Voltammetric studies of the interaction of metal chelates with DNA. 2. Tris-chelated complexes of cobalt(III) and iron(II) with 1,10-phenanthroline and 2,2'-bipyridine

نویسندگان

  • Michael T. Carter
  • Marisol Rodriguez
  • Allen J. Bard
چکیده

Voltammetric methods were used to probe the interaction (electrostatic or intercalative) of metal complexes, ML33+/2+ (M = Fe, Co; L = 1,lO-phenanthroline, 2,2'-bipyridine), with calf thymus DNA. Binding constants (Kn+) and binding site sizes (s) were determined from voltammetric data, Le., shifts in potential and changes in limiting current with addition of DNA. The exact magnitude for the parameters depends on whether the ML33+/2+/DNA reaction is assumed to be static (S) or mobile (M) within the characteristic time of a voltammetric experiment. Co(phen)$+/2+ binds via intercalation with K3+ = 1.6 (f0.2) X 104 M-I (S, s = 6 bp) to 2.6 (f0.4) X lo4 M-' (M, s = 5 bp). The 2+ ion interacts more favorably via hydrophobic interaction with the nucleotide bases than does the 3+ ion. Both forms of the F e ( ~ h e n ) ~ ~ + / ~ + couple bind with approximately the same affinity, K2+ = 7.1 (f0.2) X lo3 M-I (S, s = 5 bp) and 1.47 (h0.04) X lo4 M-' (M, s = 4 bp). C ~ ( b p y ) ~ ~ + / ~ + shows appreciable electrostatic binding in 50 mM NaCl solution [K3+ = 9.4 (f1.5) X lo3 M-I (S) to 1.4 (h0.3) X lo4 M-I (M), s = 3 bp in each case], whereas F e ( b ~ y ) ~ ' + / ~ + does not bind at these ionic strengths. At lower ionic strength (10 mM NaCI, 10 mM Tris, pH 7.1), binding of F e ( b ~ y ) ~ ~ + / ~ + is enhanced [K2+ = 1.1 (h0.6) X lo3 M-l nS, s = 4 bp) to 1.4 (hO.l) X lo3 M-' (M, s = 3 bp)]. We describe here voltammetric studies of the interaction of the extensively as structural probes5 and mediators of DNA cleavage coordination complexes C ~ ( b p y ) , ~ + , F e ( b ~ y ) ~ ~ + (bpy = 2,2'-bireactions.6 Enantioselective interactions of phen and bpy compyridyl), C ~ ( p h e n ) ~ ~ + , and F e ( ~ h e n ) ~ * + (phen = 1,lOplexes of iron(I1) have also been used as structural probes,' and phenanthroline) with calf thymus DNA. We extend our previously FenII) chelated by EDTAs and other complexing agents: tethered reported studies of c o ( ~ h e n ) ~ ~ + D N A interactions via electrochemical methods' and'describe the dependence of the electrochemical behavior on the nature of the ligands coordinated to the metal center. A number of metal chelates have been used as probes of DNA structure, in solution,2 as agents for mediation of strand scission of duplex DNA,3 and as chemotherapeutic agents4 Ruthenium(I1) complexes with phen and related ligands have been studied (1) Carter, M. T.; Bard, A. J . J . Am. Chem. SOC. 1987, 109, 7528. (2) (a) Barton, J. K. J . Biomol. Strucf. Dyn. 1983, I , 621. (b) Neidle, S.; Abraham, 2. CRC Crif . Rev. Biochem. 1984, 17, 73. (c) Dougherty, G.; Pilbrow, J. R. Int . J . Biochem. 1984, 16, 1179. (d) Barton, J. K. Commun. Inorg. Chem. 1985, 3, 321. (e) Barton, J. K. Science 1986, 233, 727. (3) (a) Dervan, P. B. Science 1986, 232, 464. (b) Sigman, D. S. Acc. Chem. Res. 1986,19, 180. (c) Schultz, P. G.; Dervan, P. B. J . Biomol. Sfrucf. Dyn. 1984, 1, 1133. (4) (a) Lippard, S. J. Acc. Chem. Res. 1978, 11, 211. (b) Roberts, J. J.; Thomson, A. J. Prog. Nucleic Acid Res. Mol Biol. 1979, 22, 71. (c) Dabrowiak, J. C. in Advances in Inorganic Biochemistry; Eichhorn, G. L.; Marzilli, L. G., Eds.; Elsevier Biomedical: New York, 1982; Vol. 4, pp 69-113. (d) Hecht, S. M. Acc. Chem. Res. 1986, 19, 383. (e) Reedijk, J. Pure Appl. Chem. 1987, 59, 181. 0002-7863/89/1511-8901$01.50/0 ( 5 ) (a) Barton, J . K.; Danishefsky, A. T.; Goldberg, J. M. J . Am. Chem. SOC. 1984, 106, 2172. (b) Barton, J. K.; Basile, L. A.; Danishefsky, A. T.; Alexandrescu, A. Proc. Natl. Acad. U.S.A. 1984,81, 1961. (c) Kelley, J. M.; Tossi, A. B.; McConnell, D. J.; OhUigin, C. Nucleic Acids Res. 1985, 13, 6017. (d) Barton, J. K.; Lolis, E. J. Am. Chem. SOC. 1985, 107, 708. (e) Kumar, C. V.; Barton, J. K.; Turro, N. J. J . Am. Chem. Soc. 1985,107, 5518. (f) Mei, H.-Y.; Barton, J. K. J . Am. Chem. SOC. 1986, 108, 7414. (g) Barton, J. K.; Goldberg, B. M.; Kumar, C. V.; Turro, N. J. J . Am. Chem. SOC. 1986, 108, 2081. (h) Goldstein, B. M.; Barton, J. K.; Berman, H. M. Inorg. Chem. 1986, 25, 842. (i) Stradowski, C.; Gorner, H.; Currell, L. J.; Schulte-Frohlinde, D. Biopolymers 1987, 26, 189. (6) (a) Basile, L. A.; Barton, J . K. J . Am. Chem. SOC. 1987, 109, 7548. (b) Basile, L. A.; Raphael, A. L.; Barton, J. K. J . Am. Chem. SOC. 1987, 109, 7550. (7) Hard, T.; Nordh , B. Biopolymers 1986, 25, 1209. (8) (a) Schultz, P. G.; Taylor, J. S.; Dervan, P. B. J. Am. ChemSoc. 1982, 104, 6861. (b) Schultz, P. G.; Dervan, P. B. Proc. Natl. Acad. Sci. U.S.A. 1983,80,6834. (c) Taylor, J. S.; Schultz, P. G.; Dervan, P. B. Tetrahedron 1984,40,457. (d) Youngquist, R. S.; Dervan, P. B. J. Am. Chem. SOC. 1985, 107, 5528. (e) Dreyer, G. B.; Dervan, P. B. Proc. Nail. Acad. Sci. U.S.A. 1985.82, 968. (f) Youngquist, R. S.; Dervan, P. B. Proc. Nafl . Acad. Sci. U.S.A. 1985, 82, 2565. (9) Griffin, J . H.; Dervan, P. B. J . Am. Chem. SOC. 1987,109,6840. (h) Schultz, P. G.; Dervan, P. B. J . Am. Chem. SOC. 1983, 105. 7148.

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تاریخ انتشار 2009