Kim Jong Moon, Lee Jeong-Mi, Choi Ji Yoon, Lee Hyun Mee, Kim Seog K
Department of Chemistry, Yeungnam University, Gyeongsan City, Gyeong-buk 712-749, Republic of Korea.
J Inorg Biochem. 2007 Oct;101(10):1386-93. doi: 10.1016/j.jinorgbio.2007.05.011. Epub 2007 Jun 2.
Large enhancement in the luminescence intensity of the Delta- and Lambda-Ru(phenanthroline)(2)dipyrido[3,2-a:2',3'-c]phenazine](2+) (Ru(phen)(2)DPPZ) complexes upon their association with single stranded poly(dA) and poly(dT) is reported in this work. As the mixing ratio ([Ru(phen)(2)DPPZ]/[DNA base]) increases, the luminescence intensity increase in a sigmoidal manner, indicating that the enhancement involves some cooperativity. At a high mixing ratio, the luminescence properties are affected by the nature of the DNA bases and not by the absolute configuration of the Ru(phen)(2)DPPZ complex, indicating that the single stranded poly(dA) and poly(dT) do not recognize the configuration of the metal complex. In the case of the Lambda-Ru(phen)(2)DPPZ-poly(dT) complex, the manner of the enhancement is somewhat different from the other Ru(II) complex-polynucelotide combinations: the luminescence intensity reached a maximum at an intermediate mixing ratio of 0.32, and gradually decreased as the mixing ratio increased. In contrast to other complexes at high mixing ratios, an upward bending curve was found in the Stern-Volmer plot, which indicates that the micro-environment of the Lambda-Ru(phen)(2)DPPZ is heterogeneous. In the Delta-Ru(phen)(2)DPPZ-poly(dT) complex case, formation of this highly luminescent species at an intermediate mixing ratio is far less effective.
本文报道了δ-和λ-钌(菲咯啉)₂二吡啶并[3,2-a:2',3'-c]吩嗪(Ru(phen)₂DPPZ)配合物与单链聚(dA)和聚(dT)缔合时发光强度的大幅增强。随着混合比([Ru(phen)₂DPPZ]/[DNA碱基])增加,发光强度呈S形增加,表明这种增强涉及某种协同作用。在高混合比下,发光性质受DNA碱基性质影响,而不受Ru(phen)₂DPPZ配合物的绝对构型影响,表明单链聚(dA)和聚(dT)不识别金属配合物的构型。对于λ-Ru(phen)₂DPPZ-聚(dT)配合物,增强方式与其他Ru(II)配合物-多核苷酸组合略有不同:发光强度在0.32的中间混合比时达到最大值,并随着混合比增加而逐渐降低。与高混合比下的其他配合物不同,在Stern-Volmer图中发现了向上弯曲的曲线,这表明λ-Ru(phen)₂DPPZ的微环境是不均匀的。在δ-Ru(phen)₂DPPZ-聚(dT)配合物的情况下,在中间混合比下形成这种高发光物种的效率要低得多。