The role of solid-state reactivity in the prebiotic selection of nucleobases and formation of peptides

doctoral thesis

• Title (croatian): Uloga reaktivnosti u čvrstom stanju u prebiotičkom odabiru nukleobaza i stvaranju peptida
• Author: Tomislav Stolar
• Mentor: Krunoslav Užarević (mentor)
• Committee member: Mirta Rubčić (predsjednik povjerenstva)
• Committee member: Sanda Rončević (član povjerenstva)
• Committee member: Oliver Trapp https://orcid.org/0000-0002-3594-5181 (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2022-08-26, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Within this thesis, solid-state reaction medium and mechanochemical methodologies were explored to unveil weather nucleobases can self-assemble and amino acids can oligomerize under these conditions. X-ray diffraction and differential scanning calorimetry analysis showed that 2,6-diaminopurine (D) selectively self-assembles with uracil (U) and thymine (T), while adenine (A) self-assembles with hypoxanthine (H). Crystal structures of D-U cocrystal hydrate, D-T cocrystal hydrate, D-T cocrystal anhydrate, A-H cocrystal hydrate, and A-H cocrystal anhydrate were determined from powder X-ray diffraction and single-crystal X-ray diffraction data. Ion-pairing high performance liquid chromatography and mass spectrometry analysis showed that glycine and alanine undergo oligomerization by mechanical activation. Based on the results, it can be concluded that minerals as additives, time, mechanical loading, and temperature are all important parameters for the mechanochemical prebiotic peptide synthesis. In summary, solid-state reactivity of nucleobases and amino acids might have been an important factor in their prebiotic chemical evolution.

Abstract (croatian)

U ovoj doktorskoj disertaciji koristili smo čvrsto stanje kao reakcijski medij i mehanokemijske metodologije da bismo istražili dolazi li do prepoznavanja nukleobaza i oligomerizacije aminokiselina u tim uvjetima. Analiza difrakcijom rentgenskog zračenja i diferencijalnom pretražnom kalorimetrijom pokazala je selektivno molekulsko prepoznavanje 2,6-diaminopurina (D) s uracilom (U) i timinom (T), kao i adenina (A) s hipoksantinom (H). Riješene su kristalne strukture D-U kokristalnog hidrata, D-T kokristalnog hidrata, D-T kokristalnog anhidrata, A-H kokristalnog hidrata te A-H kokristalnog anhidrata iz podataka difrakcije rentgenskog zračenja. Analiza tekućinskom kromatografijom visoke djelotvornosti i spektrometrijom mase pokazala je da glicin i alanin oligomeriziraju u peptide uslijed mehanokemijske aktivacije. Rezultati su pokazali da su minerali kao aditivi, vrijeme, prenošenje mehaničke energije, i temperatura ključni parametri za mehanokemijsku prebiotičku sintezu peptida. Zaključeno je da je reaktivnost nukleobaza i aminokiselina u čvrstom stanju mogla biti važan faktor u njihovoj prebiotičkoj kemijskoj evoluciji.

• Keywords: amino acids; mechanochemistry; molecular recognition; nucleobases; peptides; prebiotic chemistry; solid-state reactivity
• Keywords (english): :aminokiseline; čvrsto stanje; mehanokemija; molekulsko prepoznavanje; nukleobaze; peptidi; prebiotička kemija
• Language: english
• URN:NBN: urn:nbn:hr:217:985093
• Promotion: 2022
• 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: 160 str. ; 30 cm
• File origin: Born digital
• Access conditions: Embargoed access; Embargo expiration date: 2024-08-26
• Created on: 2022-11-03 14:33:43