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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 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.

The aim of this report is to present the electrospray ionization mass spectrometry results of the non-covalent interaction of two biologically active ligands, N-1-(p-toluenesulfonyl)cytosine, 1-TsC, 1 and N-1 methanesulfonylcytosine, 1-MsC, 2 and their Cu(II) complexes Cu(1-TsCN3)2Cl2, 3 and Cu(1-MsC-N3)2Cl2 and 4 with biologically important cations: Na+, K+, Ca2+, Mg2+ and Zn2+. The formation of various complex metal ions was observed. The alkali metals Na+ and K+ formed clusters because of electrostatic interactions. Ca2+ andMg2+ salts produced the tris ligand andmixed ligand complexes. The interaction of Zn2+ with 1–4 produced monometal and dimetal Zn2+ complexes as a result of the affinity of Zn2+ ions toward both O and N atoms.

Proučavana je samoorganizacija male molekulske mase spektrometrijom masa s ciljem dobivanja informacija koje bi mogle poslužiti kao indikator molekulskog prepoznavanja tj. dobrog geliranja. Bis-oksalamidni spojevi su otopljeni u otapalima koje dobro geliraju te su korišteni kao modelni spojevi. Potvrđeni su kao izuzetno dobri gelatori, a za njihova odlična gelirajuća svojstva odgovorne su nekovalentne interakcije (prvenstveno H-veze, ali i elektrostatske interakcije). Primjenom spektrometrije masa uz elektroraspršenje (ESI-MS) proučavana je samoorganizacija devet oksalamidnih spojeva u pozitivnom i negativnom ionizacijskom modu s obzirom na efekt krajnjih funkcionalnih skupina kao i kiralnost gelatora. Utvrdilo se da gelatori koji dobro geliraju se i sami međusobno samoorganiziraju u postojane agregate koji su stabilni i u plinskoj fazi, npr. bis- aminokiselinski oksalamid i bis-aminokiselinski oksalamid se povezuju u agregate do heksamera pa i veće neovisno o otapalu ili uvjetima mjerenja.