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。     

抗癌金属络合物与脱氧核糖核酸作用的谱学研究比较

利用紫外可见光谱、荧光光谱、表面增强拉曼光谱研究了抗癌金属络合物与ＤＮＡ的相互作用,首次提出将荧光光谱与表面增强拉曼光谱结合作了化合物是否具有抗癌活性筛选法的可能性。     

新型尾式组氨酸卟啉的合成及性质

设计并合成了新型尾式氨基酸卟啉5-(Trt-组氨酸酰胺基苯基)-10,15,20-三苯基卟啉(Trt-His-NH2-TPP,1)及其金属卟啉配合物(Zn,Co,Fe,Mn,分别标记为2～5).通过元素分析、核磁共振氨谱、质谱、紫外-可见光谱和红外光谱等对化合物进行了表征,研究了它们的荧光性质,并通过理论模拟研究了其最...     

胞嘧啶核苷键联卟啉的合成及其与牛血清白蛋白的相互作用

基于卟啉化合物的光敏性和对肿瘤细胞有特殊的亲和力以及核苷类化合物的抗肿瘤及抗癌活性, 设计合成了胞嘧啶核苷卟啉化合物6和8, 其结构由¹H NMR, IR, UV-Vis, MS 和元素分析表征. 同时, 利用荧光光谱考察了上述核苷卟啉与牛血清白蛋白(BSA)的相互作用, 结果表明它们对BSA荧光有较强的静态猝灭作用.     

锌卟啉的合成及与咪唑类客体反应的光谱性质

将一对手性丙氨酸,通过烷氧基侧链与卟啉环相连,合成了一对手性卟啉5-对(L-丙氨酰氧乙氧基)苯基-10,15,20-三苯基卟啉和5-对(D-丙氨酰氧乙氧基)苯基-10,15,20-三苯基卟啉及其各自对应的锌卟啉.通过元素分析、紫外-可见光谱、1 H核磁共振和红外光谱等方法对合成的自由卟啉及锌卟啉配合物进行了结构确定.此外,采用荧光光谱滴定实验研究了金属锌卟啉与咪唑类客体进行配位反应的光谱性质,结果表明,咪唑类客体与手性锌卟啉相互作用时均具有荧光猝灭效应,金属卟啉的手性结构对该性质未造成影响.     

金属卟啉分子印迹聚合物的合成与性能研究

以5-(4-羟基苯基)-10,15,20-三苯基卟啉锌为印迹分子,4-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了具有金属卟啉识别能力的分子印迹聚合物.紫外可见滴定光谱研究表明,功能单体与印迹分子在聚合前形成1:1的配合物.通过吸附试验、荧光光谱及斯卡查特分析法,考察了分子印迹聚合物对锌卟啉化合物的识别性能.结果表明,印迹聚合物对结构类似的卟啉化合物具有良好的识别能力,对印迹分子荧光性能的影响远大于其对应的非印迹聚合物.在浓度较低时,印迹聚合物对印迹分子的结合常数和最大结合量分别为:1.61×106L/mol和3.22×10-5mol/g.     

两种水溶性钯卟啉磷光探针的在位合成及其发光光谱特性研究

本文探索了合成水溶性钯卟啉(Pd—TAPP和Pd—TSPP)的最佳实验条件,通过紫外可见光谱、荧光光谱和室温磷光光谱研究了合成情况,并考察了其在不同有序介质中的室温磷光特性。     

低聚壳聚糖负载金属卟啉配合物的制备及生物活性研究

将低聚壳聚糖(COS)分别与不同卟啉金属(MTPPS4,M=Cu,Co,Zn)配合物结合,制备了水溶性低聚壳聚糖负载金属卟啉配合物(COS-MTPPS4),并采用红外光谱和紫外-可见光谱对其结构进行了表征。采用SRB细胞染色法,研究了壳聚糖负载金属卟啉(COS-MTPPS4)对人体肝癌细胞Bel-7402的抗肿瘤细胞活性。结果表明,金属离子配位到卟啉环中,使系列化合物对Bel-7402有较强的抑制生长活性,IC50值均小于100μg/mL,在10～20μg/mL范围内。水溶性低聚壳聚糖金属卟啉配合物作为抗肿瘤药物有很好应用前景。     

四[对-(羧基甲氧基)苯基]卟啉金属配合物(M=Zn,Cu,Ni)的π-π配合及其二丁基锡(Ⅳ)酯衍生物的抗癌活性

自 1 92 4年 Policard发现血卟啉在癌组织内聚集以来 ,人们对利用卟啉的荧光性质检测及治疗癌症进行了广泛的研究 [1,2 ] .卟啉及金属卟啉的自聚合及与配体的 π- π配合反应对理解卟啉的生物功能具有重要意义[3～ 6] .有机锡 ( )类化合物自被发现有抗癌活性以来一直受到极大的关注 [7～ 9] .Mirisola等 [9]研究了四 (对 -羧基苯基 )卟啉有机锡 ( )酯化合物的体内抗癌活性 .我们合成了四 [对 - (羧基甲氧基 )苯基 ]卟啉的 Zn2 + ,Cu2 + ,Ni2 + 配合物及其二丁基锡 ( )酯衍生物 ,测定了它们的体外抗肿瘤活性 ,并研究了四 [对 - (羧基甲…     

Absorption and fluorescence properties of aryl substituted porphyrins in different media

Absorption and fluorescence properties of aryl substituted porphyrins, 5,10,15,20-tetra-4-oxy(aceticacid)phenylporphyrin (TAPP), 5,10,15,20-tetra-(4-phenoxyphenyl) porphyrin (TPPP), 5,10,15,20-tetra-(3-bromo-4-hydroxyphenyl) porphyrin (TBHPP), and 5,10,15,20-tetra-p-chloromethylphenyl porphyrin (CMPP) were investigated. The UV/vis absorption, fluorescence and excited spectra as the fluorescence quantum yields and fluorescence lifetimes for the compounds were measured in organic solvents (chloroform (CHCl₃), tetrahydrofuran (THF)) and immobilized media (PVC film, sol–gel matrix). The fluorescence quantum yields of TAPP and TPPP were higher than the others. The fluorescence lifetimes of all studied porphyrin derivates were found to be fifty percent lower and their fluorescence intensities were increased fifty percent more in both of immobilized mediums, as compared to organic solvents.     

Investigation on DNA Binding and Photo-Cleavage Properties of Water-Soluble Porphyrin and Metalloporphyrins

A water-soluble porphyrin, tetrakis[4-(trimethylammonium)phenyl]porphyrin (TAPP), and its metal complexes with Zn(II), (ZnTAPP), have been synthesized and characterized by elemental analyses and u.v.-vis. spectra. The binding of the two complexes with calf thymus DNA has been investigated by absorption spectra, luminescence titrations, and viscosity measurements. The changes of the u.v.-vis. absorption spectra during the titration of these porphyrins with calf thymus DNA revealed a large bathochromic shift (upto 8–12 nm) and a hypochromicity of the porphyrins soret bands. The intensity of the fluorescence spectra of these porphyrins was enhanced. The cytotoxicity of the series of porphyrins TAPP and MTAPP [M = Zn(II), Cu(II), Fe(III), Co(III), Ni(II), Mn(III)] complexes was determined for Madin–Darby Canine Kindney (MDCK) cells and Vero cells with the method of cell culture, and were evaluated as anti-virus activity for influenza virus type A (H3N2), B and Herpes simplex virus type-1 (HSV-1, strain SM44), type-2 (HSV-2, strain 333) in vitro. Among the complexes evaluated, inhibited viral cytopathogenicity at lower concentrations that were found cytotoxic for the MDCK cells. Differences were observed in the 50% effective doses (based on inhibition of viral cytopathogenicity) of these complexes for a number of influenza viruses type A, B, and HSV-1, HSV-2 strains. It was found that CoTAPP displayed good inhibitory action against the virus in vitro.     

Highly ordered arrangement of meso-tetrakis（4-aminophenyl）porphyrin in self-assembled nanoaggregates via hydrogen bonding

meso-Tetrakis(4-aminophenyl)porphyrin(TAPP) can self-assemble into nanostructures with different morphologies by a phase-transfer method.The morphologies(nanospheres,nanorods and nanothorns)of porphyrin nanoaggregates could be easily tuned just by changing the concentration of porphyrin in a proper solvent at room temperature.HRTEM images revealed the formation of highly ordered supramolecular arrays of TAPP,i.e. superlattice of TAPP molecules in nanoaggregates,which agreed well with the size of one molecule of TAPP.UV–vis absorption spectra showed an obvious red shift of the Soret band of TAPP,indicating the formation of J-aggregates of TAPP in nanoaggregates.     

meso-四[(4-苯乙烯氨基)苯基]卟啉合成及其波谱特点

以吡咯和对硝基苯甲醛为原料,经过环化、还原和缩合,合成了meso-四[(4-苯乙烯氨基)苯基]卟啉(TBAPP),通过UV-Vis、FT-IR、1H NMR及元素分析等对产物进行了表征,并对其荧光和电子顺磁共振特性进行了研究。 卟啉产物的EPR测定显示出游离基特征,表明卟啉分子的大π共轭结构对周边基团产生的自由基有稳定作用。 取代基对卟啉的紫外 可见吸收、光致发光及电子顺磁共振特性均有影响。 四席夫碱苯基卟啉TBAPP的Q带比前体四氨基卟啉（TAPP）和母体四硝苯基卟啉（TNPP）红移,而Soret谱带变化较小;TBAPP的440 nm光激发的最大荧光峰658 nm分别比TAPP蓝移5 nm和比TNPP红移9 nm;TBAPP的EPR精细结构比TAPP弱,而比TNPP强。     

新型含卟啉聚肽的合成及表征

卟啉(Ｐｏｒｐｈｙｒｉｎ)是由四个吡咯环和四个碳原子组成的、有18个π电子的共轭大环化合物,其中心的四个氮原子可与金属结合生成金属卟啉.金属卟啉衍生物作为植物光合作用的中心和动物血液中氧的运载体,在生命现象中起着重要的作用,因而为化学、生物乃至医学各界所关注[1,2].近年来含卟啉聚合物的研究日益引起人们的重视[3,4].根据文献报道[5～7],胺能引发氨基酸Ｎ羧基内酸酐(ＮＣＡｓ)开环聚合生成多肽,且引发剂伯胺以共价键连接在聚合物末端,这就为合成一些具有特殊功能(如光电、输氧)的聚肽提供了条件.本文采用本实验室合成的二氨基卟…     

Study on the Supramolecular System of TAPP and Cyclodextrins by Spectroscopy

The ability of β-cyclodextrin (β-CD), γ-CD, hydroxypropyl-β-CD (HP-β-CD), trimethyl-β-CD (TM-β-CD), sulfurbutylether-β-CD (SBE-β-CD) and carboxymethyl-β-cyclodextrin (CM-β-CD) to break the aggregate of the meso-tetrakis(4-N-trimethylaminobenzyl)porphyrin (TAPP) and to form 2:1 inclusion complexes has been studied by absorption and fluorescence spectroscopy. The formation constants are calculated, respectively, by fluorimetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-β-CD (SBE-β-CD and CM-β-CD) is quite different from that of the parent β-CD. At lower pH, the complexation between TM-β-CD and H²TAPP²⁺ (the form of the diprotonated TAPP) hampers the continuous protonation of the pyrrole nitrogen of TAPP and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. ¹HNMR data support the inclusion conformation of the porphyrin–cyclodextrin supramolecular system, indicating the interaction of the meso-phenyl groups of TAPP with the cavity of CDs. For this host–guest inclusion model, cyclodextrin being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for the porphyrin, creating artificial analogues of heme-containing proteins. However, for TAPP, encapsulated within this saccharide-coated barrier, its photophysical and photochemical properties changed strongly.     

水溶性游离碱阳离子卟啉与核酸作用的光谱研究

研究了ｍｅｓｏ－四（对－三甲基氨基苯基）卟啉（ＴＡＰＰ）和ｍｅｓｏ－四（对－甲基吡啶基）卟啉（ＴＭｐｙＰ－４）与核酸作用的电子吸收光谱、荧光光谱和共振光散射光谱的特性，电子吸收和荧光光谱研究表明，这两个水溶性阳离子卟啉与核酸的摩尔比（Ｒ）大于０．２５时，核酸对卟啉的Ｓｏｒｅｔ带有减色效应和荧光猝灭效应；当Ｒ〈０．２５时，核酸与卟啉作用形成新的荧光复合物，共振光散射光谱研究表明，核酸使ＴＡＰＰ的共振     

Photophysical properties of carborane-containing derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin

Absorption, fluorescence emission, fluorescence excitation spectra and fluorescence decay kinetics of carborane derivatives of 5,10,15,20-tetra(p-aminophenyl)porphyrin have been investigated. Carborane derivatives are prepared by acylation of the amino groups of 5,10,15,20-tetra(p-aminophenyl)porphyrin by 9-carboranyl acetyl chloride. From the analysis of the absorption and fluorescence spectra, it is concluded that covalent linking of carborane molecules to the tetraphenylporphyrin molecule significantly changes the self-conjugated pi-system of the porphyrin macrocycle: positions of maxima of absorption and fluorescence spectra shift to the red region by 3-8 nm; the halfwidths of these bands are broadened by 2.5-5.0 nm; the relative intensity of the bands I-IV also changes. The fluorescence decay kinetics of the carborane derivatives are biexponential. According to the experimental data and model simulation, it is concluded that the intramolecular electron transfer proceeds from the porphyrin excited part of the molecule to carboranyls with a rate constant of 415 ps(-1) and efficiency of 0.16-0.8. Recombination of separated charges occurs within 1.4 ns.     

Study of factors influencing the fabrication of Co‐porphyrin porous coordination polymer via metal–organic gel intermediate

In this work, 5, 10, 15, 20‐Tetra‐(4‐aminophenyl) porphyrin (TAPP) was used as gelator to prepare metal‐porphyrin porous coordination polymer (PCP) via solvothermal process, Soxhlet extraction and supercritical CO₂ extraction. Firstly, the metal‐porphyrin organic gel (MOG) was prepared as intermediate with solvothermal method. The generation of gels is associated with many factors. When four acetates [Co(Ac)₂?4H₂O, Zn(Ac)₂?2H₂O, Mn(Ac)₂?4H₂O and Ni(Ac)₂?7H₂O] reacted with TAPP, only the reaction between Co(Ac)₂?4H₂O and TAPP could form desired metal‐porphyrin organic gel. The influences of solvent, concentration and anions were investigated in the gelation process. Secondly, the residual reactants and solvent molecules in MOG were removed through Soxhlet extraction and supercritical CO₂ extraction. The Co‐PCP is an amorphous material with a hierarchical porous structure can effectively catalyze the oxidation of ethylbenzene and also exhibits a strong adsorptive capacity for the strong‐polar solvent molecules.