An enhanced non-enzymatic electrochemical sensor based on the Bi2S3-TiO2 nanocomposite with HNTs for the individual and simultaneous detection of 4-nitrophenol and nitrofurantoin in environmental samples.

In the current era of rapid population growth, there has been an increase in resource consumption and the subsequent release of organic pollutants into water bodies by various industries. To address this issue, we have developed a nanocomposite material, Bi2S3-TiO2/HNTs, for electrochemical sensors capable of simultaneously detecting nitrofurantoin (NFT) and 4-nitrophenol (4-NP) contaminants. The nanocomposite material was synthesized using a novel one-pot sol-gel method, and its structural morphology was characterized using techniques such as FE-SEM, FT-IR, HR-TEM, and XRD. The electrochemical sensor exhibited a remarkably low limit of detection (3.2 nM for NFT and 3.5 nM for 4-NP) and a wide concentration range from 0 µM to 260 µM for both NFT and 4-NP, demonstrating their high sensitivity and accuracy for pollutant detection, and furthermore its potential for real-world application was assessed considering pond and tap water as real samples.

A novel and efficient voltammetric sensor for the simultaneous determination of alizarin red S and tartrazine by using poly(leucine) functionalized carbon paste electrode.

In the current work, a rapid, selective, and sensitive technique was developed for the detection of Alizarin Red S (ARS) by applying poly leucine modified carbon paste electrode (PLMCPE). Electrochemical impedance spectroscopy (EIS) and Scanning electron microscopy (SEM) were utilized to study the surface morphology of unmodified carbon paste electrode (UMCPE) and PLMCPE. The active surface area for UMCPE and PLMCPE was found to be 0.0012 cm2 and 0.0026 cm2 respectively. The electrochemical response of ARS at UMCPE and PLMCPE was analyzed using cyclic voltammetry (CV) in the potential window of 0.4 to 1.0 V. The cyclic voltammogram obtained for varying the pH of 0.2 M phosphate buffer (PB) solution showed maximum current for the oxidation of ARS at pH 6.5. The electrochemical reaction of ARS was found to be irreversible and adsorption controlled. The effect of variation of concentration of ARS on the oxidation peak current was evaluated using CV and linear scan voltammetry (LSV). A linear relationship between the concentration variation and current was obtained in the linear range of 1.5 µM-3.5 µM and 0.2 µM-5.0 µM for CV and LSV respectively. The limit of detection (LOD) of 0.68 µM for the CV method and 0.29 µM for the LSV method was exhibited by the developed sensor. The simultaneous study of ARS along with tartrazine (TZ) showed good selectivity for ARS. The interferents of foreign molecules showed no effect on the selectivity of the electrode. The applicability of PLMCPE on real samples gave good recovery ranging from 97.46-101.2%; hence, the sensor can be utilized on real samples. The developed sensor has good stability and sensitivity.

Anion Exchange Membranes Based on Chemical Modification of Recycled PET Bottles.

This study presents an innovative and effective solution for recycling PET bottles as raw for producing anion exchange membranes (AEMs) for electrochemical applications. This approach reduces the demand for pristine materials, a key principle of the circular economy and sustainability. PET was subjected to chemical modification by introducing cationic functional groups followed by methylation and OH- exchange process. The amination synthesis was optimized based on reaction time. The results indicate that ion exchange capacity, water uptake, and swelling ratio properties mainly depend on the degree of cationic functionalization. The optimized AEM exhibits ionic conductivity of 5.3 × 10-2 S·cm-1 and alkaline stability of 432 h in 1 M KOH at 80 °C. The membrane properties before and after the alkaline treatment were investigated using Fourier-transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy analysis. Computational chemistry analysis was employed to gain further insights into the membrane degradation mechanisms and pathways under alkaline conditions. This research and its findings are a step toward using recycled materials in the field of AEM technology.

Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu2SnS3, Cu2ZnSnS4, and Cu2ZnSnSe4 Chalcogenides for Thermoelectric Applications.

Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu2SnS3 (CTS), Cu2ZnSnS4 (CZTS), and Cu2ZnSnSe4 (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass-electron-crystal behavior-a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs.

Water Uptake in an Anion Exchange Membrane Based on Polyamine: A First-Principles Study.

An atomistic level study of a single monomer of polyamine interacting with water molecules and hydroxide anions (OH-) was carried out to investigate the role of the polyamine structure in the hydrated morphology of anion exchange membranes (AEMs) for alkaline fuel cells and its influence on ionic conductivity and chemical stability. DFT calculations were performed to find the ground state of the system, studying the interactions of the solvent species with three different regions of the polymer─the amine functional group, the backbone, and the carbonyl group. The hydrophilic/hydrophobic behavior of each segment was determined, with calculated binding energies and Bader charge analysis providing a more quantitative analysis of the interactions and activation and reaction energies computed to investigate the chemical degradation mechanism. The results show the tendency of both OH- and water molecules to form water clusters in the proximity of the ionized amine group. As such, these regions constitute the preferential pathway for ionic conductivity. Besides, the essential role of the water content is pointed out, not only to enhance conductivity but also to reduce degradation in an alkaline environment. The present work provides a baseline to assess the impact of polymer chemistry on the ionic conductivity of the membrane and acts as the first step for the development of high-performance AEMs and for an improvement of the overall performance of the fuel cell.

Porosity of a Fast-Setting Mortar with Crystallization Admixture and Effect of a SA-PA Modification.

Air permeability measurements according to the Hagen-Poiseuille equation, Scanning Electron Microscopy (SEM) and mercury intrusion porosimetry (MIP) tests were conducted on samples of cementitious mortar at different curing times to study the correlation between the increased crystallization and their microstructure. The mortar samples were prepared with a commercial fast-setting premix containing calcium silicates and quartz. The average permeability coefficient (K) was 2.96 × 10-15 m2 after 3 days and decreased to 3.07 × 10-17 m2 after about one month. The continuous C-S-H nucleation in the capillary pores of the cement mortar changes their shape and improves the mortar's impermeability. The SEM images showed the development of crystals that refine the pore size distribution of the cement paste, with more of the smallest pores, and fewer of the largest, as demonstrated by the MIP measurements. Adding a superabsorbent polyacrylate (SA-PA) in the amount of 0.5% wt of dry powder, without adding any extra water, makes a mortar less fluid but not faster-setting. Twenty-four hours after mixing and casting, it is still plastic and, with time, the pore size distribution differs from that of standard mortar. Over time in air, permeability remains high, but in water it could be low due to swelling of SA-PA residues.

Electrocatalytic Determination of Hydroxychloroquine Using Sodium Dodecyl Sulphate Modified Carbon Nanotube Paste Electrode.

Selective, sensitive, easy, and fast voltammetric techniques were developed for the analysis of Hydroxychloroquine (HCQ). These analysis were carried out at sodium dodecyl sulphate modified carbon nanotube paste electrode (SDSMCNTPE) using an aqueous 0.2 M phosphate buffer solution as supporting electrolyte. The field emission-scanning electron microscopy, cyclic voltammetry (CV), and electrochemical impedance spectroscopy were used for material characterization. A minute quantity of the SDS surfactant was sufficient to convey an outstanding electrocatalytic action to the electrochemical oxidation nature of HCQ. The HCQ molecule parades only electrochemical oxidation (irreversible) with the transfer of two electrons. The detection of HCQ was carried out through CV method at SDSMCNTPE and bare carbon nanotube paste electrode (BCNTPE). The corresponding analytical curve offered a decent linear nature in the considered HCQ concentration range (10-40 µM) and the detection limit was found to be 0.85 µM. The significant peak to peak split-up was observed between HCQ and interferents with a decent sensitivity and stability. The SDSMCNTPE to be an approachable electrode for the usage in the examination of HCQ independently and in the presence of paracetamol (PC) and ascorbic acid (AA). Thus, they were used to determine HCQ in pharmaceutical formulations and the results that showed good agreement with comparative methods. Furthermore, a mechanism for HCQ electro-oxidation was proposed.

Topological Anderson Insulator in Cation-Disordered Cu2ZnSnS4.

We present the first candidate for the realization of a disorder-induced Topological Anderson Insulator in a real material system. High-energy reactive mechanical alloying produces a polymorph of Cu2ZnSnS4 with high cation disorder. Density functional theory calculations show an inverted ordering of bands at the Brillouin zone center for this polymorph, which is in contrast to its ordered phase. Adiabatic continuity arguments establish that this disordered Cu2ZnSnS4 can be connected to the closely related Cu2ZnSnSe4, which was previously predicted to be a 3D topological insulator, while band structure calculations with a slab geometry reveal the presence of robust surface states. This evidence makes a strong case in favor of a novel topological phase. As such, the study opens up a window to understanding and potentially exploiting topological behavior in a rich class of easily-synthesized multinary, disordered compounds.

Effect of High-Energy Milling on the Dissolution of Anti-HIV Drug Efavirenz in Different Solvents.

The anti-HIV drug efavirenz (EFV) displays low and variable bioavailability because of its poor aqueous solubility. Ball milling is a simple and cost-effective alternative to traditional micronization to improve the solubility and dissolution rate of EFV. A multibody dynamics model was employed to optimize the milling process parameters, while the motion of the balls in the mill jar was monitored in operando. This led to a better understanding of the milling dynamics for efficient comminution and enhancement of EFV dissolution. The variability of results for different EFV batches was also considered. Depending on the EFV batch, there were intrinsic differences in how the milling affected the dissolution behavior and inhibition of HIV-1 infection. High-energy grinding is more effective on EFV materials containing an amorphous fraction; it helps to remove agglomeration and enhances dissolution. Polyvinylpyrrolidone (PVP) addition improves the dissolution by forming a hydrophilic layer on the EFV surface, thereby increasing the drug wettability. Polymorphism also affects the quality, dosage, and effectiveness of the drug. The mechanical stress effect and PVP addition on the EFV polymorphic transformation were monitored by X-ray powder diffraction, while the residual of ground EFV was collected after dissolution, analyzed by scanning electron microscopy, and provided insights into the morphological changes.

Synthesis and Post-Annealing of Cu2ZnSnS4 Absorber Layers Based on Oleylamine/1-dodecanethiol.

Cu2ZnSnS4 (CZTS) nanocrystals in oleylamine (OLA) and 1-dodecanethiol (1-DDT) solvents were successfully prepared via hot-injection method, to produce inks for the deposition of absorber layers in photovoltaic cells. In this process, 1-DDT acts as a coordinating ligand to control the nucleation and growth of CZTS nanocrystals, whereas lower amounts of OLA promote a homogeneous growth of the grains in the absorber layer. X-Ray Diffraction (XRD) revealed both tetragonal and hexagonal phases of CTZS in films obtained after soft thermal treatments (labeled TT0). In particular, 1-DDT is responsible for the formation of a greater percentage of the hexagonal phase (ZnS-wurtzite type) than that formed when only OLA is used. The thermal treatments have been varied from 500 °C to 600 °C for improving crystallization and eliminating secondary phases. Both features are known to promote CZTS thin films with band gap values typical of CZTS (1.5-1.6 eV) and suitable resistivity. This study let to compare also the CZTS post-annealing without (TT1) and with sulfur vapor (TT2) in a tubular furnace. Only tetragonal CZTS phase is observed in the XRD pattern of CZTS thin films after TT2. A small presence of localized residues of secondary phases on the same samples was revealed by µRaman measurements. The best values of band gap (1.50 eV) and resistivity (1.05 ohm.cm) were obtained after thermal treatment at 500 °C, which is suitable for absorber layer in photovoltaic application.

Solution-Based Synthesis and Characterization of Cu2ZnSnS4 (CZTS) Thin Films.

Cu2ZnSnS4 (CZTS) ink was synthesized from metal chloride precursors, sulfur, and oleylamine (OLA), as a ligand by a simple and low-cost hot-injection method. Thin films of CZTS were then prepared by spin coating, followed by thermal annealing. The effects of the fabrication parameters, such as ink concentration, spinning rate, and thermal treatment temperatures on the morphology and structural, optical, and electrical properties of the films were investigated. As expected, very thin films, for which the level of transmittance and band-gap values increase, can be obtained either by reducing the concentration of the inks or by increasing the rate of spinning. Moreover, the thermal treatment affects the phase formation and crystallinity of the film, as well as the electrical conductivity, which decreases at a higher temperature.