| الوصف: |
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- 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. 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- 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. |
