine: 1.06, 2.74, 0.978; epinephrine: 0.905, 2.20, 0.989; norepinephrine: 0.919, 9.75, 0.953. Spike and recovery from five samples yielded a mean average recovery of 93.4% for dopamine, 100% for epinephrine and 98.1% for norepinephrine. For linearity 4 samples were diluted and the mean % difference from expected was -1.66% for dopamine, -0.25% for epinephrine and 1.78% for norepinephrine. Blanks were injected following the high standard and carryover was negligible. LOD was determined by running a low sample pool along with a blank over 20 assays. The LOD was determined to be less than the LLOQ. Sixty-two common drugs/vitamins along with varying levels of hemolysis, lipemia, and bilirubin were also tested to ensure no interferences were seen. Conclusions The LC-MS/MS method exceeded the performance of the historical Shimdazu HPLC system with ESA Coluochem III electrochemical detector method. We anticipate that the better analytical performance will improve the testing quality of our patients.

Electrochemical upcycling of indium-gallium-zinc oxide scraps

At present, the processes of recovering indium-gallium-zinc oxide (IGZO) scraps through hydrometallurgy, pyrometallurgy, or molten salt electro-deoxidation are cumbersome, impurities cannot well be effectively removed, and the environmental benefits are inferior. We herein firstly propose a facile electrochemical method for upcycling of IGZO scraps in ammonium salt aqueous solution at ambient temperature. The feasibility of electro-deoxidation of IGZO in aqueous solution has been verified, using IGZO scraps without further crushing as the cathode and anode. The electro-deoxidation behavior of various oxides exhibits differentiation, among which indium oxide is the most easily deoxidized. This difference hinders the formation of a dense alloy layer on the surface of the IGZO substrate, facilitating the transfer of oxygen ions and enabling continuous electro-deoxidation. Impurities such as aluminum and silicon can be significantly removed, with removal rates of 95.8 % and 75.7 %, respectively, which is also attributed to the difference in electrochemical reduction ability between impurity oxides and IGZO, as well as the solid-state existence of cathode products. The process of upcycling IGZO scraps contributes to recovery with straightforward operation and more adaptable implementation environment, which endows it with optimistic application potential.

Study Effect of rGO Addition on Photocatalytic Activity of TiO2 in Reducing Carbon Dioxide Using Electrochemical Method

Abstract Increasing the carbon dioxide (CO2) concentration every year can cause various environmental problems. One of the technologies to reduce CO2 is carbon capture. The semiconductor of TiO2 is widely used as a photocatalyst to reduce CO2. However, TiO2 has limitations in absorbing light in the visible region because it has a large band gap value. Besides, TiO2 has a fast recombination of electron-hole pairs so it can reduce photocatalytic activity. An addition of rGO is expected to cover the shortcomings of TiO2 because rGO has good conductivity and a small band gap. We synthesized rGO-TiO2 photocatalyst and measured its activity in capturing and converting CO2 using an electrochemical method. By using voltage difference as an electron driver in reacting with CO2 we observe the reaction between electrons and CO2. The measurements were carried out under irradiated and unirradiated conditions. The CV measurements show that the rGO-TiO2 electrode with 60% rGO content has reduction and oxidation peaks. Based on the electrochemical half-reaction table, the reduction peaks in unirradiated conditions indicate the conversion of CO2 to CH4 and (COOH)2, while under irradiated the reduction peak indicates the formation of HCOO− and CH2CH2. The results show that by using the rGO-TiO2 composite as an electrode not only reduces CO2 but also converts the CO2 into hydrocarbon.

Investigating the synergistic effect of fish waste extract and KI on the corrosion inhibition of carbon steel in sulfuric acid solution

Biowaste has become a serious problem that can lead to serious environmental pollution and waste of resources if not handled properly. Waste materials are often high in proteins, which are easily extracted and hydrolyzed to provide an adequate quantity of amino acids. This indicates that biowastes can be used as green and efficient corrosion inhibitors (CIs). This work aimed to prepare fish waste extract (FWE) by acid hydrolysis with alkaline leaching using fish waste as the raw material. The results of the characterization analysis identified the presence of 17 amino acids, with Leucine, Phenylalanine, Methionine, and Alanine being the most abundant. FWE was then tested as a corrosion inhibitor (CI) for carbon steel in 0.5 mol/L H2SO4. Further, the effect of KI on the corrosion inhibition performance of FWE for carbon steel in 0.5 mol/L H2SO4 was systematically investigated by the weight loss method, electrochemical method, and surface analysis. The maximum corrosion inhibition efficiencies were 88.7 % and 63.9 % for the FWE and KI alone, and 97.10 % for the combination of FWE and KI. The synergistic coefficient study confirmed that the synergistic coefficients of the FWE and KI exceeded 1 across all concentration conditions, indicating a synergistic effect between them. The surface analysis results showed that the deterioration of carbon steel after adding the compounded CI was mild, and pitting and crevice corrosion was not observed. Theoretical calculations revealed the active reaction sites of four major amino acid molecules via quantum chemical and molecular dynamics simulations. The effect of different types of side chains and heteroatoms of amino acid molecules on their corrosion inhibition performance was elucidated to provide theoretical guidance for designing biowaste CIs.

On the Optimization of Roughness and Corrosion Resistance of Laser Beam Powder Bed Fusion Fabricated Ti–6Al–4V Parts—An Electrochemical Approach

Laser beam powder bed fusion is emerging as a technology for fabricating components made of advanced alloys, such as Ti–6Al–4V. However, it suffers from rough as‐built (AB) surfaces, necessitating postprocessing for desired quality and performance. Electrochemical methods such as electrochemical polishing (ECP) and anodization (AN) are promising postprocessing methods; ECP can effectively smoothen surfaces irrespective of their complexity and hardness, while AN enhances the material's corrosion resistance. However, literature lacks research that discusses combined ECP and AN treatment on surface texture evaluation and corrosion behavior. This work presents a detailed study on the effects of different processing factor levels using a Taguchi design of experiment (DOE) approach and discusses the underlying process mechanisms. The optimized treatment conditions to achieve highest roughness improvement and best corrosion resistance are discussed and the most influential postprocessing factors are revealed and ranked. The treatment that achieved smooth surfaces and high corrosion resistance is ECP at 20 V and 15 °C for 20 min, followed by AN at 15 V for 5 min. This treatment achieves a 72% roughness improvement, providing an arithmetic areal surface roughness of 2.63 μm and a corrosion current density of 0.09 μA cm−2, which is almost similar to the AB part.

Enhancing interfacial locking of the CF and PBPESK resin by in-situ electrochemical deposition of MOF nanoparticles

The interfacial bonding of carbon fiber reinforced polymer composites plays a critical role in the overall performance of the composites. Poor interfacial bonding leads to catastrophic damage of composites when subjected to external loads. In this study, three-dimensional (3D) NH2-UiO-66 nanoparticles in-situ synthesis on the carbon fiber (CF) surface using an electrochemical method was achieved facilely and efficiently to enhance the interfacial adhesion of CF/PBPESK composites. The influence of incorporating 3D NH2-UiO-66 nanoparticles into the interphase on the interfacial and mechanical properties of carbon fiber reinforced composites was systematically investigated. The NH2-UiO-66 nanoparticles significantly increased the carbon fibers surface energy. The flexural, interlaminar shear and interfacial shear strength of the N–CF–6min/PBPESK composite were improved by 19 %, 31 %, and 93 %, respectively, compared to the D-CF/PBPESK composite. Furthermore, the interfacial failure mechanism of the composites was investigated. This approach offered a simple and efficient strategy for the in-situ synthesis of interfacial phase characterized by robust mechanical locking effects.

Characteristics of shear stress fluctuations in polymer solutions and their relation to turbulent structures in channel flows

In this study, the wall shear stress in the channel flow of polyacrylamide polymers was investigated through electrochemical experiments, and the effects of the polymer concentration were evaluated at different Reynolds numbers. The objective was to explore the relationship between the changes in the drag reduction and near-wall turbulence structure induced by the polymer. The experiments were conducted using polymer concentrations of 0, 20, 50, 100, and 150 ppm, and a drag reduction of approximately 23% was achieved at a bulk Reynolds number of Reb = 18 750. In the electrochemical method, the working electrode was arranged spanwise, and simultaneous measurements were performed for eight electrodes to discuss the scale of the near-wall low-speed streaks and burst events. A comprehensive analysis of the correlation of the wall shear stress in the streamwise direction and the cross-spectrum of two points in the spanwise direction revealed that large streamwise and spanwise scales of near-wall low-speed streaks were generated at high polymer concentrations. Furthermore, the results obtained using the variable interval time averaging technique indicated that polymer incorporation suppressed the wall shear stress fluctuations and weakened both the intensity and frequency of the bursting events.

Fast tailoring the ZIF-8 surface microenvironment at ambient temperature to boost glucose oxidase-like activity of AuNPs for biosensing

Rational design and tailoring of the surface microenvironment surrounding the catalytic sites, such as noble metal nanoparticles, is an effective way to enhance the catalytic activity of mimicking enzymes. However, it remains on-going challenges to regulate the microenvironment of the catalytic sites due to the lack of tunable variability in structural precision of conventional solid catalysts. Herein, three types of zeolitic imidazolate framework-8 (ZIF-8) with different major crystal facet orientations, i.e., cubic with (100) facets (denoted ZIF-8c), truncated dodecahedral with (100), (110) facets (denoted ZIF-8tr), and dodecahedral with (110) facets (denoted ZIF-8r), were developed facilely using an electrochemical method by switching the potential at ambient temperature. Because the Zn2+ nodes were predominantly exposed on the (100) facets of ZIF-8, while the ligands were mainly exposed on the (110) facets. Hence, gold nanoparticles (AuNPs) showed differential glucose oxidase (GOx)-like activities when anchored in situ on different crystal facets of ZIF-8 and obeyed the following order ZIF-8c/Au>ZIF-8tr/Au>ZIF-8r/Au. Notably, both the metal nodes and aromatic linkers of ZIF-8 interacted with AuNPs through coordination and π-π interactions. The Zn2+ nodes facilitated the formation of the electron-deficient Au species. The electron transfer from AuNPs to Zn2+ sites effectively boosted the catalytic activity. It was known that directly tailoring the microenvironment at the supporting sites of noble metal catalysts to boost catalysis through a facile electrochemical method was not reported. Based on the favorable GOx-like activity and long-term stability of ZIF-8tr/Au, a highly sensitive electrochemical biosensing platform for assaying squamous cell carcinoma antigen (SCCA) was developed. It enabled fg-level detection of cancer marker.

Strengths and Weaknesses of Elimination Voltammetry with Linear Scan

Electrochemical methods have undergone many important developments initiated by efforts to increase the sensitivity, selectivity, and stability (S&S&S) and to understand the underlying electrode processes. To meet these goals, there are hardware solutions with applications of new technologies and materials, and software solutions utilizing existing instrumentation. The article presents a viable, easy-to-implement software solution to the main shortcomings of linear sweep voltammetry (low sensitivity, high share of the capacitive component of the current, and the problem of overlapping signals) in the form of elimination voltammetry with a linear scan (EVLS). Based on the different dependences of the individual currents that make up the total voltammetric current (diffusion, charging, kinetics, and various irreversible components) on the scan rate, EVLS can eliminate or preserve particular current components. Increased sensitivity and selectivity can be expected especially in the case of a fully adsorbed electroactive particle subjected to an irreversible electrode process when the elimination of kinetic and capacitive current while preserving the diffusion current provides a theoretically confirmed peak-counter peak signal. EVLS is applicable for testing changes in the polarized electrode/electrolyte interface using EVLS functions eliminating the diffusion component of the current and preserving the kinetic and capacitive currents, which should ensure zero current conduction for a purely diffusion-controlled Nernstian-type reversible process. We point out the strengths, opportunities, and weaknesses of EVLS. Nevertheless, EVLS offers a new tool that contributes to a better understanding of electrochemical processes and their mechanisms.

Electrochemical Detection of Cd2+ and Pb2+ in Wastewater by Amino C-dot-MOF/GCE

Carbon dots(C-dots) and metal-organic frameworks (MOFs) have found widespread applications in sensing, energy storage, and catalysis, yet their utilization in electrochemical sensing remains relatively limited. This study focuses on the preparation of C-dots/UiO-66-NH2 as a modified material on glassy carbon electrodes to detect cadmium and lead ions in water using electrochemical methods. The material was created by utilizing m-phenylenediamine as a C-dots source and amino-functionalized zirconium-based metal-organic frameworks, combining these two popular materials. The presence of amino groups in the structure facilitated the complexation with metal ions, providing an effective interface for metal ion adsorption. Under optimized deposition conditions, C-dots/UiO-66-NH2 demonstrated excellent linearity and low detection limits for metal ions (Cd2+ and Pb2+) within the concentration range of 30 to 180 μg l−1. The limits of detection (LOD) were LOD(Cd) = 2.16 μg l−1 and LOD(Pb) = 1.08 μg l−1 for individual detection, and LOD(Cd) = 2.62 μg l−1 and LOD(Pb) = 1.36 μg l−1 for simultaneous detection. These results highlight the suitability of C-dots/UiO-66-NH2 for the determination of Cd2+ and Pb2+ in water. Furthermore, the C-dots/UiO-66-NH2/GCE sensor exhibited robust immunity to interference and maintained detection stability, showcasing its potential for practical applications.

Electrochemical late-stage modification of hydralazine an antihypertensive drug. A green strategy for the synthesis of nano-structured new sulfonylhydrazine derivatives

This work is focused on the electrochemical late-stage modification of hydralazine (1-hydrazinylphthalazine) (HYD), a common antihypertensive drug, and the synthesis of its new sulfonylhydrazine derivatives. The synthesis of HYD derivatives has been easily accomplished in one-pot via electrochemical oxidation of HYD in the presence of arylsulfinic acid derivatives (ASA) in a water/ethanol mixture at constant current conditions. The electrochemical results show that anodically generated 1-diazenylphthalazine (HYDox) reacts with arylsulfinic acids and converts into the corresponding sulfonylhydrazine derivatives (SHD) with high yield and purity in an undivided cell equipped with graphite anode and stainless steel cathode. The main feature of this work is the synthesis of some new HYD derivatives in water/ethanol mixture as a “Green” reaction medium, using electrodes instead of toxic oxidants, having a high atom economy, having good energy efficiency and working at room temperature. These features are in accordance with the principles of green chemistry. Another advantage of this approach is that this method has led to the synthesis of sulfonylhydrazine derivatives in nano dimensions. Also, in this work, the electrochemical behavior of HYD and synthesized compounds (SHD) by different electrochemical methods were fully investigated and the results were reported. Furthermore, docking studies suggest that the products interact well with arylamine N-acetyltransferase (NAT) and show promising activity.

Sensitive Electrochemical Sensing Properties for Cyanide Detection Using Polyaniline/Cu-Vanadate Nanobelt-modified Electrode

Background: Cyanide is a toxic anion and may be discarded into the water environment, which is a serious threat to human beings and the environment. Hence, it is essential to explore a facile, sensitive method for cyanide detection. Polyaniline/Cu vanadate nanobelts serve as electrode materials for sensitive cyanide determination. Methods: Polyaniline/Cu vanadate nanobelts were obtained by a simple route using polyaniline, Cu vanadate nanobelts. The polyaniline/Cu vanadate nanobelts were measured via electron microscopy, diffraction, infrared spectrum, and electrochemical methods. Results: Amorphous polyaniline nanoparticles with a particle size of about 100 nm were attached firmly to the surface of Cu vanadate nanobelts. Electrochemical sensing properties for cyanide detection were analyzed using a cyclic voltammetry technique using the nanobelts-modified electrode. The cyclic voltammograms (CV) peaks centered at +0.64 V and +0.54 V were observed using the polyaniline/Cu vanadate nanobelts in 0.1 M KCl solution with 2 mM cyanide. The proposed composite nanobelt-modified electrode possessed the detection range and detection limit of 0.001-2 mM and 0.22 μM, respectively. Conclusion: Polyaniline greatly enhances the electro-catalytic performance of the Cu vanadate nanobelt-modified electrode for cyanide detection.

An ultra-sensitive bimetallic based electrochemical sensor for analysis of total iron, total dissolved iron, and granular iron in coastal water

Different iron species play crucial roles in the biogeochemical cycle, so their determination is important. Electrochemical methods are among the most promising and easiest methods for the rapid on-site determination of different iron species. In this study, a new electrode—Au–Bi/ITO—based on the commercial indium tin oxide (ITO) electrode was etched and functionalized with bismuth nanoparticles (BiNPs) and gold nanoparticles (AuNPs) nanocomposites for voltammetric analysis of iron species in coastal water. After etching, the ITO electrode exhibits a higher number of attachment sites for the nanomaterials, thereby improving the stability of the resulting electrode, and the introduction of the nanomaterials improves the sensitivity of the electrode, making it easier to realize on-site detection. Under the synergistic effect of the two nanomaterials, the Au-Bi/ITO electrode showed excellent performance for the determination of different iron species in coastal water. Under the optimal conditions, the Au-Bi/ITO electrode peak current was linear in the concentration range from 5 nM to 1.5 μM with an ultralow detection limit of 1.4 nM. The results are consistent with certified values when the electrode is used for the determination of Fe(III) in certified reference materials. In summary, the Au-Bi/ITO electrode, with its high stability and sensitivity, has been successfully used for the direct determination of different Fe(III) species in coastal water via cathodic stripping voltammetry. This electrode is simple to prepare, easy to use, economical, and highly promising for future applications involving the rapid on-site detection of different iron species.

Charge-induced high-valence zirconium-doped CuCo2S4/Co(OH)2 nanowires promote bifunctional water splitting

Spinel-type materials are attracting great attention as potential electrocatalysts for the hydrogen- and oxygen-evolution reactions. However, their inherent catalytic activities are not on par with those of precious-metal catalysts, and their poor stabilities continue to constrain their rapid development. In this study, we fabricated Zr-CuCo2S4 nanowires and Co(OH)2 nanosheet–nanowires using electrochemical methods, resulting in lattice defects, sulfur vacancies, and more exposed active sites that catalyze the hydrogen- and oxygen-evolution reactions. DFT calculations revealed that sulfur vacancies enhance intrinsic activity, while Zr doping reduces the energy barrier for H*–OH* adsorption, promotes the formation of additional sulfur vacancies, and modulates active-site Cu/Co valence states, which greatly enhances water-dissociation and H*-adsorption kinetics. Consequently, Zr-CuCo2S4/Co(OH)2 requires low overpotentials of 88 and 208 mV, respectively, to support highly stable alkaline hydrogen- and oxygen-evolution reactions at 10 mA cm−2. This study provides a rational strategy for designing low-cost spinels for green and clean energy.

A multifaceted approach to investigate interactions of thifluzamide with haemoglobin

This study explores the interaction between the pesticide thifluzamide (TF) and haemoglobin (Hb) to understand potential structural changes that might affect Hb's function. Using a combination of UV–visible and fluorescence spectroscopy, circular dichroism (CD), molecular docking, molecular dynamics (MD) simulations, and electrochemical methods, we investigated these interactions in detail. Spectroscopy results indicated the formation of a stable TF-Hb complex, with a binding constant of 6.64 × 105 M−1 at 298 K and a 1:1 binding ratio. The stability of this complex was confirmed by a free energy change (∆G) of −34.491 kJ mol−1. CD spectroscopy was employed to confirm structural changes in Hb due to thifluzamide binding. Molecular docking studies revealed that TF interacts with specific amino acids in Hb, such as ALA, HIS, VAL, LYS, and LEU, with a binding energy of −25.10 kJ mol−1. MD simulations supported these findings by showing conformational changes in Hb upon TF binding, as indicated by RMSD and RMSF analyses. Electrochemical experiments further confirmed the interaction, evidenced by a consistent decrease in the TF peak in the presence of Hb. Overall, our findings shed light on how TF binds to Hb, causing structural changes that could potentially impact its normal function. This research enhances our understanding of the biochemical effects of TF on Hb, which could have significant implications for biological systems.