9-[(4,5-二硫十六烷基)-1,3-二硫环戊烯-2-亚基]-10(9H)-蒽酮的合成及光电性质研究

一种新的具有D-π-A体系的有机分子9-[(4,5-二硫十六烷基)-1,3-二硫环戊烯-2-亚基]-10(9H)-蒽酮(d)被合成.通过1HNMR,13CNMR,IR,TOFMS进行了表征,确定了其结构.利用电化学装置对该体系进行了光电流响应测试,产生的光电流相对稳定、可逆,说明该体系具有明显的光电转换性质.运用Gaussian03量子化学程序包,采用B3LYP密度泛函(DFT)的方法,在6-31G(d)水平上优化了其基态几何结构,得到的几何参数与实验结果基本吻合.研究结果表明,体系中存在着分子内的电荷转移.     

异喹啉酮类衍生物的合成研究

以间甲氧基苯乙胺和氯甲酸乙酯为原料,通过亲核取代、关环、四氢铝锂还原得到1,2,3,4-四氢异喹啉衍生物.其中关键步骤环化反应实现了使用多聚磷酸(PPA)简便有效地进行了关环,合成了一系列异喹啉酮类衍生物.     

类球红杆菌羰基还原酶不对称催化还原性能与底物结构的关系

 将类球红杆菌 (Rhodobacter sphaeroides) 全细胞及其分离得到的羰基还原酶用于不对称催化还原多种潜手性酮类化合物, 通过比较产物的收率、ee 值、酶活力以及酶学动力学常数 Km, 探讨了类球红杆菌的催化还原性质与底物结构的关系. 结果表明, 对于类球红杆菌全细胞不对称催化还原苯乙酮衍生物, 产物 ee 值的变化遵循 Prelg 规则, 产物收率与底物苯环及侧链上取代基团的性质有关; 对于脂肪酮催化还原, 产物收率随底物链长的增加和分子量的增大而降低, 随支链数目的增加而升高, 产物 ee 值的变化也遵循 Prelg 规则. 利用羰基还原酶不对称催化还原潜手性酮类化合物发现, 对于芳香酮类化合物, 酶对 α 位为强电负性基团的底物专一性较强; 对于脂肪酮类化合物, 酶对五碳脂肪酮的专一性较高. 利用酶直接催化还原反应产物的 ee 值均为 99% 左右, 表明酶较全细胞有更高的立体选择性.     

Toxicity （-lgEC50） Measurement of the Fluorobenzene Derivants against Vibrio Qinghaiensis （Q67） and Their 2D,3D-QSAR Study

Toxicities (-lgEC50) of 16 fluorobenzene derivants against vibrio qinghaiensis (Q67) were measured systematically,and their quantum chemistry parameters were calculated at the B3LYP/6-311G** level. Based on the experimental toxicity data and quantum chemistry parameters,2D-QSAR model was proposed,which was validated by variance inflation factors (VIF),t-value and cross-validation method. At the mean time,comparative molecular force field (CoMFA) based on molecular simulation was used to investigate the toxicity of fluorobenzene derivants. Furthermore,the intoxicating mechanism of fluorobenzene derivants was discussed. To our interest,2D-QSAR and CoMFA models exhibit good prediction ability,with which the toxicity of similar compounds can be predicted. Finally,toxicities (-lgEC50) of 12 fluorobenzene derivants against vibrio qinghaiensis (Q67) were predicted with these models.     

Synthesis,Characterization and Theoretical Studies on a Thiocarbamide Derivative Containing Schiff Base Group

A thiocarbamide derivative containing Schiff base groups,1,5-bis[4-(dimethylamino)benzylidene]thiocarbonohydrazide,has been synthesized and characterized by elemental analysis,IR,1H NMR,UV and X-ray single-crystal diffraction.Density function theory(DFT) calculations at the B3LYP/6-31G* and PBE0/6-31G* levels for optimized geometries and electronic transition spectra have been performed.Comparative studies show that both B3LYP/6-31G* and PBE0/6-31G* methods can well reproduce the molecular structure,and the latter is more reliable than the former to simulate electronic spectra.NPA calculational results at the B3LYP/6-31G* level indicate the title compound to be a potential multidentate ligand to the metallic ions.Based on the vibrational analysis,thermodynamic properties at different temperatures have been obtained.     

Antitumor Comparison of Three α-N-Heterocyclic Thiosemicarbazone Derivatives' Crystal Structures of Bis(2-acetylpyridine)thiocarbonohydrazone and Bis(imidazole-2-carboxaldehyde)thiocarbonohydrazone

A series of ligands,HL1(2-acetylpyridine thiosemicarbazone),H2L2(bis(2-acetyl-pyridine) thiocarbonohydrazone) and H2L3(bis(imidazole-2-carboxaldehyde) thiocarbonohydrazone) was synthesized.H2L2 and H2L3 were characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction studies.Hydrogen bonds link different components to stabilize the crystal structure in the two ligands.To comprehend the structure-activity relationship well,the three ligands are all tested against human K562 leucocythemia cell line with IC50 analysis.Different substituent groups on the ligands show different levels of antitumor activity.By comparison with the other species studied,H2L2 with thiocarbonohydrazone along with 2-acetylpyridine is the most active compound with IC50 = 2.48 μM.     

四氢二嵌萘衍生物在不同环境中的电子结构及光谱特征的理论研究

采用密度泛函理论的B3LYP泛函和单激发组态相关方法(CIS)在6-31+G*基组水平下分别优化了四氢二嵌萘衍生物(THP)基态和第一单重激发态的结构,并在此基础上利用含时密度泛函理论计算了THP在不同环境中的电子结构和光谱性质.溶剂效应采用连续极化介质模型(PCM)计算.结构分析发现在酸性环境中,基态时THP二甲氨基上的N原子容易质子化.计算结果表明,尽管THP的第一单重激发态是一个电荷转移态,但是它本身并不发射双荧光.在酸性溶剂中,THP的双峰发射来源于两种物质:跃迁能为2.71eV的发射峰由激发的THP发射,而3.69eV的发射峰则来源于质子化的THP.根据计算结果,我们建议了THP在酸性溶剂中的激发与驰豫途径.理论预测的吸收和发射光谱与实验结果一致.     

THE DYADIC DERIVATIVE AND CESARO MEAN OF BANACH-VALUED MARTINGALES

In this article, the Banach space X and the martingales with values in it are considered. It is shown that the maximal operators of the one-dimensional dyadic derivative of the dyadic integral and Cesaro means are bounded from the dyadic Hardy- Lorentz space pH^-ra（X） to Lra（X） when X is isomorphic to a p-uniformly smooth space （1 〈p ≤ 2）. And it is also bounded from Hra（X） to Lra（X） （0 〈 r 〈 ∞,0 〈 a≤oc） when X has Radon-Nikodym property. In addition, some weak-type inequalities are given.     

Approximation of Derivative for a Singularly Perturbed Second-Order ODE of Robin Type with Discontinuous Convection Coefficient and Source Term

In this paper, a singularly perturbed Robin type boundary value problem for second-order ordinary differential equation with discontinuous convection coefficient and source term is considered. A robust-layer-resolving numerical method is proposed. An e-uniform global error estimate for the numerical solution and also to the numerical derivative are established. Numerical results are presented, which are in agreement with the theoretical predictions.AMS subject classifications: 65L10, CR G1.7     

色酮吡唑啉酮类衍生物的合成及抗白血病细胞活性

以色酮-吡唑啉酮作为C1合成子, 在5 mol% 的DBU催化下,与α,β-不饱和酮发生Michael加成反应, 获得了10个色酮吡唑啉酮类衍生物3a~3j,产率76%~90%, dr值为4/1~9/1, 其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征,通过单晶进一步进行了确定化合物3b的相对构型。该类化合物包含有连续两个立体中心,包括一个季碳中心,可以为生物活性筛选提供物质基础。采用MTT法研究了3a~3f对人白血病细胞(K562)的体外抗增殖活性。结果表明：化合物3a, 3c, 3d和3i对K562增殖具有一定的抑制活性。