Estimation of empirically fitted parameters for calculating pK a values of thiols in a fast and reliable way

Pérez-González, Adriana; Castañeda‐Arriaga, Romina; Verastegui, Brisa; Carreón-González, Mirzam; Álvarez-Idaboy, J. Raúl; Galano, Annia

doi:10.1007/s00214-017-2179-7

Cited by 20 publications

(33 citation statements)

References 61 publications

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“…The pK a values for species A , F and radical HOO • are experimentally measured. For the rest of the species, the pK a values were calculated as proposed in reference , using the fitted parameters m = 0.356 and C 0 = − 94.378.…”

Section: Resultsmentioning

confidence: 99%

“…As in the previous case, SET reactions with species A, D, F and L are endergonic. However if the working pH is taken into account, the HOO − anion will be immediately protonated (pK a = 11.6), and the calculated free energies must be corrected by a factor of 5.73 kcal/mol. That is because the corresponding Gibbs energy of reaction would explicitly depend on the pH. Thus, this effect has been considered here, and the reported data correspond to pH = 7.4.…”

Section: Resultsmentioning

confidence: 99%

“…When available, experimental pK a values are used. Otherwise, pK a values are calculated as proposed by Pérez‐González et al :

{pK}_{a}^{calc} = {m Δ G}_{(italicBA)}^{°} + C_{0}

where

{Δ G}_{(italicBA)}^{°}

is the difference in Gibbs free energy energy between the conjugated base ( B ) and the corresponding acid ( A ); and m and C 0 are fitted parameters directly obtained from ref. .…”

Section: Computational Detailsmentioning

confidence: 99%

“…When available, experimental pK a values are used. Otherwise, pK a values are calculated as proposed by Pérez-González et al [61] :…”

Section: Introductionmentioning

confidence: 99%

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Thiophenols, Promising Scavengers of Peroxyl Radicals: Mechanisms and kinetics

2019

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The activity of 12 thiophenols as primary antioxidants in aqueous solution has been studied using density functional theory. Twelve different substituted thiophenols were tested as peroxyl radicals scavengers. Single electron transfer (SET) and formal hydrogen transfer (FHT) were investigated. The SET mechanism was found to be the main mechanism, with rate constants that are close to the diffusion limit, which means that these thiophenolic compounds have the capacity to scavenge peroxyl radicals before they can damage biomolecules. All 12 thiophenolic compounds react faster with methylperoxyl than with hydroperoxyl radicals. In addition, it was found that pH plays an important role in the reactivity of these compounds. © 2019 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…When available, experimental pK a values are used. Otherwise, pK a values are calculated as proposed by Pérez‐González et al :

{pK}_{a}^{calc} = {m Δ G}_{(italicBA)}^{°} + C_{0}

where

{Δ G}_{(italicBA)}^{°}

is the difference in Gibbs free energy energy between the conjugated base ( B ) and the corresponding acid ( A ); and m and C 0 are fitted parameters directly obtained from ref. .…”

Section: Computational Detailsmentioning

confidence: 99%

“…When available, experimental pK a values are used. Otherwise, pK a values are calculated as proposed by Pérez-González et al [61] :…”

Section: Introductionmentioning

confidence: 99%

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Thiophenols, Promising Scavengers of Peroxyl Radicals: Mechanisms and kinetics

2019

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“…In this equation Δ G BA represents the difference in Gibbs energy between the conjugated base and the corresponding acid ( G calc(A–) – G calc(HA) ). The m and C 0 parameters are currently available, at several levels of theory for phenols, amines, carboxylic acids and thiols . In all cases the calculated p K a values result in deviations from experiments that are lower than 0.5 p K a units, in terms of mean unsigned errors.…”

Section: The Computational Approachmentioning

confidence: 99%

Computational strategies for predicting free radical scavengers' protection against oxidative stress: Where are we and what might follow?

Galano

Álvarez-Idaboy

2018

Int J of Quantum Chemistry

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203

247

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Oxidative stress, which is frequently induced by an overproduction of free radicals (FR), poses a high risk to human health. Thus, finding efficient strategies for scavenging FR is a research area of current interest. Among many other aspects, this involves identifying chemical compounds capable of offering antioxidant protection (AOP) and quantifying such protection. This review summarizes different computational approaches that can contribute to gain a deeper knowledge on this subject. Several reaction mechanisms that may contribute to AOP are discussed, as well as some key factors influencing their relative importance including the chemical nature of the reacting FR, the polarity of the environment and the pH in aqueous solution. Kinetics‐based analyses to characterize antioxidants, through their FR scavenging activity, are presented. Trends in such activity, from the data currently available in the literature are provided. Some key aspects, regarding AOP, that still deserves further investigation, are discussed.

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Melatonin: A smart molecule in the DNA repair system

Mir

Aliarab

Goodarzi

et al. 2021

Cell Biochemistry & Function

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Award Number: 112351 DNA repair is an important pathway for the protection of DNA molecules from destruction. DNA damage can be produced by oxidative reactive nitrogen or oxygen species, irritation, alkylating agents, depurination and depyrimidination; in this regard, DNA repair pathways can neutralize the negative effects of these factors. Melatonin is a hormone secreted from the pineal gland with an antioxidant effect by binding to oxidative factors. In addition, the effect of melatonin on DNA repair pathways has been proven by the literature. DNA repair is carried out by several mechanisms, of which homologous recombination repair (HRR) and non-homologous end-joining (NHEJ) are of great importance. Because of the importance of DNA repair in DNA integrity and the anticancer effect of this pathway, we presented the effect of melatonin on DNA repair factors regarding previous studies conducted in this area.

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Estimation of empirically fitted parameters for calculating pK a values of thiols in a fast and reliable way

Cited by 20 publications

References 61 publications

Thiophenols, Promising Scavengers of Peroxyl Radicals: Mechanisms and kinetics

Thiophenols, Promising Scavengers of Peroxyl Radicals: Mechanisms and kinetics

Computational strategies for predicting free radical scavengers' protection against oxidative stress: Where are we and what might follow?

Melatonin: A smart molecule in the DNA repair system

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