Priprava, konformacijska analiza i kirooptička svojstva peptidnih derivata aminoferocena

doctoral thesis

• Title (english): Synthesis, conformational analysis and chiroptical properties of peptide derivatives of aminoferrocene
• Author: Marko Nuskol
• Mentor: Mojca Čakić Semenčić (mentor)
• Committee member: Ivan Kodrin (predsjednik povjerenstva)
• Committee member: Predrag Novak (član povjerenstva)
• Committee member: Lidija Barišić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021-01-07, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U okviru ove doktorske disertacije provedena je sinteza i konformacijska analiza peptidnih
konjugata aminoferocena [Boc–(AA)n–NH–Fc, Fc = ferocenil, AA = D(L)–Pro, D(L)–Ala,
Boc (tert–butoksikarbonil), Aib (α–aminoizobutirična kiselina), n = 2–4] kao i dinuklearnih
ferocenskih derivata [Fc–CO–(AA)2–NH–Fc, AA = D(L)–Pro, D(L)–Ala] kako bi se istražio
utjecaj nabiranja aminokiselinskog slijeda na kirooptička svojstva organometalnog kromofora.
Konformacijskom analizom (IR–spektroskopija, spektroskopija NMR i CD, kristalografska
analiza, računalno modeliranje) utvrđeno je da su pripravljeni spojevi, u otopini i u čvrstom
stanju, stabilizirani unutarmolekulskim vodikovim vezama koje podržavaju okrete i uzvojnice
slične onima u prirodnim peptidima. Kombiniranim teorijskim i eksperimentalnim pristupom
pokazano je kako kiralno uređenje peptidnog segmenta inducira Cottonov efekt u blizini
UV/Vis apsorpcijskog maksimuma ferocena čiji je predznak u korelaciji s diedarskim kutom
koji opisuje rotaciju oko veze između ferocenskog kromofora i peptidnog segmenta.

Abstract (english)

In this PhD thesis peptide derivatives of aminoferrocene [Boc–(AA)n–NH–Fc, Fc =
ferrocenyl, AA = D(L)–Pro, D(L)–Ala, Aib, Boc (tert–butoxycarbonyl), Aib (α–
aminoisobutyric acid), n = 2–4] as well as the dinuclear ferrocene derivatives [Fc–CO–
(AA)2–NH–Fc, AA = D(L)–Pro, D(L)–Ala] were synthesized. The novel compounds were
subjected to conformational analysis in order to investigate the influence of folding of amino
acid sequence on the chiroptical properties of organometallic chromophore. Conformational
analysis (IR, NMR, and CD spectroscopy, crystallographic analysis, computational modeling)
of the prepared compounds revealed that they are stabilized by intramolecular hydrogen
bonds, that support turns and helices similar to those in natural peptides, in solution as well as
in solid state. The combined theoretical and experimental approach has shown that the chiral
arrangement of the peptide segment induces Cotton effect near the UV/Vis absorption
maximum of ferrocene, whose sign is in correlation with dihedral angle which describes
rotation around ferrocene–peptide linkage.

• Keywords: Spektroskopija cirkularnog dikroizma; kirooptička svojstva; konformacijska analiza; aminoferocen; peptidi; bioorganometalna kemija
• Keywords (english): Circular dichroism spectroscopy; chirooptical properties; conformational analysis; aminoferrocene; peptide; bioorganometalic chemistry
• Language: croatian
• URN:NBN: urn:nbn:hr:217:278070
• Promotion: 2021
• Study programme: Title: Doctoral study in chemistry; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 175 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2021-02-26 14:19:27