Sinteza i svojstva biološki aktivnih o-, m- i p- izomera N- supstituiranih mono- i bis(piridinijevih aldoksima) i njihovih cijano-kompleksa željeza(II)

doctoral thesis

• Title (english): Synthesis and properties of biologically active o-, m- and p-isomers of N-substituted mono- and bis(pyridinium aldoximes) and their cyano complexes of iron(II)
• Author: Vladimir Damjanović; MBZ: 322314
• Mentor: Jasna Lovrić (mentor); MBZ: 88623
• Mentor: Blaženka Foretić (mentor); MBZ: 188152
• Committee member: Marina Cindrić (predsjednik povjerenstva)
• Committee member: Jasna Lovrić (član povjerenstva); MBZ: 88623
• Committee member: Blaženka Foretić (član povjerenstva); MBZ: 188152
• Committee member: Dubravka Matković-Čalogović (član povjerenstva)
• Committee member: Ivo Piantanida (član povjerenstva); MBZ: 202026
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2015-06-08, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Primjenom spektroskopskih metoda te rentgenske difrakcije ustanovljen je suodnos strukturnih i kemijskih svojstava sintetiziranih o-, m- i p-izomera monoaldoksimskih derivata piridinijeva kationa i njihovih bis(piridinij-aldoksimskih) analoga. Sposobnost ionizacije u nizu o- > p- > m-izomer, ustanovljena u vodenom mediju, u dobrom je slaganju s njihovim strukturnim razlikama te posljedičnom rezonancijskom stabilizacijom njihovih aldoksimatnih zwitteriona. Citotoksičnost i antibakterijska svojstva svih spojeva ispitana su na odabranim humanim staničnim linijama i bakterijskim sojevima. Sposobnost i način koordinacije ispitivanih spojeva određeni su praćenjem njihovih reakcija s akvapentacijanoferat(II)-ionom u otopini. Utvrđeni kinetički parametri reakcija nastajanja i disocijacije odgovarajućih pentacijano(ligand)ferat(II)-kompleksa korelirani su sa - i -veznim svojstvima izabranih piridinij-aldoksimskih liganada. Nađeno je da su brzine nastajanja u skladu s brojem donornih atoma i nabojem liganada te je opažen sterički utjecaj na iste. Umjerena pH-ovisnost brzina disocijacije te prisutnost MLCT vrpce u elektronskim spektrima podupiru koordinaciju na željezo(II) preko dušikova atoma aldoksimske skupine. Na temelju vrijednosti konstanti brzina disocijacije svi se kompleksi mogu smatrati labilnima, dok se ligandi mogu okarakterizirati kao umjereni -akceptori. Spektroskopska i termogravimetrijska analiza izoliranih kompleksa podupiru činjenicu da su isti i u čvrstom stanju mononuklearni pentacijano(ligand)ferati(II).

Abstract (english)

The relationship between structural and chemical properties of synthesized o-, m- and p-isomers of monoaldoxime derivatives of the pyridinium cation and their bis(pyridinium aldoxime) analogues has been established by means of spectroscopic techniques and X-ray diffraction. Ionization ability in the order o- > p- > m-isomer, determined in aqueous media, was found to be in good agreement with their structural differences and consequent resonance stabilization of their aldoximato zwitterions. Cytotoxic and antibacterial properties were tested for all compounds on selected human cell lines and bacterial strains. Their ability and mode of coordination were determined by monitoring their solution reactions with aquapentacyanoferrate(II) ion. Deduced kinetic parameters for the formation and dissociation of the corresponding pentacyano(ligand)ferrate(II) complexes have been correlated with - and -bonding properties of the examined pyridinium aldoxime ligands. Sterically influenced formation rates were in accordance with a number of donor atoms and the charge within the ligands. The slightly pH-dependent dissociation rates along with presence of the MLCT band in the electronic spectra strongly support the iron(II) coordination through the nitrogen atom of aldoxime group. According to the values of dissociation rate constants, all complexes can be classified as labile while all ligands as moderate -acceptors. Spectroscopic and thermogravimetric analysis of the isolated solids support the fact that all complexes are mononuclear pentacyano(ligand)ferrates(II).

• Keywords: kinetika; konstante ionizacija; mono- i bis(piridinijevi aldoksimi); pentacijano(ligand)ferat(II)-kompleksi; UV/Vis spektroskopija
• Keywords (english): ionization constants; kinetics; mono- and bis(pyridinium aldoximes); pentacyano(ligand)ferrate(II) complexes; UV/Vis spectroscopy
• Language: croatian
• URN:NBN: urn:nbn:hr:217:596771
• Study programme: Title: Doctoral study in chemistry; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 149 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2017-02-07 13:46:17