Title Funkcionalni hidrogelovi temeljeni na Fmoc-aminokiselinama Title (english) Functional Hydrogels Based on Fmoc-Amino Acids Author Ena Dražić Mentor Daniela Kalafatović (mentor)Mentor Patrizia Janković (komentor)Committee member Daniela Kalafatović (član povjerenstva)Committee member Patrizia Janković (član povjerenstva)Committee member Christian Andrew Reynolds (predsjednik povjerenstva)Committee member Nikolina Vidović (član povjerenstva)Granter University of Rijeka Defense date and country 2024-09-09, Croatia Scientific / art field, BIOTECHNICAL SCIENCES Abstract Hidrogelatori male molekulske mase temeljeni na Fmoc-amino kiselinama predstavljaju obećavajuće molekule, nudeći brojne prednosti poput jednostavne pripreme hidrogelova, prilagodljivih svojstava i biokompatibilnosti. Ovo istraživanje usmjereno je na dizajn i karakterizaciju hidrogelova temeljenih na Fmoc-histidinu i Fmoc-cisteinu, kao gradivnim jedinicama koje su sposobne formirati supramolekularne strukture putem nekovalentnih interakcija kao što su vodikove veze i π-π slaganje. Histidin, polarna aminokiselina, često se koristi za katalizu u kombinaciji s cisteinom, neutralnom aminokiselinom poznatom po svojoj sklonosti stvaranju disulfidnih mostova oksidacijom. U ovoj studiji, hidrogelovi su dobiveni pri koncentracijama od 10 mM i 15 mM Fmoc-Cys u PBS-u, a kristali su dobiveni pri 10 mM Fmoc-His na temelju samoorganizacije pojedinačnih Fmoc-amino kiselina. Nadalje, njihova ko-samoorganizacija pri koncentracijama od 20 mM i 30 mM rezultirala je prozirnim hidrogelovima. Procijenjena je stabilnost hidrogelova, strukturna svojstva i katalitička aktivnost. Fmoc-His se samoorganizirao u kristale, a njihova struktura je riješena korištenjem rendgenske difrakcije. Stabilnost gela Fmoc-Cys i Fmoc-Cys:Fmoc-His ispitana je pomoću testa inverzije bočice, termoreverzibilnog testa i reologije. Osim toga, provedene su LC-MS analiza i Ellmanov test kako bi se istražila oksidacija Fmoc-Cys, dok je fluorescencijska analiza otkrila kritične koncentracije agregacije (CAC) Fmoc-amino kiselina. p-NPA test korišten je za procjenu katalitičke aktivnosti hidrogelova. Rezultati sugeriraju da ko-samoorganizirani hidrogeli Fmoc-Cys:Fmoc-His pokazuju superiornu katalitičku aktivnost u usporedbi sa samoorganiziranim Fmoc-Cys. Niža aktivnost Fmoc-Cys može se pripisati formiranju disulfidnih mostova putem oksidacijskih procesa, što smanjuje njegovu nukleofilnu reaktivnost. Ova studija doprinosi razumijevanju hidrogelatora male molekulska mase i njihovih potencijalnih primjena kao minimalističkih katalizatora.
Abstract (english) Low molecular weight hydrogelators based on Fmoc-amino acids are promising molecules, offering numerous advantages such as ease of hydrogel preparation, tunable properties and biocompatibility. This research focuses on the design and characterization of hydrogels based on Fmoc-Histidine and Fmoc-Cysteine, as building blocks capable of forming structures supramolecular through non-covalent interactions such as hydrogen bonding and π-π stacking. Histidine, a polar amino acid, is frequently exploited for catalysis in combination with cysteine, a neutral amino acid known for its propensity to create disulfide bridges through oxidation. In this study, hydrogels are obtained at 10 mM and 15 mM of Fmoc-Cys in PBS and crystals are obtained at 10 mM of Fmoc-His based on the self-assembly of individual Fmoc-amino acids. Furthermore, their co-assembly at 20 mM and 30 mM resulted in transparent hydrogels. Hydrogel stability, structural properties and catalytic activity were assessed. Fmoc-His self-assembled into crystals and its structure was solved using X-ray diffraction. Gel stability of Fmoc-Cys and Fmoc-Cys:Fmoc-His was conducted using a vial inversion test, the thermoreversibility test and rheology. Moreover, LC-MS analysis and Ellman’s assay were performed to investigate the Fmoc-Cys oxidation, while fluorescence analysis to reveal critical aggregation concentrations (CAC) of Fmoc-amino acids. The p-NPA assay was used to evaluate the catalytic activity of hydrogels. The results suggest that Fmoc-Cys:Fmoc-His co-assembled hydrogels exhibit superior catalytic activity compared to self-assembled Fmoc-Cys. The lower activity of Fmoc-Cys might be attributed to the formation of disulfide bridges via the oxidation processes, thereby hindering its nucleophilic reactivity. This study contributes to the understanding of low molecular weight hydrogelators and their potential applications as minimalistic catalysts.
Keywords
hidrogelatori male molekulske mase
samoorganizacija
koorganizacija
hidrogelovi
Fmoc-amino kiseline
Keywords (english)
low molecular weight gelators
self-assembly
co-assembly
hydrogels
Fmoc-amino acids
Language english URN:NBN urn:nbn:hr:193:933468 Study programme Title: Medicinal chemistry Type of resource Text File origin Born digital Access conditions Embargoed access Terms of use Public note HRZZ Uspostavni istraživački projekt (UIP-2019-04-7999) Created on 2024-09-10 14:34:36
