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Triplet-Energy Quenching Functions of Antioxidant Molecules.

ABSTRACT: UV-like DNA damage is created in the dark by chemiexcitation, in which UV-activated enzymes generate reactive oxygen and nitrogen species that create a dioxetane on melanin. Thermal cleavage creates an electronically excited triplet-state carbonyl whose high energy transfers to DNA. Screening natural compounds for the ability to quench this energy identified polyenes, polyphenols, mycosporine-like amino acids, and related compounds better known as antioxidants. To eliminate false positives such as ROS and RNS scavengers, we then used the generator of triplet-state acetone, tetramethyl-1,2-dioxetane (TMD), to excite the triplet-energy reporter 9,10-dibromoanthracene-2-sulfonate (DBAS). Quenching measured as reduction in DBAS luminescence revealed three clusters of 50% inhibitory concentration, ~50 μM, 200-500 μM, and >600 μM, with the former including sorbate, ferulic acid, and resveratrol. Representative triplet-state quenchers prevented chemiexcitation-induced "dark" cyclobutane pyrimidine dimers (dCPD) in DNA and in UVA-irradiated melanocytes. We conclude that (i) the delocalized pi electron cloud that stabilizes the electron-donating activity of many common antioxidants allows the same molecule to prevent an electronically excited species from transferring its triplet-state energy to targets such as DNA and (ii) the most effective class of triplet-state quenchers appear to operate by energy diversion instead of electron donation and dissipate that energy by isomerization.

SUBMITTER: Angele-Martinez C

PROVIDER: S-EPMC8868474 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Triplet-Energy Quenching Functions of Antioxidant Molecules.

Angelé-Martínez Carlos C Goncalves Leticia Christina Pires LCP Premi Sanjay S Augusto Felipe A FA Palmatier Meg A MA Amar Saroj K SK Brash Douglas E DE

Antioxidants (Basel, Switzerland) 20220211 2

UV-like DNA damage is created in the dark by chemiexcitation, in which UV-activated enzymes generate reactive oxygen and nitrogen species that create a dioxetane on melanin. Thermal cleavage creates an electronically excited triplet-state carbonyl whose high energy transfers to DNA. Screening natural compounds for the ability to quench this energy identified polyenes, polyphenols, mycosporine-like amino acids, and related compounds better known as antioxidants. To eliminate false positives such ...[more]

PMID: 35204239

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Project description:Weakening the triplet-triplet annihilation (TTA) self-quenching effect induced by sensitizers remains a tremendous challenge due to the very few investigations carried out on them. Herein, benzo-21-crown-7 (B21C7)-functionalized 2,6-diiodo-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (DIBDP) was synthesized to investigate the influences of huge bulks and electron-rich cavities of B21C7 moieties on the fluorescence emission and triplet-state lifetimes of DIBDP moieties. Density functional theory (DFT)/time-dependent DFT (TDDFT) computable results preliminarily predicted that B21C7 moieties had influences on the fluorescence emissions of DIBDP moieties but not on their localization of triplet states of B21C7-functionalized DIBDP (B21C7-DIBDP). The UV-vis absorption spectra, fluorescence emission spectra, and cyclic voltammograms verified that there was an electron-transfer process from the B21C7 moiety to the DIBDP moiety in B21C7-DIBDP. However, the calculated results of ΔG CS and E CS values and nanosecond time-resolved transient absorption spectra demonstrated that the electron-transfer process from the B21C7 moiety to the DIBDP moiety in B21C7-DIBDP had direct influences on the fluorescence emission of DIBDP moieties but not on the triplet states of DIBDP moieties. The experimental values of triplet-state lifetimes of B21C7-DIBDP were obviously longer than those of DIBDP at a high concentration (1.0 × 10-5 M); however, the fitted values of intrinsic triplet-state lifetimes of B21C7-DIBDP were slightly greater than those of DIBDP in the same solvent. These results demonstrated that the steric hindrance of B21C7 moieties could weaken the TTA self-quenching effect of DIBDP moieties at a high concentration and the a-PET effect induced a proportion of the produced singlet states of DIBDP moieties and could not emit fluorescence in the form of radiation transition but they could be transformed into triplet states through intersystem crossing (ISC) processes due to the iodine atoms in the DIBDP moiety. The stronger a-PET effects in polar solvents induced smaller fluorescence quantum yields so that more singlet states of DIBDP moieties were transformed into triplet states to weaken the TTA self-quenching effects.

Dataset Information

Triplet-Energy Quenching Functions of Antioxidant Molecules.

Publications

Triplet-Energy Quenching Functions of Antioxidant Molecules.

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