Palladium complexes of amido-functionalized N-heterocyclic carbenes as effective precatalysts for the Suzuki-Miyaura C-C cross-coupling reactions of aryl bromides and iodides

A series of air-stable, robust and highly active palladium based precatalysts of amido-functionalized N-heterocyclic carbenes for the Suzuki-Miyaura C-C cross-coupling reaction has been designed. In particular, the [1-R-3-{N-(benzylacetamido)imidazol-2-ylidene]₂PdCl₂ [R = i-Pr (1c) and CH₂Ph (2c)] complexes efficiently carried out the Suzuki-Miyaura coupling of the aryl bromide and iodide substrates with phenyl boronic acid in good to excellent yields in air at 90 °C in 12 h. Quite interestingly, of these palladium precatalysts, the i-propyl derivative (1c) exhibited superior activity as compared to the benzyl derivative (2c). The density functional theory (DFT) studies carried out on the 1c and 2c complexes revealed the strong σ-donating nature of the NHC ligand as reflected in their high d/b ratio [i.e. forward σ-donation (d) to backward π-donation (b)] of these complexes and, thus, point towards greater stability of the Pd-NHC interaction in these complexes.     

Spontaneous CdTe --> alloy --> CdS transition of stabilizer-depleted CdTe nanoparticles induced by EDTA

CdTe nanoparticles stabilized by l-cysteine are chemically transformed into CdS nanoparticles of the same diameter via an intermediate CdTeS alloy without any auxiliary source of sulfur. The reaction is induced by ethylenediaminetetraacetic acid dipotassium salt dehydrate (EDTA), which was demonstrated experimentally to act as a catalyst by partially removing thiol stabilizers from the nanoparticle surface. It is hypothesized that addition of EDTA facilitates Te(2-) release, and oxidation of Te(2-) drives the nanoparticle transition process. Unlike many reports on reactions catalyzed by nanocolloids, this is likely to be the first observation of a catalytic reaction in which nanoparticles function as a substrate rather than a catalyst. It opens new pathways for the synthesis of novel nanoscale II-VI and other semiconductors and represents an interesting case of chemical processes in nanocolloids with reactivity increased by depletion of the surface layer of thiol stabilizers. This includes but is not limited to accurate control over the particle composition and crystallization rate. The slow rate of the CdTe --> alloy --> CdS transition is important for minimizing defects in the crystal lattice and results in a substantial increase of the quantum yield of photoluminescence over the course of the transition.     

Solitons and other nonlinear waves of the Boussinesq equation

This paper studies the dynamics of shallow water waves that are governed by the Boussinesq equations. A few perturbation terms are taken into account. The ansatz method is used to carry out the perturbed Boussinesq equation. Later on, the mapping method is used to extract a few more analytical solutions. Additionally, the Weierstrass elliptic function method is also used to obtain solitary waves and singular soliton solutions. Finally, the Lie symmetry approach is used to extract a few more additional solutions.     

The Active Phase of Nickel/Ordered Ce(2) Zr(2) O(x) Catalysts with a Discontinuity (x=7-8) in Methane Steam Reforming

Breaking news: A unique discontinuous property and an active phase of Ni/ordered Ce(2) Zr(2) O(x) (x=7-8) solid-solution catalysts were observed during methane steam reforming. The catalytic performance of Ni/Ce(2) Zr(2) O(x) strongly depended on the phase and oxygen content of the Ce(2) Zr(2) O(x) support.     

Novel synthesis of 1,2,4‐triazolophanes and 1,3,4‐oxadiazolophanes: A dieckmann condensation approach

The Dieckmann condensation has been used for the first time for the syntheses of novel 1,2,4‐triazolophanes and 1,3,4‐oxadiazolophanes. The bis‐1,3,4‐oxadiazol‐2‐thiols 1a and 1b were reacted with ethyl bromoacetate to give the diesters 2a and 2b . Diesters 2a and 2b were treated under dry conditions with sodium methoxide in methanol to afford desired symmetrical 1,3,4‐oxadiazolophanes 3a and 3b . Similarly, diesters of macrocycle precursors containing 1,2,4‐triazole moiety, that is, 6a , 6b , 10 , 13a , 13b , and 13c were synthesized from 5a , 5b , 9 , 12a , 12b , and 12c , respectively. Dieckmann condensation of these diesters afforded symmetrical ketones 7a , 7b , 11 , 14a , 14b , and 14c . Extrusion of CO₂ was observed after in situ hydrolysis of the conventional Dieckmann product during neutralization by dilute mineral acids to afford highly symmetrical ketone in good yields. Further, the ketones 14a , 14b , and 14c were converted into their respective thiones by the reaction with Lawesson's reagent. All the products were synthesized with good yields, and structures were confirmed by various spectroscopic tools and elemental analyses. J. Heterocyclic Chem.,, (2012).     

The t-analog of the level one string function for twisted affine Kac–Moody algebras

We study Lusztig?s t-analog of weight multiplicities, or affine Kostka–Foulkes polynomials, associated to level one representations of twisted affine Kac–Moody algebras. We obtain an explicit closed form expression for the unique t-string function, using constant term identities of Macdonald and Cherednik. This extends previous work on t-string functions for the untwisted simply-laced affine Kac–Moody algebras.     

Analytical rheology of blends of linear and star polymers using a Bayesian formulation

A Bayesian data analysis technique is presented as a general tool for inverting linear viscoelastic models of branched polymers. The proposed method takes rheological data of an unknown polymer sample as input and provides a distribution of compositions and structures consistent with the rheology, as its output. It does so by converting the inverse problem of analytical rheology into a sampling problem, using the idea of Bayesian inference. A Markov chain Monte Carlo method with delayed rejection is proposed to sample the resulting posterior distribution. As an example, the method is applied to pure linear and star polymers and linear–linear, star–star, and star–linear blends. It is able to (a) discriminate between pure and blend systems, (b) accurately predict the composition of the mixtures, in the absence of degenerate solutions, and (c) describe multiple solutions, when more than one possible combination of constituents is consistent with the rheology.     

Interfacially active particles in droplet/matrix blends of model immiscible homopolymers: Particles can increase or decrease drop size

Particles have been shown to adsorb at the interface between immiscible homopolymer melts and to affect the morphology of blends of those homopolymers. We examined the effect of such interfacially active particles on the morphology of droplet/matrix blends of model immiscible homopolymers. Experiments were conducted on blends of polydimethylsiloxane and 1,4-polyisoprene blended in either a 20:80 or 80:20 weight ratio. The effects of three different particle types, fluoropolymer particles, iron particles, and iron oxyhydroxide particles, all at a loading of 0.5 vol.%, were examined by rheology and by direct flow visualization. Particles were found to significantly affect the strain recovery behavior of polymer blends, increasing or decreasing the ultimate recovery, slowing down or accelerating the recovery kinetics, and changing the dependence of these parameters on the applied stress prior to cessation of shear. These rheological observations were found to correlate reasonably well with particle-induced changes in drop size. The particles can both increase as well as decrease the drop size, depending on the particle type, as well as on which phase is continuous. The cases in which particles cause a decrease in drop size are analogous to the particle stabilization of “Pickering emulsions” well-known from the literature on oil/water systems. We hypothesize that cases in which particles increase drop size are analogous to the “bridging–dewetting” mechanism known in the aqueous foam literature.     

Synthesis and characterization of ETS-10: supported hollow carbon nano-polyhedrons nanosorbent for adsorption of krypton at near ambient temperatures

Hollow carbon nano-polyhedrons (HCNPHs) supported on Engelhard Titanosilicate-10 (ETS-10) were synthesized by wet impregnation technique using tetrahydrofuran as a solvent. Synthesized HCNPHs/ETS-10 nanosorbent was characterized by X-ray diffraction, Raman spectra, N₂-adsorption–desorption isotherm, BET surface area, and scanning electron microscopy to confirm the morphology and uniformity of carbon particles ranging from 50 to 70 nm in diameter. Sorption characteristics of this nanosorbent for krypton at various carbon loadings were determined using a bench-scale column apparatus. The dynamic sorption capacity of HCNPHs/ETS-10 nanosorbent calculated from the breakthrough curve, 0.75 mmol/kg, which was ~15 % higher than for that of activated carbon. The effect of temperature on the adsorption capacity was studied between 263–293 K. Operational capacity of the nanosorbent was found to be 0.45 mmol/kg at 263 K. The experimental results indicate that 10 wt% HCNPHs/ETS-10 nanosorbent showed promising results for krypton adsorption, indicating its potential as an economical and active sorbent for krypton removal from the off-gas streams resulting from operations for recycle of used nuclear fuel.