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This paper explores the photochemical synthesis of noble metal nanoparticles, specifically gold (Au) and silver (Ag) nanoparticles, using a one-component photoinitiator system. The synthesis process involves visible light irradiation at a wavelength of 419 nm and an intensity of 250 mW/cm2. The radical-generating capabilities of the photoinitiators were evaluated using electron spin resonance (ESR) spectroscopy. The main objective of this study was to investigate how the concentration of metal salts influences the size and distribution of the nanoparticles. Proposed mechanisms for the photochemical formation of nanoparticles through photoinitiated radicals were validated using cyclic voltammetry. The results showed that the concentration of AgNO3 significantly impacted the size of silver nanoparticles, with diameters ranging from 1 to 5 nm at 1 wt% and 3 wt% concentrations, while increasing the concentration to 5 wt% led to an increase in the diameter of silver nanoparticles to 16 nm. When HAuCl4 was used instead of AgNO3, it was found that the average diameters of gold nanoparticles synthesized using both photoinitiators at different concentrations ranged between 1 and 4 nm. The findings suggest that variations in HAuCl4 concentration have minimal impact on the size of gold nanoparticles. The photoproduction of AuNPs was shown to be thermodynamically favorable, with the reduction of HAuCl4 to Au0 having ∆G values of approximately −3.51 and −2.96 eV for photoinitiators A and B, respectively. Furthermore, the photoreduction of Ag+1 to Ag0 was demonstrated to be thermodynamically feasible, with ∆G values of approximately −3.459 and −2.91 eV for photoinitiators A and B, respectively, confirming the effectiveness of the new photoinitiators on the production of nanoparticles. The synthesis of nanoparticles was monitored using UV-vis absorption spectroscopy, and their sizes were determined through particle size analysis of transmission electron microscopy (TEM) images.

Novel mononuclear complexes 2–8 derived from hybrid Urea Schiff base HL were synthesized using various metal Ni2+, Fe3+, Cu2+, Co2+, Mn2+, Zn2+, and Cr3+. The results revealed the ligand HL reacts with metal ions as monobasic or neutral monodentate chelator it via the nitrogen of azomethine and deprotonated/protonated phenolic oxygen atom adopting octahedral geometry. The elemental analysis of the complexes showed the bonding of the ligand with the metal ions in a ratio of 1: 1 in all-metal complexes. XRD analysis of the ligand and its complexes indicate a monoclinic, tetragonal, orthorhombic corresponding to urea Shiff base (1) and zinc complex (7), nickel complex (2), and cobalt complexes (5), respectively. The bioactivity of synthesized compounds was tested and screened against three cancer cell lines PC3 (prostate), SK-OV-3 (ovarian), and HeLa (cervical). The results revealed a weak activity for the ligand, whereas nickel and iron complexes present moderate activities against three cancer cells. The best results were mentioned with copper and proved the best results against three cancer cells PC3, SKOV3, and HeLa displaying an excellent activity with IC50 values of 0.71 ± 0.06, 0.12 ± 0.06, and 0.79 ± 0.23 μg/mL respectively. Moreover, the urea Schiff base complexes showed good safety in vivo toxicity test. The present study demonstrates that all urea Schiff base complexes is inactive against saint tissue and five metal complexes investigated herein can be effective and promising chemotherapeutic drugs for ovarian cancer cell SKOV3, emphasizing the copper-urea Schiff base complex.

Advanced oxidation processes (AOPs) are eco-friendly, and promising technology for treating dye containing wastewater. This study focuses on investigating the removal of methyl orange (MO), an azo dye, from a synthetic wastewater through the use of hydrodynamic cavitation (HC), both independently and in combination with hydrogen peroxide (H2O2), as an external oxidant, as well as photocatalysis (PC) employing catalyst coated on glass fibers tissue (GFT). The examination of various operating parameters, including the pressure drop and the concentration of H2O2, was systematically conducted to optimize the degradation of MO. A per-pass degradation model was used to interpret and describe the experimental data. The data revealed that exclusive employment of HC using a vortex-based cavitation device at 1.5 bar pressure drop, resulted in a degradation exceeding 96 % after 100 passes, equivalent to 230 min of treatment (cavitation yield of 3.6 mg/kJ for HC), with a COD mineralization surpassing 12 %. The presence of a small amount of H2O2 (0.01 %) significantly reduced the degradation time from 230 min to 36 min (16 passes), achieving a degradation of 99.8 % (cavitation yield of 6.77 mg/kJ for HC) with COD mineralization rate twice as much as HC alone, indicating a synergistic effect of 4.8. The degradation time was further reduced to 21 min by combining HC with PC using TiO2-coated glass fibers and H2O2, (cavitation yield of 11.83 mg/kJ for HC), resulting in an impressive synergistic effect of 9.2 and COD mineralization twice as high as the HC/H2O2 system. The results demonstrate that HC based hybrid AOPs can be very effective for treating and mineralizing azo dyes in water.

This study explores efficient Sicomet Green (SG) dye degradation using Fe(III)/Lig and Fe(II)/Lig complexes in modified photo-Fenton processes under UV, LED, and sunlight. Sunlight irradiation showed rapid kinetics with over 70% degradation efficiency. Multi-objective grey wolf optimization achieved 98% degradation and 96% mineralization yield using Fe(III)/Lig without pH adjustment. Inorganic ions inhibited the modified photo-Fenton process. A user-friendly app aided predictions and optimal parameters selection, emphasizing natural light sources and pH-neutral medium for dye removal through photo-Fenton.

The chemical composition and the biological activities of aromatic plants may be influenced by seasonal changes. Therefore, the essential oil of Inula graveolens (IGEO), collected at Chebba salt marsh, was studied in terms of yields, compositions and biological activities, throughout four different seasons, namely spring, summer, autumn and winter (April, July, October and January, respectively). GC/MS analysis identified 30 compounds. Mostly quantitative rather than qualitative, variation was observed in the oil composition of each sample. It had been revealed a predominant presence of bornyl acetate and borneol, as well as significant differences of several compound amounts in function of the seasonal change. Biological activities were also related to the harvest season; hence, IGEO from spring gave the best antioxidant activity results and IGEO from autumn seemed to be the most potent against pathogenic microorganisms, while oils from summer and winter were the strongest inhibitors of acetylcholinesterase and tyrosinase.A matrix linking IGEO major compounds to biological was composed to identify relationships between concentrations of the volatile molecules and the biological activities of the samples. Furthermore, the seasonal variation of these main volatile constituents was also investigated through principal compound analysis (PCA). The obtained results revealed that each biological activity depends on the seasonal fluctuation of the amounts of certain chemical compounds. Keywords: Inula graveolens, Essential oil, Seasonal variations, Chemical composition, Biological activities, PCA

The main objective of this work was to assess the performance of combined processes, adsorption/ photodegradation of the ciprofloxacin antibiotic (CIP). Adsorption was achieved on natural hydroxyapatite (nat-HA) in the batch mode. The effect of pH (3–12), initial ciprofloxacin concentration (C0, 25–200 mg L−1), adsorbent dose (m, 0.25–3 g L−1), and temperature (T, 298–328 K) on the ciprofloxacin adsorption capacity was studied. At 298 K, the maximum uptake of 147.7 mg g−1 was observed with pH close to 8, 1 g L−1nat-HA dose, and 150 mg L−1 initial CIP concentration. Adsorption was effective, with a removal percentage of 82% within 90 minutes of contact time. For ciprofloxacin adsorption onto nat-HA, a pseudo-second-order kinetic model is well-suited. The Langmuir isotherm model successfully fit the experimental data and the process was spontaneous and exothermic. The coupling processes (adsorption/photocatalysis) were examined and found to be highly effective. For the remaining concentrations, the maximum degradation efficiency and mineralization yield were ~100% and 98.5%, respectively, for 1 mg L−1 initial CIP. The combination of the strong adsorption capacity of natural hydroxyapatite and the high photocatalytic activity of TiO2 can be an effective technique for removing fluoroquinolone antibiotics from wastewater.

Mineralization of gaseous chlorobenzene (major VOC from cement plants) was studied in a continuous reactor using three advanced oxidation processes: (i) photocatalysis, (ii) Dielectric Barrier Discharge (DBD) plasma and (iii) DBD/TiO2-UV coupling. The work showed an overproduction of OH * and O * radicals in the reaction medium due to the interaction of Cl * and O3. A parametric study was carried out in order to determine the evolution of the removal efficiency as a function of the concentration, the flow rate and the applied voltage. Indeed, a variation of the flow rate from 0.25 to 1 m3/h resulted in a decrease in the degradation rate from 18 to 9%. Similarly, an increase in concentration from 13 to 100 mg/m3 resulted in a change in degradation rate from 18 to 4%. When the voltage was doubled from 6 to 12 kV, the degradation rate varied from 22 to 29 % (plasma) and from 53 to 75% (coupling) at 13 mg/m3. The evolution of COX and O3 was monitored during the experiments. When the voltage was doubled, the selectivity increased from 28 to 37% in the plasma alone and from 48 to 62 % in the coupled process. In addition, at this same voltage range, the amount of ozone formed varied from 10 to 66 ppm in plasma and 3 to 29 ppm in coupling. This degradation performance can be linked to a synergistic effect, which resulted in an increase in the intensity of the electric field of plasma by the TiO2 and the improvement in the performance of the catalyst following the bombardment of various high-energy particles of the plasma.

In the present research, zeolite is used for the removal of toxic Congo red dye from water solution. The effects of different operating conditions such as hydrogen potential (pH), contact time (time), zeolite dose (D), initial dye concentration (C0), and ionic strength (I) are investigated for Congo red adsorption under batch mode. It was found that the adsorption process was greatly affected by the initial pH of the dye solution. The removal efficiency decreased from 97.68 to 5.22% when the pH varied from 3 to 5; thus, acidic conditions clearly improve Congo red adsorption on zeolite. At pH 3, an increase in C0 and I and decrease in D resulted in an increase in the adsorption capacity qe. The effects of these three parameters and their interactions were also investigated using the 23 full factorial design experiments approach where qe was chosen as the response. The results obtained from this method followed by the analysis of variance and the Student’s t-test show that, the influence of these parameters on dye adsorption process are in the order I < C0 < D. The kinetic studies revealed that adsorption follows a pseudo-second-order kinetic model. The adsorption isotherms experimental data were analyzed using the Langmuir, Freundlich, and Temkin isotherms models. The Freundlich isotherm was the best-fit model to the experimental data. The fitting of kinetics and isotherm models was evaluated by using non-linear modeling, R2, MSE, and RMSE.

This research aimed to assess the adsorption properties of raw walnut shell powder (WNSp) for the elimination of methylene blue (MB) from an aqueous medium. The initial MB concentration (2–50 mg/L), the mass of the biomaterial (0.1–1 g/L), the contact time (10–120 min), the medium’s pH (2–12), and the temperature (25–55 °C) were optimized as experimental conditions. A maximum adsorption capacity of 19.99 mg/g was obtained at an MB concentration of 50 mg/L, a medium pH of 6.93 and a temperature of 25 °C, using 0.2 g/L of WNSp. These conditions showed that the MB dye elimination process occurred spontaneously. Different analytical approaches were used to characterize the WNSp biomaterial, including functional groups involved in MB adsorption, the surface characteristics and morphological features of the WNSp before and after MB uptake, and identification of WNSp based on their diffraction pattern. The experimental isotherm data were analyzed by the Langmuir and Freundlich models for the adsorption of MB dye. The corresponding values of parameter RL of Langmuir were between 0.51 and 0.172, which confirmed the WNSp’s favorable MB dye adsorption. The experimental kinetic data were examined, and the pseudo-second-order model was shown to be more suitable for describing the adsorption process, with an excellent determination coefficient (R2 = 0.999). The exchanged standard enthalpy (H° = −22.456 KJ.mol−1) was calculated using the van ‘t Hoff equation, and it was proven that the adsorption process was exothermic. The spontaneous nature and feasibility of the MB dye adsorption process on WNSp were validated by negative standard enthalpy values (G°) ranging from −2.580 to −0.469 at different temperatures. It was established that WNSp may be employed as a novel, effective, low-cost adsorbent for the elimination of methylene blue in aqueous solutions.

In arid regions, starchy agricultural products such as wheat and rice provide essential carbohydrates, minerals, fibers and vitamins. However, drought, desiccation, high salinity, potentially toxic metals and hydrocarbon accumulation are among the most notable stresses affecting soil quality and cereal production in arid environments. Certain soil bacteria, referred to as Plant Growth-Promoting Rhizobacteria (PGPR), colonize the plant root environment, providing beneficial advantages for both soil and plants. Beyond their ability to improve plant growth under non-stressed conditions, PGPR can establish symbiotic and non-symbiotic interactions with plants growing under stress conditions, participating in soil bioremediation, stress alleviation and plant growth restoration. Moreover, the PGPR ability to fix nitrogen, to solubilize insoluble forms of nutrients and to produce other metabolites such as siderophores, phytohormones, antibiotics and hydrolytic enzymes makes them ecofriendly alternatives to the excessive use of unsuitable and cost-effective chemicals in agriculture. The most remarkable PGPR belong to the genera Arthrobacter, Azospirillum, Azotobacter, Bacillus, Enterobacter, Klebsiella, Pseudomonas, etc. Therefore, high cereal production in arid environments can be ensured using PGPR. Herein, the potential role of such bacteria in promoting wheat and rice production under both normal and derelict soils is reviewed and highlighted.

Heterogeneous photo-electro-Fenton process is an attractive technology for the removal of recalcitrant pollutants. To better exploit the presence of an irradiation source, a bifunctional catalyst with TiO2 nanoparticles embedded into an iron–chitosan matrix was developed. The catalytic activity of the catalyst was improved by the optimization of the loaded TiO2 content. The prepared composite catalysts based on TiO2, Fe3O4 and chitosan were called TiO2/Fe3O4-CS beads. The best catalyst with an optimal ratio TiO2/Fe = 2 exhibited a high efficiency in the degradation and mineralization of chlordimeform (CDM) insecticide. Under the optimum conditions (concentration of catalyst equal to 1 g L−1 and applied current intensity equal to 70 mA), a real effluent doped with 30 mg L−1 of CDM was efficiently treated, leading to 80.8 ± 1.9% TOC reduction after 6 h of treatment, with total removal of CDM after only 1 h.The generated carboxylic acids and minerals were identified and quantified. Furthermore, the stability and reusability of the developed catalyst was examined, and an insignificant reduction in catalytic activity was noticed for four consecutive cycles of the photo-electro-Fenton process. Analyses using SEM, XRD and VSM showed a good stability of the physicochemical properties of the catalyst after use.

This study investigated the potential of 4A zeolite, named4AZW in this work, generated by natural gas dehydration units as solid waste after several treatment cycles, as a low-cost adsorbent to separately remove two cationic dyes, methylene blue (MB) and malachite green (MG), from an aqueous solution within a batch process. The adsorbent material was characterized by N2gas adsorption–desorption, X-ray fluorescence spectrometry, X-ray diffraction, FT-IR spectroscopy, and the determination of its cation exchange capacity and point of zero charge. The influence of key operating parameters, such as the pH, adsorbent dosage, ionic strength, contact time, initial dye concentration, and temperature, was investigated. Three independent variables acting on MB adsorption performance were selected from the Box–Behnken design (BBD) and for process modeling and optimization. An analysis of variance (ANOVA), an F-test, and p-values were used to analyze the main and interaction effects. The experimental data were satisfyingly fitted with quadratic regression with adjusted R2= 0.9961. The pseudo-second-order kinetic model described the adsorption of the dyes on 4AZW. The equilibrium data were well-fitted by the Langmuir model for each adsorption system (MB-4AZW and MG-4AZW) with maximum adsorption capacity (qmax) values of 9.95 and 45.64 mg/g, respectively, at 25 °C. Thermodynamics studies showed that both adsorption systems are spontaneous and endothermic.

A simple and efficient new electrochemical sensor based on molecularly imprinted polymer has been developed for selective detection of an anticancer agent Etoposide (ETP). The sensor was prepared by electropolymerization via cyclic voltammetry (CV) of pyrrole onto a glassy carbon electrode (GCE) in the presence of ETP molecules. The extraction of ETP molecules embedded in the polymeric matrix was carried out by overoxidation in sodium hydroxide medium using CV. Various important parameters affecting the performance of the imprinted film (MIP) coated sensor were studied and optimized using differential pulse voltammetry (DPV). Under optimal conditions, the sensor response exhibited a linear dependence on ETP concentration (R2 = 0.999) over the range 5.0×10−7 M – 1.0×10−5 M with a LOD (3σ/m) of 2.8×10−9 M. The precision (% RSD, n=6) of the proposed sensor for intra- and interdays was found to be 0.84 and 2.46%, respectively. The selectivity of MIP/GCE sensor toward ETP was investigated in the presence of different interfering molecules including excipients and ETP metabolites. The developed sensor showed great recognition ability toward ETP and was successfully applied for its determination in injectable dosage forms and biological human fluids.