Malonic Ester Amide Synthesis: An Efficient Methodology for Synthesis of Amides

A general methodology “malonic ester amide synthesis” has been demonstrated, which uses α-substituted/unsubstituted diethyl malonates for the decarboxylative acylation of various aromatic/heteroaromatic primary/secondary amines to form one-carbon homologated amides, thus providing easy access to amides with odd/even chain lengths and an array of substituents on the alkyl/aryl part while avoiding use of acyl chlorides or peptide coupling reagents.

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Comprehensive study towards the desulfonylation/desulfinylation of cis-3-functionalized 3-phenylsulfonyl/sulfinyl-β-lactams to access novel cis-3-monosubstituted-β-lactams

An inclusive study towards the stereospecific synthesis of novel cis-3-monosubstituted-β-lactams from cis-3-functionalized 3-phenylsulfonyl/sulfinyl-β-lactams is described. 3-Sulfinyl-β-lactams 5/5? successfully furnished stereospecific cis-3-monosubstituted-β-lactams 6, however 3-sulfonyl-β-lactams 2 failed to give the desulfurized product 6?. The final stereochemical and structural conformations of novel β-lactams were established by single crystal X-ray crystallographic study (5c). The cis configuration of the β-lactams 5/5? and 6 was assigned in relevance to E and C4-H and C3-H and C4-H respectively.     

Mössbauer study of CO-precipitated Fischer-Tropsch iron catalysts

Mössbauer spectroscopy studies of precipitated Fischer-Tropsch (FT) iron catalysts, viz. 100 Fe/5 Cu/4.2 K/x SiO₂, wherex=0,8, 16, 24, 25, 40, or 100, have shown that reduction of the oxide precursor in CO gives rise to -carbide Fe₅C₂ whose amount decreases with an increase of SiO₂ content. The -carbide is converted into magnetite Fe₃O₄ while catalyzing the FT synthesis reaction. A correlation between FT activity and the content of -carbide in the catalysts was found, which indicated that -carbide is active for FT synthesis reaction.     

NUMERICAL ANALYSIS ON THE VELOCITY AND PRESSURE FIELDS INDUCED BYMULTI-OSCILLATIONS OF AN UNDERWATER EXPLOSION BUBBLE

假设水下爆炸气泡的内部气体在膨胀收缩过程中满足绝热条件,周围流体无黏无旋不可压缩. 基于势流理论,采用边界元法研究气泡动力学行为,重点关注气泡引起的流场脉动载荷以及滞后流特性,给出了相关的理论推导和数值计算方法. 通过将数值结果与解析解、实验值进行对比,数值模型的收敛性和有效性能够得到保证. 利用编写的程序进行计算和分析,发现在气泡加速膨胀阶段,流场压力在气泡径向不一定是逐渐衰减,还有可能以先增后减的规律变化;气泡射流后,为了能够继续描述环状气泡的运动以及流场特性,将此时的流场分为无旋场和一个布置在气泡内部涡环的叠加,计算过程中采用了一些数值技巧处理气泡的拓扑结构,得以连续模拟多个周期的气泡运动. 环状气泡具有相对较高的上浮迁移速度,而且在其顶部和底部附近分别形成两个高压区,顶部的高压区峰值相对较大,底部的高压区范围相对较大. 环状气泡中心轴上的流场速度会在气泡中心有一个加速过程,在气泡顶部附近又迅速减小.     

Synthesis and characterization of layered perovskite oxides (La, Sr) n + 1(Ti, Cr) n O3n + 1 (n = 1, 2)

We report here the synthesis of layered perovskite oxides of the composition La_0.5Sr_1.5Ti_0.5Cr_0.5O₄ and LaSr₂TiCrO₇ by conventional solid-state reaction method. Results of XRD analysis show that the phases crystallize with tetragonal unit cell in the space group I4/mmm. Both phases behave as insulators and the linearity of log ρ versus T ^?1/4 plot in the temperature range 150–350 K suggests that the electronic conduction occurs by Mott’s variable range hopping mechanism. The antiferromagnetic interactions observed for the samples arise from Cr³⁺–O–Cr³⁺ superexchange interaction.     

Near‐field optical enhancement by lead‐sulfide quantum dots and metallic nanoparticles for SERS

There is a growing interest in using quantum dots (QDs) and metallic nanoparticles (NPs), both for luminescence enhancement and surface‐enhanced Raman scattering (SERS). Here, we study the electromagnetic‐field enhancement that can be generated by lead‐sulfide (PbS) QDs using three‐dimensional finite‐element simulations. We investigate the field enhancement associated with combinations of PbS QDs with metallic NPs and substrates. The results show that high field enhancement can be achieved by combining PbS QDs with metallic NPs of larger sizes. The ideal size for Ag NPs is 25 nm, providing a SERS enhancement factor of ~5*10⁸ for light polarization parallel to the NP dimer axis and a gap of 0.6 nm. For Au NPs, the bigger the size, the higher is the field for the studied diameters, up to 50 nm. The near‐field values for PbS QDs above metallic substrates were found to be lower compared to the case of PbS QD‐metal NP dimers. This study provides the understanding for the design and application of QDs for the enhancement of near‐field phenomena. Copyright © 2013 John Wiley & Sons, Ltd.     

Mercury(II) ion-selective electrodes based on p-tert-butyl calix[4]crowns with imine units.

A PVC membrane incorporating p-tert-butyl calix[4]crown with imine units as an ionophore was prepared and used in an ion-selective electrode for the determination of mercury(II) ions. An electrode based on this ionophore showed a good potentiometric response for mercury(II) ions over a wide concentration range of 5.0 x 10(-5) - 1.0 x 10(-1) M with a near-Nernstian slope of 27.3 mV per decade. The detection limit of the electrode was 2.24 x 10(-5) M and the electrode worked well in the pH range of 1.3 - 4.0. The electrode showed a short response time of less than 20 s. The electrode also showed better selectivity for mercury(II) ions over many of the alkali (Na+, -1.69; K+, -1.54), alkaline-earth (Ca2+, -3.30; Ba2+, -3.32), and heavy metal ions (Co2+, -3.67; Ni2+, -3.43; Pb2+, -3.31; Fe3+, -1.82). Ag+ ion was found to be the strongest interfering ion. Also, sharp end points were obtained when the sensor was used as an indicator electrode for the potentiometric titration of mercury(II) ions with iodide and dichromate ions.     

Short and long distance contributions to B→Kγγ

We study the decay of the neutral B meson to K^*γγ within the framework of the Standard Model, including long distance contributions.     

New mesogens with a fluoro-substituted bent core

Ferroelectric properties in liquid crystals are no longer restricted to materials with a chiral molecular structure; ferroelectricity has been observed in a smectic phase formed by bent achiral molecules. Accordingly, two homologous series possessing a central biphenyl methane core have been synthesized, the central core having two lateral fluoro substituents. Both the series have six-ring structures and exhibit smectic mesophases of high thermal stability. The flexible biphenyl methane core imparts a slight curve to the molecules, giving them a bent shape.