Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes.

Calixarenes, as novel organic materials, can play a pivotal role in the development of high-performance nonlinear optical materials due to the ease of design and fabrication. In this study, DFT simulations were employed to investigate the geometric, electronic, and NLO responses of calix[4]arene doped with Li3O, Na3O, and K3O superalkalis. The computed values of the vertical ionization energies and interaction energies indicate the chemical and thermodynamic stabilities of the targeted M3O@calix[4]arene complexes. The corresponding energy gaps (2.01 to 3.49 eV) are notably reduced, indicating the semiconductor nature of the materials. Surprisingly, the M3O@calix[4]arene complexes exhibit transparency in the UV/visible range as the absorption peaks are shifted in the near infrared (NIR) region. The highest values of 5.9 × 105 a.u. and 2.3 × 108 a.u. for the respective first and second hyperpolarizabilities are observed for Na3O@calix[4]arene. Furthermore, the Na3O@calix[4]arene complex exhibits maximum values of 2.3 × 105 a.u. for second harmonic generation (SHG) and (K3O@calix[4]arene) 2.3 × 106 a.u. for the electro-optical Pockels effect (EOPE) at 1064 nm. Similarly, approximations are made for the dynamic second hyperpolarizability coefficients (EOKE and EFISHG) at different wavelengths. Notably, the Na3O@calix[4]arene complex demonstrates the highest quadratic nonlinear refractive index (n2) of 9.5 × 10-15 cm2 W-1 at 1064 nm. This research paves the way for the development of stable calix[4]arenes doped with superalkalis, leading to an improved nonlinear optical (NLO) response.

Development of a sensitive and inexpensive electrochemical sensor for indigotin using poly(valine) modified carbon paste electrode.

In this study, an electro-polymerized valine (VLN) stimulated carbon paste electrode (CPE) was used to create a straightforward, inexpensive, and renewable electrochemical sensor for accurate and selective indigotin (IGN) determination. Comparing the CPE, to the modified electrode, it exhibits excellent sensibility for the IGN oxidation-reduction reaction. Multiple techniques, including cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) were utilized in this case to characterize the electrode materials. IGN was analyzed using CPE and poly(valine) modified carbon paste electrodes (P(VLN)MCPE) taking a 6.5 pH in 0.2 M phosphate buffer solution (PBS). Because it has more active spots than the CPE and a strong electrocatalytic nature, P(VLN)MCPE exhibits excellent electrochemical performance. The impact of pH, scan rate, numerous interferents, and fluctuation in analyte concentration were only a few of the important electrochemical factors that were investigated. The variation in scan rate proves that the IGN oxidation-reduction reaction on the surface of P(VLN)MCPE is as follows an adsorption-controlled pathway. The P(VLN)MCPE displays a good electrochemical nature for IGN in the 0.2 to 5.0 µM range, with a low limit of detection (LOD) is 0.0069 µM and a limit of quantification (LOQ) is 0.023 µM. P(VLN)MCPE shows good reproducibility, stability, and repeatability for the detection of IGN. Additionally, P(VLN)MCPE's analytical applicability for IGN detection in water sample was assessed with impressive recovery.

Enhanced Sunlight-Powered Photocatalysis and Methanol Oxidation Activities of Co3O4-Embedded Polymeric Carbon Nitride Nanostructures.

The contamination of water by organic substances poses a significant global challenge. To address these pressing environmental and energy concerns, this study emphasizes the importance of developing effective photocatalysts powered by sunlight. In this research, we achieved the successful synthesis of a novel photocatalyst comprised of polymeric carbon nitride (CN) nanosheets embedded with Co3O4 material, denoted as CN-CO. The synthesis process involved subjecting the mixture to 500 °C for 10 h in a muffle furnace. Structural and morphological analyses confirmed the formation of CN-CO nanostructures, which exhibited remarkable enhancements in photocatalytic activity for the removal of methylene blue (MB) pollutants under replicated sunlight. After 90 min of exposure, the degradation rate reached an impressive 98.9%, surpassing the degradation rates of 62.3% for pure CN and 89.32% for pure Co3O4 during the same time period. This significant improvement can be attributed to the exceptional light captivation capabilities and efficient charge separation abilities of the CN-CO nanostructures. Furthermore, the CN-CO nanostructures demonstrated impressive photocurrent density-time (j-t) activity under sunlight, with a photocurrent density of 2.51 µA/cm2 at 0.5 V. The CN-CO nanostructure exhibited excellent methanol oxidation reaction (MOR) activity with the highest current density of 83.71 mA/cm2 at an optimal 2 M methanol concentration, benefiting from the synergy effects of CN and CO in the nanostructure. Overall, this study presents a straightforward and effective method for producing CN-based photocatalysts decorated with semiconductor nanosized materials. The outcomes of this research shed light on the design of nanostructures for energy-related applications, while also providing insights into the development of efficient photocatalytic materials for addressing environmental challenges.

Exploring the electrochemical properties of CuSe-decorated NiSe2 nanocubes for battery-supercapacitor hybrid devices.

Chalcogenides, a promising class of electrode materials, attracted massive popularity owing to their exciting features of high conductive nature, high capacity, rich redox activities, and structural functionalities, making them the first choice for the electrochemical energy domain. This paper reported a new NiSe2-CuSe nanocomposite prepared via a wet-chemical synthesis followed by a low-cost and simple hydrothermal reaction. The physical characterization showed cubes and nanoparticles type morphological features of NiSe2 and CuSe products, while their composite reveals a combined morphological characteristic. The electrochemical properties were tested in an aqueous solution, demonstrating that the NiSe2-CuSe nanocomposite exhibits a high capacity of 376 C g-1, low resistance, good reversibility and rate capability in a three-electrode mode than bulk counterparts. For practical aspects, a battery-hybrid supercapacitor (BHSC) is developed with NiSe2-CuSe nanocomposite, and activated carbon (AC) serves as cathode and anode in two-cell mode operation. The built NiSe2-CuSe||AC/KOH BHSC expanded the voltage to 1.8 V and delivered the highest capacitance of 148 F g-1 and 55 F g-1 from 1 to 10 A g-1, suppressing most of the previously existing literature reports. Also, our built NiSe2-CuSe||AC/KOH BHSC displayed a high-power delivery of 8928 W kg-1 at a maximum energy density of 66.6 W h kg-1 and retained 91.7% capacitance after a long way of 10,000 cycles. These outstanding results demonstrate that metal selenides can be effectively utilized as alternative electrodes with high energy, rate performance, and long-term durability for advanced energy conversion and storage devices.

Electrochemical detection and quantification of catechol based on a simple and sensitive poly(riboflavin) modified carbon nanotube paste electrode.

In the present research work, selective and sensitive catechol (CT) detection and quantification were shown in the presence of resorcinol (RS) in 0.2 M phosphate buffer (PB) solution by preparing a low-cost, simple, and green carbon nanotube paste electrode (CNTPE) surface activated with electropolymerized riboflavin (PRF). The morphological, conductivity, and electrochemical features of the modified electrode (PRFMCNTPE) and bare carbon nanotube paste electrode (BCNTPE) materials were analyzed using electrochemical impedance spectroscopy (EIS), field emission scanning electron microscopy (FE-SEM), cyclic voltammetry (CV), and differential pulse voltammetry (DPV). The PRF-activated electrode displays outstanding sensitivity, stability, selectivity, reproducibility, and repeatability for the redox feature of CT with improved electrochemical current and declined electrochemical potential compared to BCNTPE. The peak currents of CT are correlated to the different CT concentrations (CV method: 6.0-60.0 µM & DPV method: 0.5-7.0 µM), and the obtained detection limit (DL) and quantification limit (QL) are found to be 0.025 µM and 0.085 µM (CV method) and 0.0039 µM and 0.0132 µM (DPV method), respectively. The prepared PRFMCNTPE material was advantageous for the examination of CT in environmentally important tap water sample as a real-time application.

Electrochemical Polymerisation of Glutamic Acid on the Surface of Graphene Paste Electrode for the Detection and Quantification of Rutin in Food and Medicinal Samples.

Rutin (RU) is one of the best-known natural antioxidants with various physiological functions in the human body and other plant species. In this work, an efficient voltammetric sensor to detect RU in food samples was explicated using a poly (glutamic acid)-modified graphene paste electrode (PGAMGPE). In order to detect RU, the proposed sensor diminishes material resistance and overpotential while increasing kinetic rate, peak currents, and material conductance. Using differential pulse voltammetry (DPV) and cyclic voltammetry (CV), the analysing efficiency of a PGAMGPE and a Bare graphene paste electrode (BGPE) was evaluated in 0.2 M phosphate buffer (PB) at an ideal pH of 6.5. in a potential window of -0.25 V to 0.6 V. Electrochemical impedance spectroscopy (EIS) was used to analyse the prepared electrode materials' conductivity, charge transfer resistance, and the kinetics of electron transport. Field emission scanning electron microscopy (FE-SEM) images were considered to compare the exterior morphology of the PGAMGPE and the BGPE. It was discovered that the PGAMGPE and the BGPE have electroactive surfaces of 0.062 cm2 and 0.04 cm2, respectively. It was determined that two protons and two electrons participated in the redox process. The resultant limit of detection (LOD) was found to be 0.04 µM and 0.06 µM, respectively, using DPV and CV methods. In spite of common interferents such as metal ions and chemical species, the developed sensor's selectivity for RU detection was impressive. For the simultaneous analysis of RU in the presence of caffeine (CF), the PGAMGPE affords a good electrochemical nature for RU with good selectivity. Due to the good stability, repeatability, reproducibility, and ease of use of the present RU sensor, it is useful for real sample analysis such as food and medicinal samples with recovery ranging from 94 to 100%.

Highly Selective and Sensitive Voltammetric Method for the Detection of Catechol in Tea and Water Samples Using Poly(gibberellic acid)-Modified Carbon Paste Electrode.

Despite the wide range of applications of catechol (CC) in agrochemical, petrochemical, textile, cosmetics, and pharmaceutical industries, its exposure to the environment leads to health issues as it is carcinogenic. This increased the concern over the risk of exposure level of CC in the environment, and monitoring its level has become critical. In this work, we report the fabrication of poly-gibberellic acid-modified carbon paste electrode (PGBAMCPE) to be a simple, viable, and effective electrochemical electrode for the determination of CC. This was synthesized by a simple electropolymerization method by the cyclic voltammetry (CV) technique. The electrodes were characterized by field emission electron microscopy, energy-dispersive X-ray spectroscopy, and electrochemical impedance spectroscopy. Compared to the bare carbon paste electrode, the sensitivity for CC fortified at PGBAMCPE in both CV and differential pulse voltammetry (DPV). We succeeded attaining a lower detection limit of 0.57 µM by the DPV method. The developed electrode was observed to be highly conductive, transducing, stable, and reproducible and was highly selective with anti-interfering properties from the determination of CC with hydroquinone simultaneously. The applicability of the electrode was confirmed from the detection CC in tea and water samples with good recoveries. This substantiates that PGBAMCPE is promising and consistent for the rapid monitoring of CC-contaminated area and clinical diagnosis.