Dataset Information

Relative Order of Acidity among Hydroxyl Groups of Oxyluciferin and Emission Light Colors in Aqueous Solution.

ABSTRACT: The magnitude of the acidity of the oxyluciferin in water in the ground and excited state is investigated, and it is found for the first time using computational approach that the enol group of the phenol-enol species is the most acidic in the ground state, but the deprotonation of the phenol of the phenol-keto form is the most favored in the excited state. The relative order of the acidity among the hydroxyl groups in the oxyluciferin is attributed to the sequence of the O-H bond lengths in the enol and phenol group of the phenol-enol form, and the phenol group of the phenol-keto species. The mechanism of determining the dominant emissive species in the excited state is proposed, and the dependence of emission light colors on the photoexcitation energy is elucidated by the high relative concentration of six chemical forms in the ground state and the absorption efficiency.

SUBMITTER: Zhou JG

PROVIDER: S-EPMC7328863 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Relative Order of Acidity among Hydroxyl Groups of Oxyluciferin and Emission Light Colors in Aqueous Solution.

Zhou Jian-Ge JG Yang Shan S Deng Zhen-Yan ZY Leszczynski Jerzy J

Journal of photochemistry and photobiology. A, Chemistry 20200402

The magnitude of the acidity of the oxyluciferin in water in the ground and excited state is investigated, and it is found for the first time using computational approach that the enol group of the phenol-enol species is the most acidic in the ground state, but the deprotonation of the phenol of the phenol-keto form is the most favored in the excited state. The relative order of the acidity among the hydroxyl groups in the oxyluciferin is attributed to the sequence of the O-H bond lengths in the ...[more]

PMID: 32612342

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Project description:In this study, steady-state and time-resolved radiolysis methods were used to determine the primary reaction pathways and kinetic parameters for the reactions of hydroxyl radical with microcystin-LR (MC-LR). The fundamental kinetic data is critical for the accurate evaluation of hydroxyl-radical based technologies for the destruction of this problematic class of cyanotoxins. The bimolecular rate constant for the reaction of hydroxyl radical with MC-LR is 2.3 (+/-0.1) x 10(10) M(-1)s(-1) based on time-resolved competition kinetics with SCN-at low conversions using pulsed radiolysis experiments. The reaction of hydroxyl radical with MC-LR can occur via a number of competing reaction pathways, including addition to the benzene ring and diene and abstraction of aliphatic hydrogen atoms. LC-MS analyses indicate the major products from the reaction of hydroxyl radicals with MC-LR involve addition of hydroxyl radical to the benzene ring and diene moieties of the Adda side chain. Transient absorption spectroscopy monitored between 260-500 nm, following pulsed hydroxyl radical generation, indicate the formation of a transient species with absorption maxima at 270 and 310 nm. The absorption maxima and lifetime of the transient species are characteristic of hydroxycyclohexadienyl radicals resulting from the addition of hydroxyl radical to the benzene ring. The rate constant for the formation of hydroxycyclohexadienyl radical is 1.0 (+/-0.1) x 10(10) M(-1)s(-1) accounting for approximately 40% of the primary reaction pathways. Representative rate constants and partitioning of hydroxyl radical reactions were assessed based on the reactivities of surrogate substrates and individual amino acids. Summation of the individual reactivities of hydroxyl radical at the different reactive sites (amino acids) leads to a rate constant of 2.1 x 10(10) M(-1) s(-1) in good agreementwith the rate constant determined in our studies. The relative magnitude of the rate constants for the reactions of hydroxyl radical with the individual amino acids and appropriate surrogates, suggest 60-70% reactions of hydroxyl radical occur at the benzene and diene functional groups of the Adda moiety.

Dataset Information

Relative Order of Acidity among Hydroxyl Groups of Oxyluciferin and Emission Light Colors in Aqueous Solution.

Publications

Relative Order of Acidity among Hydroxyl Groups of Oxyluciferin and Emission Light Colors in Aqueous Solution.

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