title: Deglyco-peplomycin metal complexes on DNA fibers: a role of the sugar moiety for the stability and the orientation of the complexes.
abstract: Binding structures of metal complexes of deglyco-peplomycin (dPEP) on DNA were investigated by comparing dPEP complexes with those of bleomycin (BLM) using DNA fiber EPR spectroscopy. A low spin species of Fe(III)dPEP observed in the DNA pellet changed irreversibly to several high spin species after the fabrication of the DNA fibers. The g values of the high spin species were different from those of Fe(III)BLM. The high spin species could not be nitrosylated reductively to ON-Fe(II)dPEP, suggesting that some nitrogen atoms coordinated to the Fe(III) were displaced on the DNA fibers. On the other hand, O(2)-Co(II)dPEP remained intact on the fibers similarly to O(2)-Co(II)BLM but with an increased randomness in the orientation on the DNA. In contrast to Cu(II)BLM, a considerable amount of Cu(II)dPEP bound almost randomly on B-form DNA fibers. These results indicated that the sugar moiety in peplomycin or bleomycin is playing an important role in enhancing the stability of the metal-binding domain and in the stereospecificity of the binding on DNA.
authors.forename: Takamasa
authors.initials: T
authors.lastname: Iiyama
authors.forename: Makoto
authors.initials: M
authors.lastname: Chikira
authors.forename: Takanori
authors.initials: T
authors.lastname: Oyoshi
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Sugiyama
mesh_terms: D000818:Animals; D000903:Antibiotics, Antineoplastic / Q000737:chemistry* / Q000378:metabolism; D001761:Bleomycin / Q000031:analogs & derivatives / Q000378:metabolism; D003300:Copper / Q000737:chemistry* / Q000378:metabolism; D004247:DNA / Q000737:chemistry* / Q000378:metabolism; D018736:DNA Adducts / Q000737:chemistry* / Q000378:metabolism; D004578:Electron Spin Resonance Spectroscopy / Q000379:methods; D005296:Ferrous Compounds / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry; D006031:Glycosylation; D008297:Male; D008358:Mannose / Q000737:chemistry; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000378:metabolism; D017663:Peplomycin / Q000737:chemistry* / Q000378:metabolism; D012474:Salmon; D013094:Spermatozoa / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000903:Antibiotics, Antineoplastic; D018736:DNA Adducts; D005296:Ferrous Compounds; D009942:Organometallic Compounds; D001761:Bleomycin; D017663:Peplomycin; D003300:Copper; D004247:DNA; D005947:Glucose; D009584:Nitrogen; D008358:Mannose