Charge photoinjection in intercalated and covalently bound [Re(CO)3(dppz)(py)]+-DNA constructs monitored by time-resolved visible and infrared spectroscopy.
Charge photoinjection in intercalated and covalently bound [Re(CO)3(dppz)(py)]+-DNA constructs monitored by time-resolved visible and infrared spectroscopy.
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在插入和共价结合[RE（CO）3（DPPZ）（PY）]+DNA构建体中，通过时间分辨可见和红外光谱监测的DNA构建体。
DOI：
10.1021/ja205568r
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发表时间：
2011-08-31
影响因子：
15
通讯作者：
Barton, Jacqueline K.
中科院分区：
文献类型：
--
作者：
Olmon, Eric D.;Sontz, Pamela A.;Blanco-Rodriguez, Ana Maria;Towrie, Michael;Clark, Ian P.;Vlcek, Antonin, Jr.;Barton, Jacqueline K.
配合物[Re（CO）3（dppz）（py′-OR）]+（dppz = dipyrido[3，2-a：2′，3 ′-c]phenazine; py′-OR = 4-functionalized pyridine）具有很高的红外灵敏度，并能直接氧化DNA，使其成为研究DNA介导的电荷传输（CT）的理想探针。几个共价和非共价Re-DNA构建体的行为进行了监测，通过时间分辨红外光谱（TRIR）和紫外/可见光谱，以及生化方法，证实了DNA的长程氧化的激发复合物。复合物的光学激发导致MLCT的群体和至少两个不同的配体内状态。与这些激发态的电荷注入一致的实验观察结果包括长时间TRIR光谱和光谱电化学观察到的还原态光谱之间的相似性，TRIR光谱中鸟嘌呤自由基信号的出现，以及永久鸟嘌呤氧化产物的最终形成。大多数反应发生在超快的时间尺度上，尽管也观察到依赖于DNA的较慢构象运动的过程，例如鸟嘌呤处的氧化损伤的积累。TRIR能够在不同的时间尺度上测量事件，与其他光谱技术相比具有上级选择性，并且能够同时监测羰基配体和DNA IR吸收带，这使得TRIR成为研究DNA中CT的有价值的工具。
The complex [Re(CO)3(dppz)(py′-OR)]+ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine; py′-OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re-DNA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the excited complex. Optical excitation of the complex leads to population of MLCT and at least two distinct intraligand states. Experimental observations that are consistent with charge injection from these excited states include similarity between long-time TRIR spectra and the reduced state spectrum observed by spectroelectrochemistry, the appearance of a guanine radical signal in TRIR spectra, and the eventual formation of permanent guanine oxidation products. The majority of reactivity occurs on the ultrafast timescale, although processes dependent on slower conformational motions of DNA, such as the accumulation of oxidative damage at guanine, are also observed. The ability to measure events on such disparate timescales, its superior selectivity in comparison to other spectroscopic techniques, and the ability to simultaneously monitor carbonyl ligand and DNA IR absorption bands makes TRIR a valuable tool for the study of CT in DNA.
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影响因子：
4.7
作者：
Gorodetsky, Alon A.;Buzzeo, Marisa C.;Barton, Jacqueline K.
通讯作者：
Barton, Jacqueline K.
影响因子：
3.1
作者：
Cao, Qian;Creely, Caitriona M.;George, Michael W.
通讯作者：
George, Michael W.
影响因子：
15
作者：
Dohno, C;Stemp, EDA;Barton, JK
通讯作者：
Barton, JK
影响因子：
2.8
作者：
Busby, Michael;Matousek, Pavel;Vlcek, Antonin, Jr.
通讯作者：
Vlcek, Antonin, Jr.
DOI：
10.1039/b105864a
发表时间：
2001-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
影响因子：
--
作者：
Encinas, S;Morales, AF;George, MW
通讯作者：
George, MW