Sinteza i fotokemija halogeniranih BODIPY fotokaveza

master's thesis

• Title (english): Synthesis and photochemistry of halogenated BODIPY photocages
• Author: Matija Popović
• Mentor: Nikola Basarić (mentor)
• Committee member: Đani Škalamera (predsjednik povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Committee member: Adriana Kenđel (član povjerenstva)
• Committee member: Željka Car (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021-09-17, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog rada provedena je sinteza četiri nova BODPY fotokaveza te su im istražena fotofizička
svojstva i fotokemijska reaktivnost. Spojevi su supstituirani na meso metilnoj poziciji s fotouklonjivom
fenolnom skupinom za koju se očekuje da daje kinon-metide u reakcijama otpuštanja. 4,4-Dimetil-8-
{[(2-hidroksimetil)fenoksi]metil}-2,6-dijod-1,3,5,7-tetrametil-4-bora-3a,4a-diaza-s-indacen (5), 4,4-
... More dimetil-8-{[(2-hidroksimetil)fenoksi]metil}-2,6-dibrom-1,3,5,7-tetrametil-4-bora-3a,4a-diaza-sindacen (6), 4,4-dimetil-8-{[(2-acetoksimetil)fenoksi]metil}-2,6-dijod-1,3,5,7-tetrametil-4-bora-3a,4adiaza-s-indacen (7) i 4,4-dimetil-8-{[(2-acetoksimetil)fenoksi]metil}-2,6-dibrom-1,3,5,7-tetrametil-4-
bora-3a,4a-diaza-s-indacen (8) sintizirani su i okarakterizirani 1H,
13C NMR spektroskopijom te pomoću
masene spektrometrije. Fotofizička svojstva dobivenih spojeva ispitana su UV/Vis spektroskopijom,
stacionarnom i vremenski razlučenom fluorescencijskom spektroskopijom. Usporedbom kvantnih
prinosa fluorescencije (ΦF) nehalogeniranih i halogeniranih BODIPY fotokaveza utvrđeno je da su ΦF
niži za halogenirane BODIPY fotokaveze što ukazuje na veću učinkovitost međustavnog križanja.
Vremenski koreliranim brojanjem pojedinačnih fotona određena su vremena života singletnog
pobuđenog stanja te konstante brzine deaktivacije zračenjem i bez zračenja. Laserskom pulsnom
fotolizom detektirana su tripletna pobuđena stanja koja sudjeluju u reakciji heterolize. Fotokemijska
reaktivnost ispitana je reakcijama fotosolvolize u metanolnim otopinama uz pobuđivanje vidljivim
svjetlom. Fotokemijske reakcije praćene su HPLC-om te su dobiveni kvantni prinosi reakcija. Za
spojeve 5-8 provedena su antiproliferativna ispitivanja na ljudskim tumorskim stanicama čuvanim u
mraku ili ozračenim vidljivim svijetlom. Spojevi pokazuju pojačanu antiproliferativnu aktivnost nakon
ozračivanja što ih čini prikladnima u razvoju antitumorskih fototerapeutika. Less

Abstract (english)

This master thesis features the synthesis of four new BODIPY photocages and investigation of their
photophysical properties and photochemical reactivity. The compounds are substituted at the meso
methyl position with a photocleavable phenolic group that is anticipated to deliver quinone methides in
the decaging reaction. 4,4-Dimethyl-8-{[(2-hydroxymethyl)phenoxy]methyl}-2,6-diiodo-1,3,5,7-
... More tetramethyl-4-bora-3a,4a-diaza-s-indacene (5), 4,4-dimethyl-8-{[(2-hydroxymethyl)phenoxy]methyl}-
2,6-dibromo-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (6), 4,4-dimethyl-8-{[(2-
acetoxymethyl)phenoxy]methyl}-2,6-diiodo-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (7) and
4,4-dimethyl-8-{[(2-acetoxymethyl)phenoxy]methyl}-2,6-dibromo-1,3,5,7-tetramethyl-4-bora-3a,4adiaza-s-indacene (8) were synthesized and characterized by 1H, 13C NMR and HRMS. Photophysical
properties were examined by UV/Vis, steady-state and time-resolved fluorescence spectroscopy. By
comparing fluorescence quantum yields (ΦF) of non-halogenated and halogenated BODIPY photocages,
it was found that ΦF were lower for the halogenated BODIPY photocages, indicating more efficient
intersystem crossing. The time-correlated single photon counting was used to determine lifetimes of the
singlet excited states and rate constants for radiative and non-radiative decay. Laser flash photolysis was
used to detect triplet excited states, which are involved in the heterolysis reaction. The photochemical
reactivity was investigated by conducting photosolvolyses in methanolic solutions upon excitation by
visible light. The progress of the reactions was monitored by HPLC and quantum yields of the reactions
were obtained. For compounds 5-8, aniproliferative investigations against human cancer cells were
performed with cells kept in dark or irradiated. Compounds show enhanced antiproliferative activity
upon irradiation, which renders them applicable in the development of cancer phototerapeutics. Less

• Keywords: BODIPY; fotokavez; fotokemija; kinon-metidi
• Keywords (english): BODIPY; photocages; photochemistry; quinone mthides
• Language: croatian
• URN:NBN: urn:nbn:hr:217:310458
• Project: Number: IP-2019-04-8008; Title: Fotokemija: Reakcijski mehanizmi i primjene u organskoj sintezi i biologiji; Title: Photochemistry: Reaction Mechanisms and Applications in Organic Synthesis and Biology; Acronym: PhotoApp; Leader: Nikola Basarić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• 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; Embargo expiration date: 2023-09-17
• Created on: 2021-10-15 12:26:33