Ferocen kao kirooptički senzor za određivenje kiralnosti aminokiselina i pepida

doctoral thesis

• Title (english): Ferrocene as a chiroptical sensor for determining the chirality of amino acids and peptides
• Author: Petar Šutalo
• Mentor: Ivan Kodrin (mentor)
• Committee member: Branimir Bertoša (predsjednik povjerenstva)
• Committee member: Lidija Barišić (član povjerenstva)
• Committee member: Gordan Horvat (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2023-11-15, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U radu je provedena konformacijska analiza i karakterizacija obrazaca vodikovih veza na
odabranim skupovima monosupstituiranih ferocenskih peptidomimetika hijerarhijskim
pristupom odnosno kombinacijom molekulsko- i kvantno-mehaničkih metoda. Računalno
dobiveni rezultati uspoređeni su s eksperimentalnim podacima. Računalnom kemijom utvrđeno
je da središnja kiralnost aminokiseline i/ili helična kiralnost kratkog peptidnog lanca izravno ili
preko kratke akiralne poveznice vezanih na ferocensku skupinu utječu na predznak
apsorpcijskog maksimuma ferocenskog kromofora (oko 470 nm) u spektru cirkularnog
dikroizma. Predznak i veličina Cottonovog efekta u korelaciji su s predznakom i veličinom
diedarskog kuta χ kojim je opisana rotacija amidne skupine izravno vezane na ferocenski
ciklopentadienilni prsten. Uvođenje akiralnih aminokiselina, poput 2-amino-2-metilpropanske
kiseline (Aib) i 1-aminocikloheksankarboksilne kiseline (Ac6c), stvaranjem β-okreta i 310
uzvojnica vodi k većoj zastupljenosti jednog od konformera u Boltzmannovoj raspodjeli pri
298 K. Navedeno bi se moglo iskoristiti u dizajnu nove skupine selektivnih kirooptičkih senzora
temeljenih na ferocenskom kromoforu za određivanje središnje kiralnosti aminokiselina i
helične kiralnosti kratkih peptidnih lanaca.

Abstract (english)

n this thesis conformational analysis and characterization of hydrogen bond patterns were
performed using a hierarchical approach combining molecular and quantum mechanics
methods on selected groups of monosubstituted ferrocene peptidomimetics. The computational
results were compared with experimental data. Computational chemistry confirmed the central
chirality of the amino acid and/or the helical chirality of the short peptide chain, directly or via
a short achiral linker attached to the ferrocene group, affect the sign of the absorption maximum
of the ferrocene chromophore (at 470 nm) in the circular dichroism spectrum. The sign and
magnitude of the Cotton effect correlates with the sign and magnitude of the dihedral angle χ
describing the rotation of the amide group directly attached to the cyclopentadienyl ring of
ferrocene. The introduction of achiral amino acids, such as 2-amino-2-methylpropanoic acid
and 1-aminocyclohexanecarboxylic acid, through the formation of β-turns and 310 helices,
results in a greater prevalence of a single conformer in the Boltzmann distribution at 298 K.
This information could be used in the development of a new group of selective chiroptical
sensors based on ferrocene chromophores to determine the central chirality of amino acids and
the helical chirality of short peptide chains.

• Keywords: cirkularni dikroizam; ferocenski peptidi; kiralnost; konformacijska analiza; teorija funkcionala gustoće (DFT)
• Keywords (english): chirality; circular dichroism (CD); conformatonal analysis; density functional theory (DFT); ferrocene peptides
• Language: croatian
• URN:NBN: urn:nbn:hr:217:585726
• Promotion: 2023
• Study programme: Title: Doctoral study; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica u području prirodnih znanosti (doktor/doktorica u području prirodnih znanosti)
• Type of resource: Text
• Extent: LV, 138 str. ; 30 cm
• File origin: Born digital
• Access conditions: Embargoed access; Embargo expiration date: 2024-11-15
• Created on: 2023-11-23 14:26:39