García-Raso Angel, Fiol Juan J, Adrover Bartomeu, Moreno Virtudes, Mata Ignasi, Espinosa Enrique, Molins Elies
Departament de Quĭmica, Universitat de les Illes Balears, Cra. Valldemossa Km 7.5, 07122, Palma de Mallorca, Spain.
J Inorg Biochem. 2003 Jun 1;95(2-3):77-86. doi: 10.1016/s0162-0134(03)00121-1.
Three new ternary peptide-Cu(II)-1,10-phenanthroline (phen) complexes, [Cu(L-ala-gly)(phen)].3.5H(2)O 1, [Cu(L-val-gly)(phen)] 2 and [Cu(gly-L-trp)(phen)].2H(2)O 3, have been prepared and structurally characterised. These compounds exist as distorted square pyramidal complexes with the five co-ordination sites occupied by the tridentate peptide dianion and the two heterocyclic nitrogens of the phenanthroline ligand. The bulk of the lateral chain in the peptide moiety determines the relative disposition of the phen ligand. Thus, in [Cu(L-val-gly)(phen)] 2, the phenanthroline plane is deviated towards the opposite side of the isopropyl group of the L-valine moiety. On the other hand, in [Cu(gly-L-trp)(phen)].2H(2)O 3 the absence of stacking interactions between phen and indole rings and the presence of an intramolecular CH...pi interaction should be pointed out. These complexes exhibit significant differences in their nuclease activity which depends on the nature of the peptidic moiety, the complex [Cu(gly-L-trp) (phen)].2H(2)O 3 being the most active.
制备并表征了三种新型三元肽 - 铜(II)-1,10 - 菲咯啉(phen)配合物,即[Cu(L - 丙氨酸 - 甘氨酸)(phen)]·3.5H₂O 1、[Cu(L - 缬氨酸 - 甘氨酸)(phen)] 2和[Cu(甘氨酸 - L - 色氨酸)(phen)]·2H₂O 3。这些化合物以扭曲的四方锥配合物形式存在,五个配位位点被三齿肽二价阴离子和菲咯啉配体的两个杂环氮原子占据。肽部分中侧链的大部分决定了菲咯啉配体的相对取向。因此,在[Cu(L - 缬氨酸 - 甘氨酸)(phen)] 2中,菲咯啉平面朝着L - 缬氨酸部分异丙基的相反侧偏离。另一方面,在[Cu(甘氨酸 - L -色氨酸)(phen)]·2H₂O 3中,应指出菲咯啉环与吲哚环之间不存在堆积相互作用以及存在分子内CH…π相互作用。这些配合物在核酸酶活性方面表现出显著差异,这取决于肽部分的性质,[Cu(甘氨酸 - L -色氨酸)(phen)]·2H₂O 3是活性最高的。