钌卟啉/MCM-41催化剂的制备、表征及性质

应用３氨丙基三乙氧基硅烷对ＭＣＭ４１ 介孔分子筛进行了改性． 改性产物（ 记为ＭＣＭ４１（ｍ））具有较强的装载钌卟啉［Ｒｕ（ Ⅱ）Ｌ（ＣＯ）（ＥｔＯＨ）］ （Ｌ＝ ｍｅｓｏｔｅｔｒａｋｉｓ（４ｃｌｏｒｏｐｈｅｎｙｌ）ｐｏｒｐｈｙｒｉｎ） 的能力． 制备了裹载０－１％ ～８－３ ％ 钌卟啉的产物（ 记为Ｒｕ／ ＭＣＭ４１（ｍ）） ． 应用Ｘ 射线衍射、差热热失重分析和紫外可见光谱等方法对裹载产物进行了表征． 结果表明,钌卟啉在ＭＣＭ４１（ｍ） 孔道中是以单分子态存在,而不是以晶态存在． 装载后钌卟啉仍保持其基本结构,并且热稳定性增加． 轴向配体取代反应使钌卟啉固定在ＭＣＭ４１（ｍ） 孔道表面上． 低钌含量的Ｒｕ／ＭＣＭ４１（ｍ） 具有高催化活性,这是有效的位置分离和扩散孔道通畅的结果． 以０－１ ％ Ｒｕ／ＭＣＭ４１（ｍ） 和自由的钌卟啉为催化剂进行的６ 种烯烃的氧化反应结果表明,前者的催化转换数是后者的２０ ～４０倍．Ｒｕ／ ＭＣＭ４１（ｍ） 催化剂具有特殊的形状选择性,较长的寿命, 并且容易过滤回收．     

强磁场对四苯基卟啉及其Co(Ⅱ)/Zn(Ⅱ)配合物的影响

为研究强磁场对卟啉类化合物的影响,以四苯基卟啉(TPP)为研究对象,比较分析了无外加磁场和强磁场条件下TPP的结晶,及Co~(2+)、Zn~(2+)与TPP的配位反应。采用X射线粉末衍射测试不同磁场强度下获得的TPP晶体,紫外分光光度计快速测定了不同磁场强度下配合物产率,并分析了配位反应的动力学。TPP的结晶度随磁场强度的增强而提高,晶体尺寸随磁场强度的增加而增大;随磁场的增强,四苯基钴卟啉(CoTPP)和四苯基锌卟啉(ZnTPP)的产率下降,但两者的反应动力学不受磁场影响,其反应速率随磁场强度提高而下降。由研究结果可知,强磁场有利于四苯基卟啉的结晶取向,四苯基卟啉在溶液中垂直于磁场取向是配位反应速率降低的主要原因,随磁场强度的增加,四苯基卟啉的取向程度提高。     

Water-soluble Porphyrin as Temperature Sensor Based on Fluorescent Enhancement

A novel water-soluble porphyrin[5,10,15,20-tetra（3-ethoxy-4-hydroxy-5-sulfonate）phenyl porphyrin, H2TEHPPS] was designed and synthesized, which could be used as a potential fluorescence sensor to detect temperature changes. The studies were performed in solution phase and the concentration of H2TEHPPS was 2.0×10^-5 mol/L. The optical properties of H2TEHPPS were investigated based on the UV and fluorescence spectra. The results show that the fluorescence intensity of H2TEHPPS is directly proportional to temperature in the range of 293-353 K So H,TEHPPS can be used as a molecular temoerature sensor in biomedical and other fields.     

Supramolecular Luminescent Lanthanide Dimers for Fluoride Sequestering and Sensing

Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C₂‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM .     

Self-Assembly and X-Ray Crystal Structures of Novel Sn(IV)Porphyrin Phenolates

A series of complexes of the type [Sn(TTP)L₂] have been prepared by the condensation of [Sn(TTP)OH₂] (TTP = meso-tetratolylporphyrin) with a range of substituted phenols. The resulting complexes were characterised using ¹H NMR and single crystal X-ray diffraction techniques. In each case, the condensation of the phenols with the Sn(IV)porphyrin in CDCl₃ solution is slow (h) but essentially quantitative. The slow kinetics of the formation of the diaxial phenolate complexes allows for the identification, by ¹H NMR spectroscopy, of three independent complexes within this process, namely an outer-sphere (H-bonded) complex as well as two independent phenolate complexes. The rate of condensation is in the order phenol 4-methoxyphenol > 4-nitrophenol and suggests a steric rather than pKa dependency.     

共价键合铁卟啉有序多层膜电极的组装及其对H2O2的电催化还原

以玻碳电极为基础电极,先用静电自组装方法将带负电荷的四磺酸基苯基铁卟啉和带正电荷的含重氮盐基团的重氮树脂在电极表面进行层-层组装,然后在紫外光的照射下,使铁卟啉的磺酸基与重氮树脂的重氮基引发交联反应,使层与层之间的离子键变成共价键,从而使铁卟啉在电极表面形成稳定、有序、分子水平的层-层构筑.用UV-Vis和IR光谱表征了组装过程,用CV方法研究了该电极的电化学性能.结果表明,该电极不但具有非常优异的稳定性,而且对H₂O₂的电还原反应也表现出很好的催化活性.     

钌-菲罗啉卟啉的合成及与DNA的相互作用

以5-(4-羟基苯基)-10,15,20-三苯基卟啉和钌-菲罗啉衍生物为原料, 合成了3个两亲性钌-菲罗啉卟啉化合物, 并通过核磁共振波谱、红外光谱、紫外-可见光谱、质谱和元素分析等对化合物的结构进行了确证. 采用紫外-可见光谱、 荧光发射光谱和圆二色光谱考察了目标化合物与ct-DNA的相互作用, 研究了它们与DNA的结合模式. 实验结果表明, Por1, Por2和Por3与DNA的结合常数分别为1.46×10⁵, 2.75×10⁵和5.69×10⁵ L/mol. 此外, 在不同DNA浓度下, Por1和Por2与DNA的结合模式为插入模式和外部结合模式共存, Por3与DNA的结合模式主要为自堆积的外部键合和静电作用. 结果表明, 钌-菲罗啉卟啉化合物是新型的光动力治疗试剂.     

NEW LIPOPHILIC BISPOCKET-PORPHYRINS FOR CHEMOTHERAPY OF CANCER (PART I); PREPARATION AND PROPERTIES OF 5,10,15,20-TETRAKIS(3′,5′-DI-t-BUTYLPHENYL) PORPHYRIN METAL COMPLEXES1

Abstract

A series of highly lipophilic bis-pocket porphyrins, 5,10,15,20-tetrakis(3′, 5′-di-t-butylphenyl)porphyrin with five metals (copper(II), nickel(II), zinc(II), cobalt(II), and iron(III)), have been prepared and characterized on the basis of electronic, infrared and ¹H NMR spectra. Although electronic spectra of these porphyrins are substantially the same as their prototype tetraphenylporphyrin complexes of the respective metals, their solubility in common organic solvents such as chloroform, benzene, and hexane is dramatically enhanced.     

新型1,4-二氢吡啶基尾式卟啉的合成及其抗菌活性研究

以乙酰乙酸乙酯、4-羟基苯甲醛、碳酸氢铵和二溴烷烃为原料,经两步反应合成溴烷氧基1,4-二氢吡啶;再将其与5-对羟基苯基-10,15,20-三苯基卟啉缩合,得到了12种新型的卟啉-二氢吡啶及其金属锌配合物,结构通过NMR,IR和HRMS进行详细表征.研究中测试了这些复杂的卟啉-二氢吡啶化合物对金黄色葡萄球菌(Staphylococcus aureus,ATCC 25923)和大肠杆菌(Escherichia coli,ATCC 25922)的抑菌活性,实验结果显示这12种化合物都有很好的抑菌活性,其中对金黄色葡萄球菌抑菌效果较好,且卟啉-二氢吡啶二元化合物的抑菌效果优于两种单体.     

PMADQUAT/PSt-PAA聚离子复合物聚集体增强卟啉和富勒烯类衍生物单重态氧产率

采用原子转移自由基聚合(ATRP)法合成了嵌段共聚物聚苯乙烯-聚丙烯酸叔丁酯(PSt-PtBuA), 在酸性条件下水解得到聚苯乙烯-聚丙烯酸(PSt-PAA), 利用核磁共振氢谱(¹HNMR)、凝胶渗透色谱(GPC)等对产物进行了表征. PSt-PAA在Tris-HCl缓冲溶液中(pH=7.0)形成临界聚集浓度(CAC)为0.015 g/L的聚集体. PSt-PAA与聚2-甲基丙烯酰氧基乙基三甲基氯化铵(PMADQUAT)可通过静电相互作用形成聚离子复合物(polyion complex, PIC), 当 m_(PMADQUAT)/m_(PSt-PAA)=3时, 形成的聚离子复合物的CAC为0.005 g/L. 动态光散射(DLS)和透射电镜(TEM)结果表明, 形成聚离子复合物后, 聚集体粒径变小. 聚合物形成聚集体可包载二乙二醇单甲醚修饰的C₇₀(MDG-C₇₀)、原卟啉(PPIX)、四苯基锌卟啉(ZnTPP)和四苯基卟啉(TPP)等光敏剂, 并增强光敏剂在缓冲溶液中的溶解度. 光照条件下, MDG-C₇₀、PPIX、ZnTPP和TPP在聚离子复合物聚集体m_(PMADQUAT)/m_(PSt-PAA)=3的溶液中的单重态氧量子产率分别是在PSt-PAA聚集体溶液中的1.64、2.63、2.60和2.20倍. 而在缓冲溶液中,由于光敏剂的聚集作用,未能检测到单重态氧的产生。研究结果表明,聚离子复合物聚集体能够包载光敏剂,是提高单重态氧产率的一个有效途径.