Employment of pyridyl oximes and dioximes in zinc(II) chemistry: Synthesis, structural and spectroscopic characterization, and biological evaluation

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• 作者：Konstantis F. Konidaris^a ; Maria Giouli^b ; Catherine P. Raptopoulou^c ; Vassilis Psycharis^c ; Ioannis I. Verginadis^b ; Anastasios Vasiliadis^d ; Amalia S. Afendra^d ; Spyridon Karkabounas^b ; ^{skarkabu@cc.uoi.gr} ; Evy Manessi-Zoupa^a ; ^{emane@upatras.gr} ; Theocharis C. Stamatatos^a ; ^e ; ^{tstamatatos@brocku.ca}
• 关键词：Mononuclear Zn(II) complexes ; Pyridyl oximes and dioximes ; Crystal structures ; Physicochemical characterization ; Cytotoxic activity ; Apoptosis
• 刊名：Inorganica Chimica Acta
• 出版年：2013
• 出版时间：24 February, 2013
• 年：2013
• 卷：396
• 期：Complete
• 页码：49-59
• 全文大小：972 K

文摘

The employment of pyridine-2-amidoxime (ampaoH), 2,6-diacetylpyridine dioxime (dapdoH₂) and pyridine-2,6-diamidoxime (dampdoH₂) in zinc(II) chemistry is reported. The syntheses, crystal structures, spectroscopic and physicochemical characterization, and biological evaluation are described of [Zn(O₂CMe)₂(ampaoH)₂] (1), [Zn(O₂CPh)₂(ampaoH)₂] (2), [Zn(dapdoH₂)₂](NO₃)₂ (3) and [Zn(dampdoH₂)₂](NO₃)₂ (4). The reactions between Zn(NO₃)₂¡¤4H₂O and two equivalents of either dapdoH₂ or dampdoH₂ in MeOH led to the mononuclear, cationic complexes 3 or 4, respectively. The Zn^II center in 3 and 4 is coordinated by two N,N¡ä,N¡å-tridentate chelating (¦Ç³) dapdoH₂ or dampdoH₂ ligands, and it thus possesses a distorted octahedral coordination geometry. Strong intermolecular hydrogen bonding interactions provide appreciable thermodynamic stability and interesting supramolecular chemistry for compounds 1-4. The characterization of all four complexes with ¹H and ¹³C NMR, and positive ion electrospray mass spectroscopies confirmed their integrity in DMSO solutions. The biological evaluation of complex 3 showed the highest cytotoxic activity against LMS and MCF-7 cells, among the other three complexes (1, 2 and 4). Flow cytometry analysis revealed that all four complexes cause apoptosis to LMS cells, at a dose-dependent manner. The combined work demonstrates the ability of pyridyl monoxime and pyridyl dioxime chelates not only to lead to polynuclear 3d-metal complexes with impressive structural motifs and interesting magnetic and optical properties, but also to yield new, mononuclear transition metal complexes with biological implications.