MOLECULAR-COMPLEXES OF NUCLEOSIDES AND NUCLEOTIDES WITH A MONOMERIC CATIONIC PORPHYRIN AND SOME OF ITS METAL DERIVATIVES
MOLECULAR-COMPLEXES OF NUCLEOSIDES AND NUCLEOTIDES WITH A MONOMERIC CATIONIC PORPHYRIN AND SOME OF ITS METAL DERIVATIVES
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DOI：
10.1021/ja00312a061
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发表时间：
1985-12-25
影响因子：
15
通讯作者：
PERREEFAUVET, M
中科院分区：
文献类型：
--
作者：
PASTERNACK, RF;GIBBS, EJ;PERREEFAUVET, M
四（4-N-甲基吡啶基）卟啉（H2 TMPyP）及其衍生物在水溶液中与单核苷酸和单核苷酸具有广泛的相互作用。所形成的复合物是堆叠型的，涉及π-π的广泛重叠。卟啉和嘌呤或嘧啶碱基的系统。库仑吸引力有助于稳定的配合物，但没有证据的基地连接到轴向网站的金属卟啉。通过NMR和分光光度滴定法测定的稳定常数是较大的嘌呤碱比嘧啶与给定的卟啉衍生物。卟啉的变化对稳定性的影响更大。不具有轴向配体的卟啉（例如，无金属的铜（II）、钯（II）和镍（II）衍生物）或一个轴向配体（Zn（II））与给定核苷酸或核苷产生比具有两个轴向配体的金属卟啉（例如，Mn（III）、Fe（III）或Co（III））。用激光拉曼温度跃变法研究了H_2TMPyP与5 "-脱氧腺苷单磷酸（dAMP）相互作用的动力学。测得的速率常数是一致的一个简单的模型的相互作用。
Tetraskis(4-N-methylpyridyl) porphine (H2TMpyP) and a number of its metal derivatives interact extensively with mononucleotides and mononucleosides in aqueous solution. The complexes formed are of a stacking-type involving extensive overlap of the .pi.-systems of the porphyrin and purine or pyrimidine bases. Coulombic attractions help stabilize the complexes but there is no evidence for ligation of the bases to axial sites of the metalloporphyrins. Stability constants determined via NMR and spectrophotometric titrations are larger for purine bases than pyrimidines with a given porphyrin derivative. More dramatic influences on stability result from changing porphyrins. Porphyrins having no axial ligands (e.g., metal-free copper(II), palladium (II), and nickel(II) derivatives) or one axial ligand (Zn(II) produce much larger interactions with a given nucleotide or nucleoside than do metalloporphyrins having two axial ligands (e.g., Mn(III), Fe(III), or Co(III)). The kinetics of the interaction of H2TMpyP with 2''-deoxyadenosine 5''-monophosphate (dAMP) were studied via the laser raman temperature-jump method. The measured rate constants are consistent with a simple model for the interaction.