Interakcije metalnih iona s konjugatima ciklamskih derivata citozina praćene spektrometrijom masa

doctoral thesis

• Title (english): Metal interactions with cyclam derivatives of cytosine investigated by mass spectrometry
• Author: Valentina Ključarić
• Mentor: Biserka Žinić (mentor)
• Mentor: Renata Kobetić (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Biserka Žinić (član povjerenstva)
• Committee member: Renata Kobetić (član povjerenstva)
• Committee member: Sanda Rončević (član povjerenstva)
• Committee member: Vesna Petrović Peroković (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2016-09-20, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry; Organic Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U ovom doktorskom radu sintetizirani su Cu(II) molekulski kompleksi [Cu(1-TsC-N3)2Cl2] i [Cu(1-MsC-N3)2Cl2] biološki aktivnih N-sulfonilcitozinskih (C) liganada s tosilom (Ts) i mezilom (Ms) te novi ciklam-TsC konjugati. Mannichova reakcija TsC liganda, paraformaldehida i ciklama u prisutnosti octene kiseline daje C-aminometilirani konjugat u kojem je ciklam vezan preko metilenskog mosta na C5 položaj citozina. Ista reakcija sa zaštićenim ciklamom daje C4 aminometilirani produkt. Pomoću ESI-MS metode provedena je studija stabilnosti i utjecaja biološki važnih metalnih iona (Na+, K+, Ca2+, Mg2+, Zn2+, Cu2+) na ligande, Cu(II) komplekse, te na poliaza makrocikličke konjugate. U interakciji s ligandima i Cu(II) kompleksima alkalijski metali uslijed elektrostatskih interakcija stvaraju klastere, dok je nastanak bis i tris te miješanih kompleksa uočen u interakciji s Ca2+ i Mg2+. Interakcija Zn2+ s ligandima i Cu(II) kompleksima rezultira nastankom monometalnih kompleksa kao i dimetalnih kompleksa zbog afniteta Zn2+ prema atomima kisika i dušika koji u strukturu uključuju molekule vode. Novi poliaza makrociklički konjugati u interakciji s CuCl2 stvaraju molekulske komplekse u kojima je CuCl2 u ciklamskom prstenu, a u interakciji s ZnSO4 nastaju ionski kompleksi u kojima je Zn2+ smješten u ciklamskom prstenu.

Abstract (english)

Abstract In this doctoral thesis, Cu (II) molecular complexes [Cu(1-TsC-N3)2Cl2] and [Cu(1-MsC-N3)2Cl2] of biologically active N-sulfonylcytosine ligands (C) with tosyl (Ts) and mesyl (Ms) and new cyclame-TsC conjugates were synthesized. The Mannich reaction of TsC, paraformaldehyde and cyclame in the presence of acetic acid yields C-aminomethylated konjugate in which the cyclame was introduced through a methylene bridge at C5 position of cytosine. The same reaction with protected cyclame gives C4 aminomethylated product. Using ESI-MS method was conducted stability studies and the influence of biologically important metal ions (Na+, K+, Ca2+, Mg2+, Zn2+, Cu2+) to ligands, Cu (II) complexes, and polyaza macrocyclic conjugates. The interaction of ligands and Cu (II) complexes with biologically important metal ions results with formation of various metal complex. Alkali metals Na+ and K+ formed clusters due to the electrostatic inetractions. Bis, tris and mixed ligand complexes were observed upon mixing with Ca2+ or Mg2+ salt. Interaction with Zn2+ sieed monometal Zn2+ complexes and mixed ligand dimetal complexes that includ water molecules in the structures of the complexes because of affinity of Zn2+ for both O and N atoms. Both ions Cu2+ and Zn2+ were located within the cyclamic ring upon their interaction with polyaza macrocyclic conjugates. Newly formed Cu2+complexes were molecular while the ionic complexes were formed with zinc ions.

• Keywords: N-sulfonilcitozinski derivati; Cu(II) kompleksi; ciklam; metalni ioni; ESI-MS
• Keywords (english): N-sulfonilcytosine derivatives; Cu(II) complexes; cyclam; metal ions; ESI-MS
• Language: croatian
• URN:NBN: urn:nbn:hr:217:491708
• 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: 169 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2017-02-03 12:13:41