Dataset Information

Oxygen Radicals Entrapped between MgO Nanocrystals: Formation, Spectroscopic Fingerprints, and Reactivity toward Water.

ABSTRACT: Compaction of dehydroxylated MgO nanocrystal powders produces adsorbed oxygen radicals with characteristic UV-vis spectroscopic fingerprints. Identical absorption bands arise upon UV excitation in an oxygen atmosphere but in the absence of uniaxial pressure. Photophysical calculations on MgO gas-phase clusters reveal that the observed optical transitions at 4.4 and 3.0 eV are consistent with adsorbed superoxide (O₂^·-) and ozonide (O₃^·-) species, respectively. The presence of these oxygen radicals is corroborated by electron paramagnetic resonance spectroscopy. Upon reaction with interfacial water, oxygen radicals convert into diamagnetic products with no absorptions in the UV-vis range. Since superoxide O₂^·- and ozonide anions O₃^·- play a key role in a variety of processes in heterogeneous catalysis, sensing, or as transient species in cold sintering, their UV-vis spectroscopic detection will enable in situ monitoring of transient oxygen radicals inside metal oxide powders.

SUBMITTER: Schwab T

PROVIDER: S-EPMC10711787 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Oxygen Radicals Entrapped between MgO Nanocrystals: Formation, Spectroscopic Fingerprints, and Reactivity toward Water.

Schwab Thomas T Muchová Eva E Aicher Korbinian K Berger Thomas T Ončák Milan M Diwald Oliver O

The journal of physical chemistry. C, Nanomaterials and interfaces 20231122 48

Compaction of dehydroxylated MgO nanocrystal powders produces adsorbed oxygen radicals with characteristic UV-vis spectroscopic fingerprints. Identical absorption bands arise upon UV excitation in an oxygen atmosphere but in the absence of uniaxial pressure. Photophysical calculations on MgO gas-phase clusters reveal that the observed optical transitions at 4.4 and 3.0 eV are consistent with adsorbed superoxide (O2·-) and ozonide (O3·-) species, respec ...[more]

PMID: 38090143

Similar Datasets

Project description:The reactivity of 10 charged phenyl radicals toward several amino acids was examined in the gas phase in a dual-cell Fourier transform ion cyclotron resonance mass spectrometer. All radicals abstract a hydrogen atom from the amino acids, as expected. The most electrophilic radicals (with the greatest calculated vertical electron affinities (EA) at the radical site) also react with these amino acids via NH(2) abstraction (a nonradical nucleophilic addition-elimination reaction). Both the radical (hydrogen atom abstraction) and nonradical (NH(2) abstraction) reaction efficiencies were found to increase with the electrophilicity (EA) of the radical. However, NH(2) abstraction is more strongly influenced by EA. In contrast to an earlier report, the ionization energies of the amino acids do not appear to play a general reactivity-controlling role. Studies using several partially deuterium-labeled amino acids revealed that abstraction of a hydrogen atom from the α-carbon is only preferred for glycine; for the other amino acids, a hydrogen atom is preferentially abstracted from the side chain. The electrophilicity of the radicals does not appear to have a major influence on the site from which the hydrogen atom is abstracted. Hence, the regioselectivity of hydrogen atom abstraction appears to be independent of the structure of the radical but dependent on the structure of the amino acid. Surprisingly, abstraction of two hydrogen atoms was observed for the N-(3-nitro-5-dehydrophenyl)pyridinium radical, indicating that substituents on the radical not only influence the EA of the radical but also can be involved in the reaction. In disagreement with an earlier report, proline was found to display several unprecedented reaction pathways that likely do not proceed via a radical mechanism but rather by a nucleophilic addition-elimination mechanism. Both NH(2) and (15)NH(2) groups were abstracted from lysine labeled with (15)N on the side chain, indicating that NH(2) abstraction occurs both from the amino terminus and from the side chain. Quantum chemical calculations were employed to obtain insights into some of the reaction mechanisms.

Dataset Information

Oxygen Radicals Entrapped between MgO Nanocrystals: Formation, Spectroscopic Fingerprints, and Reactivity toward Water.

Publications

Oxygen Radicals Entrapped between MgO Nanocrystals: Formation, Spectroscopic Fingerprints, and Reactivity toward Water.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets