Significant Fluorescence Enhancement of N,N-Dimethylaminobenzophenone after Embedding as a C-Nucleoside in DNA

Significant Fluorescence Enhancement of N,N-Dimethylaminobenzophenone after Embedding as a C-Nucleoside in DNA
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DOI:
10.1002/cptc.201700183
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发表时间:
2018-01-01
期刊:
影响因子:
3.7
通讯作者:
Unterreiner, Andreas-Neil
Unterreiner, Andreas-Neil
中科院分区:
化学3区
文献类型:
--
作者:
Schweigert, Caroline;Gass, Nadine;Unterreiner, Andreas-Neil

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N,N-二甲基氨基二苯甲酮(DMABP)是一种分子内给体-受体系统,由于扭曲的分子内电荷转移(TICT),导致对局部环境高度敏感的发光特性。在这项研究中,DMABP共价连接到一个单一的(SS)或双链(DS)的DNA和研究相结合的UV/维斯吸收和荧光光谱以及飞秒泵浦探测测量。将DMABP嵌入DNA环境的结果是,检测到荧光量子产率(QY)急剧增加了100倍以上,相关激发态的寿命从小于10 ps增加到大于100 ps进一步证明了这一点。ss-和ds-DNA系统之间的直接比较通过QY和荧光寿命的两倍差异进一步证明了对周围区域的高灵敏度。因此,相应的DNA部分(堆叠和折叠结)通过与DMABP相互作用显著影响无辐射弛豫过程和荧光之间的竞争。
N,N-dimethylaminobenzophenone (DMABP) represents an intramolecular donor--acceptor system resulting in luminescent properties that are highly sensitive to the local surrounding due to twisted intramolecular charge transfer (TICT). In this study, DMABP was covalently linked to a single (ss) or double-stranded (ds) DNA and studied by a combination of UV/Vis absorption and fluorescence spectroscopy as well as femtosecond pump-probe measurements. As a result of embedding DMABP into a DNA environment, a drastic increase of the fluorescence quantum yield (QY) by a factor of more than 100 was detected, as further evidenced by an increase of the lifetime of the relevant excited states from less than 10ps to more than 100ps. A direct comparison between the ss- and ds-DNA systems further demonstrates the high sensitivity to the surrounding area by means of a two-fold difference in QY and fluorescence lifetimes. As a consequence, the respective DNA moiety (stacking and folding knot) affects significantly the competition between radiationless relaxation processes and fluorescence by interacting with DMABP.