Efficient and green syntheses of novel γ-aminophosphonate and phosphine oxide derivatives

Two synthetic protocols leading to novel γ-aminophosphonate and phosphine oxide derivatives, by reductive amination of γ-phosphonylketones, are reported. The first method involved a two-step procedure. Imine intermediates were first isolated from the p-toluenesulfonic acid-catalyzed reaction of primary amines with γ-ketophosphonates and phosphine oxides, then reduced with NaBH₄ in refluxing ethanol. The second method consists of a one-pot procedure which includes the condensation of γ-ketophosphonates and phosphine oxides with primary amines, in the presence of molecular sieves, followed by reduction with NaBH₄. These methods offer significant advantages over prior reports, such as efficiency, generality, and good yields. Furthermore, they are green protocols avoiding hazardous hydrides and solvents.     

Log-Polynomial Period Functions for Hecke Groups

In this article we shall determine the automorphic integrals of positive and negative integral weight associated with the full modular group and some Hecke groups. This will be done by using the Hecke Correspondence. We will also give a characterization of multiplier systems of real weight for Hecke groups.     

母乳中溴代/氯代阻燃剂及其代谢产物的分析检测方法

建立了低分辨气相色谱-负化学源质谱法(GC/NCI-LRMS)定性与定量检测母乳中的溴代/氯代阻燃剂及其代谢产物的方法。所检测的溴代/氯代阻燃剂及其代谢产物分为中性化合物和羟基化合物两部分。采用RTX-1614(30 m)作为色谱分离柱,在优化的色谱条件下对8种多溴联苯醚PBDEs(包括BDE209)及其甲氧基代谢产物MeO-PBDEs,多种其它阻燃剂及代谢物等中性化合物同时进行了分离检测;采用DB-5(30 m)作为色谱分离柱,在优化的色谱条件下分离检测了9种羟基多溴联苯醚OH-PBDEs。在母乳样本中加入代用标准或内标,经过超声提取、液液萃取、硅胶净化和浓缩定容等预处理后,分别对中性和羟基化合物进行测定。十溴联苯醚、其它多溴联苯醚、甲氧基多溴联苯醚、得克隆及脱氯产物、其它阻燃剂等中性化合物,及羟基多溴联苯醚在两个添加浓度水平的回收率分别为66.5%～75.4%,84.2%～126.4%,60.9%～115.1%,86.7%～104.9%,42.9%～113.8%和64.7%～129.5%;中性化合物的相对标准偏差均小于22%,羟基化合物的相对标准偏差均小于30%。利用本方法对我国电子垃圾拆解区人体母乳中的目标物进行了分析检测,结果可靠。     

Impact of rough silicon buffer layer on electronic quality of GaAs grown on Si substrate

The electronic and the structural properties of n-GaAs layers grown on rough surface of silicon substrate by molecular beam epitaxy (MBE) has been investigated by photoluminescence (PL), time resolved photoluminescence (TRPL) and high resolution X-ray diffraction (HRXRD). The relationship between electronic and structural properties of the n-GaAs layer was checked, showing that the defect density is a strong cause for trapping the minority carriers. The impact of introducing intermediate rough silicon layer between silicon substrate and n-GaAs layer on the electronic properties was observed, showing that the structure grown on rough Si involves higher lifetime than those developed on flat silicon substrate. Such structure could be used for economic solar cells fabrication.     

Intersubband transitions in In_xAl_(1-x)N/In_yGa_(1-y)N quantum well operating at 1.55 μm

In this paper, we theoretically study the effects of doping concentration NDand an external electric field on the intersubband transitions in InxAl(1-x)N/InyGa(1-y)N single quantum well by solving the Schr¨odinger and Poisson equations self-consistently. Obtained results including transition energies, the band structure, and the optical absorption have been discussed. The lowest three intersubband transitions(E2- E1),(E3- E1), and(E3- E2) are calculated as functions of doping concentration ND. By increasing the doping concentration ND, the depletion effect can be reduced, and the ionized electrons will compensate the internal electric field which results from the spontaneous polarization. Our results show that an optimum concentration NDexists for which the transition 0.8 eV(1.55 μm) is carried out. Finally, the dependence of the optical absorption α13(ω) on the external electric field and doping concentration is studied. The maximum of the optical absorption can be red-shifted or blue-shifted through varying the doping concentration and the external electric field. The obtained results can be used for designing optical fiber telecommunications operating at 1.55 μm.     

Intersubband transitions in InxAl（l-x）N/InyGa（l-y）N quantum well operating at 1.55 μm

In this paper, we theoretically study the effects of doping concentration ND and an external electric field on the intersubband transitions in InxAl（l-x）N/InyGa（l-y）N single quantum well by solving the Schrodinger and Poisson equations self-consistently. Obtained results including transition energies, the band structure, and the optical absorption have been discussed. The lowest three intersubband transitions （E2 -El）, （E3 -El）, and （E3 -E2） are calculated as functions of doping concentration ND. By increasing the doping concentration ND, the depletion effect can be reduced, and the ionized electrons will compensate the internal electric field which results from the spontaneous polarization. Our results show that an optimum concentration ND exists for which the transition 0.8 eV （1.55 μm） is carried out. Finally, the dependence of the optical absorption α13（ω） on the external electric field and doping concentration is studied. The maximum of the optical absorption can be red-shifted or blue-shifted through varying the doping concentration and the external electric field. The obtained results can be used for designing optical fiber telecommunications operating at 1.55 μm.     

Ab initio computational studies on molecular conformation of N-methyl-glyphosate

Conformational analysis of N-methyl-glyphosate has been carried out using an ab initio molecular orbital (MO) method at the HF/3-21G* levels of theory and the results are compared with the results of a previously studied compound, namely glyphosate. The potential energy surface of the molecule obtained by varying the central torsion angles (Φ, ψ) was investigated in detail. Fourteen conformers with 5 kcal mol^?1 energy cut-off have been selected from the potential energy surface for geometry optimization to locate the true minimum on the conformational space. The minimum has been found to be at (—62°, 110°.) for the central torsion angles. This conformation is stabilized by hydrogen bond interactions (O-H…O and C-H…O) and the interactions due to protons nearer to each other. This cationic field leads to the formation of a hydrophobic patch in this structure, as well as in the structures closer to the global minimum. This patch may destabilize the favourable interaction of N-methyl-glyphosate with the surrounding amino acid residues in the binding cavity as they form the cationic field throughout the glyphosate binding region.     

Electroconvection between coaxial cylinders of arbitrary ratio subjected to strong unipolar injection

This study deals with the electroconvection phenomenon that takes place in a dielectric liquid layer placed between two annular electrodes and subjected to the action of an electric field.The full set of governing equations describing the combined Electro-Hydro-Dynamic (EHD) flow is directly solved with the finite volume method.The development of electroconvective motion is investigated in details in the case of strong injection when the emitter electrode is the inner cylinder.We first examine the stability of such flow. As in the plane–plane configuration we have highlighted the existence of a linear and non-linear critical electric Rayleigh numbers giving rise to a hysteresis loop. The flow structure under the effect of the electric field is analyzed and the distribution of electric charge density is presented. In particular we investigate the effect of various parameters involved in this configuration, such as the radius ratio, injection strength and electric Rayleigh number.A multicellular convective pattern is particularly observed and it is shown that the number of cells is increased when the annular gap is narrower. Finally a significant increase of the rotational speed of the vortex with the electric Rayleigh number is recorded.     

Raman study of cation effect on sulfate vibration modes in solid state and in aqueous solutions

Raman spectra of potassium, sodium, and ammonium sulfates (K₂SO₄, Na₂SO₄, and (NH₄)₂SO₄) are reported and analyzed. These sulfates have been investigated under two states: solid (anhydrous and hydrated) salts and aqueous solutions. The effects of monovalent ions (K⁺, Na⁺, and NH₄⁺) and hydration on the position of Raman lines assigned to internal vibrations of sulfate anion SO₄²⁻ are discussed. In solid salts, the line position of each Raman peak is shown to decrease with increasing radius of the cation. The main ν₁ mode of sulfate molecule is particularly affected. It is emphasized that this sensitivity in solid sulfates vanishes in aqueous solutions. As a consequence, this mode can be probed by Raman spectroscopy as the main signature of SO₄²⁻ to determine its concentration within a single calibration. Copyright © 2013 John Wiley & Sons, Ltd.     

Selected Reactions of Diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate with Secondary and Tertiary Amines

An easy regio‐ and stereoselective synthesis of new nitrogenous molecules 2a–e was successfully realized via an effective coupling reaction of diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate 1 with various secondary amines in methanol. Hence, the use of less and more bulky secondary amines gives rise, respectively, to the successive (S_N2′) substitution–isomerization and (S_N2) substitution derivatives 2a–c and 2d–e . Moreover, the addition of tertiary amines to 1 in the same reaction conditions, leads exclusively to the rearranged vinyl ether 3 in good yields.