Linear pentablock quintopolymers (l‐SIDMV) with five incompatible blocks: Polystyrene,polyisoprene‐1,4, poly(dimethylsiloxane), poly(tert‐butyl methacrylate), and poly(2‐vinylpyridine)

Three linear pentablock quintopolymers (l‐SIDMV), where S is polystyrene (PS), I polyisoprene‐1,4 (PI), D poly(dimethylsiloxane) (PDMS), M poly(tert‐butyl methacrylate) (PtBuM), and V poly(2‐vinylpyridine) (P2VP), were synthesized by anionic polymerization high vacuum techniques. The approach involves the following: (a) The synthesis of living triblock terpolymer PS‐b‐PI‐b‐PDMSLi and diblock copolymer P2VP‐b‐PtBuMK by sequential polymerizations of the corresponding monomers with sec‐BuLi and benzyl potassium, respectively; and (b) The selective linking of the living triblock terpolymer with the chlorosilane group of 2‐(chloromethylphenyl)ethyldimethylchlorosilane (CMPDMS), followed by linking of the living block copolymer with the remaining chloromethyl group of CMPDMS. Molecular characterization carried out by size exclusion chromatography, membrane osmometry, solution (in CDCl₃ or d₈‐toluene) and solid‐state ¹H‐NMR spectroscopy indicated a high degree of molecular and compositional homogeneity. Differential scanning calorimetry results on the precursors and final polymers were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3938–3946, 2008     

Fifty Years of Inorganic Biomimetic Chemistry: From the Complexation of Single Metal Cations to Polynuclear Metal Complexes by Multidentate Thiolate Ligands

This article covers 50 years of coordination chemistry of transition metal complexes and metal-sulfur aggregates involving thiolate-incorporating ligands by reviewing selected examples. The studies in the coordination chemistry of sulfur-rich ligands have been undoubtedly triggered and fed by the concomitant development of bioinorganic chemistry, particularly of iron-sulfur enzymes. The review is broken down in five sections, which examine complexes of increasing nuclearity, including binuclear complexes based on compartmental macrocyclic ligands. We show also how ligand engineering has allowed the researchers in the field to control the nuclearity of the complexes, which was a particularly difficult task for sulfur-based ligands, as thiolates show a strong tendency to coordinate to more than one metal cation at once.     

单圈混合图的极大谱半径

设U＊为一个未定向的n个顶点上的单圈混合图，它是由一个三角形在其某个顶点上附加”一3个悬挂边而获得．在文[Largest eigenvalue of aunicyclic mixed graph，Applied Mathematics A Journal of Chinese Universities （Ser．B），2004，19（2）：140-J48]中，作者证明了：在相差符号同构意下，在所有n个顶点上的单圈混合图中，U＊是唯一的达到最大Laplace谱半径的混合图．本文应用非负矩阵的Perron向量，给出上述结论的一个简单的证明．     

甘油对白酒中甲醇含量测定的影响

应用水浴控温(<90℃)蒸馏,可消除化学比色法测定白酒中甲醇含量时甘油的干扰,效果良好。     

Characterization of the network properties of poly(ethylene glycol)–acrylate hydrogels prepared by variations in the ethanol–water solvent composition during crosslinking copolymerization

The characteristics of poly(ethylene glycol) (PEG)–acrylate hydrogel networks were investigated as a function of the ethanol–water solvent composition during free‐radical crosslinking copolymerization. Macromonomer (88% ω‐methoxy‐PEG–acrylate and 10% ω‐phenoxy‐PEG–acrylate) and crosslinker (2% PEG–diacrylate) concentrations were kept constant. As the copolymerization progressed, the polymer solution in 100% ethanol became increasingly turbid, indicating the development of a heterogeneous network structure. In 100% water, however, the initially turbid polymer solution became increasingly transparent as the crosslinking copolymerization progressed. All the gels were optically clear upon equilibration in water. Kinetic studies, with attenuated total reflectance‐infrared, showed a long induction period, along with a lowered reaction rate, in 100% ethanol, and a decrease in conversion with an increase in ethanol content. These results agree with the UV analysis of the sol fractions, which indicated an increase in the amounts of unreacted PEG–acrylates with an increase in the ethanol content. The gels which were formed with a high ethanol concentration exhibited lower Young's modulus and higher swelling ability, suggesting that the network structure was significantly affected by the solvent composition during free‐radical crosslinking copolymerization. From the stress–strain and swelling experiments, the Flory–Huggins interaction parameter was evaluated. The creep characteristics of the hydrogels were modeled with two Kelvin elements. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2677–2684, 2002     

Spin fluctuation effects in substituted CeRu2Si2 and YbPd2Si2 alloys

Effects of chemical substitution in CeRu₂Si₂, a well-studied heavy fermion system and YbPd₂Si₂ have been investigated through magnetic susceptibility and x-ray diffraction in the systems CeRu _x Si₂, CeRu_2−x Os _x Si₂, CeRu₂Si_2−x Ge _x and YbPd₂Si_2−x Ge _x . Replacing silicon by germanium generates normal chemical pressure effect, namely, Ce and Yb atoms in CeRu₂Si₂ and YbPd₂Si₂ became more and less magnetic respectively. With increasing Ge concentration, CeRu₂Si_2−x Ge _x exhibits larger susceptibility at low temperature, goes to an antiferromagnetic state and finally becomes ferromagnetic. In YbPd₂Si_2−x Ge _x , increasing Ge concentration drives Yb atoms to more divalent state. Electronic effects are more pronounced in CeRu_2−x Os _x Si₂ though CeRu₂Si₂ and CeOs₂Si₂ have very nearly the same lattice parameters. It is conjectured that CeRu₂Si_2−x Ge _x may be the first Ce-based heavy fermion having a magnetic ground state. The authors felicitate Prof. D S Kothari on his eightieth birthday and dedicate this paper to him on this occasion.     

Palladium complexes of bis(acyclic diaminocarbene) ligands with chiral N-substituents and 8-membered chelate rings

Reaction of cis-dichloridobis(p-trifluoromethylphenylisocyanide)palladium(II) with N,N′-bis[(R)-1-phenylethyl]-1,3-diaminopropane afforded an enantiomerically pure, C₁-symmetric bis(acyclic diaminocarbene)PdCl₂ complex in 41% yield. The X-ray crystal structure of the complex revealed that three of the four carbene nitrogens are twisted out of conjugation with the carbene units, apparently as a result of steric interactions between one phenyl group and the propylene backbone of the chelate. A similar reaction with N,N′-bis[(R)-1-(1-naphthyl)ethyl]-1,3-diaminopropane did not lead to an isolable bis(carbene) complex, instead forming significant amounts of bis(ammonium) salt as a decomposition product. However, reaction of the same palladium isocyanide precursor with a mixture of all diastereomers of N,N′-bis[1-(1-naphthyl)ethyl]-1,3-diaminopropane provided an achiral, C_s-symmetric palladium bis(acyclic diaminocarbene) complex derived exclusively from the (R,S) diamine in 20% yield. An X-ray structure showed that the (R,S) stereochemistry allows the bulky naphthyl groups to adopt an orientation that avoids steric interactions with the backbone that likely lead to the instability of the homochiral analogue. The two palladium carbene complexes catalyzed the aza-Claisen rearrangement of an allylic imidate to an allylic amide in 24–34% yield, with an enantiomeric excess of 8% ee for the [(R)-1-phenylethyl]-substituted complex.     

伪单调广义混合变分不等式的改进k步预解算法

在算子的分裂技巧基础上介绍了求解伪单调广义混合变分不等式的改进五步预解算法，算法的收敛性只要求算子的g-伪单调和g—Lipschitz连续性，算子的伪单调比单调更弱．本文的新算法推广了文献中某些已有的结果．     

A convective weakly viscoelastic rotating flow with pressure Neumann condition

The objective of this work is to investigate through the numeric simulation, the effects of the weakly viscoelastic flow within a rotating rectangular duct subject to a buoyancy force due to the heating of one of the walls of the duct. A direct velocity–pressure algorithm in primitive variables with a Neumann condition for the pressure is employed. The spatial discretization is made with finite central differences on a staggered grid. The pressure field is directly updated without any iteration. Numerical simulations were done for several Weissemberg numbers (We) and Grashof numbers (Gr) . The numerical results show that for high Weissemberg numbers (We>7.4 × 10^?5) and for ducts with aspect ratio 2:1 and 8:1, the secondary flow is restabilized with a stretched double vortex configuration. It is also observed that when the Grashof number is increased (Gr>17 × 10^?4) , the buoyancy force neutralizes the effects of the Coriolis force for ducts with aspect ratio 8:1. Copyright © 2008 John Wiley & Sons, Ltd.