Sequence specific double-strand DNA cleavage by an optical active dinuclear iron complex and application for artificial restriction enzyme

1-1)In my approach to create metal complexes that are capable of cleaving double-strand DNAsimultaneously and sequence-selectively (like bleomycin，which is an antitumor antibiotic which causes single and double strand cleavage of DNA at 5‘-GC-3’or 5'-GT-3' sites), I prepared an optical active pentadentate ligandN，N，N'-tri(2-pyridylmethyl)-2-S-(aminomethyl)piperidine = S- p3pipda obtained from the reaction ofS-2-aminopiperidine with 3 equimolar amounts of 2-chloromethylpyridine，and investigated the X-ray crystal结构copper(II) and nickel(II) complexes of S-P3pipda，[cu (3 s - p pipda)](cio _ 4)_ 2 and [ni (s - p 3 pipda)(oh 2)](cio译文:4)_ 2 complexes,[cu (s-p3pipda)] (cio 4) _ 2 and [ni (s-p3pipda) 2 (oh)] (cio 4) _ 2,were prepared from the reaction of an equimolar amount of Cu(cplo_4)_2 / 6h_2o or Ni(so_4)_2 / 6h_2ofollowed by addition of liclo_4 with the ligand S-P3pipda in methanol under argon.The X-raycrystal structure of [Cu(S-P3pida)] shows an intermediate structure between trigonal bipyramidand square pyramid in which equatrial positions are occupied by two tertiary amines (N2 and N3) andtwo pyridine nitrogens (N1 and N4) and axial position by a pyridine nitrogen (N5). Perchlorate ioncoordinates weakly：Cu-O is 3.55 A .1-2)We synthesized1、8 -(n - anthranylmethyl)- bis (n ', n '- dipyridylmethyl - r, r - cyclohexane - 1, 2 - diamine), 1,and cleaving activity of 1 to DNA was evaluated in the presence of sodium ascorbate under air. Anovel Fe complex 1 and sodium ascorbate system cleaved A-T rich region of DNA.2)MoreoverI have synthesized two new dinuclear platinum(II) complexes，1,3-and 1,4-(benzenedimethanethiolate- s)di(2,2',2"-terpyridine)platinum(II) chloride tetrahydrate (2)and 3),were synthesized in order to investigate the binding of platinum complexes with calf thymus DNA，which was examined by UV and CD spectroscopies. Complex 2 interacted strongly with DNAintercalation compared to 3。

1-1)In my approach to create metal complexes that are capable of cleaving double-strand DNA simultaneously and sequence-selectively (like bleomycin, which is an antitumor antibiotic which causes single and double strand cleavage of DNA at 5'-GC-3' or 5'-GT-3' sites), I prepared an optical active pentadentate ligand, N,N,N'-tri(2-pyridylmethyl)-2-S-(aminomethyl)piperidine = S-P3pipda obtained from the reaction of S-2-aminopiperidine with 3 equimolar amounts of 2-chloromethylpyridine, and investigated the X-ray crystal structures of copper(II) and nickel(II) complexes of S-P3pipda, [Cu(S-P3pipda)](ClO_4)_2 and [Ni(S-P3pipda)(OH_2)](ClO_4)_2 Complexes, [Cu(S-P3pipda)](ClO_4)_2 and [Ni(S-P3pipda)(OH_2)](ClO_4)_2, were prepared from the reaction of an equimolar amount of Cu(ClO_4)_2・6H_2O or Ni(SO_4)_2・6H_2O (followed by addition of LiClO_4) with the ligand S-P3pipda in methanol under argon.The X-ray crystal structure of [Cu(S-P3pida)]^<2+> shows an intermediate structure between trigonal bipyramid and square pyramid in which equatrial positions are occupied by two tertiary amines (N2 and N3) and two pyridine nitrogens (N1 and N4) and axial position by a pyridine nitrogen (N5). Perchlorate ion coordinates weakly : Cu-O is 3.55 Å.1-2)We synthesized 1,8-(N-anthranylmethyl)-bis(N',N'-dipyridylmethyl-R,R-cyclohexane-1,2-diamine), 1, and cleaving activity of 1 to DNA was evaluated in the presence of sodium ascorbate under air. A novel Fe complex 1 and sodium ascorbate system cleaved A-T rich region of DNA.2)Moreover, I have synthesized two new dinuclear platinum(II) complexes, 1,3-and 1,4-(benzenedimethanethiolate-S)di(2,2',2"-terpyridine)platinum(II) chloride tetrahydrate (2 and 3), were synthesized in order to investigate the binding of platinum(II) complexes with calf thymus DNA, which was examined by UV and CD spectroscopies. Complex 2 interacted strongly with DNA by intercalation compared to 3.