Changenet-Barret Pascale, Hua Ying, Markovitsi Dimitra
CNRS, IRAMIS, LIDYL, Laboratoire Francis Perrin, URA 2453, Gif-sur-Yvette, 91191, France.
Top Curr Chem. 2015;356:183-201. doi: 10.1007/128_2013_511.
Guanine rich DNA strands, such as those encountered at the extremities of human chromosomes, have the ability to form four-stranded structures (G-quadruplexes) whose building blocks are guanine tetrads. G-quadruplex structures are intensively studied in respect of their biological role, as targets for anticancer therapy and, more recently, of their potential applications in the field of molecular electronics. Here we focus on their electronic excited states which are compared to those of non-interacting mono-nucleotides and those of single and double stranded structures. Particular emphasis is given to excited state relaxation processes studied by time-resolved fluorescence spectroscopy from femtosecond to nanosecond time scales. They include ultrafast energy transfer and trapping of ππ* excitations by charge transfer states. The effect of various structural parameters, such as the nature of the metal cations located in the central cavity of G-quadruplexes, the number of tetrads or the conformation of the constitutive single strands, are examined.
富含鸟嘌呤的DNA链,比如在人类染色体末端发现的那些,有能力形成四链结构(G-四链体),其结构单元是鸟嘌呤四联体。G-四链体结构因其生物学作用、作为抗癌治疗靶点以及最近在分子电子学领域的潜在应用而受到深入研究。在这里,我们聚焦于它们的电子激发态,并将其与非相互作用单核苷酸以及单链和双链结构的电子激发态进行比较。特别强调了通过飞秒到纳秒时间尺度的时间分辨荧光光谱研究的激发态弛豫过程。这些过程包括超快能量转移以及电荷转移态对ππ*激发的俘获。我们还研究了各种结构参数的影响,比如位于G-四链体中心腔中的金属阳离子的性质、四联体的数量或者组成单链的构象。