Naslov
The role of guaiacyl moiety in radical scavenging by 3, 5-dihydroxy-4-methoxybenzyl alcohol

Autori
Amić, Ana ; Marković, Zoran ; Dimitrić Marković, Jasmina ; Lučić, Bono ; Amić, Dragan

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

Izvornik
Math/Chem/Comp 2017, 29th MC2 Conference : Book of Abstracts / Vančik, Hrvoj ; Cioslowski, Jerzy - , 2017, 1-1

Skup
Math/Chem/Comp 2017, MC2-29 : The 29th International Course and Conference on the Interfaces among Mathematics, Chemistry and Computer Sciences

Mjesto i datum
Dubrovnik, Hrvatska, 19.06.2017. - 24.06.2017

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Nije recenziran

Ključne riječi
radical scavenging ; guaiacyl moiety ; DHMBA ; DFT ; tHAt ; tET-PT ; tSPLET

Sažetak
The thermodynamic preference of different radical scavenging mechanisms of 3, 5- dihydroxy- 4-methoxybenzyl alcohol (DHMBA), a natural product identified in oysters, was studied using DFT. Geometry optimizations and frequency calculations were carried out using the M06-2X functional and the 6-311++G(d, p) basis set, in conjunction with the SMD continuum solvation model [1]. The involvement of guaiacyl moiety in multiple radical scavenging processes was investigated considering reaction energetics of triple hydrogen atom transfer (tHAT), triple electron transfer-proton transfer (tET-PT) and triple sequential proton loss electron transfer (tSPLET) mechanisms. All these mechanisms result in production of phenoxyl radical of 6- (hydroxymethyl)-1, 3-benzodioxol-4-ol (sesamol like structure – sesamol: potent plant antioxidant with 1, 3-benzodioxole core). The Gibbs free energy change for reactions of inactivation of radicals of different chemical nature (HO•, HOO•, CH3O•, CH3OO•, CH2=CH–O–O•, PhO•, Cl3COO• etc.) indicate tHAT and tSPLET mechanisms as thermodynamically feasible. Exceptional antioxidant activity of DHMBA can be explained by consideration of triple processes (based on involvement of guaiacyl moiety, i.e., vicinal phenolic –OH and –OCH3 group) in addition to single processes (dealing only with single phenolic –OH group of DHMBA) recently studied by Villuendas-Rey et al. [2]. References: [1] M.J. Frisch, G.W. Trucks, H.B. Schlegel et al., Gaussian 09, Wallingford, CT, 2009. [2] Y. Villuendas-Rey, J.R. Alvarez- Idaboy, A. Galano, J. Chem. Inf. Model. 55 (2015) 2552- 2561. Acknowledgment Financial support from The Foundation of the Croatian Academy of Sciences and Arts (project No. 10- 102/244-1-2016.: Investigations of the antioxidant mechanisms of polyphenols and their metabolites) is gratefully acknowledged.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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