扑热息痛分子印迹膜电化学传感器的制备

以邻苯二胺为功能单体,扑热息痛为模板,采用循环伏安法在玻碳电极表面电聚合形成邻苯二胺电聚合膜,经无水乙醇将模板分子洗脱,制得扑热息痛分子印迹膜电极.通过方波伏安法研究此印迹传感器的分析性能,建立了以K3[Fe(CN)6]为活性电子探针的间接分析法.实验表明,该传感器具有高选择性和灵敏度.在2.0×10-6 ～8.0×1...     

3-取代-4-氧-3H-咪唑并[5,1-d][1,2,3,5]四嗪-8-羧酸衍生物抗癌活性的构效关系

采用量子化学和分子力学方法研究3-取代-4-氧-3H-咪唑并[5,1-d] [1,2,3,5]四嗪-8-羧酸衍生物分子结构与抗癌活性的关系.结果表明,3-取代-4-氧-3H-咪唑并[5,1-d] [1,2,3,5]四嗪-8-羧酸衍生物抗癌活性与分子疏水性参数logP、8位取代基R1上的净电荷等因素有关,可通过向8位引入带正电荷取代基的办法来提高先导化合物的抗癌活性.     

N-(1-萘基)氨基乙酸的激发态分子内电荷转移和电子转移

氨基酸是蛋白质的基本结构单位 ,水溶液中基态氨基酸分子以内盐形式存在 [1] .由于质子化氨基的正诱导效应 ,羧基的离解常数显著提高 ,如氨基乙酸的羧基离解常数 ( 4.57× 1 0 -3mol/L,2 5℃ [1] )是乙酸 ( 1 .74× 1 0 -5 mol/L[2 ] )的 2 63倍 ;同时内盐结构亦使氨基酸和肽链具有分子内电偶极 ,后者已在肽链上电荷转移过程的调控中发挥重要作用 [3,4] .激发态氨基酸或肽的诱导效应和电偶极性质的研究尚未见报道 ,其主要原因可能是难有合适的激发方式和研究方法 .然而相关研究应予重视 ,因为研究结果将可能为生物酶活性的调节提供一种新的…     

饱和链状分子中C 1s电子电离能与基团拓扑电负性指数

由X-射线光电子谱测定的原子内层电子的电离能(也称结合能)能反映分子内部不同区域的原子特性,常用于估计分子内不同部位的化学活性、分子中的电子结构变化以及取代基效应[1]。还用于研究价电子性质[2-4]和化合物的气相酸碱性[5]。目前,对原子内层电子电离能的研究有实验测定和     

哌嗪取代卟啉的合成、表征及其抗癌活性

设计并合成了6个具有抗癌活性的哌嗪取代卟啉化合物,分别为5,10,15,20-四[4-(4'-乙基哌嗪基)苯基]卟啉(TEPPH2,8a),5,10,15,20-四[4-(4'-丁基哌嗪基)苯基]卟啉(TBPPH2,8b),5,10,15,20-四[4-(4'-庚基哌嗪基)苯基]卟啉(THPPH2,8c),5,10,15,20-四[4-(4'-苯基哌嗪基)苯基]卟啉(TPhPPH2,8d),5-[4-(4'-乙基哌嗪基)苯基]-10,15,20-三苯基卟啉(EPTPPH2,8e)和5-[4-(4'-丁基哌嗪基)苯基]-10,15,20-三苯基卟啉(BPTPPH2,8f).这些卟啉化合物都由取代苯甲醛与吡咯缩合而成,每一个卟啉分子中含有一个或四个具有抗癌活性的取代哌嗪结构,结构经元素分析,MS,1H NMR,IR和UV-vis等表征.初步的生物活性研究表明,这些化合物具有一定的抗癌活性,因而在医学上可能具有潜在应用前景.     

3,4,5-三羟基苯甲酸二聚体氢键结构性质

分子间相互作用在生物和材料等科学中发挥着关键作用,研究分子间相互作用的本质意义重大。氢键是分子间相互作用的一种主要形式,在确定分子构象和晶体结构以及生物分子尤其是核酸和蛋白质的结构功能中起着重要作用[1-3]。苯甲酸衍生物广泛存在于生物大分子内,与生物活性离子通过氢键作用等改变生物活性分子的活性功能,研究苯甲酸衍生物分子间氢键相互作用对于了解生物体内的化学现象具有重要意义。研究表明菱角的抗肿瘤作用明显,实验上已经从菱角中成功提取了活性单体化合物:3,4,5-三羟基苯甲酸二聚体[4],理论研究标题化合物的氢键结构与氢…     

5,6-二氢-(9H)-吡唑[3,4-c]-1,2,4-三唑[4,3-a]吡啶类抑制剂的HQSAR研究

应用分子全息定量构效关系(HQSAR)分析方法,以5,6-二氢-(9H)-吡唑[3,4-c]-1,2,4-三唑[4,3-a]吡啶类抑制剂为研究对象,建立了一组对磷酸二酯酶4有抑制活性的化合物HQSAR模型,分析化合物活性与分子结构之间的关系.探讨了分子全息长度、分子碎片大小以及碎片区分参数对模型质量的影响.最优模型的交叉验证相关系数q2=0.628,非交叉验证相关系数r2=0.930,标准偏差SE=0.277.该模型具有较好的预测能力,对该类化合物性质的预测及进一步合成工作有指导意义.     

L-α-二油酸磷酯酰胆碱和芦丁硬脂酸酯混合单分子膜的相容性

黄酮类化合物广泛存在于植物中,具有抗氧化、抗肿瘤和抗病毒等多种生物活性[1-3]。许多研究表明,具有相同苷元的黄酮类化合物比其糖苷具有更优秀的抗氧化活性,这是由于苷元亲脂性强能嵌入生物膜流水层的内核发挥作用,以及糖基的空间位阻减弱了黄酮化合物和生物分子的结合能力[4     

吡喃并[3,2-c]吡啶酮-嘧啶核苷杂化体与白蛋白相互作用的光谱和分子模拟研究

在模拟生理条件下,用荧光、紫外吸收光谱法及分子模拟研究了具有抗病毒活性的吡喃并[3,2-c]吡啶酮-嘧啶核苷杂化体-3 ′,5 ′-二-O-乙酰基-5-[2-氨基-7-甲基-5-氧代-5,6-二氢-4H-吡喃并[3,2-c]吡啶-3-氰基]-2 ′-脱氧尿苷(PPNH)与牛血清白蛋白( BSA)的相互作用.PPNH对牛...     

对叔丁基-杯[8]芳烃膜修饰电极的电化学性质研究

本文报道对叔丁基-杯[8]芳烃膜修饰电极的电化学性质,目的在于利用杯芳烃特殊的空腔结构对靶向物质具有定向选择功能。将该膜修饰电极用于分离用一般伏安方法不能分辩的物质如手性分子、同分异构体、电化学性质相近的物质等,从而拓宽了伏安分析领域。利用多种电化学手段研究了该膜修饰电极的电化学性质,求得了电极过程动力学参数。本文报道对叔丁基-杯[8]芳烃修饰电极膜的电化学性质。     

浅谈中国化学会《有机化合物命名原则2017》的教学要点

比较了中国化学会《有机化合物命名原则2017》与1980版命名原则的不同,指出了新版的主要变化之处。通过举例,说明母体氢化物、特性基团的概念、含义及其在命名有机化合物时的重要意义。归纳出命名有机物时确定母体氢化物和主特性基团所依据原则和方法,梳理出命名有机化合物的一般步骤,并通过实例来说明2017版命名原则的实施方法。     

Biologically active molecules with a "light switch"

Biologically active compounds which are light-responsive offer experimental possibilities which are otherwise very difficult to achieve. Since light can be manipulated very precisely, for example, with lasers and microscopes rapid jumps in concentration of the active form of molecules are possible with exact control of the area, time, and dosage. The development of such strategies started in the 1970s. This review summarizes new developments of the last five years and deals with "small molecules", proteins, and nucleic acids which can either be irreversibly activated with light (these compounds are referred to as "caged compounds") or reversibly switched between an active and an inactive state.     

某些新型冠醚-卟啉化合物的合成

本文以内消旋不对称单羟基-卟啉化合物1a～d合成了七种新型的冠醚-卟啉化合物3a～g和它们的中间体2a～g.这些化合物中的某些金属络合物对链烯的环氧化作用起催化作用, 它们的结构经元素分析,IR, UV和^1H NMR波谱证实.     

Study of the absorption and emission spectroscopy of "A-B" type photosensitive compounds including two-photon chromophore and benzophenone moiety

"A-B" type photosensitive compounds including two-photon chromophore and benzophenone moiety have been designed, synthesized and characterized. The UV-vis absorption and fluorescence emission of the compounds have been extensively studied in various solvents. The results show that the absorption of "A-B" type compounds displays obvious double absorption bands, one of which at short-wavelength is related to the benzophenone moiety, the other at long-wavelength is mainly contributed by chromophore. The emission of "A-B" type compounds at 500-700nm shows an "unexpected" blue-shift comparing with that of the sole chromophore. The photosensitive compounds with amino group display strong emission in apolar solvents and have a low fluorescence quantum yields in polar solvents. In contrast, the compounds without amino group exhibit strong fluorescence emission in polar solvents, and low fluorescence quantum yields in apolar solvents. The fluorescence quantum yields of "A-B" type compounds are higher than those of the sole chromophore. The discoveries suggest that charge redistribution induced by the introduction of benzophenone moiety plays a key role on the absorption and emission spectroscopy.     

"Volatilizable" supports for high-throughput organic synthesis

The concepts and use of "volatilizable" solid supports are presented. Such supports, which are completely removed by volatilization following decomposition, improve the efficiency of the solid-phase synthesis of both individual and mixtures of low-molecular weight acyclic and heterocyclic compounds as well as peptides, peptidomimetics, and protected peptide fragments. The "volatilizable" silica-based solid supports and linkers used to illustrate this concept were found to be completely removed by their decomposition and ultimate "volatilization" during the final cleavage step of synthetic process to yield solely the desired synthetic product(s) in the final reaction vessel.     

常用中药藁本中新化合物的结构, 合成及活性研究

藁本是常用中药。中国药典收录的藁本有两种植物: 中国藁本(Ligusticumsinense Oliv. )和辽藁本(L. jeholense Thell), 另外新疆藁本(Conioselinumvaginatum Thell)做为藁本代用品在新疆地区广泛应用。我们对三种藁本植物中的化学成分进行深入研究, 从中共分到30种单体化合物并进行结构鉴定, 其中4种新化合物。初步药理实验发现从新疆藁本中分到的几个化合物具明显降酶保肝活性; 从中国蒿本中分到的蒿本酚显示较强的免疫抑制活性, 为探讨构效关系,作者完成了这些具活性成分的合成研究, 并合成一些结构类似物, 详细的活性研究还在进行中。     

纳米级无机聚钼酸盐“二级有序聚集体”

介绍了纳米级水溶性无机聚钼酸盐分子的逐步生长合成, 对近年来水溶液中纳米级无机聚钼酸盐分子的奇特自聚集行为进行了简述, 从两亲分子“有序聚集体”概念的角度, 提出了水溶性纳米级无机聚钼酸盐“二级有序聚集体”的概念.     

"Green" pyrotechnics: a chemists' challenge

Fireworks are probably the application of chemistry which resonates best with the general public. However, fireworks and (civil and military) pyrotechnic applications cause environmental pollution and thus have given rise to the development of new, environmentally friendly pyrotechnic compounds and formulations. Nitrogen-rich energetic materials, such as the derivatives of tetrazoles and tetrazines, are about to revolutionize traditional pyrotechnic compositions. This Review summarizes the sources of pollution in current formulations and recent efforts toward "green" pyrotechnics.     

Tetrahedral boron chemistry for the preparation of highly efficient "cascatelle" devices

The replacement of the two fluorine atoms on the boron center of the well-known Bodipy fluorophore by functionalized acetylenic groups opens the way to a new family of highly luminescent, redox active, and stable fluorophores termed "E-Bodipy" species. The substitution is effective for ethynyl-lithium reagents incorporating tolyl, naphthyl, pyrenyl, fluorenyl, and terpyridinyl units. The protocol also tolerates the presence of various functional groups in the dipyrromethene meso position such as pyrene, phenylethynylpyrene, 4'-terpyridine, and iodophenyl. The last of these is particularly useful for a further coupling reaction enabling introduction of a flexible arm bearing a succinimidyl unit reactive toward primary amines. X-ray structure determinations of two E-Bodipy compounds confirm the introduction of the ethynyl units and show the boron atoms to have a distorted tetrahedral environment, with B-C(ethynyl) approximately 1.59 A and both boron atoms lying essentially in the mean planes of the dipyrromethene units. All the new compounds show intense electronic absorption bands (epsilon 60,000-70,000 M-1 cm-1), high quantum yields (>80%), and slow rates of nonradiative decay. Absorption by the aromatic substituents results in a "cascatelle" process leading to emission exclusively through the boradiazaindacene entity and thus large virtual Stokes' shift (>10,000 cm-1). The new compounds are also redox active, with the formation of both Bodipy+* and Bodipy-* occurring more readily than for F-Bodipy species. The molecules in their excited states are strong reducing agents.