Studies on SO 4 2− Ion Incorporation into Apatite Structure

Calcium sulphate-apatites were synthesised by precipitation from aqueous solutions with different fluorine content and analyzed by chemical, x-ray diffraction (XRD), Raman, and Fourier transform infrared (FTIR) analyses. Their thermal stability was studied by differential scanning calorimetry (TG/DSC) and high-temperature XRD. It was established that the introduction of SO 4 2 m into apatite structure and the thermal changes depend on the fluorine content in the apatite structure. At temperatures above 600;C the structure of apatite reorganizes and CaSO 4 forms a separate phase.     

Photo‐physical Properties of N‐methyl‐3,4‐fulleropyrrolidine and Its Derivatives: A DFT and TD‐DFT Investigation

A series of N‐methyl‐3,4‐fulleropyrrolidine (NMFP) derivatives were designed by selecting different π‐conjugated linkers and electron‐donating groups as D‐π‐A and D‐A systems. The optimised structures and photo‐physical properties of NMFP and its derivatives have been determined using density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) methods with the B3LYP functional and the 6‐31G basis set. According to the computation analysis, both the π‐conjugated linkers and the electron‐donating groups can influence the electronic and photo‐physical properties of the NMFP derivatives. Our calculated results demonstrated that the electron‐donating groups, with significant electron‐donating ability, had the tendency to increase the highest occupied molecular orbital (HOMO) energy. The π‐conjugated linkers with lower resonance energy decreased the lowest occupied molecular orbital (LUMO) energy and caused a significant decrease in the energy gap (E_g) between the E_HOMO and E_LUMO. A Natural Bond Orbital (NBO) analysis examines the effect of the electron‐donating group, π conjugated linker, and electron‐withdrawing group for these NMFP derivatives. For the NMFP derivatives, a projected density of state (PDOS) analysis demonstrated that the electron density of HOMO and LUMO are concentrated on the electron‐donating group and the π‐conjugated linker, respectively. A TD‐DFT/B3LYP calculation was performed to calculate the electronic absorption spectra of these NMFP derivatives. Both the electron‐donating group and the π‐conjugated linker contribute to the major absorption peaks, which are assigned as HOMO to LUMO transitions and are red‐shifted relative to those of non‐substituted NMFP.     

Oxidation of Primary Aromatic Amines under Irradiation with Ultrasound and/or Microwaves

The oxidation of primary aromatic amines, p-methylaniline, p-ethylaniline and p-chloroaniline to the corresponding azo- and azoxy-compounds has been observed in ultrasound and/or microwaves systems. The individual irradiation of microwaves and its simultaneous irradiation with ultrasound obviously elevate the conversion of amines, as compared with the individual irradiation of ultrasound and the heating in a plain water bath. However, the formation of formamidine resulted in poor selectivity toward azo and azoxy products in the presence of dimethylformamide (DMF).     

Preparation of Polymers with Viologen Moieties and Their Application to the Selective Reduction of Substituted Nitroarenes

Abstract

Polymers with viologen moieties were synthesized by using poly-chlorethyl vinyl ether (PCEVE) as mother supports. These polymers were used as electron-transfer catalysts (ETC) for the reduction of substituted nitroarenes under heterophase conditions (reductant: Na₂S₂O₄ in CH₂CI₂-H₂O). The experimental results show that the substituted nitroarenes were reduced selectively and efficiently to the corresponding aniline derivatives in the presence of viologen polymers. The catalytic active species of viologen were detected by ESR and electrochemical methods. It was found that the viologen cation radical (V⁺) acts as the active species during the viologen-mediated reduction of substituted nitroarenes.     

Gold-catalyzed heteroannulation and allyl migration: synthesis of highly functionalized indole derivatives

Highly substituted indole derivatives have been prepared in good to excellent yields by a novel gold-catalyzed cyclization accompanied by [3,3]-migration of the allyl strategy. We have been able to introduce an allyl group at the C1 position of pyrano[3,2-e]indol-6(7H)-one and pyrrolo[3,2-f]quinolin-7(6H)-one moieties that provide a scope for further transformation.     

碱法直接合成茂钠的研究

在四氢呋喃中以环戊二烯(茂)与固体氢氧化钠反应合成环戊二烯钠,研究了反应物配比、反应温度、时间和固体粒度对环戊二烯钠收率和纯度等的影响。结果表明,环戊二烯钠的收率可达96%以上。     

Iron-Catalysed [3+3] Annulation of Oxime Acetates and Enaminones towards the Synthesis of Multi-Substituted Pyridines

A direct access to unsymmetrical and symmetrical multi-substituted pyridines has been accomplished via iron-catalysed [3+3] annulation of oxime acetates with enaminones. This protocol is featured by easily available starting materials, no requirement of expensive additives and ligands, operational simplicity, and good tolerance with diverse functional groups.