The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine.
The interaction of native calf thymus DNA with the Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine (ZnL(2+) and CuL(2+)), in 1 mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectrophotometry, circular dichroism (CD) and fluorescence spectroscopy. The results support for an intercalative interaction of both ZnL(2+) and CuL(2+) with DNA, showing CuL(2+) an affinity of approximately 10 times higher than ZnL(2+). In particular, the values of the binding constant, determined by UV spectrophotometric titration, equal to 7.3x10(4) and 1.3x10(6)M(-1), for ZnL(2+) and CuL(2+), respectively, indicate the occurrence of a marked interaction with a binding size of about 0.7 in base pairs. The temperature dependence of the absorbance at 258 nm suggests that both complexes strongly increase the DNA melting temperature (Tm) already at metal complex-DNA molar ratios equal to 0.1. As evidenced by the quenching of the fluorescence of ethidium bromide-DNA solutions in the presence of increasing amounts of metal complex, ZnL(2+) and CuL(2+) are able to displace the ethidium cation intercalated into DNA. A tight ZnL(2+)-DNA and CuL(2+)-DNA binding has been also proven by the appearance, in both metal complex-DNA solutions, of a broad induced CD band in the range 350-450 nm. In the case of the CuL(2+)-DNA system, the shape of the CD spectrum, at high CuL(2+) content, is similar to that observed for psi-DNA solutions. Such result allowed us to hypothesize that CuL(2+) induces the formation of supramolecular aggregates of DNA in aqueous solutions.
Silvestri
Arturo
A
Dipartimento di Chimica Inorganica e Analitica S. Cannizzaro, Università di Palermo, Viale delle Scienze, Parco d'Orleans II, Edificio 17, 90128 Palermo, Italy. asilves@unipa.it
Barone
Giampaolo
G
Ruisi
Giuseppe
G
Anselmo
Daniele
D
Riela
Serena
S
Liveri
Vincenzo Turco
VT
D000818:Animals; D002417:Cattle; D002942:Circular Dichroism; D003300:Copper / Q000737:chemistry*; D004247:DNA / Q000737:chemistry* / Q000378:metabolism; D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry*; D009691:Nucleic Acid Denaturation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000138:chemical synthesis / Q000737:chemistry; D012545:Schiff Bases / Q000138:chemical synthesis / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D015032:Zinc / Q000737:chemistry*
D007097:Imines; D009942:Organometallic Compounds; D000644:Quaternary Ammonium Compounds; D012545:Schiff Bases; D003300:Copper; D004247:DNA; C427203:calf thymus DNA; D015032:Zinc