Sinteza i fizikalno-kemijska karakterizacija bis-fosfatnih estera

master's thesis

• Title (english): Synthesis and physico-chemical characterisation of bis-phosphate esters
• Author: Doroteja Lončarić
• Mentor: Nikola Bregović (mentor)
• Committee member: Nikola Bregović (predsjednik povjerenstva)
• Committee member: Ivana Biljan (član povjerenstva)
• Committee member: Vladimir Stilinović (član povjerenstva)
• Committee member: Vladislav Tomišić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2020-07-10, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog rada provedena je priprava i fizikalno-kemijska karakterizacija nekoliko bis-fosfatnih estera s ciljem razvoja njihove primjene u supramolekulskoj kemiji. Istraživanje je potaknuto ranijim rezultatima koji su ukazali na stabilnost dimera i homoasocijata fosforne kiseline u aprotičnim organskim otapalima. Osnovna hipoteza ovog istraživanja jest da se stabilizacija supramolekulskih kompleksa bis-fosfatnih receptora može temeljiti na interakcijama analognim homoasocijaciji fosfata.
Pripravljeni su bis-fosfoesterski liganadi koji sadrže dvije fosfatne skupine povezane alkilnom, eterskom ili aromatskom eterskom poveznicom. Optimirana je sinteza liganada, pri čemu su ispitana tri pristupa uvođenju fosfatne skupine te su sintetizirana četiri liganda.
Određena je kiselost liganada s trietilenglikolnom poveznicom (DL1 i DL4) u acetonitrilu pomoću spektroskopije NMR. Deprotonacija aromatskog liganda DL4 s različitim bazama dodatno je istražena mikrokalorimetrijskim titracijama. Dimerizacija jednostruko deprotoniranog oblika liganda DL4 ispitana je tehnikom DOSY spektroskopije NMR te je određena pripadna konstanta ravnoteže. Homoasocijacija liganda DL4 ispitana je mikrokalorimetrijskim titracijama.

Abstract (english)

In the scope of this diploma thesis preparation and physico-chemical characterization of several bis-phosphate esters were performed with the goal of developing their application in supramolecular chemistry. The research was inspired by earlier results, which have pointed out the stability of dimers and homoassociates of phosphoric acid in aprotic organic solvents. The hypothesis of this research is that the stabilization of bis-phosphate receptor complexes could be based on the interactions analogous to the homoassociation of phosphate.
Bis-phosphate ester ligands containing two phosphate groups connected by either alkyl, ether or aromatic ether linker were prepared. Synthesis of ligands was optimized, three approaches of introducing the phosphate group in the molecule were tested and four ligands were successfully prepared.
The acidity of ligands containing triethylenegylcolic linker (DL1 and DL4) was determined in acetonitrile by NMR spectroscopy. Deprotonation of aromatic ligand DL4 with different bases was additionaly investigated by microcalorimetric titrations. Dimerisation of monodeprotonated form of DL4 was studied by DOSY NMR technique and the accompanying equilibrium constant was determined. Homoassociation of ligand DL4 was tested by microcalorimetric titrations.

• Keywords: dimerizacija; fosfatni esteri; homoasocijacija; konstanta ravnoteže; protonacija; supramolekulska kemija
• Keywords (english): dimerisation; equilibrium constant; homoassociation; phosphate esters; protonation; supramolecular chemistry
• Language: croatian
• URN:NBN: urn:nbn:hr:217:069004
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2020-07-16 09:44:30