Aggregation effects in maximum covering models

The level of aggregation is critical in discrete location analyses as it affects the level of data collection required, computation times and the usefulness of the analyses. We examine the effects of three alternative nodal aggregation schemes on (i) the model's solution times, (ii) the locational decisions indicated by the maximum covering model, (iii) the coverage provided by the aggregate solutions compared with the optimal solutions, and (iv) the coverage predicted by the aggregate model compared with the coverage that results from using the aggregate model's facility sites and the disaggregate demands. The results suggest that considerable aggregation can be tolerated without incurring large errors in total coverage, but that location errors are introduced at moderate levels of aggregation. The magnitude of these errors is significantly affected by the aggregation scheme employed.     

α-Hydroxymethylation of conjugated nitroalkenes via the Morita-Baylis-Hillman reaction

The Morita-Baylis-Hillman reaction (MBHR) of conjugated nitroalkenes has been successfully carried out for the first time. A variety of aromatic and heteroaromatic nitroalkenes react with formaldehyde at room temperature in the presence of stoichiometric amounts of imidazole and catalytic amounts of anthranilic acid in THF providing moderate to good yields of the multifunctional adducts in most of the cases.     

Thermo and mechanoluminescence studies of BZT phosphor

Mechanoluminescence (ML) and thermoluminescence (TL) in barium zirconium titanate (BZT) is reported for the first time. The BZT powder sample, belonging to perovskite category is synthesized using solid state reaction technique. The sample is prepared at a temperature of 1200 °C. The obtained specimen is thoroughly characterized paying particular attention to their structure, composition, morphology and optical properties. The surface morphology and structural properties are analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD patterns confirm the formation of crystalline perovskite type cubic structure. Also, highly agglomerated, porous and regular shaped particles are seen by SEM. The optical properties of as prepared sample is presented and discussed in terms of ML and TL. The ML intensity is found to be maximum for the sample irradiated for 10 min. More than one maxima in TL glow curve reveals that the traps are distributed in separate groups at different depths and corresponding values are calculated using initial rise method.     

Aggregation Behavior of Pluronic-L64 in Presence of Sodium Dodecyl Sulphate in Water

The effect of sodium dodecyl sulfate (SDS) on the micellization and aggregation behavior of a poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) amphiphilic copolymer (Pluronic L64: EO₁₃ PO₃₀ EO₁₃) have been investigated by various techniques like, cloud point, viscosity, isothermal titration calorimetry (ITC), differential scanning calorimetry (DSC), fluorescence spectroscopy, room temperature phosphorescence (RTP), and small angle neutron scattering (SANS). Addition of SDS in L64 solutions shows mark alteration of different properties. We observed synergistic interaction between SDS and Pluronic L64. The changes in the critical micelle concentration (CMC), critical micelle temperature (CMT), cloud point (CP), micelle size, and shape has been correlated and reported in terms of structure dynamics and mechanics. The ITC titrations have been used to explore the different stages of binding and interactions of SDS with L64. The enthalpies of aggregation for copolymer-SDS aggregates binding, organizational change of bound aggregates, and the threshold concentrations of SDS in the presence of copolymer were estimated directly from ITC titration curves. The effect of temperature on enthalpy values has been reported in terms of different aggregation state. Fluorescence and RTP for L64 were used to investigate the change in micellar environment on the addition of SDS at different temperature. Appearance and shifting of SANS peaks have been used to monitor the size and inter micellar interaction on addition of SDS in L64 solution. Cloud point and viscosity elaborate the penetration of SDS molecule in L64 micelle and hence changing the micellar architect.     

Nickel‐Catalyzed α‐Carbonylalkylarylation of Vinylarenes: Expedient Access to γ,γ‐Diarylcarbonyl and Aryltetralone Derivatives

We report a Ni‐catalyzed regioselective α‐carbonylalkylarylation of vinylarenes with α‐halocarbonyl compounds and arylzinc reagents. The reaction works with primary, secondary, and tertiary α‐halocarbonyl molecules, and electronically varied arylzinc reagents. The reaction generates γ,γ‐diarylcarbonyl derivatives with α‐secondary, tertiary, and quaternary carbon centers. The products can be readily converted to aryltetralones, including a precursor to Zoloft, an antidepressant drug.     

Hydrolysis of carboxylate and phosphate esters using monopyridinium oximes in cationic micellar media

The reactions of p‐nitrophenyl acetate (PNPA) with a series of monopyridinium oximes, viz. 2‐PAM (2‐hydroxyiminomethyl‐1‐methylpyridinium iodide), 3‐PAM (3‐hydroxyiminomethyl‐1‐methylpyridinium iodide), and 4‐PAM (4‐hydroxyiminomethyl‐1‐methylpyridinium iodide) have been studied in the presence of cationic surfactants of same hydrophobic chain length (C₁₆) within the concentration range of 0.5–6.0 mM at pH 8.0 under the pseudo‐first‐order condition. The observed rate constant (k_obs) increases with increasing surfactant concentration culminating into a maximum, and this has been analyzed in detail following the concepts of micellar catalysis. The structure–activity relationship of the investigated oximes has been discussed, and 2‐PAM was found to be the most reactive among all the three investigated oximes for the cleavage of PNPA. Esterolytic decomposition of p‐nitrophenyldiphenyl phosphate with oximate ions (? CH?NO^?) was followed in cetyltrimethylammonium bromide micelles at pH 9.0, and 4‐PAM was the most reactive oxime for the micellar hydrolysis of phosphate ester. The apparent acid dissociation constants (pK_a) of the investigated oximes have been determined spectrophotometrically. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 569–578, 2011     

Reactivity studies of carbon,phosphorus and sulfur‐based acyl sites with tertiary oximes in gemini surfactants

Kinetic studies of the reactions of tertiary oximes (monoisonitroso acetone; MINA and butane 2,3 dione monooxime; BDMO) with some carboxylate (p‐nitrophenyl acetate and p‐nitrophenyl benzoate), phosphate (p‐nitrophenyl diphenyl phosphate and bis (2,4‐dinitrophenyl) phosphate) and sulfonate (p‐nitrophenyl p‐toluene sulphonate) esters in gemini surfactants have been conducted. The observed first‐order rate constant versus surfactant profiles show micelle‐assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase. Experimental results showed that MINA exhibited better nucleophilic activity towards ester cleavage than BDMO. Pseudophase model has been applied in order to determine micellar second‐order rate constants and binding constants. Copyright © 2013 John Wiley & Sons, Ltd.