缺电子联吡啶环蕃的研究

基于4,4'-联吡啶基础上构筑的缺电子环蕃是超分子化学的一个重要组成部分,由于其在光物理、光化学和电化学方面的可控性变化,而使其成为分子水平机器研究的热点之一。该类化合物的合成方法较多,本文总结了近20年来该领域的研究进展。     

盒状主体缺电子联吡啶大环的性质、应用和制备

详细描述了盒状主体缺π电子联吡啶大环CPQT的结构和性质,总结比较了它的各种制备方法,并对其与富π电子氢醌醚链衍生物自组装合成索烃、轮烷和准轮烷等方面的应用进行了综述.     

新型缺电子联吡啶大环化合物的模板合成

通过富电子对苯二酚醚链衍生物和缺电子联吡啶间的模板效应, 成功地合成了一种新型联吡啶大环化合物, 利用元素分析、核磁共振和质谱等手段对新化合物进行了表征。     

新型氟代缺联吡啶环蕃的合成

以1,3-二溴甲基-5-氟苯为原料,在低温条件下利用模板效应制得"联吡啶环蕃化合物"(1);1经过连续萃取及离子交换合成了新型氟代缺电子联吡啶环蕃单体——环蕃F-CPQT,收率7.6%,其结构经1H NMR和13C NMR表征。     

“黑洞型”缺电子联吡啶环蕃的合成

利用2,3,5,6-四氟-1,4-苯二甲酸为原料, 经过酯化、还原及溴代, 合成1,4-二溴甲基-2,3,5,6-四氟苯. 以其为原料在低温下利用模板效应合成高度缺电子的“黑洞型”缺电子联吡啶环蕃化合物, 经过连续液液萃取及离子交换得到“黑洞型”缺电子联吡啶环蕃单体. 产品经¹H NMR, ¹³C NMR, MS表征. 利用变温核磁共振技术研究“黑洞型”缺电子联吡啶环蕃与经典的双环(百草枯-对苯撑)型缺电子联吡啶环蕃在溶液中的变化.     

新型含硫代乙酸酯缺电子环蕃的合成

以3,5-二甲基苯酚为原料,经4步反应合成了1,1’-【{5-[3-(乙酰硫基)丙氧基]-1,3-亚苯基}双(亚甲基)】双{[(4,4’-联吡啶)-1-鎓]}二六氟磷酸盐(4);4与1,4-二溴甲基苯和萘模板在低温反应制得含硫代乙酸酯的缺电子环蕃(5);5经连续萃取及离子交换除去萘模板合成了新型含硫代乙酸缺电子环蕃——5,13,20,27-四氮杂七环[25,2,2,22,5,17,11,213,16,217,20,222,25]四十-9-(1-丙基硫代乙酸酯)氧-1(28),2,4,7,9,12,14,16,18,21,23,26,29,31,33,35,37,39-十八烯四六氟磷酸盐(6),其结构经1H NMR和13C NMR表征。     

可利用酸碱调控的分子器件—富电子二苯醚客体和缺电子联吡啶大环组成的准轮

利用π－π堆积作用,富电子４,４‘－二氨基二苯醚（Ａ）和４,４‘－二羟基二苯醚（Ｂ）分别与缺电子联吡啶大环（ＣＰＱＴ）自组装成准轮烷Ａ－ＣＰＱＴ和Ｂ－ＣＰＱＴ;利用酸碱调控准轮烷Ａ－ＣＰＱＴ与“开”与“关”,此过程可利用体系的核磁共振氢谱的化学永化进行跟踪。     

氨基富π电子醚链的合成与超分子性能研究

合成、表征了含氨基的富π电子醚链四甘醇-二(2-氨基-4-苄氧基)苯基醚(5),并与不同的缺π电子联吡啶环蕃CPQT、FCPQT、5FCPQT作用形成了新型准轮烷5.CPQT、5.FCPQT、5.5FCPQT。利用核磁共振技术研究了它们在温度和酸碱调控下的分子开关功能。     

可利用酸碱调控的分子器件富——电子二苯醚客体和缺电子联吡啶大环组成的准轮烷的“开”与“关”

利用π-π堆积作用,富电子4,4′-二氨基二苯醚(A)和4,4′-二羟基二苯醚(B)分别与缺电子联吡啶大环(CPQT)自组装成准轮烷A-CPQT和B-CPQT;利用酸碱调控准轮烷A-CPQT的“开”与“关”,此过程可利用体系的核磁共振氢谱的化学位移变化进行跟踪.     

含丁三醇端基富电子醚链与阳离子环蕃超分子准轮烷的表征和性能研究

以4-(2-(4-(苄氧基)苯氧基)乙氧基)-1,2,3-丁三醇(C)为富电子供体的醚链,与缺电子联吡啶大环化合物环双(百草枯-亚苯基)四阳离子环蕃(CPQT)和四氟取代环蕃(4FCPQT)自组装形成超分子准轮烷C(CPQT)和C(4FCPQT),并利用1HNMR的化学位移变化来研究两种不同准轮烷在温度变化时它们的相互作用。实验结果表明,由于富电子供体的一端含有3个羟基,易和缺电子联吡啶大环形成氢键,因此醚链的丁三醇端不能进入大环;缺电子联吡啶大环的一个苯环上的氢被氟取代后,由于电场力的作用,使富电子供体进入大环的概率相对降低,并使富电子醚链供体穿入大环的位置发生偏心作用。     

Three New Phenyl Ether Derivatives from Aspergillus carneus HQ889708

Three new phenyl ether derivatives, 3‐hydroxy‐5‐(3‐hydroxy‐5‐methylphenoxy)benzoic acid ( 1 ), 3,4‐dihydroxy‐5‐(3‐hydroxy‐5‐methylphenoxy)benzoic acid ( 2 ), 3‐[3‐hydroxy‐5‐(hydroxymethyl)phenoxy]‐5‐methylphenol ( 3 ), and three known compounds 4 – 6 were obtained from the fermentation broth of Aspergillus carneus HQ889708, which was isolated from sea water from South China Sea. The structures of compounds 1 – 3 were established on the basis of spectroscopic methods including ESI‐MS and NMR. Compounds 4 – 6 were reported before as synthesized products, herein, they are reported from nature for the first time.     

TATB基PBX结合能的分子动力学模拟

用分子动力学（MD）方法, 模拟计算了四种氟聚合物(聚偏二氟乙烯（PVDF）、聚三氟氯乙烯（PCTFE）、氟橡胶（F₂₃₁₁)、氟树脂(F₂₃₁₄))与TATB(1,3,5- 三氨基- 2,4,6- 三硝基苯)晶体的相互作用. 结果发现, 四种氟聚物与TATB的结合能大小排序为PVDF>F₂₃₁₁>F₂₃₁₄>PCTFE, 各氟聚物在TATB不同晶面上的结合能大小排序为(001)>(010)>(100), 结合能主要由分子间氢键决定.     

甲烷分子价电子的能谱和动量谱

利用电子动量谱仪对甲烷分子价电子测量了电子动量谱和束缚能谱。实验中的入射电子能量为１０００ｅＶ加电子束缚。实验结果与Ｈａｒｔｒｅｅ－Ｆｏｃｋ理论及组态相互作用理论进行比较表明，两者相当一致。     

Effects of Side Arm Length and Structure of Para-Substituted Phenyl Derivatives on Their Binding to the Host Cyclobis(paraquat-p-phenylene)

The binding constants with the host cyclobis(paraquat-p-phenylene), 1(4+), have been determined in CH(3)CN by UV-vis spectrophotometry for a series of p-phenylene guests, symmetrically substituted with side arms of varying length and functionality. Semiempirical molecular orbital theory was employed to provide a detailed structural and energetic interpretation of the experimental binding data. In particular, the length of the side arms and the type and position of the heteroatoms on the side arms were systematically varied in order to understand the effects of external interactions on the association constants of the guests with host 1(4+). A large chelate effect involving the ethyleneoxy side arm oxygen atoms and a cooperative effect between the guest aromatic core and the side arms are significant factors which determine the binding with this host. Sequential ethyleneoxy linkages along the side arms markedly increase the binding constant with respect to a compound in which the same number of oxygens along the side arms are separated by longer aliphatic linkages. In addition, a multiplicative rather than additive effect on the binding constant is observed which demonstrates that the oxygen atoms exhibit a strong chelate effect. It was also discovered that while the side arms of these guests contribute most of the driving force for complexation, an aromatic core is necessary for the guest to reside in the cavity of the host. The binding of these guests then is dependent upon cooperation between the arms and the aromatic core. Furthermore, elongation of the central aromatic core with aliphatic side arms containing no heteroatoms leaves the association constant relatively unchanged and replacement of the oxygen atoms with sulfur markedly decreases the observed binding. These effects have been used to rationalize several observations regarding this system in the literature and may serve to improve the design of new supramolecular systems and to better understand the host/guest interaction process.     

Quantitative Studies on Structure－Activity Relationships （QSAR） of Cytokinin－Active Phenyl Urea Derivatives（PUD）

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Inhibition Mechanism of Hydroxyproline-like Small Inhibitors to Disorder HIF-VHL Interaction by Molecular Dynamic Simulations and Binding Free Energy Calculations

Protein-protein interactions are vital for a wide range of biological processes. The interactions between the hypoxia-inducible factor and von Hippel Lindau (VHL) are attractive drug targets for ischemic heart disease. In order to disrupt this interaction, the strategy to target VHL binding site using a hydroxyproline-like (pro-like) small molecule has been reported. In this study, we focused on the inhibition mechanism between the pro-like inhibitors and the VHL protein, which were investigated via molecular dynamics simulations and binding free energy calculations. It was found that pro-like inhibitors showed a strong binding affinity toward VHL. Binding free energy calculations and free energy decompositions suggested that the modification of various regions of pro-like inhibitors may provide useful information for future drug design.     

7-羟基香豆素类及其烯基醚衍生物的合成

以间苯二酚、乙酰乙酸乙酯和1,3-丙酮二羧酸为原料,经Pechmann反应和Knoevenagel反应合成了4个7-羟基香豆素类化合物——7-羟基-4-甲基香豆素(1),7-羟基-4-乙酸甲酯香豆素-(2),7-羟基-3-甲酸乙酯香豆素(5)和7-羟基-3-乙酰基香豆素(6)。以四丁基溴化铵为相转移催化剂,1,2,5和6分别经O-异戊烯基化或O-法尼烯基化反应合成了6个7-羟基香豆素类的烯基醚衍生物,其中5个为新化合物,其结构经1H NMR,IR和MS表征。     

A Molecular Modeling for the Complexation of Cyclobis(paraquat-p-phenylene) with Substituted Benzenes and Biphenyls

The molecular recognition of cyclobis(paraquat-p-phenylene), 14+, has drawn great attention recently, due to its important applications in the design and synthesis of electrochemically and chemically switchable rotaxanes, photoactive rotaxanes, and other molecular devices1. Usually, this type of molecular recognition was investigated with the methods including X-ray, NMR, UV, and IR. However, since these methods usually have difficulties in providing a detailed understanding of the energeti…     

Ar原子电离能谱和Ar3p电子动量谱研究

电子动量谱学（ElectronMomentumSPectroscoP则是近．二十年来发展起来的一种新兴的探测原子、分子和固体结构的手段，它不仅能够获得轨道结合能的信息，而且能够能壳分辨地得到轨道电子的动量分布（即动量表象中的波函数模方）；同时它还是研究电子关联的最有效的实验手段．其     

激酶ABL与肉豆蔻酰位点小分子作用机理的分子动力学模拟及自由能计算

采用分子动力学方法研究激酶ABL 与ATP 位点小分子imatinib、P16 及变构位点小分子STJ、MS7、MS9、3YY、MYR等的结合, 并用GBSA (generalized Born surface area)方法将结合自由能分解到各残基. 自由能计算结果表明, 小分子STJ、MS7、MS9 有利于imatinib 与ABL 结合; 小分子STJ、MS7、MS9 与激酶ABL的结合自由能接近, 绝对值均大于ABL 与3YY、MYR 的结合自由能. 能量分解表明, ABL 残基ILE502、VAL506、LEU510与STJ和MYR的相互作用是αI 螺旋处于弯曲状态的重要原因. 模拟过程中ABL肉豆蔻酰口袋残基均方根偏差(RMSD)变化值表明, STJ等小分子抑制剂与ABL结合后降低了肉豆蔻酰口袋残基的柔性.