Stereoflexible total synthesis of (−)-epiquinamide

Hydroxy propiolate rearrangement to conjugated diene, Sharpless asymmetric dihydroxylation and one-pot quinolizine construction have been used as key steps in the total synthesis of (−)-epiquinamide.     

The Electronic and Magnetic Properties of a Few Transition-Metal Clusters

Using density functional theory we present a systematic study of the electronic and magnetic properties of various nickel clusters and two small bimetallic clusters, Ni _n Co _m and Ni _n Fe _m (n + m ≤ 6). A detail study of binding energy, magnetic moment and stability function of pure nickel clusters of nuclearity (N) 40–60 have been performed. We observe that the magic numbers occur at N = 43, 46, 49, 53, 55, and 58, which correspond to the most stable clusters. We find that, with increase in substitution of Co and Fe atoms in Ni cluster, while Ni _n Co _m becomes more stable, the Ni _n Fe _m clusters become less stable. The significant enhancement of average magnetic moment and suppression of local magnetic moment of nickel atoms are found in both clusters with increase in Co and Fe concentration.     

Amine functionalized MCM-41: An active and reusable catalyst for Knoevenagel condensation reaction

This paper reports preparation, characterization of amine modified mesoporous crystalline MCM-41 and its application in Knoevenagel condensation reaction. Amine modified MCM-41 was prepared by co-condensation and post-synthesis methods. The samples were characterized by X-ray powder diffraction, Fourier-transfer infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron micrograph (SEM), ²⁹Si magic-angle spinning (MAS), nuclear magnetic resonance (NMR), diffuse reflectance spectra (DRS), nitrogen adsorption–desorption and CHN analysis. X-ray diffraction patterns indicate that the modified materials retain the standard MCM-41 structure. SEM study exhibits that the arrangement of particles for 12.8% amine modified MCM-41 is well ordered and spherical in nature. CHN analysis supports that complete hydrolysis of ethoxy groups take place in 12.8% amine modified sample. From the NMR study it is confirmed that the surface coverage is 40% in 12.8% amine modified sample. The base catalytic activity of hybrid MCM-41 materials such as amine (post-synthesis and co-condensation methods) and surfactant functionalized materials for condensation reaction between benzaldehyde and diethyl malonate in solvent free, room temperature synthesis of cinnamic acid was evaluated and correlated with the surface and textural properties. Sample containing 12.8 wt% amine loaded by co-condensation method showed highest malonic ester conversion (92%) and selectivity (98%) for cinnamic acid.     

Physico-chemical characterization and photocatalytic activity of zinc oxide prepared by various methods

Zinc oxide was prepared by different methods by varying precipitating agents, the source of the salt precursors and the microwave irradiation time and was characterized by XRD, BET-surface area, surface acidity and crystallite sizes. The photocatalytic reactions were carried out under solar radiation in batch reactors towards oxidation of 4-nitrophenol and reduction of Cr(VI) by varying different parameters such as irradiation time, pH of the solution, catalyst amount and substrate concentration and the activities were correlated with the physico-chemical parameters. Zinc oxide samples prepared by microwave irradiation and calcined at 300 degrees C exhibit highest surface area, acid sites and lowest crystallite sizes and show highest activity towards photocatalytic reactions.     

Synthesis, characterization, and catalytic activity of phosphomolybdic acid supported on hydrous zirconia

A series of ecofriendly solid acid catalyst was synthesized by phosphomolybdic acid impregnated on hydrous zirconia (ZPMA) by an incipient wetness impregnation technique. The support and the resulting catalysts were characterized by X-ray diffraction, FTIR, EPMA, BET surface area, acid sites, etc. These studies indicate that the phosphomolybdic acid keeps its Keggin-type structure unaltered up to 500 degrees C. Catalytic activities of the material were evaluated for the esterification of acetic acid reaction. The 12 wt% of phosphomolybdic acid supported on hydrous zirconia shows highest surface area, acid sites and gives about 86% conversion with 100% selectivity of n-butyl acetate.     

Adsorption of hexavalent chromium on manganese nodule leached residue obtained from NH3-SO2 leaching

Adsorption of hexavalent chromium onto manganese nodule leached residues was investigated as a possible alternative to the conventional methods of its removal from aqueous synthetic solutions. Adsorption behavior was studied as a function of time, pH, temperature, and concentration of adsorbate and adsorbent in acetic acid-sodium acetate buffer medium. Cr (VI) removal was pH dependent and was found to be of a maximum at pH 3. The applicability of the Langmuir isotherm to the present system was tested. Increased adsorption capacity with increased temperature indicates that the adsorption reaction was endothermic in nature. Based on these studies, thermodynamic parameters such as Gibbs free energy change (DeltaG0), standard enthalpy change (DeltaH0), and standard entropy change (DeltaS0) were calculated.     

试射法在求解二阶线性微分方程边值问题中的应用

对二阶线性微分方程的边值问题(第一类、第二类及第三类边值条件),通常可利用古典的差分方法进行求解,即通过对微分方程离散化而求解线性方程组得到原微分方程的解.通过数值实验说明试射法也可作为求解二阶线性微分方程的一种有效算法且能保证具有较高的精度.     

Characterization and microhardness of Co−W coatings electrodeposited at different pH using gluconate bath: A comparative study

Electrodeposition of Co–W alloy coatings has been carried out with DC and PC using gluconate bath at different pH. These coatings are characterized for their structure, morphology and chemical composition by X‐ray diffraction, field emission scanning electron microscopy, differential scanning calorimetry and X‐ray photoelectron spectroscopy (XPS). Alloy coatings plated at pH8 are crystalline, whereas coatings electrodeposited at pH5 are nanocrystalline in nature. XPS studies have demonstrated that as‐deposited alloy plated at pH8 with DC contain only Co²⁺ and W⁶⁺ species, whereas that alloy plated at pH5 has significant amount of Co⁰ and W⁰ along with Co²⁺ and W⁶⁺ species. Again, Co²⁺ and W⁶⁺ are main species in all as‐deposited PC plated alloys in both pH. Co⁰ concentration increases upon successive sputtering of all alloy coatings. In contrast, mainly W⁶⁺ species is detected in the following layers of all alloys plated with PC. Alloys plated at pH5 show higher microhardness compared to their pH8 counterparts. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrogen sorption–desorption studies on ZrCo–hydrogen system

The ZrCo–H₂ system was investigated in this study owing to its importance as a suitable candidate material for storage, supply, and recovery of hydrogen isotopes. Desorption hydrogen pressure-composition isotherms were generated at six different temperatures in the range of 524–624 K. A van’t Hoff plot was constructed using the plateau pressure data of each pressure-composition isotherms and the thermodynamic parameters were calculated for the hydrogen desorption reaction of ZrCo hydride. The enthalpy and entropy change for the desorption of hydrogen were found to be 83.7 ± 3.9 kJ mol^?1 H₂ and 122 ± 4 J mol^?1 H₂ K^?1, respectively. Hydrogen absorption kinetics of ZrCo–H₂ system was studied at four different temperatures in the range of 544–603 K and the activation energy for the absorption of hydrogen by ZrCo was found to be 120 ± 5 kJ mol^?1 H₂ by fitting kinetic data into suitable kinetic model equation.     

Calorimetric investigation of order–disorder transition in Cu0.6Pd0.4 and Cu0.85Pd0.15 alloys

Order–disorder phase transitions in Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys have been investigated using differential scanning calorimetry and drop calorimetry. The differential scanning calorimetry measurements show that the transition in both these alloys are reversible in nature and the enthalpy increment measurements reveal that these transitions are first order in nature. The transition temperature of first-order phase transition in Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys have been evaluated to be 884(±2) and 799(±2) K, respectively, from drop calorimetric measurements. The latent heat of first-order phase transition in Cu_0.6Pd_0.4 alloy were evaluated to be 31.2(±0.6) and 28.9(±0.5) J g^?1, by enthalpy increment and differential scanning calorimetry measurements, respectively. Similarly, the latent heat of first-order phase transition in Cu_0.85Pd_0.15 alloy were evaluated to be 23.1(±0.6) and 21.3(±0.5) J g^?1, by enthalpy increment and differential scanning calorimetry measurements, respectively. The solidus temperatures of Cu_0.6Pd_0.4 and Cu_0.85Pd_0.15 alloys were found to be 1,457(±2) and 1,360 K, respectively.