Piperidine‐functionalized silica: an efficient and environmentally benign catalyst for Claisen–Schmidt condensation

Piperidine‐functionalized silica as a basic heterogeneous catalyst was synthesized via a simple protocol by condensing silica chloride with piperidine. The catalyst was characterized with various techniques (FT‐IR, solid state NMR, scanning electron microscopy, energy‐dispersive X‐ray, thermogravimetric, elemental, and NH₃ and CO₂ temperature‐programmed desorption analyses). Surface area was also evaluated through Brunauer–Emmett–Teller analysis. Its catalytic activity was evaluated for Claisen–Schmidt condensation under solvent‐free conditions. The catalyst was easily recovered and reused up to five cycles without considerable loss of activity and was not deactivated due to amide formation. Also, this method has attractive advantages such as short reaction time, mild reaction conditions, good to excellent yield of products, easy handling of the catalyst and simple operational procedure. Copyright © 2014 John Wiley & Sons, Ltd.     

Optimization of process parameters and its effect on structure and morphology of CuO nanoparticle synthesized via the sol−gel technique

This article describes systematic basic research on the optimization of the processing parameters of sol?gel technique for synthesis of the high purity CuO nanoparticles. Effect of the synthesis parameters such as copper salt concentration, solvent and gelating agent, optimized one at a time, was investigated by employing XRD, TEM, FESEM, micro-Raman, UV-visible-NIR and PL spectroscopies. XRD results clearly demonstrate the monoclinic structure of CuO nanoparticles with traceable impurities at a lower molar concentration of Cu²⁺, transition of nucleation system from homogeneous to heterogeneous state with the increase in concentration of Cu²⁺ from 0.05 to 0.15?M. It was also found that the isopropyl alcohol offers better results in comparison to ethanol and water. Moreover, the lattice parameters, space group, and crystal system were determined by powder X-ray diffraction method. Further we propose the optimization of synthesis process using ethylene glycol and citric acid (EG:CA). The Raman analysis confirmed the influence of ethylene glycol and citric acid ratio and TEM observations confirmed that EG:CA 1:2 ratio formulate homogenous flower-like nanostructures. The optical absorption of CuO nanostructures can be easily tuned by varying the concentration of citric acid without changing other conditions; it shows the role of synthesis parameters more significant. Our results suggest that the prepared CuO nanostructures have a potential to be used as absorbing material in solar cell applications.

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2D hydrogen-bonded manganese–picolinate coordination network: ionic liquid-induced synthesis,crystal structure and thermogravimetric analysis

A new manganese coordination complex of formula [Mn(2-picolinate)₂·2H₂O]·H₂O based on 2-picolinic acid has been synthesized hydrothermally at 120 °C for 48 h in presence of ionic liquid tetraethylammonium hydroxide (25% methanolic solution). 1 crystallizes in monoclinic crystal system and is hydrogen-bonded metal-organic network in which aqua ligands are instrumental in deciding structural features. The reported complex 1 is insoluble in almost all organic solvents as well as in water and shows good thermal stability upto 450 °C.     

Silanylidene and Germanylidene Anions: Valence‐Isoelectronic Species to the Well‐Studied Phosphinidene

The reduction of TipMCl₃ (Tip=2,4,6‐triisopropylphenyl) (M=Si, Ge) with KC₈ in the presence of cyclic alkyl(amino) carbene (cAAC) afforded the acyclic silanylidene and germanylidene anions in the form of potassium salt [K(cAAC)MTip]₂ (M=Si ( 1 ); Ge ( 2 )). The silanylidene and germanylidene anions are valence‐isoelectronic to the well‐studied phosphinidene and are a new class of acyclic anions of Group 14. Compounds 1 and 2 were isolated and well characterized by NMR and single‐crystal X‐ray structure analysis. Furthermore, the structure and bonding of compounds 1 and 2 was investigated by computational methods.     

2‐[N‐(2,3‐Dimethylphenyl)carbamoyl]benzenesulfonamide and the 3,4‐ and 2,6‐dimethylphenyl analogues

The structures of 2‐[(2,3‐dimethylphenyl)carbamoyl]benzenesulfonamide, 2‐[(3,4‐dimethylphenyl)carbamoyl]benzenesulfonamide and 2‐[(2,6‐dimethylphenyl)carbamoyl]benzenesulfonamide, all C₁₅H₁₆N₂O₃S, are stabilized by extensive intra‐ and intermolecular hydrogen bonds. In all three structures, the sulfonamide and carbamoyl groups are involved in hydrogen bonding. In the 2,3‐dimethyl and 2,6‐dimethyl derivatives, dimeric units and chains of molecules are formed parallel to the c axis. In the 3,4‐dimethyl derivative, the hydrogen bonding creates tetrameric units, resulting in macrocyclic R₄⁴(22) rings that form sheets in the ab plane. The three analogues are closely related to the fenamate class of nonsteroidal anti‐inflammatory drugs.     

Glass bead grafting with poly(carboxylic acid) polymers and maleic anhydride copolymers

Glass beads were etched with acids and bases to increase the surface porosity and the number of silanol groups that could be used for grafting materials to the surfaces. The pretreated glass beads were functionalized using 3‐aminopropyltriethoxysilane (APS) coupling agent and then further chemically modified by reacting the carboxyl groups of carboxylic acid polymers with the amino groups of the pregrafted APS. Several carboxylic acid polymers and poly(maleic anhydride) copolymers, such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), poly(styrene‐alt‐maleic anhydride) (PSMA), and poly(ethylene‐alt‐maleic anhydride) (PEMA) were grafted onto the bead surface. The chemical modifications were investigated and characterized by FT‐IR spectroscopy, particle size analysis, and tensiometry for contact angle and porosity changes. The amount of APS and the different polymer grafted on the surface was determined from thermal gravimetric analysis and elemental analysis data. Spectroscopic studies and elemental analysis data showed that carboxylic acid polymers and maleic anhydride copolymers were chemically attached to the glass bead surface. The improved surface properties of surface modified glass beads were determined by measuring water and hexane penetration rates and contact angle. Contact angles increased and porosity decreased as the molecular weights of the polymer increased. The contact angles increased with the hydrophobicity of the attached polymer. The surface morphology was examined by scanning electron microscopy (SEM) and showed an increase in roughness for etched glass beads. Copyright © 2007 John Wiley & Sons, Ltd.     

Comprehensive structural studies of 2',3'-difluorinated nucleosides: comparison of theory, solution, and solid state

The conformations of three 2',3'-difluoro uridine nucleosides were studied by X-ray crystallography, NMR spectroscopy, and ab initio calculations in an attempt to define the roles that the two vicinal fluorine atoms play in the puckering preferences of the furanose ring. Two of the compounds examined contained fluorine atoms in either the arabino or xylo dispositions at C2' and C3' of a 2',3'-dideoxyuridine system. The third compound also incorporated fluorine atoms in the xylo configuration on the furanose ring but was substituted with a 6-azauracil base in place of uracil. A battery of NMR experiments in D 2O solution was used to identify conformational preferences primarily from coupling constant and NOE data. Both (1)H and (19)F NMR data were used to ascertain the preferred sugar pucker of the furanose ring through the use of the program PSEUROT. Compound-dependent parameters used in the PSEUROT calculations were newly derived from complete sets of conformations calculated from high-level ab initio methods. The solution and theoretical data were compared to the conformations of each molecule in the solid state. It was shown that both gauche and antiperiplanar effects may be operative to maintain a pseudodiaxial arrangement of the C2' and C3' vicinal fluorine atoms. These data, along with previously reported data by us and others concerning monofluorinated nucleoside conformations, were used to propose a model of how fluorine influences different aspects of nucleoside conformations.     

PVP Assisted Shape-Controlled Synthesis of Self-Assembled 1D ZnO and 3D CuO Nanostructures

Self-assembled one-dimensional (1D) zinc oxide (ZnO) rods and three-dimensional (3D) cupric oxide (CuO) cubes like nanostructures with a mean crystallite size of approximately 33 and 32 nm were synthesized through chemical route in the presence of polyvinylpyrrolidone (PVP) under mild synthesis conditions. The technique used for the synthesis of nanoparticles seems to be an efficient, inexpensive and easy method. X-Ray diffraction patterns confirmed well crystallinity and phase purity of the as prepared samples, followed by the compositional investigation using Fourier Transform Infrared (FT-IR) spectroscopy. The formation of ZnO nanorods and CuO nanocubes like structures were through Scanning Electron Microscopy (SEM) images. The mechanism and the formation factors of the self-assembly were discussed in detail. It was clearly observed from results that the concentration of precursors and PVP were important factors in the synthesis of self-assembly ZnO and CuO nanostructures. These self-assembly nanostructures maybe used as novel materials in various potential applications.     

Basic Ionic Liquid Promoted Domino Knoevenagel–Thia‐Michael Reaction: An Efficient and Multicomponent Strategy for Synthesis of 1,3‐Thiazines

An efficient, three‐component strategy for synthesis of 1,3‐thiazines with high atom economy in one‐pot mediated by room temperature basic ionic liquid is described here. The strategy involves basic ionic liquid, [bmim]OH‐catalyzed Knoevenagel condensation between ethyl cyanoacetate and aromatic aldehyde and subsequent thia‐Michael addition with substituted thioureas. The reaction sequence is smooth and quantitative under ambient temperature. [bmim]OH was recovered and reused four times without any appreciable decrease in its reactivity and product yield.     

Protein-protein interactions studied by EPR relaxation measurements: cytochrome c and cytochrome c oxidase

The complex formed between cytochrome c oxidase from Paracoccus denitrificans and its electron-transfer partner cytochrome c has been studied by multi-frequency pulse electron paramagnetic resonance spectroscopy. The dipolar relaxation of a fast-relaxing paramagnetic center induced on a more slowly relaxing center can be used to measure their distance in the range of 1-4 nm. This method has been used here for the first time to study transient protein-protein complex formation, employing soluble fragments for both interacting species. We observed significantly enhanced transversal relaxation of the CuA center in cytochrome c oxidase due to the fast-relaxing iron of cytochrome c upon complex formation. The possibility to measure cytochrome c oxidase in the presence and absence of cytochrome c permitted us to separate the dipolar relaxation from other relaxation contributions. This allowed a quantitative simulation and interpretation of the relaxation data. The specific temperature dependence of the dipolar relaxation together with the high orientational selectivity achieved at high magnetic field values may provide detailed information on distance and relative orientation of the two proteins with respect to each other in the complex. Our experimental results cannot be explained by any single well-defined structure of the complex of cytochrome c oxidase with cytochrome c, but rather suggest that a broad distribution in distances and relative orientations between the two proteins exist within this complex.