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Aliaksandra Lisouskaya (Alexandra Lisovskaya)

Aliaksandra Lisouskaya (Alexandra Lisovskaya)

Belarusian State University, Minsk, Belarus, M.Sc. Chem.(2009), Ph.D.(2012)

View Dr. Lisouskaya's webpage

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. The structures and kinetics of radicals formed upon irradiation of ionic liquids and/or ligands that can be identified may raise concerns about their suitability for the extraction of spent nuclear fuel.

Free Radical and Redox Chemistry of Bioorganic Compounds

Mechanisms of free radical reactions in organic compounds and biomolecules are investigated using pulse radiolysis, flash photolysis, and EPR spectroscopy, with applications spanning from the nuclear power industry to photochemistry significant in biology and medicine.

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Recent Accomplishments

Arrows surrounding Ni2+/+ ions

Reactions of nickel ions in water radiolysis up to 300°C

Reaction kinetics of Ni2+/+ ions and spectral changes in Ni+ absorbance under critical conditions of temperature and pressure are revealed by pulse radiolysis. We found that the absorption spectrum of short-lived monovalent nickel ion shifts to shorter wavelength with increasing temperature. This phenomenon might be explained by a decrease in the average number of water molecules coordinated to the metal in the first solvation shell. To obtain
the reaction constants, we performed extensive experiments and further fitting of the Ni+ kinetics in various salt and pH solutions. All measured rate constants followed approximate Arrhenius behavior. These new data on the reactivity of nickel ions dissolved in water upon irradiation at high temperatures and pressures is key for understanding future studies of the effect of Ni2+/+ on the bulk coolant radiolysis chemistry under typical pressurized and boiling water reactors (PWR/BWR) conditions.

Structure and kinetics of organic acid radicals formed in reaction with •OH radicals

Structure and kinetics of organic acid radicals formed in reaction with •OH radicals
The structure and decay kinetics of •OH-derived radicals from certain organic acids used in nuclear fuel processing and separation were identified using rapid-flow EPR spectroscopy and quantum chemistry. The results obtained in this study advance EPR spectroscopy, chemical kinetics, and computational chemistry, with significant implications for the separation of spent nuclear fuel and other radioactive wastes. Of fundamental importance, HFC constants of radicals and the impact of organic acid radical deprotonation on their EPR parameters are of particular interest. The LPBE functional, which had not been previously tested, demonstrated good performance in characterizing electron spin densities of organic molecules, thus enabling extensive benchmarking across a wide range of compounds. Information on the structures and reactivity of •OH-induced radicals is essential for separation processes, since radicals serve as intermediates in the radiation-induced degradation of compounds widely utilized in industrial applications. The results are crucial for accurate simulation of decay processes and are intended to advance techniques for improving the stability and efficiency of separation systems.

Unveiling the mechanism of photodamage to sphingolipid molecules via laser flash photolysis and EPR

Unveiling the mechanism of photodamage to sphingolipid molecules via laser flash photolysis and EPR
The work reported here is designed to uncover details of the mechanism of damage to such lipids by UV radiation. Our approach employs laser flash photolysis and EPR spectrometry to explore the mechanism of the decay reactions, and to determine the associated kinetic parameters. To interpret our experiments, we computed both excitation energies and EPR parameters of radicals formed during photolysis. Employing the spin-trap EPR method confirmed the formation of both carbon- and nitrogen-centered radicals. Thus, we can conclude that the photodecomposition of sphingolipids and their analogues proceeds by Norrish type I reactions with the formation of both nitrogen-centered and alkyl radicals. These data provide insights for the development of UV-protective approaches based on a detailed understanding of molecular events that occur in the skin lipids after UV exposure.

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Selected Publications

Sosulin I.S., Lisouskaya A. (2024) Structure and kinetics of organic acid radicals formed in reaction with •OH radicals. J. Phys. Chem. A. ASAP. link

Sosulin I.S., Lisouskaya A. (2024) Assessing the radiation stability of key ligands in nuclear waste separation. Radiat. Phys. Chem. 222 111785. link

Wang J., Schaefer T., Lisouskaya A., Firak D. S., Xin X., Herrmann H., Sharma V. K., Huang C.H. (2024) Unveiling the environmental significance of acetylperoxyl radical: reactivity quantification and kinetic modeling. PNAS Nexus 3 330. link

Sosulin I.S., Ryan D.H., Lisouskaya A. (2023) Radicals from tributyl phosphate decomposition: a combined electron paramagnetic resonance spectroscopic and computational chemistry investigation. Phys. Chem. Chem. Phys. 25 29350-7. link

Lisouskaya A., Markad U., Bartels D.M. (2023) Reactions of nickel ions in water radiolysis up to 300 °C. J. Phys. Chem. B, 127 2784–91. link

Lisouskaya A, Schiemann O, Carmichael I. (2023) Unveiling the mechanism of photodamage to sphingolipid molecules via laser flash photolysis and EPR. Photochem. Photobiol. 99 1400-11. link

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

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