Ligand-receptor docking with the Mining Minima optimizer

The optimizer developed for the Mining Minima algorithm, which uses ideas from Genetic Algorithms, the Global Underestimator Method, and Poling, has been adapted for use in ligand-receptor docking. The present study describes the resulting methodology and evaluates its accuracy and speed for 27 test systems. The performance of the new docking algorithm appears to be competitive with that of previously published methods. The energy model, an empirical force field with a distance-dependent dielectric treatment of solvation, is adequate for a number of test cases, although incorrect low-energy conformations begin to compete with the correct conformation for larger sampling volumes and for highly solvent-exposed binding sites that impose little steric constraint on the ligand.     

稳定同位素方法研究正构烷烃与四氢萘二元体系的反应

以正构烷烃作为模型化合物的热反应、临氢反应、临氢催化反应中,添加供氢剂抑制正构烷烃所裂化;气相氢和供氢剂的供氢参与饱和烯烃,两者是性质不同的氢源,前者加速裂化,后者抑制裂化。供氢剂供氢行为依赖于反应体系自由基的多少和温度以及反应过程,反应体系较多的自由基和较高的反应温度有利于供氢行为。稳定同位素方法研究模型化合物的裂化反应表明,供氢剂的作用是通过脱氢湮灭自由基来抑制裂化反应,同时发现H12－四氢萘和D12－四氢萘的供氢（氘）率上存在着动力学同位素效应,在临氢及临氢催化体系中尤其是临氢催化体系中,动力学同位素效应变得不再明显。     

利用分子烙印技术分离中草药活性组分

用非共价法,在极性溶剂中,以丙烯酰胺作功能单体,以强极性化合物槲皮素为模板 ,制备了分子烙印聚合物(MIP). 液相色谱实验表明, MIP 对槲皮素具有特异的亲合性.将此 MIP直接分离银杏叶提取物水解液, 得到主要含模板槲皮素及与槲皮素结构相似化合物山奈 酚两种黄酮的组分.研究证实了MIP技术用于直接分离、提取中草药中具有特定药效化合物的 可行性.     

锆氢化反应热力学函数的计算

用B3LYP/SDD密度泛函方法计算了ZrH的微观性质,气态ZrH(D,T)的能量(E),熵(S)以及 Zr与氢同位素气体反应的热力学函数.在ZrH(s)、ZrD(s)和ZrT(s)的E和S的计算中,近似以分 子总能量中的振动能Ev代替固态能量,以电子和振动熵SEv代替固态熵.在这种近似下,计算了 不同温度下Zr与H2、D2、T2反应的ΔH、ΔG、ΔS及氢化反应平衡压力,导出了与温度 的依赖关系.计算结果表明,ZrH(s)的生成热为161.34 kJ穖ol-1,与实验值(173.5 kJ穖ol -1)接近,表明这种近似处理方法是合理的,可以用于研究贮氢材料氢化反应的热力学.     

Analysis of nonvolatile species in a complex matrix by headspace gas chromatography

This study developed a phase reaction conversion (PRC) headspace gas chromatographic (HS-GC) technique for the measurements of nonvolatile species in liquid or solid samples. The technique is demonstrated by the measurements of carbonate in aqueous carbonate solutions and in kraft pulp mill liquor samples. A very small amount of sulfuric acid (volume of 0.5 ml, concentration of 2 mol/l) is used to acidify a sample of less than 300 microl in volume and convert the dissolved carbonate into carbon dioxide (gas) in a sample vial (reactor) that is analyzed by thermal conductivity detection through a headspace sampler. The carbonate concentrations measured by PRC-HS-GC in seven kraft liquor samples agree very well with those measured using a coulometric and a titrametric method. Simultaneous analysis of multiple species was also conducted to demonstrate the versatility of the method. The present method is very simple, rapid, reliable, accurate, and fully automated. It can be applied to analyze other nonvolatile species in various industrial and environmental samples.     

High-throughput semi-automated 96-well liquid/liquid extraction and liquid chromatography/mass spectrometric analysis of everolimus (RAD 001) and cyclosporin a (CsA) in whole blood

A semi-automated high-throughput liquid/liquid extraction (LLE) assay was developed for RAD001 and cyclosporin A (CsA) in human blood. After addition of internal standard and ammonium hydroxide, samples were extracted twice with methyl tert-butyl ether (MTBE). The organic extract was evaporated to dryness and reconstituted in mobile phase. Where possible, sample transfer and LLE steps were automated using a Tomtec Quadra 96 workstation. Samples were analyzed using ESI-LC/MS/MS employing the transitions of ([M + NH(4)](+) --> [M + H](+)) for CsA and ([M + NH(4)](+) --> [M + H-(CH(3)OH + H(2)O)](+)) for RAD001, under isocratic chromatographic conditions (75:25, (v/v), acetonitrile/20 mM ammonium acetate) with a run time of 3.6 min. A lower limit of quantitation (LLOQ) of 0.368 ng/mL and 5.23 ng/mL was achieved for RAD001 and CsA, respectively, using a sample volume of 0.3 mL for the analysis. The method was validated over a 3-day period and the resulting calibration curves had a correlation coefficient >0.99 over the concentration range 0.368 to 409 ng/mL and 5.24 to 1748 ng/mL for RAD001 and CsA, respectively. The inter-day coefficient of variation (CV) was less than 15% at the LLOQ for both compounds. The method was applied to the analysis of clinical samples. Under normal working conditions four 96-well plates could be extracted and LC/MS analysis completed in less than 28 h. A marked improvement in sample throughput efficiency was realized with this LLE method when compared to existing solid phase extraction (SPE) methods which deal with both RAD001 and CsA.     

没食子单宁类化合物的合成研究

研究了三苄基没食子酰氯与两种葡萄糖衍生物（1,2-O-,1,2：5,6-二-O-异丙叉-α-D-呋喃葡萄糖）的酯化特性。合成了4种典型没食子单宁类化合物,基于薄层色谱与核磁谱图解析,这些化合物的结构得以确定。     

有机官能团对硅基MSU-X织构性能的影响

采用有机硅氧烷(RTES)与硅氧烷(TEOS)共水解缩聚合成了有机官能化的MSU-1中孔材料(R=甲基,苯基,乙烯基,脲丙基)。当前驱体中RTES与TO64EOS的摩尔比为0.1:0.9时合成R10-MSU-1分子筛,通过现化分析技术证明BA所选有机官能团均能进入分子筛骨架,而且在相同摩尔数的各数有机硅氧烷存在下,由于其反应速率、空间位阻的不同使其对骨架的缩聚程度、孔道和表面性质有不同的影响。利用SAXS实验技术对所合成R10-MSU-1材料结构表面以及由于有机官能团的存在对无机骨架产生的影响进行了研究。SAXS较强的散射强度分布对Porod定理形成负偏离,表明孔和基体之间有明显的界而层存在,并求得界面层的平均厚度。实验证明有机基团的均匀分布于孔道表面而形成有机界面层。SAXS测试还显示上述分子筛呈质量分形特征,其形成过程可能为非平衡非线性的聚集机制。     

Voltammetric Studies of the Interaction of Tris (1,10-phenanthroline) Cobalt (III) with Bovine Serum Albumin

Recently, the studies on the interaction of DNA with small molecules have been attracting much interest1-6. These researches not only gave the important information about thermodynamics and kinetics, but also can prompt the combination between the electrode substances and biomacromolecule with super catalysis and sensor character. It is of great significance in understanding energy conversion and metabolism in live body, biomolecular structure, various physical and chemical characters for e…     

Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones

The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein.