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钯卟啉的光谱表征及其与小牛胸腺DNA相互作用的研究

Study on spectroscopic characterization of Pd porphyrin and its interaction with ctDNA.

作者信息

Guo Limin, Dong Wenjuan, Tong Xiaofei, Dong Chuan, Shuang Shaomin

机构信息

College of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China.

出版信息

Talanta. 2006 Oct 15;70(3):630-6. doi: 10.1016/j.talanta.2006.01.031. Epub 2006 Mar 7.

Abstract

The fluorescence and solid substrate room temperature phosphorescence (SS-RTP) properties of Pd(II) meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin (Pd(II)TMPyP) were studied. The factors influencing the SS-RTP emission, such as filter type, inorganic salt sort, drying temperature, pre-drying time and drying time were investigated in detail. Strong SS-RTP signal can be induced on the slow speed filter paper in the presence of the external inorganic salt, Ca(NO(3))(2), with the maximum excitation and emission wavelengths at 421nm and 675nm, respectively. The interaction between calf thymus DNA (ctDNA) and Pd(II)TMPyP was investigated at pH 7.2 using SS-RTP, fluorescence and UV-vis spectroscopy. The SS-RTP intensity of Pd(II)TMPyP was enhanced efficiently with the increasing amount of ctDNA. This phenomenon demonstrates that the intercalated porphyrin is shielded by ctDNA to avoid collision quenching. This result was supported by SS-RTP lifetime measurement, SS-RTP anion quenching experiment and fluorescence polarization measurement. Furthermore, with the addition of ctDNA, the UV-vis spectra of Pd(II)TMPyP shows apparent hypochromicity (40%) at the Soret maximum of 417nm and a red shift of Deltalambda=15nm, also indicating that Pd(II)TMPyP intercalates into ctDNA bases. The binding constant of Pd(II)TMPyP to ctDNA was calculated to be 4.41x10(5)L/mol based on the derivative McGhee-von Hippel plots.

摘要

研究了钯(II)中-四(4-N-甲基吡啶基)卟啉(Pd(II)TMPyP)的荧光和固体基质室温磷光(SS-RTP)性质。详细研究了影响SS-RTP发射的因素,如滤光片类型、无机盐种类、干燥温度、预干燥时间和干燥时间。在外部无机盐Ca(NO₃)₂存在下,慢速滤纸上可诱导出强SS-RTP信号,其最大激发波长和发射波长分别为421nm和675nm。在pH 7.2条件下,利用SS-RTP、荧光和紫外可见光谱研究了小牛胸腺DNA(ctDNA)与Pd(II)TMPyP之间的相互作用。随着ctDNA量的增加,Pd(II)TMPyP的SS-RTP强度有效增强。这一现象表明,插入的卟啉被ctDNA屏蔽,以避免碰撞猝灭。SS-RTP寿命测量、SS-RTP阴离子猝灭实验和荧光偏振测量支持了这一结果。此外,加入ctDNA后,Pd(II)TMPyP的紫外可见光谱在417nm的Soret最大值处出现明显的减色(40%),且红移Δλ = 15nm,这也表明Pd(II)TMPyP插入到ctDNA碱基中。根据导数McGhee-von Hippel图计算出Pd(II)TMPyP与ctDNA的结合常数为4.41×10⁵L/mol。

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