Hydrogen bonding mediated enantioselective organocatalysis in brine: significant rate acceleration and enhanced stereoselectivity in enantioselective Michael addition reactions of 1,3-dicarbonyls to β-nitroolefins

Brine provides remarkable rate acceleration and a higher level of stereoselectivity over organic solvents, due to the hydrophobic hydration effect, in the enantioselective Michael addition reactions of 1,3-dicarbonyls to β-nitroolefins using chiral H-donors as organocatalysts.     

Low-Prandtl-number Rayleigh-Bénard convection with stress-free boundaries

Results of direct numerical simulations on Rayleigh-Bénard convection in low-Prandtl-number convection with stress-free horizontal boundaries are presented. Simulations are done in a three dimensional rectangular simulation box of dimensions L _x × L _y × 1. Instabilities and the corresponding fluid patterns near onset of convection are investigated by varying the horizontal aspect ratio η = L _y /L _x in a range 1 ≤ η ≤ 4. Fluid patterns are complex and unsteady at the instability onset for η ≥ 2. They consist of wavy rolls, rhombic patterns and oblique wavy rolls. The patterns near onset are time periodic for η < 2. We observe periodic wavy rolls for η = 4 / 3. Homoclinic bifurcations are observed for η = 1 for 0 ≤ Pr ≤ 0.03. We observe spontaneous breaking of a single limit cycle in two and again spontaneous merging of two limit cycles into one in a simulation box with η = 1, as the reduced Rayleigh number r = Ra/R a _c is raised at a fixed value of Pr. The effect of Prandtl number on the homoclinic bifurcations is also investigated. We also present a low-dimensional model, which captures the instability sequence quite accurately for η = 1.     

A Solution State Study of the Complexation and Thermodynamic Parameters of Binary Complexes of the Inner Transition Metals with Piracetam in Aqueous and Mixed Solvents

An equilibrium study on complexation behavior of the inner transition metals, where M = {Y(III), La(III, Ce(III, Pr(III), Nd(III), Sm(III), Gd(III), Dy(III), Th(IV)} and L = piracetam, has been carried out using the Irving–Rossotti titration technique in aqueous media at different temperatures and ionic strengths. The protonation constant and stability constants (log₁₀ β _n ) of the resulting inner metal–ligand complexes have been calculated with the Fortran IV program BEST using the method of least squares and considering the BESTFIT model. Thermodynamic parameters were also evaluated, yielding negative ΔG°, ΔH° and positive ΔS° values that indicate complex formation is favorable at ordinary temperatures. Species distribution curves of complexes have been plotted as function of pH using the SPEPLOT FORTRAN IV program to visualize the presence of various species in equilibrium in the pH range 2–6. To understand more about these equilibria, the stability of these complexes was studied at different percentages of solvent (10–30 % v/v) in different aqua-organic solvent mixtures with methanol, ethanol, 1-butanol and dimethylformamide.     

Resonance Raman study of He+ ion implanted nanostructured ZnS

ZnS nanocrytsals of size ∼2.5 nm were prepared by chemical precipitation technique. Pressed pellets of nanostructured ZnS were implanted with He⁺ ions at doses of 5 × 10¹⁴, 1 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Raman spectra of both unimplanted and He⁺ ion implanted samples were recorded with ultraviolet (UV) excitation. LO, 2LO, 2TO, (LO + TA) and (2TO − TA) modes of ZnS were observed in the resonance Raman spectra of the unimplanted nanostructured ZnS samples. In addition, a surface mode was observed at 294 cm⁻¹. With the implantation of He⁺ ions, the 2TO mode disappeared and 2LO mode became prominent and this observation was attributed to the decrease in band gap of ZnS nanocrytsals due to ion implantation. The exciton–LO phonon coupling strength was determined from the intensity ratio of 2LO to LO modes and it was observed that the exciton–LO phonon coupling strength increases with increase in implantation dose. In the present work, we report for the first time the observation of 2TO mode in the resonance Raman spectrum of nanostructured ZnS and also the modification of exciton–LO phonon coupling strength of semiconductor nanoparticles by ion implantation. Copyright © 2008 John Wiley & Sons, Ltd.     

Single-Source Precursors for the Chemical Vapor Deposition of Iron Germanides

Binary iron-germanium phases are promising materials in magnetoelectric, spintronic or data storage applications due to their unique magnetic properties. Previous protocols for preparation of Fe_xGe_y thin films and nanostructures typically involve harsh conditions and are challenging in terms of phase composition and homogeneity. Herein, we report the first example of single source chemical vapor deposition (CVD) of Fe_xGe_y films. The appreciable volatility of [Ge[Fe₂(CO)₈]₂], [Cl₂GeFe(CO)₄]₂ and ^Me₂iPr₂NHC ⋅ GeCl₂ ⋅ Fe(CO)₄ allowed for their application as precursors under standard CVD conditions (^Me₂iPr₂NHC=1,3-diisopropoyl-4,5-dimethylimidazol-2-ylidene). The thermal decomposition products of the precursors were characterized by TGA and powder XRD. Deposition experiments in a cold-wall CVD reactor resulted in dense films of Fe_xGe_y. During the optimization of synthetic conditions for precursor preparation the new iron-germanium cluster Cl₂Ge[Fe₂(CO)₈]Ge[Fe₂(CO)₈] was obtained in experiments with a higher stoichiometric ratio of GeCl₂ ⋅ 1,4-dioxane vs. Fe₂(CO)₉.     

Lattice Mismatch Guided Nickel-Indium Heterogeneous Alloy Electrocatalysts for Promoting the Alkaline Hydrogen Evolution

The immiscibility of crystallographic facets in multi-metallic catalysts plays a key role in driving the green H₂ production by water electrolysis. The lattice mismatch between tetragonal In and face-centered cubic (fcc) Ni is 14.9 % but the mismatch with hexagonal close-packed (hcp) Ni is 49.8 %. Hence, in a series of Ni−In heterogeneous alloys, In is selectively incorporated in the fcc Ni. The 18–20 nm Ni particles have 36 wt % fcc phase, which increases to 86 % after In incorporation. The charge transfer from In to Ni, stabilizes the Ni⁰ state and In develops a fractional positive charge that favors *OH adsorption. With only 5 at% In, 153 mL h⁻¹ H₂ is evolved at −385 mV with mass activity of 57.5 A g⁻¹ at—400 mV, 200 h stability at −0.18 V versus reversible hydrogen electrode (RHE), and Pt-like activity at high current densities, due to the spontaneous water dissociation, lower activation energy barrier, optimal adsorption energy of OH⁻ ions and the prevention of catalyst poisoning.     

Morphology of InN nanorods using spectroscopic Raman imaging

We report the vibrational properties of vertical and oblique InN nanorods (NRs) grown by molecular beam epitaxy (MBE). Surface optical (SO) Raman mode at 561 cm⁻¹, belonging to E₁ symmetry [SO(E₁)], is identified along with symmetry allowed Raman modes of E₂(low), E₂(high), and E₁(LO) at 87, 489, and 589 cm⁻¹, respectively, corresponding to wurtzite InN phase. Usually, SO phonon modes arise due to breakdown of translational symmetry of surface potential at surface defects, which are attributed by the surface roughness. Intensity distribution of E₁(LO) and SO(E₁) phonon modes over a specified area have been analysed using Raman area mapping with an optical resolution of 400 nm. Imaging with E₁(LO) phonon mode, originating from the bulk of the sample, distinguishes the vertical NRs alone. We are able to resolve NR morphologies in both vertical and oblique cases with additional Raman mapping analysis of SO(E₁) phonon mode, emerging from the surface irregularities, which are confined to the tip of MBE grown NRs. Copyright © 2013 John Wiley & Sons, Ltd.