ORGANIC-PHOTOCHEMISTRY .98. TOWARD THE DEVELOPMENT OF PHOTO CISPLATINUM REAGENTS - REACTION OF CIS-DICHLOROBIS(1,10-PHENANTHROLINE)RHODIUM(III) WITH CALF THYMUS DNA, NUCLEOTIDES, AND NUCLEOSIDES

ORGANIC-PHOTOCHEMISTRY .98. TOWARD THE DEVELOPMENT OF PHOTO CISPLATINUM REAGENTS - REACTION OF CIS-DICHLOROBIS(1,10-PHENANTHROLINE)RHODIUM(III) WITH CALF THYMUS DNA, NUCLEOTIDES, AND NUCLEOSIDES
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DOI:
10.1021/ja00050a002
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发表时间:
1992-11-18
影响因子:
15
通讯作者:
MORRISON, H
MORRISON, H
中科院分区:
化学1区
文献类型:
--
作者:
MAHNKEN, RE;BILLADEAU, MA;MORRISON, H

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标题化合物(cisDCBPR)与小牛胸腺DNA的光解导致共价加合物的形成。该反应不依赖于氧气,以温和的(约100)进行。10(-3))量子效率,并且以适度的对映选择性发生,其在低离子强度介质中增强,其中静电和/或嵌入缔合是明显的。从金属化DNA的酶促降解中分离出至少两种涉及脱氧鸟苷作为配体的共价加合物,其中一种在光谱上与从cisDCBPR与dG的反应制备的加合物相同。广泛的光谱表征的第二dG加合物暗示N1作为连接点的Rh的基地。一个稳定的加合物与dA也已被分离的光解的金属配合物与核苷,并涉及绑定到N3的结构被暂定分配。
Photolysis of the title compound (cisDCBPR) with calf thymus DNA leads to the formation of covalent adducts. The reaction is not dependent on oxygen, proceeds with moderate (ca. 10(-3)) quantum efficiency, and occurs with modest enantioselectivity which is enhanced in low ionic strength media, where electrostatic and/or intercalatory association is evident. At least two covalent adducts involving deoxyguanosine as a ligand have been isolated from the enzymatic degradation of the metalated DNA, one of which is spectroscopically identical with an adduct prepared from the reaction of cisDCBPR with dG. Extensive spectral characterization of the second dG adduct implicates N1 as the point of attachment of Rh to the base. A stable adduct with dA has also been isolated from photolysis of the metal complex with the nucleoside, and a structure involving binding to N3 is tentatively assigned.