Self-assembled gold nanofilms as a simple, recoverable and recyclable catalyst for nitro-reduction

Hexaazamacrocycle (L) stabilized gold nanoparticles (AuNPs) were prepared by combining L with HAuCl4 center dot 3H(2)O in a variety of alcohol-water (1 : 1) mixtures. The dual roles of L as a reducing and stabilizing agent were exploited for the synthesis of AuNPs under the optimized ratio of L to Au3+ (2 : 1). Self-assembled gold nanofilms (AuNFs) were constructed at liquid-liquid interfaces by adding equal volumes of hexane to the dispersions of AuNPs in the alcohol-water systems. The nanofilms were formed spontaneously by shaking the two-phase mixture for a minute followed by standing. The alcohols explored for the self-assembly phenomenon were methanol, ethanol, i-propanol and t-butanol. The systems containing methanol or t-butanol resulted in AuNFs at the interfaces, whereas the other two alcohols were found not suitable and the AuNPs remained dispersed in the corresponding alcohol-water medium. The AuNFs prepared under suitable conditions were coated on a variety of surfaces by the dip and lift-off method/solvent removal approach. The AuNFs were characterized by UV-vis, SEM, TEM, AFM and contact angle measurement techniques. A coated glass-vial or cuvette was used as a catalytic reservoir for nitro-reduction reactions under ambient and aqueous conditions using NaBH4 as the reducing agent. The reduced products (amines) were extracted by aqueous work-up using ethyl acetate followed by evaporation of the organic layer; the isolated products required no further purification. The catalyst was recovered by simply decanting the reaction mixture whereupon the isolated catalyst remained coated inside the vessel. The recovered catalyst was found to be equally efficient for further catalytic cycles.

Organic fluorine involved intramolecular hydrogen bonds in the derivatives of imides: NMR evidence corroborated by DFT based theoretical calculations

The rare occurrence of intramolecular hydrogen bonds (HBs) of the type N-H center dot center dot center dot F-C is detected in the derivatives of imides in a low polarity solvent by using multi-dimensional and multinuclear NMR experiments. The observation of (1h)J(FH), (2h)J(FN), and (2h)J(FF), where the spin magnetization is transmitted through space among the interacting NMR active nuclei, provided strong and unambiguous evidence for the existence of intra-molecular HBs. The variation in the chemical shifts of labile protons depending on physical conditions, such as the solvent dilution and the systematic alteration of temperature confirmed the presence of weak interactions through intramolecular HBs in all the investigated fluorine substituted molecules. The self or cross dimerization of molecules is unequivocally discarded by the analysis of the rates of diffusion obtained using pseudo-two dimensional DOSY experiments. The Density Function Theory (DFT) calculations based on the Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings.

On the control of rapidly rotating convection by an axially varying magnetic field

The magnetic field in rapidly rotating dynamos is spatially inhomogeneous. The axial variation of the magnetic field is of particular importance because tall columnar vortices aligned with the rotation axis form at the onset of convection. The classical picture of magnetoconvection with constant or axially varying magnetic fields is that the Rayleigh number and wavenumber at onset decrease appreciably from their non-magnetic values. Nonlinear dynamo simulations show that the axial lengthscale of the self-generated azimuthal magnetic field becomes progressively smaller as we move towards a rapidly rotating regime. With a small-scale field, however, the magnetic control of convection is different from that in previous studies with a uniform or large-scale field. This study looks at the competing viscous and magnetic mode instabilities when the Ekman number E (ratio of viscous to Coriolis forces) is small. As the applied magnetic field strength (measured by the Elsasser number Lambda) increases, the critical Rayleigh number for onset of convection initially increases in a viscous branch, reaches an apex where both viscous and magnetic instabilities co-exist, and then falls in the magnetic branch. The magnetic mode of onset is notable for its dramatic suppression of convection in the bulk of the fluid layer where the field is weak. The viscous-magnetic mode transition occurs at Lambda similar to 1, which implies that small-scale convection can exist at field strengths higher than previously thought. In spherical shell dynamos with basal heating, convection near the tangent cylinder is likely to be in the magnetic mode. The wavenumber of convection is only slightly reduced by the self-generated magnetic field at Lambda similar to 1, in agreement with previous planetary dynamo models. The back reaction of the magnetic field on the flow is, however, visible in the difference in kinetic helicity between cyclonic and anticyclonic vortices.

Pattern-Formation During Self-organization in Three-Phase Eutectic Solidification

Eutectic growth is an interesting example for exploring the topic of pattern-formation in multi-phase systems, where the growth of the phases is coupled with the diffusive transport of one or more components in the melt. While in the case of binary alloys, the number of possibilities are limited (lamellae, rods, labyrinth etc.), their number rapidly increases with the number of components and phases. In this paper, we will investigate pattern formation during three-phase eutectic solidification using a state-of-the art phase-field method based on the grand-canonical density formulation. The major aim of the study is to highlight the role of two properties, which are the volume fraction of the solid phases and the solid-liquid interfacial energies, in the self-organization of the solid phases during directional growth. Thereafter, we will show representative phase-field simulations of a micro-structure in a real alloy (Ag-Al-Cu) using an asymmetric phase diagram as well as interfacial properties.

Template-free coordination-driven self-assembly of discrete hexanuclear prismatic cages employing half-sandwich octahedral Ru-2(II) acceptors and triimidazole donors

Coordination-driven self-assembly of dinuclear half-sandwich p-cymene ruthenium(II) complexes Ru-2(mu-eta(4)-C2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) and Ru-2(mu-eta(4)-C6H2O4)(CH3OH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) separately with imidazole-based tritopic donors (L-1-L-2) in methanol yielded a series of hexanuclear 3+2] trigonal prismatic cages (2-5), respectively L-1 = 1,3,5-tris(imidazole-1-yl) benzene; L-2 = 4,4',4 `'-tris(imidazole-1-yl) triphenylamine]. All the self-assembled cages 2-5 were characterized by various spectroscopic techniques (multinuclear NMR, Infra-red and ESI-MS) and their sizes, shapes were obtained through geometry optimization using molecular mechanics universal force field (MMUFF) computation. Despite the possibility due to the free rotation of donor sites of imidazole ligands, of two different atropoisomeric prismatic cages (C-3h or C-s) and polymeric product, the self-selection of single (C(3)h) conformational isomeric cages as the only product is a noteworthy observation. (C) 2015 Elsevier B.V. All rights reserved.

Vesicular Nanostructure Formation by Self-Assembly of Anisotropic Penta-phenol-Substituted Fullerene in Water

A study on self-assembly of anisotropically substituted penta-aryl fullerenes in water has been reported. The penta-phenol-substituted amphiphilic fullerene derivative C60Ph5(OH)(5)],exhibited self-assembled vesicular nanostructures in water under the experimental conditions. The size of the vesicles Was observed to depend upon the kinetics of self-assembly and could be varied from similar to 300 to similar to 70 nm. Our mechanistic study indicated that the self-assembly of C60Ph5(OH)(5) is driven by extensive intermolecular as well as water-mediated hydrogen :bonding along with fullerene-fullerene hydrophobic interaction in water. The cumulative effect of these interactions is responsible for the stability of vesicular structures even on the removal of solvent. The substitution of phenol with anisole resulted in different packing and interaction of the fullerene derivative, as Indicated in the molecular dynamics studies, thus resulting in different self-assembled nanostructures. The hollow vesicles were further encapsulated with a hydrophobic conjugated polymer and water-soluble dye as guest molecules. Such confinement of pi-conjugated polymers in fullerene has significance in bulk heterojunction devices for efficient exciton diffusion.