Aliaksandra Lisouskaya (Alexandra Lisovskaya)
Belarusian State University, Minsk, Belarus, M.Sc. Chem.(2009), Ph.D.(2012)
Phone: (574) 631-5457
Email: alisousk@nd.edu
Office: 105C Radiation Research Building
Radiation Chemistry and Photochemistry in Aqueous Solutions
Scientific Interests
Pulse Radiolysis of Aqueous Media
Kinetics and mechanisms of radical reactions of nuclear reactor water under high temperatures and pressures. Pulse radiolysis of transition metal ions over wide temperature ranges to solve radiolytic corrosion problems for both current and future generation reactors.
Radiation Chemical Impacts on the Nuclear Waste Stream
Radiolytic stability of solvents and organic ligands used in separation systems in nuclear waste reprocessing.Time resolved EPR spectroscopic techniques to establish identity and kinetics of transients from organic ligands used in solvent extraction processes.
Free Radical and Redox Chemistry of Bioorganic Compounds
Mechanisms of free radical reactions of organic compounds and biomolecules probed by pulse radiolysis and EPR spectroscopy. Detection and characterization of radical intermediates derived from irradiated organic compounds. Direct and sensitized photodestruction of organic compounds.
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Recent Accomplishments
Reactivity of 𝐙𝐧+𝒂𝒒 in high-temperature water radiolysis
We have developed a successful kinetic model on the reactivity of transients involving Zn+ in high-temperature water radiolysis over the temperature range of 25–300oC. The Zn+ species can subsequently be oxidized by the radiolytically-produced oxidizing species: ●OH, H2O2 and ●H. We find that the absorption of monovalent zinc is very sensitive to the pH of the medium. The optical spectrum of Zn+aq cannot be fully explained in terms of a charge-transfer to solvent (CTTS) process, which was previously proposed. The longest wavelength bands well described as Zn-centered s-p like transition. Reaction rates of most of the recombination reactions investigated follow the empirical Arrhenius relationship at temperatures up to 200 oC and have been determined at higher temperatures for the first time.
Persistent radicals in irradiated imidazolium ionic liquids probed by EPR spectroscopy
EPR spectroscopy has revealed the persistence of long-lived radical cations after irradiation of imidazolium ionic liquids (ILs) used in spent nuclear fuel separations. The kinetics data obtained indicate the existence of at least two distinct radical cations that have different formation and decay rates. Extensive quantum chemistry calculations were performed to attempt to identify the structure of these persistent radicals. The most likely candidates are imidazole radical cations having methyl groups at the nitrogen atoms and substituents in the second position of the imidazole ring.
Charting hydroxyl radical attack on aminodiols
We compared the stopped-flow EPR spectroscopy and pulse radiolysis with optical detection methods to characterize radical intermediates formed in the reaction of OH radicals with glycerol, serinol and N-boc-serinol. Quantum chemical calculations were also performed to help interpret the observed experimental data. Intramolecular hydrogen bonds between OH and NH2 groups guide the mechanisms of destruction of serinol and its analogs during their interaction with hydroxyl radicals modeling behavior of lipid polar head groups
Selected Publications
Lisouskaya A.; U. Markad; I. Carmichael; D.M. Bartels "Reactivity of Zn+aq in high-temperature water radiolysis" Phys. Chem. Chem. Phys. 24 (2022) 19882-9 link
Lisouskaya, A.; P. Tarábek; D.M. Bartels; I. Carmichael "Persistent radicals in irradiated imidazolium ionic liquids probed by EPR spectroscopy" Rad. Phys. Chem. 202 (2022) 110513 link
Lisovskaya A.; I. Carmichael: A. Harriman "A pulse radiolysis investigation of radicals derived from water-soluble cyanine dyes: Implications for super-resolution microscopy" J. Phys. Chem. A 125 (2021) 5779–93 link
Lisovskaya A.; O. Shadyro; O. Schiemann; I. Carmichael "OH radical reactions with the hydrophilic component of sphingolipids" Phys. Chem. Chem. Phys. 23 (2021) 1639-48 link
Lisovskaya A.; K. Kanjana; D.M. Bartels "One-electron redox kinetics of aqueous transition metal couples Zn2+/+, Co2+/+, and Ni2+/+ using pulse radiolysis" Phys. Chem. Chem. Phys. 22 (2020) 19046-58 link
Lisovskaya A.; D.M. Bartels "Reduction of CO2 by hydrated electrons in high temperature water" Rad. Phys. Chem. 158 (2019) 61-3 link