Sulfinimine-mediated asymmetric synthesis of 1,3-disubstituted tetrahydroisoquinolines: a stereoselective synthesis of cis- and trans-6,8-dimethoxy-1,3-dimethyl-1,2,3,4-tetrahydroisoquinoline

[reaction: see text] The highly diastereoselective addition of lateral lithiated o-tolunitriles to sulfinimines followed by treatment of the resulting sulfinamide with MeLi, hydrolysis, and reduction represents a concise new methodology for the asymmetric synthesis of 1,3-disubstituted tetrahydroisoquinolines.     

On the use of high order difference methods for the system of one space second order nonlinear hyperbolic equations with variable coefficients

Implicit difference schemes of O(k⁴ + k²h² + h⁴), where k0, h 0 are grid sizes in time and space coordinates respectively, are developed for the efficient numerical integration of the system of one space second order nonlinear hyperbolic equations with variable coefficients subject to appropriate initial and Dirichlet boundary conditions. The proposed difference method for a scalar equation is applied for the wave equation in cylindrical and spherical symmetry. The numerical examples are given to illustrate the fourth order convergence of the methods.     

Improvement in micro-structural and mechanical properties of zinc film by surface treatment with low temperature argon plasma

Nanocrystalline zinc films were deposited on gold coated borosilicate glass substrates by thermal evaporation method using zinc powders as the source material and then treated with argon plasma at various temperatures. From X-ray diffraction study, the as-deposited films are found to be metallic Zn and polycrystalline in nature. The crystalline nature improves with the increase of temperature up to 200 °C and decreases with the further increase of temperature to 300 °C. The binding energy observed for Zn 2p_3/2, and the binding energy separation between Zn 2p_3/2 and Zn 2p_1/2 in the X-ray photoelectron spectrum indicate that the films are metallic zinc films. Transmission electron microscopic study shows hexagonal shaped grains having size ∼58 nm upon treatment with Ar plasma. It is clearly shown the grain growth and distinct grain boundary with the increase in temperature. The average Young's modulus (E) and hardness (H) are measured to be 84 GPa and 4.0 GPa for as-deposited film, whereas 98 GPa and 5.8 GPa for plasma treated film at 200 °C. The enhancement in mechanical properties is attributed to improvement in crystalline nature of the film and better interlinking between grains and boundaries.     

Modeling wealth distribution in growing markets

We introduce an auto-regressive model which captures the growing nature of realistic markets. In our model agents do not trade with other agents, they interact indirectly only through a market. Change of their wealth depends, linearly on how much they invest, and stochastically on how much they gain from the noisy market. The average wealth of the market could be fixed or growing. We show that in a market where investment capacity of agents differ, average wealth of agents generically follow the Pareto-law. In few cases, the individual distribution of wealth of every agentcould also be obtained exactly. We also show that the underlying dynamics of other well studied kinetic models of markets can be mapped to the dynamics of our auto-regressive model.     

Surface modification of coir fibers I: studies on graft copolymerization of methyl methacrylate on to chemically modified coir fibers

Graft copolymerization of methyl methacrylate (MMA) onto chemically modified coir fiber was studied using a CuSO₄–KIO₄ combination as initiator in an aqueous medium in the temperature range of 50–70 °C. Concentrations or [IO₄−] = 0.005 mol/l and [Cu2+] = 0.002 mol/l produce optimum grafting. The effects of time, temperature, amount of coir fiber, some inorganic salts and organic solvents on graft yield have also been investigated. On the basis of experimental findings, a reaction mechanism has been proposed. Evidence of grafting was studied from fourier transform infrared spectroscopy and scanning electron microscopy of chemically modified coir and MMA‐grafted coir. Tensile properties such as maximum stress at break, extension at break and Young's modulus of untreated, defatted, chemically treated and grafted coir fibers were evaluated and compared. Grafted coir fiber showed an increase in tensile properties such as maximum stress at break, extension at break and Young's modulus. Copyright © 1999 John Wiley & Sons, Ltd.     

Two N‐(2‐phenylethyl)nitroaniline derivatives as precursors for slow and sustained nitric oxide release agents

Notwithstanding its simple structure, the chemistry of nitric oxide (NO) is complex. As a radical, NO is highly reactive. NO also has profound effects on the cardiovascular system. In order to regulate NO levels, direct therapeutic interventions include the development of numerous NO donors. Most of these donors release NO in a single high‐concentration burst, which is deleterious. N‐Nitrosated secondary amines release NO in a slow, sustained, and rate‐tunable manner. Two new precursors to sustained NO‐releasing materials have been characterized. N‐[2‐(3,4‐Dimethoxyphenyl)ethyl]‐2,4‐dinitroaniline, C₁₆H₁₇N₃O₆, (I), crystallizes with one independent molecule in the asymmetric unit. The adjacent amine and nitro groups form an intramolecular N—H…O hydrogen bond. The anti conformation about the phenylethyl‐to‐aniline C—N bond leads to the planes of the arene and aniline rings being approximately perpendicular. Molecules are linked into dimers by weak intermolecular N—H…O hydrogen bonds such that each amine H atom participates in a three‐center interaction with two nitro O atoms. The dimers pack so that the arene rings of adjacent molecules are not parallel and π–π interactions do not appear to be favored. N‐(4‐Methylsulfonyl‐2‐nitrophenyl)‐l ‐phenylalanine, C₁₆H₁₆N₂O₆S, (II), with an optically active center, also crystallizes with one unique molecule in the asymmetric unit. The l enantiomer was established via the configuration of the starting material and was confirmed by refinement of the Flack parameter. As in (I), there is an intramolecular N—H…O hydrogen bond between adjacent amine and nitro groups. The conformation of the molecule is such that the arene rings display a dihedral angle of ca 60°. Unlike (I), molecules are not linked via intermolecular N—H…O hydrogen bonds. Rather, the carboxylic acid H atom forms a classic, approximately linear, O—H…O hydrogen bond with a sulfone O atom. Pairs of molecules related by twofold rotation axes are linked into dimers by two such interactions. The packing pattern features a zigzag arrangement of the arene rings without apparent π–π interactions. These structures are compared with reported analogues, revealing significant differences in molecular conformation, intermolecular interactions, and packing that result from modest changes in functional groups. The structures are discussed in terms of potential NO‐release capability.     

Phase-controlled growth of metastable Fe5Si3 nanowires by a vapor transport method

We report the synthesis of single-crystalline nanowires (NWs) of metastable Fe5Si3 phase via an iodide vapor transport method. Free-standing Fe5Si3 NWs are grown on a sapphire substrate placed on a Si wafer without the use of any catalyst. The typical size of the Fe5Si3 nanowires is 5-15 microm in length and 100-300 nm in diameter. Synthesis of the metastable phase is induced by composition-dependent nucleation from the gas-phase reaction. Depending on the concentration ratio of FeI2(g) to SiI4(g), different phases of iron silicides are formed. The growth of nanowires is facilitated by the initial nucleation of silicide particles on the substrate and further self-seeded growth of the NWs. The present work not only provides a method for the synthesis of metastable Fe5Si3 nanowires but also suggests that the phase controlled synthesis can be further optimized to produce other metal-rich silicide nanostructures for future spintronic devices.     

Bio-based tri-functional epoxy resin (TEIA) blend cured with anhydride (MHHPA) based cross-linker: Thermal,mechanical and morphological characterization

A novel renewable resource based tri-functional epoxy resin from itaconic acid (TEIA) was blended with petroleum based epoxy resin (DGEBA) and fabricated at different ratios. Then, it was by thermally cured with methylhexahydrophthalic anhydride (MHHPA) in presence of 2-methylimidazole (2-MI) catalyst. The tensile, modulus, strength of virgin epoxy resin (41.97 MPa, 2222 MPa) increased to 47.59 MPa, 2515 MPa, respectively, with the addition of 30% of TEIA. The fracture toughness parameter, critical stress intensity factor (K_IC) revealed enhancement of toughness in the TEIA bio-based blends system. The thermomechanical properties of TEIA (tri-functional epoxy resin from itaconic acid) modified petroleum-epoxy networks were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The fracture morphology was also studied by the scanning electron microscopy and atomic force microscopy respectively.     

Epoxy‐based composite adhesives: Effect of hybrid fillers on thermal conductivity,rheology, and lap shear strength

Thermal management is an important parameter in an electronic packaging application. In this work, three different types of fillers such as natural graphite powder (Gr) of 50‐μm particle size, boron nitride powder (h‐BN) of 1‐μm size, and silver flakes (Ag) of 10‐μm particle size were used for thermal conductivity enhancement of neat epoxy resin. The thermal properties, rheology, and lap shear strength of the neat epoxy and its composite were investigated. The analysis showed that the loading of different wt% of Gr‐based fillers can effectively increase the thermal conductivity of the epoxy resin. It has also been observed that the thermal conductivity of the hybrid filler (Gr/h‐BN/Ag) reinforced epoxy adhesive composite increased six times greater than that of neat epoxy resin composite. Further, the viscosity of hybrid filler reinforced epoxy resin was found to be increased as compared with its virgin counterpart. The adhesive composite with optimized filler content was then subsequently subjected to determine single lap shear strength. The degree of filler dispersion and alignment in the matrix were determined by scanning electron microscopy (SEM) analysis.     

Analysis and evaluation of biobased polyester of PTT/PBAT blend: thermal,dynamic mechanical,interfacial bonding,and morphological properties

Novel blends were prepared from biobased poly(trimethylene terephthalate) (PTT) and poly(butylene adipate‐co‐terephthalate) (PBAT) using a twin screw extrusion process as a function of different weight ratios. Thermal stability, mechanical, and interfacial properties of PTT/PBAT blends were investigated using a thermogravimetric analyzer and mechanical analyzer. Phase behavior and surface morphology of the blends were characterized using scanning electron microscopy. Interfacial bonding value of the PTT/PBAT blend was evaluated from the Pukanszky empirical relationship. Viscoelastic properties of PTT/PBAT blends were investigated using the dynamic mechanical analyzer. PTT/PBAT blend exhibited higher thermal stability than the neat PTT matrix. The entire blend showed better interfacial adhesion between the matrixes. Storage and loss modulus of the PTT/PBAT blend reduces with increasing PBAT content. PTT/PBAT blend exhibited higher impact energy than the neat PTT matrix, because of its flexible and amorphous nature of PBAT polymer and increasing toughness. Copyright © 2016 John Wiley & Sons, Ltd.