Double-strand DNA cleavage by copper complexes of 2,2'-dipyridyl with electropositive pendants.
Two highly charged cationic copper(II) complexes have been synthesized and characterized structurally and spectroscopically: [Cu(L1)2(Br)](ClO4)5 (1) and [Cu(L2)2(Br)](ClO4)5 (2) (L1= 5,5'-di(1-(triethylammonio)methyl)-2,2'-dipyridyl cation and L2= 5,5'-di(1-(tributylammonio)methyl)-2,2'-dipyridyl cation bidentate ligands). X-Ray structures show that Cu(II) ions in both complexes have a trigonal-bipyramidal CuN4Br-configuration. Two nitrogen atoms of the electropositive pendants and coordinated bromine atom basically array in a straight line. Their close distances of N[dot dot dot]Br atoms are 5.772 and 5.594 A, respectively, which is comparable to that of adjacent phosphodiesters in B-form DNA (ca. 6 A). In the absence of reducing agent, supercoiled plasmid DNA cleavage by the complexes has been performed and their hydrolytic mechanisms have been investigated. The pseudo-Michaelis-Menten kinetic parameters (kcat), 4.15 h(-1) for 1, 0.43 h(-1) for 2 and 0.61 h(-1) for [Cu(bipy)(NO3)2], were obtained. This result indicates that 1 exhibits markedly higher nuclease activity than its corresponding analogues. The high ability of DNA cleavage for 1 is attributed to the effective cooperation of the metal moiety and two positive pendants since the array of linear tri-binding sites matches with one of three phosphodiester backbones of nucleic acid.
An
Yan
Y
School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, China. cesmzw@zsu.edu.cn.
Tong
Ming-Liang
ML
Ji
Liang-Nian
LN
Mao
Zong-Wan
ZW
D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004247:DNA / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009691:Nucleic Acid Denaturation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet
D009942:Organometallic Compounds; D015082:2,2'-Dipyridyl; D003300:Copper; D004247:DNA