Nature of the near‐IR band in the electronic absorption spectra of neutral bis(tetrapyrrole) rare earth(III) complexes: Time‐dependent density functional theory calculations

The nature of the near‐IR band in the electronic absorption spectra of bis(tetrapyrrole) rare earth(III) complexes Y(Pc)₂ (1), La(Pc)₂ (2), Y(Pc)(Por) (3), Y(Pc)[Pc(α‐OCH₃)₄] (4), Y(Pc)[Pc(α‐OCH₃)₈] (5), and Y(Pc)[Pc(β‐OCH₃)₈] (6) was studied on the basis of time‐dependent density functional theory (TD‐DFT) calculations. The electronic dipole moment along the z‐axis in the electronic transition of the near‐IR band in all the studied neutral bis(tetrapyrrole) yttrium(III) and lanthanum(III) double‐deckers is well explained on the basis of the composition analysis of the orbitals involved. The electronic transition in the near‐IR band causes the reversion of the orbital orientation of one tetrapyrrole ring in both homoleptic and heteroleptic bis(tetrapyrrole) rare earth complexes and induces electron transfer from the tetrapyrrole ring with lower orbital energy to the other ring in the heteroleptic bis(tetrapyrrole) rare earth(III) complexes. The near‐IR band can work as an ideal characteristic absorption band to reflect the π–π interaction between the two tetrapyrrole rings in bis(tetrapyrrole) rare earth(III) double‐decker complexes because of its peculiar electronic transition nature. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Internal flow numerical simulation of a cross‐flow fan in refrigerant operating condition using user‐defined functions

In the paper, a cross‐flow fan in refrigerant operating condition is systematically simulated using user‐defined functions. Three‐dimensional simulations are acquired with Navier–Stokes equations coupled with k–ε turbulence model, and internal flow characteristics of an indoor split‐type air conditioner are obtained, which is mainly composed of cross‐flow fan and heat exchanger. It has systematically been simulated in the isothermal flow condition that the performance of cross‐flow fan may be reduced easily with dry or humid air, and in the refrigerant operating condition in which user‐defined functions are applied to the humid air, considered as a mixture of dry air and vapor. A density‐modulated function is adopted to deal with the condensation of the vapor at the heat‐transfer region approximately. The results show flow mechanism of the two gas‐phase flow, including phase‐vary process. The distribution of the parameters is not uniform at the inlet of the machine, the intensity and position of pressure and velocity vary along the axial direction of the fan, the distribution of vapor volume fraction and turbulent intensity in heat‐transfer region is obtained, and the external characteristic data of the indoor machine are obtained and analyzed. Compared with the experimental data, the calculated characteristic curves and designed parameters are on target. © British Crown Copyright 2010/MOD. Reproduced with permission. Published by John Wiley & Sons, Ltd.     

Synergistic effect between Sn and K promoters on supported platinum catalyst for isobutane dehydrogenation

Catalytic dehydrogenation of isobutane has recently received considerable attention because of the increasing demand for isobutene.In this study,the synergistic effect between Sn and K on PtSnK/γ-Al2O3 catalysts has been investigated by changing the content of Sn.It was found that with the presence of potassium,suitable addition of Sn could not only increase the metal dispersion,but also reduce the catalyst acidity.In these cases,the synergistic effect could also strengthen the interactions between the metal and support,which resulted in an increase in both catalytic activity and stability.In our experiments,Pt-0.6SnK/Al catalyst exhibited the lowest deactivation rate (12.4%) and showed a selectivity to isobutene higher than 94% at the isobutane conversion of about 45.3% after running the reaction for 6 h.However,with the excessive loading of Sn,surface property of active sites and the interactions between metal and support were changed.As a result,the initial optimal ratio between the metallic function and acid function would be destroyed,which was disadvantageous to the reaction.     

Structure elucidation of four prenylindole derivatives from Streptomyces sp. isolated from Ailuropoda melanoleuca feces

Four new prenylindole derivatives, (R)‐6‐(2,3‐dihydroxy‐3‐methylbutyl)indole (1), (R)‐6‐(2,3‐dihydroxy‐3‐methylbutyl)indolin‐2‐one (2), and an unseparated mixture of (Z)‐6‐(4‐hydroxy‐3‐methylbut‐2‐en‐1‐yl)indolin‐2‐one (3a) and (E)‐6‐(4‐hydroxy‐3‐methylbut‐2‐en‐1‐yl)indolin‐2‐one (3b) with a ratio of 3 : 2, were isolated from the culture broth of a streptomycete isolated from Ailuropoda melanoleuca feces. Their structures were elucidated on the basis of 1D and 2D NMR spectroscopic techniques. The absolute configuration of 1 was determined by Mosher's method. Copyright © 2013 John Wiley & Sons, Ltd.     

Phosphorus ligands for iron(III)‐mediated ATRP of styrene via generation of activators by monomer addition

Styrene polymerization via generation of activators by monomer addition (GAMA) for atom transfer radical polymerization (ATRP) has been examined extensively with bulk FeX₃ and FeX₂ at 110 °C in conjunction with various phosphorus‐bearing ligands. It was found that GAMA possesses advantages over normal ATRP. Most importantly, narrower polydispersity index (PDI) values were observed from the styrene polymerizations with Fe(III) over those with Fe(II). Every instance of 2‐(diphenylphosphino)‐N,N′‐dimethyl‐[1,1′‐biphenyl]‐2‐amine and 2‐(diphenylphosphino) pyridine with the Fe(III) system were controlled excellently without addition of any radical initiator or reducing agent additives. Initiator type was found to exert a significant factor to influence on the controllability of polymerization. The initiation of 1‐phenylethyl chloride and methyl‐2‐chloropropionate gave rise to formation of polymers with narrow PDI (1.05–1.20), whereas those from 1‐phenylethyl bromide increased to 1.35. The GAMA of bulk styrene exhibited the best performance in terms of both rate and controllability compared with toluene and anisole. Both formation of block copolymer from the macroinitiator and efficient perturbation of polymerization with 2,2,6,6‐tetramethylpiperidine 1‐oxyl provided firm evidence to support the living and radical characteristics for the GAMA of styrene. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 144–151, 2010     

DECAY RATE OF SAINT-VENANT END EFFECTS FOR PLANE DEFORMATIONS OF PIEZOELECTRIC-PIEZOMAGNETIC SANDWICH STRUCTURES

This paper is concerned with the decay of Saint-Venant end effects for plane deformations of piezoelectric （PE）-piezomagnetic （PM） sandwich structures, where a PM layer is located between two PE layers with the same material properties or reversely. The end of the sandwich structure is subjected to a set of self-equilibrated magneto-electro-elastic loads. The upper and lower surfaces of the sandwich structure axe mechanically free, electrically open or shorted as well as magnetically open or shorted. Firstly the constitutive equations of PE mate- rials and PM materials for plane strain are given and normalized. Secondly, the simplified state space approach is employed to arrange the constitutive equations into differential equations in a matrix form. Finally, by using the transfer matrix method, the characteristic equations for eigen- values or decay rates axe derived. Based on the obtained characteristic equations, the decay rates for the PE-PM-PE and PM-PE-PM sandwich structures are calculated. The influences of the electromagnetic boundary conditions, material properties of PE layers and volume fraction on the decay rates are discussed in detail.     

New generalization of perturbed Ostrowski type inequalities and applications

Generalizations of perturbed Ostrowski type inequality for functions of Lipschitzian type are established. Applications in numerical integration and cumulative distribution functions are also given.