杯芳烃-卟啉化合物及其金属配合物的Langmuir-Blodgett膜研究

通过对杯芳烃-卟啉化合物及其锌、钯配合物LB膜的表面压-表面积等温线、紫外可见光谱和傅里叶变换红外光谱的检测,研究了它们在气/液界面和Langmuir-Blodgett膜中的性质,并用量子力学方法优化了杯芳烃-卟啉化合物的构型.结果表明,成膜时3种化合物分子中卟啉环都倾斜地排列在亚相表面,且卟啉环间存在π-π相互作用.连接杯芳烃和卟啉之间的碳氢链在膜性质中起着重要的作用,杯芳烃-卟啉化合物分子中这种碳氢链的有序性小于其锌、钯配合物分子中的这种碳氢链有序性.     

杯芳烃-卟啉化合物及其锌、钯配合物的制备与成膜性能研究

将广泛用作分子构架和分子载体的杯芳烃和卟啉结合,合成了具有更多功能和用途的杯芳烃-卟啉化合物及其锌、钯配合物,并成功地在气/液界面得到它们的单分子膜,并对其成膜性能作了初步的探讨.结果表明,无论是杯芳烃-卟啉化合物还是它的锌、钯配合物均能形成稳定的单分子膜.     

杯芳烃-金属卟啉仿酸酶模型化合物的合成及其电子光谱研究

本文首次报导杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中, 杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

杯芳烃-金属卟啉仿酶模型化合物的合成及其电子光谱研究(英文)

本文首次报道杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物的光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中,杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

新型主体化合物在生物活性分子分析中的应用新进展

主体化合物对客体分子具有高度的分子识别能力，对从分子水平上研究生物体内各种信息传递及酶与底物，抗体与抗原的结合等过程具有重要的理论与实际意义，它的应用为发展新型生物活性分子分析方法提供了广阔的前景，本文着重评述近年来冠醚，环糊精，杯芳烃及卟啉类超分子主体化合物在生物活性分子分析方面的研究进展。     

杯［4］芳烃衍生物一维超分子的晶体结构研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子 ,在主客体化学、超分子化学中占有重要地位 [1～ 3] .据文献报道 ,在杯 [4]芳烃衍生物中存在各种各样的作用力 [4 ] ,如分子内氢键 [3,4 ]、分子间氢键 [5]、阳离子 -π作用 [6 ]、CH3-π作用 [7]和 π-π相互作用 [8,9]等 .本文报道了杯 [4]芳烃衍生物 5 ,1 1 ,1 7,2 3 -四叔丁基 -2 6,2 8-二 [2 -(甲氧基羰基 )苄氧基 ]-2 5 ,2 7-二羟基杯 [4]芳烃 (简称 L,结构式见 Scheme1 )的晶体结构 .研究中发现 ,分子中存在分子内氢键和分子间π-π相互作用 ,后者使化合物 L形成了一维锯齿形的超分子…     

杯芳烃—卟啉键连化合物的合成及其紫外—可见光谱特性

本文合成了一种新型的杯芳烃-卟啉模型化合物5及其金属锌的络合物6,用紫外-可见光谱考察了引入对-叔丁基杯[4]芳烃后对卟啉各特征吸收带的影响。     

共价键链杯芳烃-四硫富瓦烯超分子体系研究进展

综述了共价键链的杯芳烃-四硫富瓦烯超分子主体化合物的设计合成及其在电化学调控的分子识别、离子调节的电子转移行为和分子组装等领域的研究进展.     

杯芳烃化金属卟啉及其苯乙烯环氧化的催化性能

将单功能化四苯基卟啉与对叔丁基杯［４］芳烃通过单链相连，随后插入金属离子，合成了杯芳烃化金属卟啉１－３．在两相条件下对苯乙烯环氧化催化反应研究表明，化合物２的锰络合物中杯芳烃的存在对氧化反应有明显影响．可以根据连接于卟啉分子中憎水杯芳烃造成催化活性中心微环境差异来解释观察到的现象．各杯芳烃化锰卟啉的催化性能按以下次序降低：１ｂ＞２ｂ＞３ｂ－７．     

巨型给-受体分子开关化合物的合成及性质研究

以构象可变的间苯二酚杯[4]芳烃孔穴化合物(Cavitand)为分子开关母体, 合成了一种新颖的给-受体(D-A)型分子开关化合物(化合物1), 该分子是目前已知分子量最大的D-A型间苯二酚杯[4]芳烃Cavitand (分子量为3064.9966). 其中, 以卟啉为给体, 富勒烯为受体. 在pH诱导下, 化合物1可发生构象变化, 即由原来的关闭状(vase)转为打开状(kite); 而在降低温度和引入Zn²⁺的条件下, 不能促使化合物1发生构象变化. pH诱导构象发生变化的原因, 是酸的加入会导致喹喔啉手臂上的N原子发生质子化, 从而使得形成的静电排斥作用促使手臂之间相互远离. 此外, 对化合物1的光物理性质研究表明, 存在卟啉向富勒烯的单线态能量转移, 其单线态能量转移速率常数为1.1×10⁷ s^-1, 单线态能量转移效率为9.63%.     

模板剂在分子筛合成过程中的作用机理

启用分子模拟途径,通过Lennard-Jones势对模板剂分子与分子筛骨架间非成键作用的能学分析,论证n=5、6的双季铵盐［(CH₃)₃N(CH₂)_nN(CH₃)₃］Br₂在ZSM-50分子筛骨架合成过程中所起的模板作用。     

Pharmacophore mapping and electronic feature analysis for a series of nitroaromatic compounds with antitubercular activity

A five point pharmacophore was generated using PHASE for a series of nitroaromatic compounds and their congeners as antitubercular agents. The generated pharmacophore yielded significant 3D‐QSAR model with r² of 0.890 for a training set of 92 molecules. The model also showed excellent predictive power with correlation coefficient Q² of 0.857 for a test set of 31 compounds. The pharmacophore indicated that presence of a nitro group, a piperazine moiety, one aromatic ring feature and two acceptor features are necessary for potent antitubercular activity. The pharmacophore was supported by electronic property analysis using density functional theory (DFT) at B3LYP/3–21*G level. Molecular electrostatic profile of the compounds was consistent with the generated pharmacophore model, particularly appearance of localized negative potential regions near both the oxygen atoms of nitro group extending laterally to the isoxazole ring system/amide bond in the most active compounds. Calculated data further revealed that all active compounds have smaller LUMO energies located over the nitro group, furan ring, and isoxazole ring/amide bond attached to it. Higher negative values of LUMO energies concentrated over the nitro group are indicative of the electron acceptor capacity of the compounds, suggesting that these compounds are prodrugs and must be activated by TB‐nitroreductase. The results obtained from this study should aid in efficient design and development of nitroaromatic compounds as antitubercular agents. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

1,2,5-Thiadiazole 1,1-dioxides and Their Radical Anions: Structure,Properties, Reactivity,and Potential Use in the Construction of Functional Molecular Materials

This work provides a summary of the preparation, structure, reactivity, physicochemical properties, and main uses of 1,2,5-thiadiazole 1,1-dioxides in chemistry and material sciences. An overview of all currently known structures containing the 1,2,5-thiadiazole 1,1-dioxide motif (including the anions radical species) is provided according to the Cambridge Structural Database search. The analysis of the bond lengths typical for neutral and anion radical species is performed, providing a useful tool for unambiguous assessment of the valence state of the dioxothiadiazole-based compounds based solely on the structural data. Theoretical methodologies used in the literature to describe the dioxothiadiazoles are also shortly discussed, together with the typical ‘fingerprint’ of the dioxothiadiazole ring reported by means of various spectroscopic techniques (NMR, IR, UV-Vis). The second part describes the synthetic strategies leading to 1,2,5-thiadiazole 1,1-dioxides followed by the discussion of their electrochemistry and reactivity including mainly the chemical methods for the successful reduction of dioxothiadiazoles to their anion radical forms and the ability to form coordination compounds. Finally, the magnetic properties of dioxothiadiazole radical anions and the metal complexes involving dioxothiadiazoles as ligands are discussed, including simple alkali metal salts and d-block coordination compounds. The last section is a prospect of other uses of dioxothiadiazole-containing molecules reported in the literature followed by the perspectives and possible future research directions involving these compounds.     

Discovery of Potential Antiviral Compounds against Hendra Virus by Targeting Its Receptor-Binding Protein (G) Using Computational Approaches

Hendra virus (HeV) belongs to the paramyxoviridae family of viruses which is associated with the respiratory distress, neurological illness, and potential fatality of the affected individuals. So far, no competitive approved therapeutic substance is available for HeV. For that reason, the current research work was conducted to propose some novel compounds, by adopting a Computer Aided Drug Discovery approach, which could be used to combat HeV. The G attachment Glycoprotein (Ggp) of HeV was selected to achieve the primary objective of this study, as this protein makes the entry of HeV possible in the host cells. Briefly, a library of 6000 antiviral compounds was screened for potential drug-like properties, followed by the molecular docking of short-listed compounds with the Protein Data Bank (PDB) structure of Ggp. Docked complexes of top two hits, having maximum binding affinities with the active sites of Ggp, were further considered for molecular dynamic simulations of 200 ns to elucidate the results of molecular docking analysis. MD simulations and Molecular Mechanics Energies combined with the Generalized Born and Surface Area (MMGBSA) or Poisson–Boltzmann and Surface Area (MMPBSA) revealed that both docked complexes are stable in nature. Furthermore, the same methodology was used between lead compounds and HeV Ggp in complex with its functional receptor in human, Ephrin-B2. Surprisingly, no major differences were found in the results, which demonstrates that our identified compounds can also perform their action even when the Ggp is attached to the Ephrin-B2 ligand. Therefore, in light of all of these results, we strongly suggest that compounds (S)-5-(benzylcarbamoyl)-1-(2-(4-methyl-2-phenylpiperazin-1-yl)-2-oxoethyl)-6-oxo-3,6-dihydropyridin-1-ium-3-ide and 5-(cyclohexylcarbamoyl)-1-(2-((2-(3-fluorophenyl)-2-methylpropyl)amino)-2-oxoethyl)-6-oxo-3,6-dihydropyridin-1-ium-3-ide could be considered as potential therapeutic agents against HeV; however, further in vitro and in vivo experiments are required to validate this study.     

轮烷研究－从超分子组装到分子器件

轮烷是一类由两端带有大的基团的线性分子和有机环化合物组成的互相锁连的分子化合物。主要综述了近年来这类超分子化合物的合成方法进展、在合成中的应用及其作为分子器件方面的研究进展。     

Metric properties of the functions of distances between molecular graphs

The metric properties of several functions of distances between the molecular (marked) graphs, depending on the size of the largest common subgraphs, are discussed. Recommendations are given on how to use these functions in investigations of samples of chemical compounds.     

含四硫富瓦烯大环化合物的合成与研究进展

简要介绍了含有四硫富瓦烯(TTF)单元的大环化合物的分类, 概括了各类含四硫富瓦烯大环化合物的合成方法, 主要包括含有1,3-二硫杂环戊烯-2-硫酮单元的大环化合物在亚磷酸三烷基酯参与下的偶合反应, 以及带有氰乙基硫等取代基的预先合成的官能化TTF与二卤代低聚醚的反应. 综述了含四硫富瓦烯大环化合物的电化学性能及其在分子识别方面应用研究的最新进展, 提出了含四硫富瓦烯大环化合物的发展趋势.     

Synthesis and testing of new end-functionalized oligomers for molecular electronics

Several new classes of oligomers have been synthesized with functionalities designed to aid in the understanding of molecular device behavior, specifically when molecules are interfaced between proximal electronic probes. The compounds synthesized are series of azobenzenes, bipyridines and oligo(phenylene vinylene)s that bear acetyl-protected thiols for ultimate attachment to metallic surfaces. Some initial electrochemical and solid-state test results are also reported.     

组合化学、分子库与新药研究

组合化学是进入90 年代以来寻找及优化新药先导化合物的主要研究方法, 其特点是改变了传统的逐一合成、逐一纯化、逐一筛选的模式, 而是以合成和筛选化学库的形式完成寻找及优化药物先导化合物, 极大地加快了药物先导化合物出现的速度。本文就目前有关组合化学研究的基本理论、基本方法、发展趋势、研究成果以及我国应当采取的措施进行了综述。     

杂氮硅三环类化合物结构的固体NMR实验研究

采用固体NMR实验方法研究了取代的三个杂氮硅三环羧酸化合物的结构,针对实验结果讨论了环上取代对化合物构型和配键的影响,以及硅和氮化学位移对环上取代的反映。