Istraživanje inkluzijskih kompleksa diamantoidnih amonijevih soli s ciklodekstrinima

master's thesis

• Title (english): Investigation of inclusion complexes of diamondoid ammonium salts with cyclodextrins
• Author: Amalija Ernečić
• Mentor: Irena Škorić (mentor)
• Mentor: Marija Alešković (komentor)
• Committee member: Irena Škorić (predsjednik povjerenstva)
• Committee member: Dragana Mutavdžić Pavlović (član povjerenstva)
• Committee member: Marija Alešković (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2023-09-29, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog rada provedena je sinteza adamantanskih i diamantanskih amonijevih soli 1–8 koje su ispitane kao molekule gosti u vezivanjima s β- i γ-ciklodekstrinima (CD) molekulama domaćinima u vodenim otopinama. Nizom reakcijskih koraka pripravljen je 2-aminoadamantan iz adamantan-2-ona, a funkcionalizacijom diamantanskog ugljikovodika dobiveni su različiti regioizomeri aminodiamantana, 1- i 3-supstituirani diamantanski amini. Sintetizirani amini prevedeni su u odgovarajuće amonijeve soli 1–3, a potom u različite funkcionalizirane, dimetilirane 4–6 i permetilirane 7 i 8, amonijeve soli. Svi pripravljeni spojevi okarakterizirani su uobičajenim spektroskopskim metodama. Studij vezivanja molekula 1–8 s β- i γ-ciklodekstrinima proveden je titracijskim 1H NMR eksperimentima u D2O otopinama te se temeljem dobivenih rezultata zaključuje da nastaju kompleksi 1:1 stehiometrije uz vrijednosti konstanti stabilnosti ≥ 10^3 i 10^4 mol^–1 dm^3. Adamantanske amonijeve soli stvaraju inkluzijske komplekse samo s β-CD makrociklom, dok diamantanske amonijeve soli stvaraju inkluzijske komplekse s oba ispitana makrocikla. Stabilnije komplekse tvore s manjim makrociklom, β-CD-om. Inkluzijski kompleksi potvrđeni su NOESY spektroskopijom.

Abstract (english)

In the scope of this thesis, adamantane and diamantane ammonium salts 1–8 were synthesized and compounds were tested as guest molecules in binding with β- and γ-cyclodextrin (CD) host molecules in aqueous solutions. Throughout a multistep synthesis, 2-aminoadamantane was prepared from adamantan-2-one, and by functionalization of diamantane hydrocarbon, different regioisomers of aminodiamantane, 1- and 3-substituted diamantane amines, were obtained. The synthesized amines were converted into the corresponding ammonium salts 1–3, and then into various functionalized dimethylated 4–6 and permethylated 7 and 8 ammonium salts. All prepared compounds were characterized by standard spectroscopic methods. The binding study of the molecules 1–8 with β- and γ-cyclodextrins was carried out by 1H NMR titration experiments in D2O solutions. Based on the obtained results, it was concluded that complexes of 1:1 stoichiometry were formed with values of stability constants ≥ 10^3 and 10^4 mol^–1 dm^3. Adamantane ammonium salts form inclusion complexes only with the β-CD macrocycle, while diamantane ammonium salts form inclusion complexes with both tested macrocycles, more stable being with the smaller macrocycle, β-CD. Inclusion complexes were confirmed by NOESY spectroscopy.

• Keywords: diamantoidne amonijeve soli; ciklodekstrini; inkluzijski kompleksi; domaćin-gost interakcije; NMR titracija
• Keywords (english): diamondoid ammonium salts; cyclodextrins; inclusion complexes; host-guest interactions; NMR titration
• Language: croatian
• URN:NBN: urn:nbn:hr:149:448412
• Project: Number: UIP-2017-05-9653; Title: Diamantoidni sustavi s heteroatomima – priprava i primjena u razvoju naprednih materijala; Acronym: DiamMat; Leader: Marina Šekutor; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: UIP
• Study programme: Title: Applied Chemistry - Graduate study; specializations in: Environmental chemistry and green technologies, Advanced materials and technologies, Applied organic chemistry; Course: Applied organic chemistry; Study programme type: university; Study level: graduate; Academic / professional title: sveučilišni/a magistar/magistra primijenjene kemije (sveučilišni/a magistar/magistra primijenjene kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Embargoed access; Embargo expiration date: 2025-09-29
• Created on: 2023-11-24 13:40:53