Experimental and Theoretical Study of Enhanced Photocatalytic Activity of Mg‐Doped ZnO NPs and ZnO/rGO Nanocomposites

A systematic experimental and theoretical study of the origin of the enhanced photocatalytic performance of Mg‐doped ZnO nanoparticles (NPs) and Mg‐doped ZnO/reduced graphene oxide (rGO) nanocomposites has been performed. In addition to Mg, Cd was chosen as a doping material for the bandgap engineering of ZnO NPs, and its effects were compared with that of Mg in the photocatalytic performance of ZnO nanostructures. The experimental results revealed that Mg, as a doping material, recognizably ameliorates the photocatalytic performance of ZnO NPs and ZnO/graphene nanocomposites. Transmission electron microscopy (TEM) images showed that the Mg‐doped and Cd‐doped ZnO NPs had the same size. The optical properties of the samples indicated that Cd narrowed the bandgap, whereas Mg widened the bandgap of the ZnO NPs and the oxygen vacancy concentration was similar for both samples. Based on the experimental results, the narrowing of the bandgap, the particle size, and the oxygen vacancy did not enhance the photocatalytic performance. However, Brunauer–Emmett–Teller (BET) and Barret–Joyner–Halenda (BJH) models showed that Mg caused increased textural properties of the samples, whereas rGO played an opposite role. A theoretical study, conducted by using DFT methods, showed that the improvement in the photocatalytic performance of Mg‐doped ZnO NPs was due to a higher electron transfer from the Mg‐doped ZnO NPs to the dye molecules compared with pristine ZnO and Cd‐doped ZnO NPs. Moreover, according to the experimental results, along with Mg, graphene also played an important role in the photocatalytic performance of ZnO.     

Synthesis of molecular imprinted polymer nanoparticles followed by application of response surface methodology for optimization of metribuzin extraction from urine samples

A molecular imprinted polymer was prepared with precipitation polymerization technique and applied as a sorbent for selective extraction and enrichment of metribuzin herbicide prior to high performance liquid chromatography. Optimization of critical variables affecting the efficiency of molecularly imprinted solid-phase extraction (MISPE), such as sorbent mass, sample pH and flow rate of sample, volume, concentration, and flow rate of elution solvent was done by employing central composite design (CCD) of the response surface methodology. Two separate models were developed for the adsorption and recycling steps. The analysis of variance (ANOVA) demonstrated that, experimental data were excellently fitted to the proposed response models. The optimum operating conditions were: a sorbent mass of 25 mg, sample pH 6.19, sample flow rate of 2.15 mL/min, and a 5 mL portion of methanol/acetic acid with 92.7:7.3 (v/v) ratio and flow rate of 2.1 mL/min for the extraction process. Under the optimized conditions, the linear range was obtained from 20 to 120 µg/L (R²?=?0.999) and the lowest detectable concentration (LOD) and the lowest quantitative concentration (LOQ) were calculated as 5.75 and 19.86 µg/L, respectively. Finally, the designed MISPE method was successfully applied to determine trace amount of metribuzin in real samples. The diluted urine samples were spiked with metribuzin at 4 levels and extracted with recoveries ranging from 93.82 to 97.84% and the relative standard deviation (RSD) less than 4.8%.     

Modified Magnetite Nanoparticles for Hexavalent Chromium Removal from Water

Water treatment is an important concern of human societies. Using magnetic nanoparticles as adsorbents for metal removal has been greatly considered due to their particular characteristics such as small sizes, high surface area to volume ratios, and good magnetic properties. In the present study, a modification was implemented in magnetite particles by functionalized carbon nanotubes and carboxylic groups to enhance the performance of magnetite particles in removing hexavalent chromium from water using the adsorption method. The applicability of the nanoadsorbent and magnetic nanoparticles was compared based on adsorption factors affecting the chromium removal including pH, contact time, pollutant concentration, and the adsorbent amount. Properties of the nanocomposites were analyzed by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results show that the highest percentage of Cr (VI) removal for both adsorbents was under acidic ambient conditions and lasted less than 45 minutes. The study of Langmuir, Freundlich, and Temkin isotherms in the prediction of adsorption behavior revealed that the Langmuir model better fitted the adsorption equilibrium data. The kinetic analysis of pseudo-first and second-order equations showed that the pseudo-second-order equation was more suitable for describing the kinetic behavior of data. Moreover, the obtained nanocomposite had a better performance in Cr (VI) removal from water in comparison to magnetite nanoparticles.     

Betti base‐modified magnetic nanoparticles as a novel basic nanocatalyst in Knoevenagel condensation and its related palladium nanocatalyst in Suzuki coupling reactions

Betti base‐modified Fe₃O₄ nanoparticles have been successfully designed and synthesized for the first time through the condensation of Fe₃O₄ magnetic nanoparticles coated by (3‐aminopropyl)triethoxysilane with β‐naphthol and benzaldehyde. Their application as a novel magnetic nanocatalyst in the Knoevenagel condensation and also application to immobilization of palladium nanoparticles for Suzuki coupling reactions have been investigated which opens a new field for application of Betti base derivatives in organic transformations. The synthesized inorganic–organic hybrid nanocatalyst has been fully been characterized using Fourier transform infrared, X‐ray diffraction, vibrating sample magnetometry, transmission and scanning electron microscopies, energy‐dispersive X‐ray, wavelength‐dispersive X‐ray and X‐ray photoelectron spectroscopies and inductively coupled plasma techniques. The catalyst was easily separated with the assistance of an external magnet from the reaction mixture and reused for several consecutive runs with no significant loss of its catalytic efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

Efficient organocatalytic α-sulfenylation of substituted piperazine-2,5-diones

Organocatalytic α-sulfenylation of substituted piperazine-2,5-diones is reported through the use of cinchona alkaloids as Lewis bases and electrophilic sulfur transfer reagents. 1-Phenylsulfanyl[1,2,4]triazole, a novel sulfur transfer reagent, gave excellent product yields with a number of substituted piperazine-2,5-diones under mild conditions. Catalyst loading, stoichiometry of sulfur electrophile, temperature, and solvent were optimized to achieve high product yields.     

On the equality of interfacial and critical composition

It is shown that interfacial composition of the liquid–liquid interfaces is equal to the critical composition. The idea has been rigorously proven for binary regular solutions and has been reasonably supported for non-regular multicomponents, making use of the experimental mutual solubility data and the available information on titration, pulsed gradient spin-echo NMR, and differential scanning calorimetry of some W/O and O/W microemulsions. Using this finding, we, moreover, developed a simple equation for prediction of plait point concentration, having known just one tie-line data. The equation suggests a simple consistency test for measured solubility data, which is shown reliable for a large number of ternary systems. A molecular dynamic simulation also has been performed to support the idea.