Novel ZnS/Carbon Nanofiber Photocatalyst for Degradation of Rhodamine 6G: Kinetics Tracking of Operational Parameters and Development of a Kinetics Model

A novel nanocomposite in the role of photocatalyst was prepared by composition of zinc sulfide (ZnS) nanoparticles with carbon nanofibers (CNFs) and was characterized. The XRD, EDX, and FE‐SEM analysis revealed that ZnS is successfully embedded in CNFs matrix. The DRS results indicated that supporting of ZnS by CNFs led to a decrease of the band gap energy. The photocatalytic degradation of a hazardous xanthine dye, Rhodamine 6 G (Rh‐6G), by the prepared ZnS/CNFs composite was examined from the kinetics point of view. Nonlinear regression analysis was used to develop a mathematical kinetics model based on the Langmuir–Hinshelwood mechanism, and an empirical equation was obtained for the estimation of apparent pseudo‐first‐order rate constant (k_ap) as a function of operational parameters (viz. initial dye concentration, ZnS/CNFs content, pH, and irradiation intensity). Based on the results, k_ap increased with an increase ZnS/CNFs content, pH, and UV light intensity, whereas it decreased by increasing the initial Rh‐6G concentration. Moreover, a new kinetics model was obtained based on proposed elementary steps to determine k_ap. In the final stage of the work, intermediate materials produced within photocatalytic degradation of Rh‐6G dye were detected by GC‐MS analysis.     

Efficient copper-catalyzed Sonogashira coupling reactions and simulation studies

A practical copper-catalyzed I-substitutions of alkyl-2-iodobenzoates with alkynes have been developed using Cu powder as a catalyst under solvent, cocatalyst, and base-free conditions. This reaction system is new, facile, efficient, and economical that gives Sonogashira coupling products in excellent yields (up to 97%). The coupled products (A–J) were characterized by CHNS, ¹H NMR, and ¹³C NMR and are found soluble in ethyl acetate and dichloromethane. In addition, simulation studies of A–J were performed with aspulvinone dimethylallyltransferase enzyme and observe good binding affinity. The reported compounds may act as anti-cizmatics, anti-fobic in future and also have the inhibition of aspulvinone dimethylallyltransferase properties to control Alzheimer’s, Schizophrenia, etc. diseases.     

X‐ray induced degradation of surface bound azido groups during XPS analysis

Mesoporous silica SBA‐15 was synthesized and silanized with azidopropyl triethoxysilane in order to design a clickable material. Fourier transform infrared analysis permitted to prove the attachment of the azidopropylene groups to SBA‐15 resulting in the reactive and functional material N₃‐SBA‐15. X‐ray photoelectron spectroscopy was used to determine the surface composition of SBA‐15. However, we unexpectedly found that the surface bound azido groups undergo X‐ray induced decomposition during the X‐ray photoelectron spectroscopy analysis resulting in the formation of nitrenes. These are very reactive groups able to intercalate C―C and C―H bonds of the propylene chains as judged from the N1s peak shape. Possible mechanisms of intercalation are suggested. C1s and N1s peaks were recorded at different exposure time. N/C, N⁺/N and N⁺/C undergo exponential decay. N⁺/N reaches the value of zero in less than 80 min of exposure to the X‐ray source. The N⁺/C decay plot was fitted with first‐order kinetics, and the decomposition kinetic constant (k_dec) was found to equal to 516.4 s^?1. This is a fast X‐ray induced degradation which must be considered with care when examining clickable materials with surface bound alkyl azido groups. Copyright © 2016 John Wiley & Sons, Ltd.     

A universal blown film apparatus for <Emphasis Type="Italic">in situ</Emphasis> X-ray measurements

A setup of blown film machine combined with in situ synchrotron radiation X-ray diffraction measurements and infrared temperature testing is reported to study the structure evolution of polymers during film blowing. Two homemade auto-lifters are constructed and placed under the blown machine at each end of the beamline platform which move up and down with a speed of 0.05 mm/s bearing the 200 kg weight machine. Therefore, structure development and temperature changes as a function of position on the film bubble can be obtained. The blown film machine is customized to be conveniently installed with precise servo motors and can adjust the processing parameters in a wide range. Meanwhile, the air ring has been redesigned in order to track the structure information of the film bubble immediately after the melt being extruded out from the die exit. Polyethylene (PE) is selected as a model system to verify the feasibility of the apparatus and the in situ experimental techniques. Combining structure information provided by the WAXD and SAXS and the actual temperature obtained from the infrared probe, a full roadmap of structure development during film blowing is constructed and it is helpful to explore the molecular mechanism of structure evolution behind the film blowing processing, which is expected to lead to a better understanding of the physics in polymer processing.     

Comparison of multicomponent fuel droplet vaporization experiments in forced convection with the Sirignano model

The vaporization of multicomponent fuel droplets was studied experimentally in a heated flow and the results were compared to the model proposed by Abramzon and Sirignano. The droplet was suspended on a permanent holder which was set up in a thermal wind-tunnel. This wind-tunnel was fitted with a video recording system and an infra-red camera. The period during which the droplet was suspended on the holder before the opening of the hot air flow damper was recorded. This first sequence corresponds to the droplet vaporization in natural convection, whose initial experiment conditions, especially diameter, temperature, composition of the droplet, are well known. Then the damper was turn on, and the sequence of forced convection begun. The initial diameter of the droplet was recorded by the video system. The other initial conditions of this second sequence cannot be determined experimentally. The distribution of temperature in the droplet and the surface temperature, the mass fraction distribution in the droplet and the surface mass fraction were unknown. These unknown parameters were determined by coupling our experiment with a model using “the film concept” in natural convection. Experimental results were compared with the calculations and found satisfactory, in natural convection as well as in forced convection initiated by this method. The method was tested in the case of a fuel mixture droplets (heptane–decane) for different initial concentrations and variable durations of the sequence in natural convection.     

A nonlinear composite plate theory

A general nonlinear theory for the dynamics of elastic anisotropic plates undergoing moderate-rotation vibrations is presented. The theory fully accounts for geometric nonlinearities (moderate rotations and displacements) by using local stress and strain measures and an exact coordinate transformation, which result in nonlinear curvatures and strain-displacement expressions that contain the von Karman strains as a special case. The theory accounts for transverse shear deformations by using a third-order theory and for extensionality and changes in the configuration due to in-plane and transverse deformations. Five third-order nonlinear partial-differential equations of motion describing the extension-extension-bending-shear-shear vibrations of plates are obtained by an asymptotic analysis, which reveals that laminated plates display linear elastic and nonlinear geometric couplings among all motions.     

A density functional theory investigation of the bromide oxidation mechanism by a vanadium bromoperoxidase model complex

Abstract  

Density functional theory has been used to study the mechanism of bromide oxidation by the oxo-peroxo complex K[VO(O₂)Hheida] (heida = N-(2-hydroxyethyl)iminodiacetic acid), which has the highest reported rate constant for bromide oxidation of any vanadium complex. Two possible mechanisms were explored, involving bromide attack on a protonated or unprotonated peroxo atom. The direct nucleophilic attack of bromide on a protonated peroxo begins the reaction, i.e. the protonated peroxo ligand is the active site of reaction. We examined five different transition states in the mechanism. Two transition states were found to have lower activation barriers. A reduction in the potential energy barriers, when calculated using the polarisable continuum model, indicates that with the involvement of acetonitrile as a solvent the transition states become more stable.     

Reversed-phase dispersive liquid-liquid microextraction with central composite design optimization for preconcentration and HPLC determination of oleuropein

A reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) method was developed for the preconcentration and direct HPLC determination of oleuropein in olive's processing wastewater (OPW) and olive leaves extracts. In conventional DLLME, the sedimented phase is a micro-drop of a chlorinated organic solvent that is not compatible with RP-HPLC. Therefore, solvent evaporation and reconstitution with an appropriate solvent is often required. In RP-DLLME, this problem was overcome by overturning the solvent polarity in the ordinary DLLME and replacing the organic solvent with water. A central composite chemometrics design was used for multivariate optimization of the effects of five different parameters influencing the extraction efficiency of the method. In the optimized conditions, a mixture of 1.4 mL of an ethyl acetate extract of sample and 40 μL water (pH 5.0) was rapidly injected into 5.3 mL of cyclohexane. After centrifugation of the formed cloudy mixture, a micro-drop of the aqueous phase was sedimented at the conical bottom of the centrifuge tube. This phase, that contained the preconcentrated and partially purified analyte, was directly injected into an RP-HPLC column for analysis. A mean extraction recovery of 102.5 (±4.5) % with enrichment factors exceeding 38, was obtained for five replicated analysis. The detection limit of the method (3σ) for OE was 0.02 μg L⁻¹ for OPW and 2 × 10⁻³ mg kg⁻¹ for olive leaves samples. The results showed that, RP-DLLME is a promising technique which is quick, easily operated and can be directly coupled to HPLC.