Efficient and green telescoped process to 2-methoxy-3-methyl-[1,4]benzoquinone

A telescoped process for the preparation of 2-methoxy-3-methyl-[1,4]benzoquinone is disclosed. When this novel process is compared to the prevailing method that utilizes Na2Cr2O7 as the oxidant, the novel process represents a high yielding (95%), green, and environmentally benign alternative with H2O2 and HNO3 as the oxidants and CH3COOH as the reaction medium.     

Polyaniline/Maleic Acid Copolymers Composites: Synthesis and Characterization

Summary: Polyaniline/maleic acid copolymers composites were synthesized by chemical in situ polymerization of aniline using ammonium peroxidisulfate as oxidant, in the presence of water soluble copolymers containing carboxylic groups. Fine dispersions of composite materials, soluble in N,N-dimethylformamide or dimethyl sulfoxide were obtained which can be processed as thin films and membranes for application as proton-conductive materials for electrolyte membranes of fuel cells. The composites were characterized by FTIR spectroscopy and thermal methods.     

Asymptotic homogenization analysis for damage amplification due to singular interaction of micro-cracks

The paper investigates the overall damage amplification effect due to micro-crack interaction in a framework of two-scale modeling. A homogenization method based on asymptotic expansions is employed to deduce the macroscopic damage equations. The damage model completely results from energy-based micro-crack propagation laws. We consider a locally periodic microstructure with periods containing pairs of micro-cracks separated by small ligaments. The asymptotic solution in the ligament region allows the study of the effect of micro-crack interaction on the effective coefficients. The local macroscopic response expresses the collective coalescence of a periodic microstructure with interacting micro-cracks. We show that the slope of the homogenized coefficients is inversely proportional to the square root of the distance between the tips of the interacting micro-cracks, accounting for the singularity in the stress fields as the micro-cracks approach each other. This leads to damage amplification as the result of the interaction of micro-cracks.     

Laser prepared organic heterostructures based on star-shaped arylenevinylene compounds

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of organic bulk heterojunctions made from the mixture of a star-shaped arylenevinylene compound, 4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine as donor and fullerene derivative, [6, 6]-phenyl C61 butyric acid butyl ester, as acceptor, in the weight ratio 1:2. The mixed layer has been characterized by spectroscopic (UV–Vis, Fourier transform infrared) and microscopic (AFM) methods, and the effects of the deposition conditions (number of pulses) and of a buffer layer of poly(aniline-co-aniline propane sulfonic acid) or poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) have been analyzed. The study of the electrical properties has revealed a typical solar cell behavior for the heterostructure glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine: [6, 6]-phenyl C61 butyric acid butyl ester/Al, confirming that MAPLE could be an adequate method for the preparation of active layer based on bulk heterojunction for solar cells.     

Influence of protonation on substrate and inhibitor interactions at the active site of human monoamine oxidase-A

Although substrate conversion mediated by human monoaminooxidase (hMAO) has been associated with the deprotonated state of their amine moiety, data regarding the influence of protonation on substrate binding at the active site are scarce. Thus, in order to assess protonation influence, steered molecular dynamics (SMD) runs were carried out. These simulations revealed that the protonated form of the substrate serotonin (5-HT) exhibited stronger interactions at the protein surface compared to the neutral form. The latter displayed stronger interactions in the active site cavity. These observations support the possible role of the deprotonated form in substrate conversion. Multigrid docking studies carried out to rationalize the role of 5-HT protonation in other sites besides the active site indicated two energetically favored docking sites for the protonated form of 5-HT on the enzyme surface. These sites seem to be interconnected with the substrate/inhibitor cavity, as revealed by the tunnels observed by means of CAVER program. pK(a) calculations in the surface loci pointed to Glu32?, Asp32?, His???, and Asp132 as candidates for a possible in situ deprotonation step. Docking analysis of a group of inhibitors (structurally related to substrates) showed further interactions with the same two docking access sites. Interestingly, the protonated/deprotonated amine moiety of almost all compounds attained different docking poses in the active site, none of them oriented to the flavin moiety, thus producing a more variable and less productive orientations to act as substrates. Our results highlight the role of deprotonation in facilitating substrate conversion and also might reflect the necessity of inhibitor molecules to adopt specific orientations to achieve enzyme inhibition.     

Ruthenium‐Catalyzed Functionalization of Pyrroles and Indoles with Propargyl Alcohols

Several ruthenium‐catalyzed atom‐economic transformations of propargyl alcohols with pyrroles or indoles leading to alkylated, propargylated, or annulated heteroaromatics are reported. The mechanistically distinct reactions are catalyzed by a single ruthenium(0) complex containing a redox‐coupled dienone ligand. The mode of activation regarding the propargyl alcohols determines the reaction pathway and depends on the alcohols’ substitution pattern. Secondary substrates form alkenyl complexes by a 1,2‐hydrogen shift, whereas the transformation of tertiary substrates involves allenylidene intermediates. 1‐Vinyl propargyl alcohols are converted by a cascade allylation/cyclization sequence. The environmentally benign processes are of broad scope and allow the selective synthesis of highly functionalized pyrroles and indoles generating water as the only waste product.     

Synthesis, 5-hydroxytryptamine1A receptor affinity and docking studies of 3-[3-(4-aryl-1-piperazinyl)-propyl]-1H-indole derivatives

A series of 3-[3-(4-aryl-1-piperazinyl)-propyl]-1H-indole derivatives (12a-h) was synthesized and evaluated for binding affinity at the human 5-hydroxytryptamine(1A) receptor (5-HT(1A)R) compounds (12b) and (12h) showed the highest 5-HT(1A) receptor affinity (IC(50)=15 nM). Molecular docking studies with all the compounds in a homology model of 5-HT(1A) showed that the main interaction anchoring the ligand in the receptor was a charge-reinforced bond between the protonated nitrogen atom (N-4) of the piperazine ring and Aspartate(3.32).     

Morphological investigation of PP/nanosilica composites containing SEBS

The effect of styrene-(ethylene-co-butylene)-styrene triblock copolymer (SEBS) on the mechanical, thermal and morphological properties of polypropylene (PP) composites filled with nanosilica particles is investigated. A simultaneous increase of all tensile characteristics is observed in PP/nanosilica composites without SEBS and containing 5%SEBS and a large plastic deformation in the nanocomposite with 10%SEBS. Different amounts of β-PP are detected by X-ray diffraction analysis and the calculated K-values correlate well with differential scanning calorimetry results. Quantitative mechanical characterization of nanocomposites is performed at nanolevel, using peak force QNM. This AFM technique allows the detection of nanosilica particles and SEBS domains at the surface of samples and gives indications of local interactions between nanosilica and the matrix from the correlation of modulus and adhesion maps, and the increased local values of elastic modulus on extended areas around nanoparticles.     

A two-scale time-dependent damage model based on non-planar growth of micro-cracks

This paper presents the theoretical developments and the numerical applications of a time-dependent damage law. This law is deduced from considerations at the micro-scale where non-planar growth of micro-cracks, following a subcritical propagation criterion, is assumed. The orientation of the crack growth is governed by the maximum energy release rate at the crack tips and the introduction of an equivalent straight crack. The passage from micro-scale to macro-scale is done through an asymptotic homogenization approach. The model is built in two steps. First, the effective coefficients are calculated at the micro-scale in finite periodical cells, with respect to the micro-cracks length and their orientation. Then, a subcritical damage law is developed in order to establish the evolution of damage. This damage law is obtained as a differential equation depending on the microscopic stress intensity factors, which are a priori calculated for different crack lengths and orientations. The developed model enables to reproduce not only the classical short-term stress-strain response of materials (in tension and compression) but also the long-term behavior encountering relaxation and creep effects. Numerical simulations show the ability of the developed model to reproduce this time-dependent damage response of materials.