Fotokemijska reakcija razgradnje ferocenskih derivata purina i pirimidina

master's thesis

• Title (english): Photochemical decomposition reaction of ferrocenoyl-purines and pyrimidines
• Author: Lana Petrinec
• Mentor: Valerije Vrček (mentor)
• Committee member: Valerije Vrček (predsjednik povjerenstva)
• Committee member: Davor Šakić (član povjerenstva)
• Committee member: Tin Weitner (član povjerenstva)
• Granter: University of Zagreb; Faculty of Pharmacy and Biochemistry; (Department of organic chemistry); Zagreb
• Defense date and country: 2021-06-23, Croatia
• Scientific / art field, discipline and subdiscipline: BIOMEDICINE AND HEALTHCARE; Pharmacy; Pharmacy

Abstract

Ferocenoilne nukleobaze su osjetljive na svjetlost kada su otopljene u organskim otapalima, kao što je DMSO. Svjetlost inducira reakciju eliminacije ciklopentadiena, razgradnju ferocenskog dijela molekule i formiranje slobodne nukleobaze. Reakcija je proučena na primjeru derivata N9-ferocenoil-(6-benziloksi)purina i N1-ferocenoil-5-fluorouracila. Kompleksi željeza koji također nastaju kao produkti usporavaju reakciju. Otapalo (DMSO) djeluje kao reaktant i sudjeluje u nukleofilnom napadu na središnji atom željeza.. Red fotokemijske reakcije ovisi o molarnom apsorpcijskom (ekstinkcijskom) koeficijentu i uvjetima reakcije. Kada je reakcija pokrenuta crvenom lampom (λ = 645 nm) opaža se pseudo-prvi red, a kada je pokrenuta plavom lampom
(λ = 405 nm) opaža se pseudo-nulti red. N,N-difenil-1-ferocenakarboksamid također je osjetljiv na svjetlost, ali se mehanizam reakcije razlikuje od fotorazgradnje ferocenoilnih-nukleobaza. Ukoliko se ferocenska jezgra zamijeni benzenskom, nastali benzoil-purinski derivati (N7-4-fluorobenzoil-purin)nisu osjetljivi na djelovanje svjetlosnog zračenja.

Abstract (english)

Ferrocenoyl-substituted nucleobases are light-sensitive when dissolved in organic solvents, i.e. DMSO. Light induces an elimination reaction which results in degradation of ferrocene moiety, loss of cyclopentadiene ring and release of free nucleobase. N9-ferrocenoyl-(6-benzyloxi)purine and N1-ferrocenoyl-5-fluorouracyl were used in the study of this photochemical reaction. The formation od ring-deligated iron complexes during the reaction decreases the reaction rate. DMSO is also a reactant which assists in gradual displacement of the five-membered cyclopentadiene ring. Reaction conditions and molar absorption (extinction) coefficients of ferrocene conjugates affect the reaction order. Pseudo-first order kinetics occurs when the red lamp (λ = 645 nm) is used to trigger the reaction. When the blue lamp (λ = 405 nm) is used, it changes to pseudo-zero order. N,N-diphenyl-1-ferrocene carboxamide is also light-sensitive, but the reaction mechanism differs from the mechanism observed for ferrocenoyl-nucleobases. Different acyl-ferrocenes react in different manner in this photochemical reaction. When the ferrocene moiety is replaced by a benzene ring, like in N7-4-fluorobenzoyl-purine, the obtained compound is not light-sensitive.

• Keywords: fotokemija; ferocenoilne nukleobaze; fotorazgradnja
• Keywords (english): photochemistry; ferrocenoyl-substituted nucleobases; photoreaction
• Language: croatian
• URN:NBN: urn:nbn:hr:163:840567
• Study programme: Title: Pharmacy; Study programme type: university; Study level: integrated undergraduate and graduate; Academic / professional title: magistar/magistra farmacije (magistar/magistra farmacije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2022-03-25 14:19:11