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master's thesis
Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma
Zagreb: University of Zagreb, Faculty of Pharmacy and Biochemistry, 2019. urn:nbn:hr:163:616608
Božičević, Lucija
University of Zagreb
Faculty of Pharmacy and Biochemistry
Department of analytical chemistry

Institutional repository: Repository of Faculty of Pharmacy and Biochemistry University of Zagreb

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Božičević, L. (2019). Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma (Master's thesis). Zagreb: University of Zagreb, Faculty of Pharmacy and Biochemistry. Retrieved from https://urn.nsk.hr/urn:nbn:hr:163:616608

Božičević, Lucija. "Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma." Master's thesis, University of Zagreb, Faculty of Pharmacy and Biochemistry, 2019. https://urn.nsk.hr/urn:nbn:hr:163:616608

Božičević, Lucija. "Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma." Master's thesis, University of Zagreb, Faculty of Pharmacy and Biochemistry, 2019. https://urn.nsk.hr/urn:nbn:hr:163:616608

Božičević, L. (2019). 'Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma', Master's thesis, University of Zagreb, Faculty of Pharmacy and Biochemistry, accessed 26 November 2024, https://urn.nsk.hr/urn:nbn:hr:163:616608

Božičević L. Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma [Master's thesis]. Zagreb: University of Zagreb, Faculty of Pharmacy and Biochemistry; 2019 [cited 2024 November 26] Available at: https://urn.nsk.hr/urn:nbn:hr:163:616608

L. Božičević, "Transacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma", Master's thesis, University of Zagreb, Faculty of Pharmacy and Biochemistry, Zagreb, 2019. Available at: https://urn.nsk.hr/urn:nbn:hr:163:616608

Metadata
TitleTransacilacija u konjugatima ferocena i purinskih baza. Računalna studija mehanizma
Title (english)Transacylation in ferrocene derivatives of purine nucleobases. Computational study of the mechanism
AuthorLucija Božičević
MentorDavor Šakić (mentor)
MentorValerije Vrček (komentor)
Committee memberDavor Šakić (predsjednik povjerenstva)
Committee memberValerije Vrček (član povjerenstva)
Committee memberTin Weitner (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Pharmacy and Biochemistry
(Department of analytical chemistry)
Zagreb
Defense date and country2019-09-25, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Organic Chemistry
Abstract
Purinske baze mogu biti supstituirane ferocenoilnom skupinom pri čemu se ista može vezati na N7- te N9-atom purinskog prstena. U polarnom organskom otapalu dimetilsulfoksidu (DMSO) dolazi do interkonverzije dvaju izomera. Reakciju je moguće pratiti NMR-spektroskopijom. Iz podataka dobivenih praćenjem reakcije do uspostave ravnoteže moguće je odrediti eksperimentalne konstante brzine reakcija kobs te konstante ravnoteže Keq te izračunati promjenu Gibbsove slobodne energije potrebnu za odvijanje procesa. Korištenjem računalno-kemijskih metoda modelirana su tri reakcijska mehanizma, ranije opisana u literaturi, koja bi potencijalno mogla odgovarati mehanizmu transacilacije u konjugatima ferocena i purinskih baza. Odgovarajućim procesima smatraju se oni čije su energetske barijere niže ili jednake eksperimentalno dobivenima. Reakcija koja uključuje dimetilsulfoksid kao nukleofilni reaktant jedina odgovara eksperimentalno dobivenim parametrima, zbog čega je ova SN2-like reakcija najvjerojatnije odgovorna za transacilaciju konjugata ferocena i purinskih baza. Supstituenti na C6-atomu pokazuju znatan utjecaj na brzinu reakcije transacilacije. Izomerizacija acilnih derivata purinskih baza u polarnim organskim otapalima, ukoliko njezin mehanizam nije poznat, predstavlja problem prilikom rukovanja sa spojevima. Transacilacija u polarnom otapalu poput DMSO-a nije ograničena samo na organometalne derivate purinskih baza, a poznavanje ovakvih reakcija moglo bi se pokazati ključnim i za derivate drugih nukleobaza, ali i brojnih heterocikličkih sustava.
Abstract (english)
In ferrocene-nucleobase conjugates ferrocenoyl group can be placed at N7- and N9-atoms of purine ring. There is an interconversion between the two when the compound is dissolved in polar organic solvents, such as dimethylsulfoxide (DMSO). Reaction was followed using the NMR-spectroscopy until dynamic equilibrium is reached. From obtained experimental data, kobs and Keq can be determined, as well as ΔG‡. By use of DFT calculations, three reaction pathways, formerly described in literature, were considered and modelled. These reaction pathways are considered as potential transacylation mechanisms if the calculated energy barriers are lower or close to the experimental ones. Only the SN2-like reaction mechanism involving DMSO as a nucleophilic reactant agrees well with experimental data. It was also determined that C6-substituent of purine ring has a great influence on reaction kinetics. Isomerization of acylated purines in polar organic solvent, DMSO, is of great importance for treating or dissolving acylated purines in it. Transacylation is not limited to organometallic-nucleobase conjugates only and could possibly be important in many other purine-acyl derivatives, as well as some other heterocyclic systems in general.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:163:616608
Study programmeTitle: Pharmacy
Study programme type: university
Study level: integrated undergraduate and graduate
Academic / professional title: magistar/magistra farmacije (magistar/magistra farmacije)
Type of resourceText
File originBorn digital
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2021-05-12 13:03:50