Strong Attraction of Caffeine to the Mercurous Dumbbell in the Salt [Hg2(Caf)2](ClO4)2(H2O)2

Colourless single crystals of the caffeine adduct of mercurous perchlorate dihydrate, [Hg₂(Caf)₂](ClO₄)₂(H₂O)₂, were grown from aqueous solutions of mercurous perchlorate and caffeine by isothermal evaporation at ambient temperature. The crystal structure (monoclinic, P2₁/n, Z = 4, a = 1628.0(2), b = 780.4(1), c = 2229.6(3) pm, β = 99.84(1)°, R₁(all data) = 0.0894) contains [trans‐Caf‐Hg‐Hg‐Caf]²⁺ cations with a Hg‐Hg distance of 250.88(6) pm, Hg‐N (bond) distances of 214.4(6) and 215.1(6) pm and Hg‐Hg‐N angles of 176.9(2) and 165.1(2)°, respectively. These cations are attached via weak Hg‐O contacts to dimers which are further arranged to leave large channels into which one crystal water molecule is included. The second water molecule and the two perchlorate anions are weakly attracted to one Hg atom.     

Morphology and thermal properties of a PC/PE blend with reactive compatibilization

Reactive compatibilization of immiscible polymers is becoming increasingly important and hence a representative study of a polycarbonate/high density polyethylene (PC/HDPE) system is the focus of this paper. A grafted copolymer PC‐graft‐ethylene‐co‐acrylic acid (PC‐graft‐EAA) was generated as a compatibilizer in situ during processing operation by ester and acid reaction between PC and ethylene‐acrylic acid (EAA) in the presence of the catalyst dibutyl tin oxide (DBTO). As the polyethylene (PE) matrix does not play any part during the synthesis of the copolymer and since PC and EAA are also immiscible, to simplify the system, the influence of this copolymer formation at the interface between PC and EAA on rheological properties, phase morphology, and crystallization behavior for EAA/PC binary blends was first studied. The equilibrium torque increased with the DBTO content increasing in EAA/PC blends on Haake torque rheometer, indicating the in situ formation of the graft copolymer. Scanning electron microscopy (SEM) studies of cryogenically fractured surfaces showed a significant change at the distribution and dispersion of the dispersed phase in the presence of DBTO, compared with the EAA/PC blend without the catalyst. Differential scanning calorimetry (DSC) studies suggested that the heat of fusion of the EAA phase in PC/EAA blends with or without DBTO reduced with the formation of the copolymer compared with pure EAA. Then morphological studies and crystallization behavior of the uncompatibilized and compatibilized blends of PC/PE were studied as functions of EAA phase concentration and DBTO content. Morphological observations in PC/PE blends also revealed that on increasing the EAA content or adding the catalyst DBTO, the number of microvoids was reduced and the interface was intensive as compared to the uncompatibilized PC/PE blends. Crystallization studies indicated that PE crystallized at its bulk crystallization temperature. The degree of crystallinity of PE phase in PC/PE/EAA blends was also reduced with the addition of EAA and DBTO compared to the uncompatibilized blends of PC/PE, indicating the decrease in the degree of crystallinity was more in the presence of PC‐graft‐EAA. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of dipole moment, linkers, and chromophores at side chains on long-range electron transfer through helical peptides

Octadecapeptides carrying a ferrocene moiety at the molecular terminal were self-assembled on gold, and long-range electron transfer from the ferrocene moiety to gold was investigated by electrochemical methods. Effects on electron transfer of dipole moment of helical peptides, linkers connecting the peptide to gold, and chromophores introduced into the side chains were discussed. Cyclic voltammetry of the monolayers in an aqueous solution revealed that long-range electron transfer over 40 A occurred along the peptide molecule. Chronoamperometry showed that the long-range electron transfer should be ascribed to a hopping mechanism with use of amide groups as hopping sites. Electron transfer through the long peptide was not significantly accelerated by the dipole moment. However, the linker remarkably affected electron transfer depending on whether it was a methylene chain or a phenylene group, suggesting that local electron transfer between gold and the peptides should be the slowest step to determine the overall rate. Pyrenyl groups introduced into the side chains in the middle of the peptide molecule did not noticeably change electron transfer, probably because pyrenyl groups were too distant to allow direct electron transfer between them. Electrostatic potential profiles across the peptide monolayers were also calculated to explain reasonably the several interesting features in the present peptide systems.     

Template-synthesized LiCoO2, LiMn2O4, and LiNi0.8 Co0.2 O2 nanotubes as the cathode materials of lithium ion batteries

The first point of this work is to synthesize LiCoO2, LiNi0.8 Co0.2 O2, and LiMn2O4 nanotubes with the template of porous anodic aluminum oxide by thermal decomposition of sol-gel precursors. The as-synthesized materials were open-ended nanotubes with uniform shape and size based on the analysis of scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. An "in situ reaction from nanoparticle to nanotube" mechanism was discussed for the formation process of the nanotubes. The second point of this paper is to investigate the electrochemical properties of the as-synthesized nanotubes for the cathode materials of lithium ion batteries. It was found that the nanotube electrodes exhibited better reversibility and higher discharge capacities than that of their nanocrystalline counterparts. The reason for the improved electrochemical performance of the nanotube electrodes was also interpreted.     

Determination of Total Reduced Thiol Levels in Plasma Using a Bromide Substituted Quinone

The exploitation of 2‐bromo‐1,4‐naphthoquinone (NQBr) as a selective redox label for the determination of reduced thiol functionalities (RSH) has been investigated. The system is selective for RSH functionality, giving distinct voltammetric signals for glutathione and cysteine but can also be adapted for broad spectrum thiol detection. Ion chromatographic protocols based on conductimetric detection enable total RSH analysis (protein and monomolecular moieties) within human plasma. Bromide released through the reaction can be easily quantified and integrated within normal IC measurements. The efficacy of the approach has been assessed and the response validated through comparison with the standard colorimetric technique.     

The Purification of Glucose Type Glycosyl Nitrate and the Synthesis of Spacer—armed N—Acetyllactosamines and Their Dimers

Our previous paper1,2reported the results of selective synthesis of mannose type glycosides and their dimers in our attempt to synthesize derivatives of N-acetyllacto- samine, which could have potential activity of anti-metastasis3. Further studies on the glycosylation of the accepters exploiting glycosyl nitrate instead of the acetate as donor showed interesting chemoselectivity between the two kinds of donor, namely, the glucose type and the mannose type. The reactivity difference of the t…     

PP/LDPE共混体系的辐射效应

研究了在多官能团单体—三烯丙基异氰脲酸酯存在下ＰＰ／ＬＤＰＥ共混体系接受γ－辐射的效果。用溶解度参数和ＴＥＭ技术评估了共混体系的相容性与多官能团单体在共混体系中的分布，并用ＳＥＭ、ＤＳＣ、动态力学等方法对共混体系相容性进行了表征。结果表明，ＰＰ／ＬＤＰＥ是不相容的共混体系，三烯丙基异氰脲酸酯主要分布在共混体系的相界面区域，辐照强化了共混体系的相间结合，增加了界面厚度，改善了共混体系的相容性。     

Building addressable libraries: the use of electrochemistry for spatially isolating a heck reaction on a chip

Pd(0) was generated at preselected sites on an electrochemically addressable chip and then utilized to effect a Heck reaction. The Pd(0) was confined to the preselected electrodes with the use of allylmethyl carbonate. Unlike most mediated electrochemical reactions, the electrolysis in this case was not used to convert a stoichiometric process into a catalytic one by recycling the metal. Instead, the unique environment of the chip was used to interfere with a catalytic process to make it stoichiometric. This was done to gain spatial control over the reaction. The development of a strategy for conducting Pd(0)-catalyzed reactions on the chips should greatly expand the synthetic chemistry available for building chip-based libraries.     

Synthesis of Novel Benzoylphenylurea Chitin Inhibitors From Chlorothalonil(Ⅱ)

IntroductionThe insecticidal activity of benzoylphenylurea( BPU ) analogues,discovered in the early1 970′s[1_ 4] ,is connected with the process ofmoult-ing and appears to affect the chitin synthesis of in-sects. The benzoylphenylurea class of insectgrowth regulators( IGRs) ,interfere with chitinsynthesis in target pests,causing death or abortivedevelopment and are considered to be the fourthgeneration of insecticides or novel materials for in-sect control.Benzoylphenylurea type insecticides…     

Two Novel Myrinsol Diterpenes from Euphorbia prolifera

Two novel diterpenes,Euphorprolitherin A(1) and Euphorprolitherin B(2), were isolated from the roots of Euphorbia prolifera. Their structures were elucidated on the basis of spectroscopic methods.