Naslov
Making rings from amino acids. Shining light on possible (chemo)evolution of proline

Autori
Zubčić, Gabrijel ; Portada, Tomislav ; Biruš, Ivan ; Šakić, Davor

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
Book of Abstracts of the Congress of the Croatian Society of Biochemistry and Molecular Biology HDBMB22: From Science to Knowledge / Dulić, Morana ; Sinčić, Nino ; Vrhovac Madunić, Ivana - Zagreb : Hrvatsko društvo za biokemiju i molekularnu biologiju (HDBMB), 2022, 159-159

Skup
HDBMB22: From Science to Knowledge

Mjesto i datum
Brela, Hrvatska, 28.09.2022. - 01.10.2022

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
radicals, rearrangement, Hofmann-Löffler-Freytag (HLF) reaction

Sažetak
Proline is an unusual proteinogenic alfa amino acid, where the side chain is connected to the amino group, forming a pyrrolidine ring and secondary amine. Due to its unique internal bonding it has different structural properties compared to other amino acids in peptides and proteins, including different ratio of cis/trans isomerism in peptide bonds, conformational rigidity and losing hydrogen-donating characteristics. Biosynthesis of proline starts from L-glutamate, proceeds through gamma- semialdehyde, that cyclizes to pyrrolidine- ring that is then reduced to proline. Generation of proline in primordial soup is not well understood. While it is possible that generation through Schiff base mechanism is possible, here we provide an alternative. Pyrrolidine rings can be formed through Hofmann-Löffler-Freytag (HLF) reaction. This reaction starts from halogenated amine, which under illumination or heating cleaves homolytically, generating N-centred radical. Rearrangement of N- centred radical to C-centered radical, and subsequent ring formation can be one of the ways proline is formed from nor-leucine. This reaction can also be used for synthesis of pharmacologically active compounds, such as nicotine derivatives. Here presented are simulations of thermodynamic and kinetic profile, synthesis, kinetic studies, and characterisation of proline derivatives utilising HLF reaction. Results can be used to describe structural changes and degradation in proteins in oxidative stress and high UV radiation conditions.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Farmacija

POVEZANOST RADA