Living ring-opening metathesis polymerization of norbornenes bay-functionalized perylene diimides

Ring-opening metathesis polymerization (ROMP)-derived poly(oxanorbornene imide)s bearing bay-linked mono - alkoxy -M1 and 1,7-di-alkoxy M2 functionalized perylene diimides (PDIs) were synthesized using Grubb's third ( G3 ) and Hoveyda-Grubbs second generation ( HG2 ) ruthenium-alkylidene metathesis initiators. The mono-alkoxy-derived PDI-based non-ladderphane polymer poly M1 displayed 67% to 77% of the trans olefin content in the polymer chain depending on the initiator used for the polymerization. When using the symmetrical 1,7-di-alkoxy-derived PDI-based polymer poly M2 having the ladderphane type-structure, this displayed a significant amount of cis and trans olefin contents in the polymer chains, irrespective of the type of initiators used for the polymerization. ROMP of both monomers M1 and M2 proceeded in a well-controlled manner with a linear dependence of molecular weight on the monomer/initiator ratio using G3 as initiator. Optical properties of the ladderphane-based poly M2 and non-ladderphane-based poly M1 were characterized in both solution and the film state. X-ray diffraction (XRD) analysis for all the polymers showed significant π-stacking in the thin film state with ordered molecular packing and closer values of d-spacing for both poly M1 and poly M2 . Film morphology examined by AFM elucidated homogenous smooth polymer surface for both polymers in general, but with some irregularities observed for poly M1 . In addition, CV analysis revealed both polymers could be good candidates as electron-accepting materials, with excellent film-forming ability, and thermal stability.     

Thermal decomposition of model compound of algal biomass

This contribution investigates thermal decomposition of leucine, as a representative model compound for amino acids in algal biomass. We map out potential energy surface for a wide array of unimolecular and self-condensation reactions operating in the decomposition of leucine. Decarboxylation and dehydration of leucine ensues by eliminating CO₂ and –OH, respectively, from the –COOH group attached to the α-carbon. The molecular channel for deamination involves cleavage of NH₂ from α-carbon of leucine. The activation energies for direct elimination of CO₂, NH₃, and H₂O from a leucine molecule lie within 20.7 kJ/mol of each other. Activation energies for these decomposition pathways reside below the bond dissociation enthalpy of H–C(α) of 323.1 kJ/mol. The decarboxylation, deamination, and dehydration pathways, via radical-prompted pathways, systematically require lower energy barriers, in reference to closed-shell reaction corridors. Detailed computations at the CBS-QB3 level provide the Arrhenius rate parameters for the unimolecular and bimolecular reactions, and standard enthalpies of formation, standard entropies, and heat capacities for all the products and intermediates. A kinetic analysis of gas-phase reactions, within the context of a plug-flow reactor model, accounts qualitatively for the formation of major products observed experimentally in the thermal degradation of the condensed-phase leucine. Among notable N-containing species, the model predicts the prevailing of NH₃ over HCN and HNCO, in addition to corresponding appreciable concentrations of amines, imines, and nitriles. Our detailed kinetic investigation illustrates a negligible contribution of the self-condensation reactions of leucine in the gas phase.     

Microfunnel‐filter‐based emulsification microextraction followed by gas chromatography for simple determination of organophosphorus pesticides in environmental water samples

A simple and fast method named microfunnel‐filter‐based emulsification microextraction is introduced for an efficient determination of some organophosphorus pesticides including diazinon, malathion, and chlorpyrifos in the environmental samples including the river, sea, and well water. This method is based upon the dispersion of a low‐toxicity organic solvent (dihexyl ether), as the extractant, in a high volume of an aqueous sample solution (45 mL). It is implemented without a centrifugation step, and using a syringe filter and a micro‐funnel, the phase separation and transfer of the enriched analytes to the gas chromatograph are simply achieved. By filtration of the extractant phase, a suitable sample clean‐up is obtained, and the total extraction time is just a few minutes. The factors influencing the extraction efficiency are optimized, and under the optimal conditions, the proposed method provides a good linearity (in the range of 15–1500 ng/mL (R² > 0.996). A high enrichment factor is obtained (in the range of 306–342), and the method provides low limits of detection and quantification (in the ranges of 4–8 and 15–25 ng/mL, respectively).     

Kinetic modeling of ZnO-rGO catalyzed degradation of methylene blue

Photodegradation of organic pollutants strongly depends on design of metal oxide semiconductor photocatalysts. Graphene, if composited with ZnO, can effectively enhance its photocatalytic performance for the eradication of pollutants from aqueous medium. Here in, ZnO-rGO is reported as highly active catalyst for degradation of methylene blue. A 200-mg/L solution of methylene blue dye was completely degraded within 1 h in comparison to 74% and 56% degradation over ZnO and rGO, respectively. The commonly used mechanisms of heterogeneous catalytic reactions, the Langmuir-Hinshelwood mechanism, and the Eley-Rideal mechanisms, were used to describe the reaction kinetics. The Langmuir-Hinshelwood mechanism was found as more favorable in this study. Apparent activation energy, E_ap, true activation energy, E_T, entropy, ΔS, and enthalpy, ΔH were calculated as 36.2 kJ/mol, 13.1 kJ/mol, 197.5 J/mol, and 23.1 kJ/mol, respectively.     

Synthesis,characterization and application of 3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate as nanostructured catalyst for the tandem reaction of β‐naphthol with aromatic aldehydes and amide derivatives

3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate {[Msim]FeCl₄} was prepared and fully characterized by fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray analysis (EDX) and vibrating sample magnetometer (VSM) and used, as an efficient catalyst, for the tandem reaction of β‐naphthol with aromatic aldehydes and benzamide at 110 °C under solvent‐free conditions to give 1‐amidoalkyl‐2‐naphthols in high yields and very short reaction times.     

Investigation of hydrogen and methane adsorption/separation on silicon nanotubes: a hierarchical multiscale method from quantum mechanics to molecular simulation

A combination of ab initio quantum mechanical (QM) calculations and canonical Monte Carlo (CMC) simulations are employed to investigate possible usage of single-walled silicon nanotubes (SWSiNTs) as a novel media for hydrogen and methane adsorption as well as their separation from each other. By fitting the force field, a Morse potential model is selected as an efficient potential to describe the binding energies between both hydrogen-SiNTs and methane-SiNTs obtained from ab initio calculations. Then CMC simulations are performed to evaluate the adsorption and separation behaviors of H₂ and CH₄ on the three different sizes of SiNTs including (5, 5), (7, 7), and (9, 9) SiNTs at ambient temperatures and pressures from 1 up to 10 MPa. As a comparison, the adsorption and separation of H₂ and CH₄ on the (8, 8) CNTs which are isodiameter with (5, 5) SiNTs are also simulated. Results are indicative of remarkable enhancement of H₂ and CH₄ adsorption capacity on the SiNTs compared to the CNTs, which arise from stronger van der Waals (VDW) attractions. In the case of methane adsorption on SiNTs, the stored volumetric energy exceeds the goal of the US Freedom CAR Partnership by 2010, which can not be achieved by methane compression at such low pressures. Moreover, simulation results indicate that SiNTs preferentially adsorb methane relative to hydrogen in their equimolar mixture, which results in efficient separation of these gases from each other at 293 K.     

Mn(II) and VO(IV) Schiff base complexes encapsulated in nanocavities of zeolite-Y: catalytic activity toward oxidation of alkenes and reduction of aldehydes

Oxovanadium(IV) and manganese(II) complexes of two Schiff base ligands, bis(2,4-dihydroxyacetophenone)-1,2-propandiimine (H₂L₁) and bis(2,4-dihydroxyacetophenone)-ethylenediimine (H₂L₂) were synthesized and characterized. The encapsulation of these complexes in the nanocavities of zeolite-Y was achieved by a flexible ligand method. The prepared heterogeneous catalysts have been characterized by FTIR, NMR and atomic absorption spectroscopy, X-ray diffraction patterns, scanning electron microscopy and BET. The catalytic activities of the encapsulated complexes were studied in the oxidation of alkenes with H₂O₂ and the reduction of aldehydes with NaBH₄. In most cases, the manganese (II) complexes (MnL₁-Y, MnL₂-Y) showed better activity than the oxovanadium (IV) complexes (VOL₁-Y, VOL₂-Y) in both oxidation of alkenes and reduction of aldehydes. The catalytic activity of the recovered catalysts was compared with the fresh ones.