Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface.     

Preparation and electrochemistry of azobenzene self-assembled monolayers on gold--long range tunneling and end-group hydrogen bonding effect

A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect.     

线粒体热化学研究──Ⅳ．鱼类肝脏线粒体代谢的微量热学研究

线粒体热化学研究──Ⅳ．鱼类肝脏线粒体代谢的微量热学研究谭安民，刘义，谢昌礼，屈松生，顾贫，邓凤姣（武汉大学化学系武汉４３００７２）（武汉大学生命科学院武汉）关键词鱼肝脏，线粒体，微量热学，热化学线粒体在能量代谢的过程中，除一部分能量用于合成ＡＴＰ外...     

Binding of wogonin to human serum albumin: a common binding site of wogonin in subdomain IIA

The binding of wogonin to human serum albumin (HSA) has been studied by spectroscopic method including circular dichroism (CD), infrared spectra (IR) and fluorescence spectra. The fluorescence properties of HSA were examined in presence of wogonin and the fluorescence intensity of HSA was significantly decreased in the presence of wogonin. The binding parameters of wogonin were studied from the fluorescence decreasing of HSA by the fluoremetric titrations. The Stern-Volmer plots indicated that the binding of wogonin to HSA at 296, 303, 310 K is characterized by one binding site with the binding constant K(S-V) at 1.872 x 10(5), 1.561 x 10(5), 1.392 x 10(5), respectively, which are good agreement with the results from the Scatchard plots. The binding process was exothermic, enthalpy driven and spontaneous, as indicated by the thermodynamic analyses, and the major part of the binding energy is hydrophobic interaction, which were consistent with the result of molecule modelling study, and there are also a numbers of hydrogen bonds between wogonin and HSA. Furthermore, the displacement experiments indicate that wogonin can bind to the subdomain IIA, that is, the site I of HSA, which is also good agreement with the result of molecule modelling study.     

Quality evaluation of fingerprints of herbal medicine with chromatographic data

In this study, local least squares (LLS) and principal component analysis (PCA) were applied to deal with the disturbances in a data set of chromatographic fingerprints after necessary data transformations. It has been demonstrated that PCA with standard normal variate (SNV) transformation of data led to meaningful classification of 33 different Erigeron breviscapus herbal samples. The result was also corroborated by variance squares discriminant method. The quality of herbal objects was further evaluated, and the causes of this fact have been explained from a chemical point of view. At the same time, it implied an idea for qualitative evaluation of the herbal objects with a common class pattern of chromatographic fingerprints.     

A new approach to phosphoserine and phosphothreonine analysis in peptides and proteins: chemical modification,enrichment via solid-phase reversible binding,and analysis by mass spectrometry

beta-Elimination of the phosphate group on phosphoserine and phosphothreonine residues and addition of an alkyldithiol is a useful tool for analysis of the phosphorylation states of proteins and peptides. We have explored the influence of several conditions on the efficiency of this PO(4)(3-) elimination reaction upon addition of propanedithiol. In addition to the described influence of different bases, the solvent composition was also found to have a major effect on the yield of the reaction. In particular, an increase in the percentage of DMSO enhances the conversion rate, whereas a higher amount of protic polar solvents, such as water or isopropanol, induces the opposite effect. We have also developed a protocol for enrichment of the modified peptides, which is based on solid-phase covalent capture/release with a dithiopyridino-resin. The procedure for beta-elimination and isolation of phosphorylated peptides by solid-phase capture/release was developed with commercially available alpha-casein. Enriched peptide fragments were characterized by MALDI-TOF mass spectrometric analysis before and after alkylation with iodoacetamide, which allowed rapid confirmation of the purposely introduced thiol moiety. Sensitivity studies, carried out in order to determine the detection limit, demonstrated that samples could be detected even in the low picomolar range by mass spectrometry. The developed solid-phase enrichment procedure based on reversible covalent binding of the modified peptides is more effective and significantly simpler than methods based on the interaction between biotin and avidin, which require additional steps such as tagging the modified peptides and work-up of the samples prior to the affinity capture step.     

缓慢炭化部分氧化对制备煤质活性炭的影响

研究了炭化升温速度、炭化低温区引入空气部分氧化对活性炭制备过程中炭化阶段、炭化物结构、活性炭性能等的影响。结果表明，炭化时低温部分氧化可提高炭化物得率，使炭化物微晶的ｄ００２值升高和Ｌｃ值减小；而较慢的炭化升温速度有利于制备优质活性炭。缓慢炭化、部分氧化可以在一定程度上控制炭化路径，使炭化向生成取向性差、难石墨化、各向同性、呒定形炭多的炭化物的方向进行；并讨论了它们控制炭化的作用机理。以此为指导，     

铜在HOPG上电沉积过程的现场ECSTM研究

用自制的电化学扫描隧道显微镜（ＥＣＳＴＭ）现场研究Ｃｕ在ＨＯＰＧ上的电沉积过程．结果表明Ｃｕ在ＨＯＰＧ上的电沉积为三维成核的过程．当电位较低或Ｃｕ２＋离子浓度较低时，铜在本体金属生长主要沿着台阶方向．过电位较高时，铜的成核数目增加，沉积层的晶粒有所细化．同时，非现场ＥＣＳＴＭ比较研究表明，ＳＴＭ针尖对针尖局部区域的电沉积起屏蔽作用，针尖所在区域Ｃｕ的沉积速度比其它区域明显减小     

Perfectly dissolved boron nitride nanotubes due to polymer wrapping

We report for the first time that boron nitride nanotubes (BNNTs) may be dissolved in organic solvents by wrapping them with a polymer. Transmission electron microscopy and cathodoluminescence studies indicate the strong pi-pi interactions between BNNTs and the polymer. A band gap ranging from 5.2 to 5.5 eV was documented for the BNNTs independent of their geometrical characteristics by using ultraviolet-visible absorption experiments on composite films and thin BNNT films prepared from solutions.     

Transformation of arctiin to estrogenic and antiestrogenic substances by human intestinal bacteria

After anaerobic incubation of arctiin (1) from the seeds of Arctium lappa with a human fecal suspension, six metabolites were formed, and their structures were identified as (-)-arctigenin (2), (2R,3R)-2-(3',4'-dihydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (3), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (4), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3"-hydroxy-4"-methoxybenzyl)butyrolactone (5), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dihydroxybenzyl)butyrolactone (6), and (-)-enterolactone (7) by various spectroscopic means including two dimensional (2D)-NMR, mass spectrometry, and circular dichroism. A possible metabolic pathway was proposed on the basis of their structures and the time course of the transformation. Enterolactones obtained from the biotransformation of arctiin and secoisolariciresinol diglucoside (SDG, from the seeds of Linum usitatissium) by human intestinal bacteria were proved to be enantiomers, with the (-)-(2R,3R) and (+)-(2S,3S) configurations, respectively. Compound 6 showed the most potent proliferative effect on the growth of MCF-7 human breast cancer cells in culture among 1 and six metabolites, while it showed inhibitory activity on estradiol-mediated proliferation of MCF-7 cells at a concentration of 10 microM. These results indicate that the transformation of 1 by intestinal flora might be essential for the manifestation of the estrogenic and antiestrogenic activity of 1.