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doctoral thesis
Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama
Zagreb: University of Zagreb, Faculty of Science, 2020. urn:nbn:hr:217:884019
Nikšić-Franjić, Ivana
University of Zagreb
Faculty of Science
Department of Chemistry

Institutional repository: Repository of the Faculty of Science

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Nikšić Franjić, I. (2020). Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama (Doctoral thesis). Zagreb: University of Zagreb, Faculty of Science. Retrieved from https://urn.nsk.hr/urn:nbn:hr:217:884019

Nikšić Franjić, Ivana. "Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama." Doctoral thesis, University of Zagreb, Faculty of Science, 2020. https://urn.nsk.hr/urn:nbn:hr:217:884019

Nikšić Franjić, Ivana. "Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama." Doctoral thesis, University of Zagreb, Faculty of Science, 2020. https://urn.nsk.hr/urn:nbn:hr:217:884019

Nikšić Franjić, I. (2020). 'Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama', Doctoral thesis, University of Zagreb, Faculty of Science, accessed 26 November 2024, https://urn.nsk.hr/urn:nbn:hr:217:884019

Nikšić Franjić I. Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama [Doctoral thesis]. Zagreb: University of Zagreb, Faculty of Science; 2020 [cited 2024 November 26] Available at: https://urn.nsk.hr/urn:nbn:hr:217:884019

I. Nikšić Franjić, "Računalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama", Doctoral thesis, University of Zagreb, Faculty of Science, Zagreb, 2020. Available at: https://urn.nsk.hr/urn:nbn:hr:217:884019

Metadata
TitleRačunalno istraživanje reakcija slobodnih radikala s halogeniranim organskim spojevima u vodenim otopinama
Title (english)Computational study of free radical reactions with halogenated organic compounds in water solutions
AuthorIvana Nikšić-Franjić
MentorIvan Ljubić (mentor)
Committee memberIvan Kodrin (predsjednik povjerenstva)
Committee memberBorislav Kovačević (član povjerenstva)
Committee memberDarko Babić (član povjerenstva)
GranterUniversity of Zagreb
Faculty of Science
(Department of Chemistry)
Zagreb
Defense date and country2020-07-13, Croatia
Scientific / art field,
discipline and subdiscipline		NATURAL SCIENCES
Chemistry
Universal decimal classification
(UDC)		54 - Chemistry. Crystallography. Mineralogy
Abstract
U disertaciji su istraženi mehanizmi i kinetike reakcija slobodnih radikala s halogeniranim organskim spojevima u nepuferiranim i puferiranim (bikarbonatnim i fosfatnim) vodenim otopinama. Rad obuhvaća istraživanje reaktivnosti α-aminoalkilnih C-radikala: α-aminoetilnog (˙CH(CH3)NH2) i N-metil-α-aminoetilnog (˙CH(CH3)NHCH3), zatim glicil radikal aniona (˙CH(NH2)COO−) i atoma vodika (H˙) s trima halogenacetatima – klor-, brom- i jodacetatom – te s halogeniranom nukleobazom 5-bromuracilom. U reakcijama je uočeno nekoliko kompetitivnih mehanizama, od kojih je najznačajniji spregnuti prijenos protona i elektrona (PCET). Otapalo voda isprva je opisano implicitno, modelom PCM, a potom je istražen utjecaj eksplicitne molekule vode na mehanizme i reakcijsku energetiku. Na temelju parametara izračunatih teorijom funkcionala elektronske gustoće (DFT) određeni su dominantni reakcijski mehanizmi i kinetike reakcija. Kod izračuna konstanti brzina uporabljena je konvencionalna teorija prijelaznog stanja i njezina varijacijska inačica uz semiklasične popravke na tuneliranje. Sustavnim istraživanjem izmjensko-korelacijskih funkcionala duž Jakovljevih ljestvi DFT-a nađeni su funkcionali koji daju najbolje slaganje s izmjerenim konstantama brzina za niz radikalskih reakcija.
Abstract (english)
In this doctoral thesis the reaction mechanisms and kinetics of free radical reactions with halogenated organic compounds in non-buffered and buffered (bicarbonate and phosphate) aqueous solutions were investigated. This includes a study of the reactivity of C-centered α-aminoalkyl radicals: ˙CH(CH3)NH2, ˙CH(CH3)NHCH3, glycyl radical anion ˙CH(NH2)COO− and hydrogen atom (H˙) with haloacetates: chloro-, bromo- and iodoacetate and a halogenated nucleobase 5-bromouracil. Reactions exhibit a variety of fundamentally important competing mechanisms, of which the most important one is the proton coupled electron transfer. The solvent was initially described implicitly, and then the influence of explicit water molecules on the mechanisms and reaction energetics was explored. Based on the parameters calculated by the theory of density functional theory (DFT), the dominant reaction mechanisms and reaction kinetics were determined. The reaction rate constants were calculated employing the conventional and variational transition state theory with semiclassical corrections for the tunneling. By systematically climbing up the Jacob's ladders of DFT, for the set of radical reactions, we investigated which types of exchange-correlation functionals produce the rate constants in best agreement with the measured ones.
Keywords
Keywords (english)
Languagecroatian
URN:NBNurn:nbn:hr:217:884019
Promotion2020
Study programmeTitle: 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 resourceText
Extent170 str. ; 30 cm
File originBorn digital
Access conditionsOpen access
Terms of useLicence In copyright icon
Created on2020-07-17 11:23:23