Ferromagnetism in dinuclear copper(II)-phenolate complexes with exogenous O-donor bridges: a comparative study

The copper(II) complex Cu2L(OAc)(H2O)3.5, 1 x 3.5H2O was obtained and its reactivity in a basic medium investigated. Complex 1 x 3.5H2O shows different reaction patterns in air and in an inert atmosphere. Accordingly, interaction of 1 x 3.5H2O with Me4NOH x 5H2O in methanol-acetonitrile in air yields the hydroxide complex Cu2L(OH)(H2O)1.125, 2 x 1.125H2O while Cu2L(OMe)(MeOH)0.5(H2O), 3 x 0.5MeOH x H2O is isolated under an argon atmosphere. The products 1-3 were fully characterised and single crystals of {[Cu2L(OAc)] x MeCN x 3.5H2O}2, 1 x MeCN x 3.5H2O, {[Cu2L(OH)] x MeCN x 1.125H2O}2, 2 x MeCN x 1.125H2O and [Cu2L(OMe)] x 0.5MeOH x H2O, 3 x 0.5MeOH x H2O solved. The single X-ray study shows that 1-3 are dinuclear complexes with an endogenous phenol oxygen and an exogenous O-bridge. Magnetic characterisation of the three dinuclear complexes was performed, showing an apparent anomalous intramolecular ferromagnetic coupling between the metal atoms in all cases.     

Efficient Routes to Racemic and Enantiomerically Pure (S)-BINOL Diesters

A systematic study for esterification procedures to the synthesis of BINOL diesters is described. Reaction conditions with trifluoracetic acid anhydride (TFAA) and 85% H₃PO₄ were selected as the best procedure to prepare enantiomerically pure (S)-1,1′-bi-2-naphthol (BINOL) diesters VIII to XI with almost quantitative yields and very short reaction times.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications^® for the following free supplemental resources: Full experimental and spectral details.]     

Total Synthesis of a Mycolic Acid from Mycobacterium tuberculosis

In Mycobacterium tuberculosis, mycolic acids and their glycerol, glucose, and trehalose esters (“cord factor”) form the main part of the mycomembrane. Despite their first isolation almost a century ago, full stereochemical evaluation is lacking, as is a scalable synthesis required for accurate immunological, including vaccination, studies. Herein, we report an efficient, convergent, gram‐scale synthesis of four stereo‐isomers of a mycolic acid and its glucose ester. Binding to the antigen presenting protein CD1b and T cell activation studies are used to confirm the antigenicity of the synthetic material. The absolute stereochemistry of the syn‐methoxy methyl moiety in natural material is evaluated by comparing its optical rotation with that of synthetic material.     

Fracture of thick laminated composites

The fracture of thick laminated graphite/epoxy composites has been the subject of an extensive research program. The program was divided into three major areas of investigation which included laminate thickness, laminate stacking sequence, and part-through surface flaws. The results from this program are reviewed with emphasis placed on their applicability to the design of thick laminated composite structures. Paper was presented at 1985 SEM Spring Conference on Experimental Mechanics held in Las Vegas on June 9–14, 1985.     

Nonlinear and nonsmooth dynamics in a DC-DC Buck converter: Two experimental set-ups

It is well known that many nonlinear phenomena such as bifurcations and chaotic behavior occur in DC–DC converters mainly due to the switching action among all the different topologies of the circuit. Such behavior has been described with detail numerically, and also mathematical reasoning has been provided. In this paper we focuss on the experimental side of a DC–DC Buck converter controlled with two different strategies: classical Pulse Width Modulation (PWM) with a ramp and a more recently described Zero Average Dynamics (ZAD). We show some nonsmooth events and we explain with detail the experimental set-ups. In one of them, we use a FPGA card to obtain on-line results. In the other we use Virtual Instrumentation to generate an experimental two-dimensional bifurcation diagram, which will be compared to the numerical data. After the data acquisition of the system state variables some elaborated post-processing must be made. This is done through LabView. Although the main application of these results is centered in avoiding non-periodic or high-amplitude periodic behavior, they can also be applied to reducing the generated electro-magnetic interference and to the information transmission.Partially funded by SICONOS.     

C64H6的结构和光谱的理论研究

本文用INDO系列方法研究了C64H6的结构与光谱, 表明C64H6有C2v和Cs两种稳定构型, 其中C2v构型能量较低, 讨论其加成及环加成产物对称性的规律并与13C NMR谱的实验结果相结合。计算了两种构型的电子光谱, 对电子跃迁进行了理论指认,并讨论了C64H6谱带红移的原因, 理论计算结果与实验事实基本吻合。     

氢原子在Ru(0001)和Ru(1010)面上吸附扩散势能面的结构

本文构造了H-Ru相互作用的五参数Morse势,用经典的对势方法研究了氢原子在Ru(0001)和Ru(1010)面上的吸附和扩散,得到了氢原子在两个表面上的吸附位、吸附几何、结合能及本征振动等数据与实验结果符合得很好;同时研究了两个体系的吸附扩散势能面结构。     

二氧化硅悬浮体和水解聚丙烯酰胺体系的流变性

研究了二氧化硅悬浮体的流变性。在固体含量较少的情况下, 体系呈Newton型;固体含量达到一定程度以后, 产生三维结构, 为假塑性体系。三维结构的固体含量与pH值有关。实验证实, 在等电点(i,e, p)附近三维结构最为疏松。还研究了水解聚丙烯酰胺(HPAM)对悬浮体流变性能的影响。HPAM破坏了二氧化硅粒子聚集体结构, 呈絮凝体结构, 并出现触变性。当高聚物在固体表面覆盖一半时, 具有最大触变性和动剪切力。HPAM的水解度达到一定程度, 由于对固体粒子由“强”吸附转变为“弱”吸附, 固体粒子“屏蔽”了高分子间的相互作用, 出现了负触变性现象。在流动时粒子会脱附, 静止以后又产生吸附, 这种吸附与脱附是产生负触变性的主要原因。HPAM水解过度或用量过多, 均会减弱负触变性现象。     

Strain state of poly(N‐isopropylacrylamide) in polystyrene‐b‐poly(N‐isopropylacrylamide) block copolymers and binary blends with polystyrene

Three diblock copolymers of polystyrene‐b‐poly(N‐isopropylacrylamide) (PS‐b‐PNIPAM) were prepared by reversible addition‐fragmentation chain transfer technique (RAFT) with compositions f_PS = 0.84, f_PS = 0.29, and f_PS = 0.33. Block copolymers rich in PNIPAM were blended with polystyrene and its morphological effects were studied. The morphology of thin films was induced by acetone vapor and determined in the dried state by means of TEM. Copolymers with f_PS = 0.84 and f_PS = 0.29 form hexagonally packed cylinder (HPC) morphologies while that with f_PS = 0.33 corresponds to a lamellar structure. In almost all cases where PNIPAM constitutes the continuous phase, a contraction of the PNIPAM blocks with respect to their average unperturbed dimension was observed, contrary to what one expects from the physics of self‐assembly of block copolymers. In contrast, for HPC morphology where PNIPAM is confined in a PS matrix, both blocks are highly extended. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1368–1376     

Ultrasound promoted Barbier reactions and Csp3–Csp2 Stille coupling for the synthesis of diarylmethanes and substituted benzophenones

Here we present the preparation of a variety of diarylmethanes obtained via ultrasound Stille coupling under palladium catalysis between some substituted aryl compounds and benzyltributyltin compounds generated through sonicated Barbier reaction in a very short time reaction and excellent yield. The study reported below compares different methods to optimize the synthesis of usually unstable benzyltin derivatives and is another contribution to the investigation of Csp³–Csp² coupling process involving benzyl–aryl reagents. Substituted carboxylated benzophenones were easily prepared in a very good yield by oxidation of some diarylmethanes.