A Home-made Simple Set-up for Measurement of Electrochemical Surface Tension Spectrum on a Mercury Drop Electrode

A setup for recording surface tension curves at a mercury drop during potential scanning is designed based on photo-sensitive detection system. Surface tension spectrum at Hg drop can be recorded by voltammetric study. A Yb(III)-NO2- catalytic reduction system was used for characterization. The simple, sensitive technique can be expected to provide fresh information on molecular interactions at electrode surfaces.     

Structure and dynamics of metallomacrocycles: recognition of zinc xylyl-bicyclam by an HIV coreceptor

As platforms for the design of metal-based therapeutic and diagnostic agents, macrocycles are rigid enough to provide strong metal binding sites and orient functional groups stereoselectively, yet flexible enough to accommodate structural changes required for induced-fit recognition of biological targets. We consider the recognition of the Zn(II) complex of the bis-tetraazamacrocycle xylyl-bicyclam, a potent anti-HIV agent, by the coreceptor CXCR4, a G-protein-coupled receptor used by HIV for membrane fusion and cell entry. NMR studies show that the macrocycles of Zn(II)(2)-xylyl-bicyclam perchlorate exist in aqueous solution as two major configurations, trans-I (nitrogen chirality R,S,R,S), and trans-III (S,S,R,R). Acetate addition induced a major structural change. X-ray crystallography shows that the acetate complex contains the unusual cis-V cyclam configuration (R,R,R,R and folded) with bidentate coordination of acetate to Zn(II) plus second-coordination-sphere double H-bond formation between diagonal NH protons on the opposite cyclam face and acetate carboxylate oxygens. Detailed 1D and 2D NMR studies show that the major configuration of Zn(II)(2)-xylyl-bicyclam acetate in aqueous solution is cis-V/trans-I. Molecular modeling shows that an analogous cis-V site can be formed when Zn(II)(2)-xylyl-bicyclam binds to CXCR4, involving the carboxylate groups of Asp262 (Zn(II) coordination) and Glu288 (double H-bonding). The second cyclam can adopt the trans-I (or trans-III) configuration with Zn(II) binding to Asp171. These interactions are consistent with the known structure-activity relationships for bicyclam anti-HIV activity and receptor mutation. Consideration of the anti-HIV activity of xylyl-bicyclam complexes of other metal ions suggests that affinity for carboxylates, configurational flexibility, and kinetic factors may all play roles in receptor recognition. For example, Pd(II) cyclam complexes interact only weakly with axial ligands and are inflexible and inactive, whereas Co(III) cyclams bind carboxylates strongly, are configurationally flexible, and yet have low activity. Our findings should aid the design of new generations of active macrocycles including highly specific chemokine receptor antagonists.     

Dependence of Performance of Organic Light-emitting Devices on Sheet Resistance of Indium-tin-oxide Anodes

IntroductionIndium-tin-oxide(ITO) has been widely used asthe anode material in organic light-emitting devices(OLEDs) because of its high transmittance in the visi-ble region and low electrical resistivity. In the pastyears, many investigations focused on …     

石墨烯负载高活性Pd催化剂对乙醇的电催化氧化

以石墨粉为原料, 采用Hummers法液相氧化合成了氧化石墨(GO), 然后用化学一步还原制得石墨烯负载钯催化剂. X射线衍射(XRD)、透射电镜(TEM)表征表明, Pd在石墨烯载体上有较好的分散度, 粒径为3-5 nm. 电化学活性面积(EASA)、循环伏安(CV)、计时电流(CA)和计时电位(CP)等电化学测试表明, 与传统Pd/Vulcan XC-72相比, Pd/石墨烯催化剂对碱性介质中乙醇电催化氧化的催化活性有了很大的提高.     

Separation, identification, and interaction of heparin oligosaccharides with granulocyte-colony stimulating factor using capillary electrophoresis and mass spectrometry

A capillary electrophoresis (CE) method was developed for the separation of heparin oligosaccharides compatible to study the interactions between the oligosaccharides and granulocyte-colony stimulating factor (G-CSF). Unfractionated heparin was eliminitively degraded to heparin oligosaccharides by an endolytic heparinase. The degraded smaller oligosaccharides (M(r) < 1000) were baseline-separated by CE under a 50 mM phosphate buffer (pH 9.0) in 10 min. Standard heparin disaccharides and larger oligosaccharides (1000 < M(r) < 8000) were all separated under optimized separation conditions. Compared with standard heparin disaccharides, smaller oligosaccharides contained one nonsulfated, two monosulfated, and two disulfated disaccharides, but trisulfated disaccharides were not found. The smaller oligosaccharides were also identified and molecular mass was deduced by electrospray ionization-mass spectrometry (ESI-MS). Furthermore, interactions between G-CSF and the oligosaccharides were studied by using capillary zone electrophoresis (CZE) under the above separation conditions. It was found that larger oligosaccharides could interact with G-CSF while smaller oligosaccharides were not observed to bind to G-CSF under the experimental conditions. In conclusion, the purified heparinase could selectively degrade heparin into oligosaccharides and the interaction between G-CSF and heparin was correlated with the chain length of heparin.     

稀溶液中环型聚苯乙烯的激基缔合物荧光效应

采用乙酸乙酯为环型和线型聚苯乙烯的非良溶剂, 确定了Mark-Houwink方程分别为[η]_r=1.91×10~(-2)·M~(0.607)和[η]_l=4.06×10~(-2)·M~(0.572)。研究了环型和线型聚苯乙烯的激基缔合物的荧光效应。通过稀溶液中环型和线型高分子线团在柔顺性上存在着差异, 解释了二者之间在荧光效应方面的差异, 并根据实验结果,确定了(I_E/I_M)c→0～M关系式分别为(I_E/I_M)r,c→0=1.91+3.40×10~(-6)M和(I_E/I_M)l,c→0=2.15+3.05×10~(-6)M。     

Highly enantioselective 1,4-conjugate addition of diethylzinc to acyclic enones with chiral phosphite–pyridine ligands derived from H8-NOBIN

A series of new phosphite–pyridine ligands, based on the H₈-binaphthyl backbone, were synthesized and employed in the copper-catalyzed enantioselective 1,4-conjugate addition of diethylzinc to acyclic enones. Ligands derived from (S)-H₈-NOBIN provided better results than their parent ligands in the reaction. Ligand L1 provided excellent ees for trans-4-aryl-3-buten-2-ones (up to 97.8% ee) as substrates. Ligand L2 was very efficient for various para-chalcones, and up to 97.2% ee was achieved.     

Ammonia-treated activated carbon as support of Ru-Ba catalyst for ammonia synthesis

Ammonia-treated activated carbon has been studied as a support of Ru-Ba catalyst for ammonia synthesis. It is shown that the introduction of nitrogen leads to a decrease of ammonia synthesis activity for the catalysts with a low Ba/Ru molar ratio, while no significant changes are obtained for the catalysts with a high Ba/Ru molar ratio, confirming that electronegative impurities suppress the activity in ammonia synthesis and consume part of the promoters. This revised version was published online in June 2006 with corrections to the Cover Date.     

Baker''''s yeast mediated reduction of substituted acenaphthenequinones: Regio-and enantioselective preparation of mono-hydroxyacenaphthenones

Baker's yeast mediated reduction of acenaphthenequinone within 4-10 h afforded mono-hydroxyacenaphthenone mainly with low enantioselectivity, the substrate and mono-hydroxyacenaphthenone product almost converted to dihydroxyacenaphthene after 48 h. By control of the reaction time and in the presence of DMF as co-solvent, the reduction of 6-substituted acenaphthenequinones under vigorous agitation afforded the corresponding 2-hydroxyacenaphthenones in 24-84% yields with 10-93% ee.