Excited state dependent electron transfer of a rhenium-dipyridophenazine complex intercalated between the base pairs of DNA: a time-resolved UV-visible and IR absorption investigation into the photophysics of fac-[Re(CO)3(F2dppz)(py)]+ bound to either [poly(dA-dT)]2 or [poly(dG-dC)]2

Excited state dependent electron transfer of a rhenium-dipyridophenazine complex intercalated between the base pairs of DNA: a time-resolved UV-visible and IR absorption investigation into the photophysics of fac-[Re(CO)3(F2dppz)(py)]+ bound to either [poly(dA-dT)]2 or [poly(dG-dC)]2
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DOI:
10.1039/c1pp05050h
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发表时间:
2011-01-01
影响因子:
3.1
通讯作者:
George, Michael W.
George, Michael W.
中科院分区:
化学3区
文献类型:
--
作者:
Cao, Qian;Creely, Caitriona M.;George, Michael W.

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用瞬态可见光谱和红外光谱研究了fac-[Re(CO)(3)(F(2)dppz)(py)](+)(F(2)dppz = 11,12-二氟二吡啶并[3,2-a:2 ',3'-c]吩嗪)与双链多核苷酸[poly(dA-dT)](2)或[poly(dG-dC)](2)结合后在皮秒和纳秒时域内形成的瞬态物种。后一种技术已被用于监测金属络合物和DNA,分别监测1900-2100和1500-1750 cm(-1)的区域。这些数据提供了直接的证据,电子转移从鸟嘌呤的金属络合物的激发态,这两个亚皮秒的时间尺度和寿命为35 ps的收益,可能是由于两个激发态的参与。[poly(dA-dT)](2)复合物中未发现电子转移,尽管在DNA区域TRIR中观察到特征性变化,这与激发dppz复合物时嵌入位点中碱基结合的变化一致。
The transient species formed following excitation of fac-[Re(CO)(3)(F(2)dppz)(py)](+) (F(2)dppz = 11,12-difluorodipyrido[3,2-a:2',3'-c]phenazine) bound to double-stranded polynucleotides [poly(dA-dT)](2) or [poly(dG-dC)](2) have been studied by transient visible and infra-red spectroscopy in both the picosecond and nanosecond time domains. The latter technique has been used to monitor both the metal complex and the DNA by monitoring the regions 1900-2100 and 1500-1750 cm(-1) respectively. These data provide direct evidence for electron transfer from guanine to the excited state of the metal complex, which proceeds both on a sub-picosecond time scale and with a lifetime of 35 ps, possibly due to the involvement of two excited states. No electron transfer is found for the [poly(dA-dT)](2) complex, although characteristic changes are seen in the DNA-region TRIR consistent with changes in the binding of the bases in the intercalation site upon excitation of the dppz-complex.