水溶性卟啉及金属卟啉在DNA中的研究进展

近年来, 卟啉及金属卟啉与DNA的相互作用已成为研究的热点. 通过对卟啉及金属卟啉与DNA相互作用的研究将有助于更深地认识DNA本身的结构和功能, 有助于卟啉及金属卟啉在医学上的应用, 对认识很多疾病的治病机制和药物的设计也起到非常重要的作用. 本文阐述了卟啉及金属卟啉与DNA相互作用的方式和影响因素, 并将水溶性卟啉及金属卟啉分为三类: 具有吡啶基或铵基的阳离子型卟啉及金属卟啉, 具有磺酸基或羧基的阴离子型卟啉及金属卟啉, 以及非离子型的卟啉及金属卟啉. 重点论述了这三类水溶性卟啉及金属卟啉与DNA之间的相互作用, 以及这三类水溶性卟啉及金属卟啉在DNA中的应用研究进展.     

水溶性共轭聚合物PFP/DNA/卟啉复合物光谱性质的研究

开发水溶性的、可双光子激发的且可选择性产生单态氧的系统在光生物与动力治疗等方面具有应用价值. 在本文中, 利用荧光共振能量转移的原理设计了一套光动力治疗系统, 其中带正电的水溶性共轭聚合物PFP作为能量给体, 在单双光子激发下均具有较高的光捕获能力. 带正电的卟啉作为能量受体, 具有极高的单态氧量子产率, 带负电的DNA是连接桥, 使水溶性共轭聚合物PFP与卟啉之间的能量转移得以实现. 通过研究这个体系的吸收、荧光光谱, 荧光寿命, 单态氧量子产率以及双光子吸收截面等性质, 我们发现具有不同DNA序列的系统能量转移效率和单态氧量子产率均不相同, 其中癌细胞中富含的四链DNA具有最高的选择性, 这使得该系统在光动力治疗上具有非常好的应用前景.     

水溶性桥联双卟啉与DNA相互作用的研究

以4,4'-二羧酸-2,2'-联吡啶为桥联试剂, 合成了一种含8个阳离子的水溶性桥联双卟啉(PD). 以5,10,15,20-四(4-N-甲基吡啶盐)卟啉(H₂TMPyP)为参照物, 使用紫外-可见光谱、荧光光谱、圆二色谱研究了水溶性双卟啉与小牛胸腺DNA (CT DNA)的相互作用, 以溴化乙啶(EB)竞争法测定了PD与CT DNA的表观键合常数(K_app)为1.2×10⁶ L•mol^－1 (H₂TMPyP为6.9×10⁶ L•mol^－1), 并使用凝胶电泳研究了PD对pBR322质粒DNA的切割能力. 实验结果表明PD与CT DNA的作用方式是插入和外部结合的混合模式.     

水溶性金属卟啉应用于催化反应的研究进展

综述了水溶性金属卟啉作为催化剂应用于均相或非均相的催化反应的研究进展,重点介绍了水溶性金属卟啉在水或水与有机溶剂混合介质中催化底物氧化反应的催化性能,其中包括烷烃的羟基化,烯烃的环氧化,含氧、含硫及含氮化合物的氧化反应.另外水溶性金属卟啉还可用于催化Suzuki-Miyaura反应、氧化偶联反应、C=C氧化断裂反应等.水溶性金属卟啉催化剂具有水溶性、催化效率高、反应条件温和等优点,因此将在催化反应特别是氧化反应中得到更广泛的应用.     

Water-Soluble Metalloporphyrins as Mimics of Heme-containing Enzymes

Hemin is a naturally occurring metalloporphyrin (M-P), which is the common prosthetic group of heme-containing enzymes. Many M-Ps with different ligand structures and central metal ions were synthesized to mimic heme-containing enzymes1-3. To improve the catalytic capability and specificity of mimic enzyme, the effect of axial ligand was studied as well4-8. Similar to the active center of all heme-containing enzymes, M-P should show more or less catalytic activities of heme-containing enz…     

Synthesis and Characterization of Highly Water-Soluble Dendrofulleropyrrolidine Bisadducts with DNA Binding Activity

The synthesis, characterization and DNA binding studies of a series of polycationic fullerene adducts are reported. These cationic species, exhibiting reasonably high water solubility and a heterogeneous distribution of positive charges, can efficiently complex plasmid DNA. Electrophoresis studies show different DNA binding efficiencies for different adducts, some of which can be considered excellent candidates for DNA binding therapies.     

水溶性金属卟啉肿瘤靶向磁共振成像造影剂的研究

利用显微荧光－阿达玛变换三维图像分析研究了Ｃｕ－ＴＳＰＰ，Ｍｎ－ＴＳＰＰ，Ｃｕ－ＴＭＡＰ，Ｍｎ－ＴＭＡＰ４种水溶性金属卟啉人细胞间质进入肿瘤细胞内的富集过程，对金属卟啉的自旋－晶格驰豫性能（Ｒ１）的天空结果表明，Ｍｎ（Ⅱ）卟啉配合物的Ｒ１、值结Ｇｄ－ＤＴＰＡ提高１．５－２倍。     

三联吡啶-萘酰亚胺二元化合物的合成及其与DNA的相互作用

本文合成了两种三联吡啶修饰的萘酰亚胺化合物NPI1和NPI2,并利用紫外-可见吸收光谱(UV-Vis)、圆二色光谱(CD)、荧光共振能量转移(FRET)等方法研究了它们与双链CT DNA和Htelo G-四链体DNA的相互作用。实验结果表明,化合物NPI1和NPI2对G-四链体DNA具有很好的结合能力和选择性,溶液中的碱金属离子种类和萘酰亚胺基团上的取代基对NPI1和NPI2与DNA的作用有很大的影响。在含K+的缓冲液中,NPI2与G-四链体的结合常数达到1.06×108 L/mol,是与双链CT DNA结合常数的268倍。圆二色谱结果表明在不含碱金属离子的溶液中,NPI1和NPI2可诱导Htelo DNA形成反平行结构G-四链体。Autodock分子对接模拟表明NPI1和NPI2可以通过堆积作用、静电作用、氢键等作用方式与G-四链体结合,使得它们对G-四链体具有很高亲和性(Ka>107 L/mol)。     

抗卟啉抗体与卟啉的协同作用

meso -四 (α ,α ,α ,α - 0 -苯乙酰苯 )卟啉诱导的单抗 (MAb)导致meso -四 (α,α ,α ,α - 0 -苯乙酰苯 )卟啉Soret带来巨大红移 ,并且在meso -四 (α ,α ,α ,α - 0 -苯乙酰苯 )卟啉上产生巨大的诱导Cotton效应 (ICD) .借用ICD定量分析meso -四 (α ,α ,α ,α - 0 -苯乙酰苯 )卟啉同抗体的结合 ,表明在抗体超过meso -四 (α ,α ,α ,α - 0 -苯乙酰苯 )卟啉的情况下 ,既有 1∶1结合 ,又有 2∶1结合〔结合位点 :meso -四 (α ,α ,α ,α - 0 -苯乙酰苯 )卟啉〕     

新型不对称型金属卟啉的谱学性质及非线性光学性质研究

本文合成了几种新型吡啶基修饰的不对称卟啉和金属卟啉,并用核磁、质谱、元素分析、红外光谱、紫外-可见光谱等方法进行了表征,分子模拟研究得到了与光谱分析一致的结果。通过Z-扫描实验对卟啉配合物的非线性光学性质进行了详细研究,这些样品在激光作用下,在532 nm处显示出了强烈的非线性吸收,且取代基位置和金属的不同,均会对三阶非线性折射率的大小产生很大的影响。     

The Influence of Dimerization of Water-Soluble Metalloporphyrins as Photosensitizers on the Efficiency of Generation of Singlet Oxygen

Quantum yields () for the generation of singlet oxygen sensitized by Pd(II) complexes of water-soluble porphyrins: meso-tetrakis(4-N-methylpyridyl)porphine [PdTMPyP]⁴⁺ ( = 0.9), meso-tetrakis(4-N,N,N-trimethylaminophenyl)porphine [PdTTMAPP]⁴⁺ ( = 0.8), meso-tetrakis(4-carboxyphenyl)porphine [PdTCPP]^4– ( = 0.7), and meso-tetrakis(4-sulfonatophenyl)porphine [PdTSPP]^4– ( = 0.5) were determined using a chemical method. It was found that the dimerization and aggregation of metalloporphyrins greatly influence the value. The quantum yields evaluated for the formation of singlet oxygen sensitized by metalloporphyrin monomeric and dimeric forms are _{, M} 0.9 and _{, D} 0.2, respectively, and do not depend on the porphyrin nature.     

Lipophilic and Physicochemical Properties of Metalloporphyrins Separated by RP-TLC

JPC – Journal of Planar Chromatography – Modern TLC - The main objective of the study was to find a relationship between the structure and lipophilicity of metalloporphyrins with...     

新型卟啉化合物的合成及性质

利用微波反应和模板效应合成了带有苯乙烯撑单元的新型卟啉化合物和锌卟啉配合物. 通过 1H NMR, IR和MALDI-TOF-MS等技术对其结构进行了表征. 通过测定UV-Vis和PL对两种卟啉化合物光学性能进行了研究. 利用TGA和循环伏安法研究了锌卟啉配合物的热稳定性和电化学性质, 并以锌卟啉配合物作为掺杂剂利用蒸镀法制备了电致发光器件, EL谱发射峰位于556 nm.     

Synthesis and Properties of Porphyrin Nanotubes

Discrete π‐conjugated zinc porphyrin nanotubes are investigated as molecular analogues of carbon nanotubes. These porphyrin nanotubes have a diameter of 2.4 nm (Zn–Zn distance) and lengths of up to 3.6 nm, measured to the van der Waals surfaces of the outer β‐pyrrole hydrogen atoms, or 4.5 nm measured to the para hydrogen atoms of the aryl groups. We explore three different strategies for synthesizing these nanotubes. The first two strategies use a template to achieve direct or sequential stave‐joining, respectively, and proceed via linear oligomers that pre‐define the length of the nanotube. These strategies are applied to synthesize porphyrin nanotubes containing 12‐ or 18‐porphyrin subunits, with ethynylene (C₂) or butadiynylene (C₄) links between the 6‐porphyrin nanorings. The third strategy involves the covalent stacking of pre‐formed 6‐porphyrin nanorings to form a 12‐porphyrin nanotube, without using a template to guide this coupling reaction. The nanotubes show strongly red‐shifted absorption spectra and low fluorescence quantum yields, indicating structural rigidity and extensive π‐conjugation.     

Effect of the Structure of Selected Metalloporphyrins on their Chromatographic Properties

JPC – Journal of Planar Chromatography – Modern TLC - We have determined the effect of the structure of selected metallo-porphyrins on their chromatographic properties. Separations of...     

Supramolecular Assembly of Functionalized Metalloporphyrins. Porous Crystalline Networks of Zinc-Tetra(4-Carboxyphenyl)Porphyrin

Abstract

Two crystalline compounds based on the Zn-tetra (4-carboxyphenyl)porphyrin building block have been prepared and structurally analysed by x-ray diffraction in order to ellucidate the characteristic supramolecular aggregation modes of this functionalized metalloporphyrin moiety. Crystals of the 1:1 complex with sec-phenethyl alcohol (1) are monoclinic, space group I2/a (No. 15), a = 14.420(1), b = 24.678(2), c = 33.688(2) Å, β = 90.03(2)°, D_c = 1.082 g/cm³, Z = 8, R = 0.080 for 3053 data. Those of the 1:3 complex with dimethylsulphoxide (2) are monoclinic, space group P2₁/n (No. 14), a = 14.881(1), b = 8.986(2), c = 37.550(3) Å, β = 94.21(1)°, D_c = 1.444 g/cm³, Z = 4, R = 0.093 for 4200 data. The two compounds consist of nearly square-pyramidal five-coordinate metalloporphyrin species, molecules of the sec-phenethyl alcohol (in 1) and dimethylsulphoxide (in 2) linking to the metal center at the axial site. In 2, two additional molecules of dimethylsulphoxide associate through H-bonds to the terminal carboxylic substituents of the porphyrin framework. Incorporation of the carboxylic functionality into the tetraarylporphyrin unit leads to the formation of hollow hydrogen-bonded lattices in both crystals. Uniquely structured two-dimensional networks of the porphyrin building blocks with very large cavities (approximately 16 × 21 Å) are formed in 1. These networks mutually interpenetrate each other in order to fill the empty voids, yielding a spectacular ‘concatenated’ arrangement.

One-dimensional polymeric patterns with smaller cavities (6.5 × 10 Å) are built in 2 by the interacting molecular components. In the condensed crystalline environment each such cavity is occupied by two dimethylsulphoxide molecules of adjacent chains. This study is part of an ongoing evaluation of the utility of functionalized metalloporphyrin building blocks in the designed construction of hollow lattices (with varying degree of rigidity and pore size) in molecular based solids. Correlation of current results to previous findings is also discussed.     

Water-Soluble Rhenium Clusters with Triazoles: The Effect of Chemical Structure on Cellular Internalization and the DNA Binding of the Complexes

Here we explore the effect of the nature of organic ligands in rhenium cluster complexes [Re₆Q₈L₆]⁴⁻ (where Q=S or Se, and L=benzotriazole, 1,2,3-triazole or 1,2,4-triazole) on the biological properties of the complexes, in particular on the cellular toxicity, cellular internalization and localization. Specifically, the study describes the synthesis and detailed characterization of the structure, luminescence and electrochemical properties of the four new Re₆ clusters with 1,2,3- and 1,2,4-triazoles. Biological assays of these complexes are also discussed in addition to those with benzotriazole using cervical cancer (HeLa) and immortalized human fibroblasts (CRL-4025) as model cell lines. Our study demonstrates that the presence of hydrophobic and π-bonding rich units such as the benzene ring in benzotriazole significantly enhances cellular internalization of rhenium clusters. These ligands facilitate binding of the clusters to DNA, which results in increased cytotoxicity of the complexes.     

Effect of Bridging Units on Photophysical and DNA Binding Properties of a Few Cyclophanes

A few novel anthracene-based cyclophanes CP-1 , CP-2 and CP-3 were synthesized and their interactions with DNA were investigated employing photophysical and biophysical techniques. In methanol and acetonitrile, these systems exhibited optical properties characteristic of the anthracene chromophore. However, in the aqueous medium, the symmetric cyclophane CP-1 showed a dual emission having λ_max at 430 and 550 nm, due to the monomer and excimer, respectively. In contrast, the cyclophanes CP-2 and CP-3 in the aqueous medium showed structured anthracene absorption and emission spectra similar to those obtained in methanol and acetonitrile. DNA binding studies indicate that CP-1 undergoes efficient nonclassical partial intercalative interactions with DNA resulting in the exclusive formation of a sandwich-type excimer having enhanced emission intensity and lifetimes. The cyclophane CP-2 having one anthracene moiety exhibited nonclassical intercalative binding with DNA, albeit with less efficiency compared with CP-1 . In contrast, CP-3 , having sterically bulky viologen bridging group showed DNA electrostatic as well as groove binding interactions. These results demonstrate that the nature of the bridging unit plays an important role in the binding mode of the cyclophanes with DNA and in the formation of the novel sandwich-type excimer.