Experimental and computational studies of the macrocyclic effect of an auxiliary ligand on electron and proton transfers within ternary copper(II)-Histidine complexes

The dissociation of [Cu^II(L)His]^•2+ complexes [L=diethylenetriamine (dien) or 1,4,7-triazacyclononane (9-aneN₃)] bears a strong resemblance to the previously reported behavior of [Cu^II(L)GGH]^•2+ complexes. We have used low-energy collision-induced dissociation experiments and density functional theory (DFT) calculations at the B3LYP/6-31+G(d) level to study the macrocyclic effect of the auxiliary ligands on the formation of His^•+ from prototypical [Cu^II(L)His]^•2+ systems. DFT revealed that the relative energy barriers of the same electron-transfer (ET) dissociation pathways of [Cu^II(9-aneN₃)His]^•2+ and [Cu^II(dien)His]^•2+ are very similar, with the ET reactions of [Cu^II(9-aneN₃)His]^•2+ leading to the generation of two distinct His^•+ species; in contrast, the proton transfer (PT) dissociation pathways of [Cu^II(9-aneN₃)His]^•2+ and [Cu^II(dien)His]^•2+ differ considerably. The PT reactions of [Cu^II(9-aneN₃)His]^•2+ are associated with substantially higher barriers (>13 kcal/mol) than those of [Cu^II(dien)His]^•2+. Thus, the sterically encumbered auxiliary 9-aneN₃ ligand facilitates ET reactions while moderating PT reactions, allowing the formation of hitherto nonobservable histidine radical cations.     

半导体模型中退化漂移—扩散问题解的存在性

研究半导体物理中出现的漂移—扩散模型,这是一个关于带电粒子浓度n,p,静电位ψ的抛物—椭圆耦合方程组,并带有混合初边值条件.对初值在L2+(Ω)时弱解的存在性展开讨论,利用正则化方法和适当的函数变换,使抛物型方程的解具有正下界n,p≥ε>0,同时得到一系列先验估计.然后通过紧性引理和Schauder不动点定理,得到初值在L2+(Ω)时弱解的存在性.     

Theoretical Studies on the N-Phenylpyrrolidine Formation Mechanism Based on the Reaction of Phenylamine with 1,4-Butanediol

The reaction mechanism of phenylamine reacting with 1,4-butanediol to give N- phenylpyrrolidine was investigated with traditional transition state theory. Based on the experimental results, two reaction channels were discussed. The geometries of their reactants, products, intermediates and transition states were optimized. The possible transition State and activation energy were determined by vibrational analysis and IRC verification. And finally, the main reaction channel was given.     

New synthetic way to prepare 2-aryl-8-(piperidin-4-yl)-5,7-dimethoxy-4H-chromen-4-one as key intermediate for CDK inhibitor

As an important intermediate to study cyclin-dependent kinase(CDK)inhibitors,2-aryl-8-(piperidin-4-yl)-5,7-dimethoxy-4H- chromen-4-one derivatives were prepared usingβ-diketone route with low yield.In our study,chalcone route has been investigated and the result suggested that the benzaldehydes substituted with electron-donating group give much better yield thanβ-diketone route.This new method will be an efficient way to start further research on new anticancer flavonoids.     

Static Theory for Planar Ferromagnets and Antiferromagnets

Here we generalize the “BBH”-asymptotic analysis to a simplified mathematical model for the planar ferromagnets and antiferromagnets. To develop such a static theory is a necessary step for a rigorous mathematical justification of dynamical laws for the magnetic vortices formally derived in [1] and [2]. Received March 15, 2001, Accepted May 16, 2001     

Participation of ions in promoting intermolecular associations of cell wall polysaccharides

The physiological functions of the two ions, Ca²⁺ and H⁺, in controlling mechanical properties of plant cell wall are reviewed. The interactions of these ions with major cell wall polysaccharides during cell growth and development are described. Experimental results for Ca²⁺/H⁺-induced molecular associations of some polysaccharides in solutions are also given. This article aims to bridge the understandings of molecular associations in solutions (in vitro) with those occurring in cell wall matrix of high order structure (in vivo).     

Morphology,toughness mechanism,and thermal properties of hyperbranched epoxy modified diglycidyl ether of bisphenol A (DGEBA) interpenetrating polymer networks

New hyperbranched poly(trimellitic anhydride‐triethylene glycol) ester epoxy (HTTE) is synthesized and used to toughen diglycidyl ether of bisphenol A (DGEBA) 4,4′‐diaminodiphenylmethane (DDM) resin system. The effects of content and generation number of HTTE on the performance of the cured systems are studied in detail. The impact strength is improved 2–7 times for HTTE/DGEBA blends compared with that of the unmodified system. Scanning electron microscopy (SEM) of fracture surface shows cavitations at center and fibrous yielding phenomenon at edge which indicated that the particle cavitations, shear yield deformation, and in situ toughness mechanism are the main toughening mechanisms. The dynamic mechanical thermal analyzer (DMA) analyses suggest that phase separation occurred as interpenetrating polymer networks (IPNs) for the HTTE/DGEBA amine systems. The IPN maintains transparency and shows higher modulus than the neat epoxy. The glass transition temperature (T_g) decreases to some extent compared with the neat epoxy. The T_g increases with increase in the generation number from first to third of HTTE and the concentrations of hard segment. The HTTE leads to a small decrease in thermal stability with the increasing content from TGA analysis. The thermal stability increases with increase in the generation number from first to third. Moreover, HTTE promotes char formation in the HTTE/DGEBA blends. The increase in thermal properties from first to third generation number is attributed to the increase in the molar mass and intramolecular hydrogen bridges, the increasing interaction of the HTTE/DGEBA IPNs, and the increasing crosslinking density due to the availability of a greater number of end hydroxyl and end epoxide functions. Copyright © 2008 John Wiley & Sons, Ltd.     

EXISTENCE AND UNIQUENESS RESULTS FOR VISCOUS, HEAT-CONDUCTING 3-D FLUID WITH VACUUM

We prove the local existence and uniqueness of the strong solution to the 3-D full Navier-Stokes equations whose the viscosity coefficients and the thermal conductivity coefficient depend on the density and the temperature. The initial density may vanish in an open set and the domain could be bounded or unbounded. Finally, we show the blow-up of the smooth solution to the compressible Navier-Stokes equations in R^n （n 〉 1） when the initial density has compactly support and the initial total momentum is nonzero.