Review
Spectroscopy
Daniel T. Elg, Hernan E. Delgado, Daniel C. Martin, R. Mohan Sankaran, Paul Rumbach, David M. Bartels, David B. Go
Summary: This paper summarizes the current state of plasma-liquid interactions involving solvated electrons, with a particular emphasis on the work by the authors' group, and highlights potential areas of future research to drive applications forward.
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY
(2021)
Article
Chemistry, Physical
Masafumi Koga, Yuto Miyake, Mizuki Hayasaka, Hikaru Sotome, Hiroshi Miyasaka
Summary: The photoionization dynamics of N,N-dimethylaniline (DMA) from highly electronically excited states in ethanol solution were studied using femtosecond two-pulse two-photon excitation transient absorption (2PE-TA) spectroscopy. The ionization occurred via a rapid channel and a slow one, with the slow ionization regulated by the formation of anionic species just before the completion of the solvation of the electron.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Andrew R. Cook
Summary: The ultrafast hole transfer from solvent radical cations produced by radiolysis to solutes in tetrahydrofuran (THF) was investigated. The results highlight the importance of capturing holes from THF+· prior to solvation and fragmentation, with the yield of solvent hole capture being accounted for by mechanisms such as delocalized holes or rapid hopping. Low temperature results show over two times more capture, suggesting that if THF+· was longer lived, the yield of capture would have been larger.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Physics, Multidisciplinary
A. Prasselsperger, M. Coughlan, N. Breslin, M. Yeung, C. Arthur, H. Donnelly, S. White, M. Afshari, M. Speicher, R. Yang, B. Villagomez-Bernabe, F. J. Currell, J. Schreiber, B. Dromey
Summary: Understanding proton energy deposition and damage formation in matter is crucial for radiation science. Using picosecond resolution of laser-driven accelerators, ultrafast solvation dynamics for electrons due to proton radiolysis in liquid water were tracked. Results suggest a highly dynamic phase after proton interaction that current models do not account for, supported by magneto-hydrodynamic theory.
PHYSICAL REVIEW LETTERS
(2021)
Article
Chemistry, Physical
Jacy K. Conrad, Kazuhiro Iwamatsu, Michael E. Woods, Ruchi Gakhar, Bobby Layne, Andrew R. Cook, Gregory P. Horne
Summary: The impact of iodide ions on the speciation and chemical kinetics of radiation-induced transient radicals in high temperature molten salts was studied using picosecond electron pulse irradiation techniques. It was found that the presence of iodide ions resulted in the formation of at least three overlapping species: e(S)(-), Cl-2(-), and ICl-. The newly observed interhalogen radical anion, ICl-, exhibited a lifetime on the order of microseconds over the investigated temperature range, and its decay mechanism was determined to be reaction with the Cl-2(-) radical anion. These findings have implications for the transport of fission-product iodine in molten salt reactor technologies.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Engineering, Chemical
Jiayang Gong, Shaopeng Rong, Jie Wang, Yefeng Zhou
Summary: Synthesizing catalysts using organic solvents is an appealing strategy to enhance oxygen vacancy concentration and catalytic activity. By employing the reducibility of ethylene glycol (EG), α-MnO2-EG was synthesized using a reduction strategy for toluene oxidation. The results demonstrated that EG significantly increased the oxygen vacancy concentration and catalytic activity of α-MnO2-EG. The α-MnO2-EG-160 catalyst exhibited a 30% higher oxygen vacancy concentration compared to α-MnO2-H2O, resulting in remarkable low-temperature catalytic performance (T90 = 183 degrees C), surpassing currently reported MnO2-based catalysts. The structure-activity relationship and toluene catalytic mechanism of α-MnO2-EG-160 based on oxygen vacancies were also proposed.
CHEMICAL ENGINEERING SCIENCE
(2023)
Article
Chemistry, Physical
Jean Philippe Renault, Stanislas Pommeret
Summary: In this study, first-principles molecular dynamics simulations based on density-functional theory were used to investigate the reactions of the solvated electron with nitrate or nitrous oxide. A strategy combining the in situ production of the aqueous electron followed by its reaction with either NO3- or N2O was devised. The simulations showed that electron transfer events occur on a sub-picosecond time scale and are controlled by the vibrational degree of freedom of the oxidants.
RADIATION PHYSICS AND CHEMISTRY
(2022)
Article
Acoustics
Glyus L. Sharipov, Bulat M. Gareev, Kristina S. Vasilyuk, Dim I. Galimov, Airat M. Abdrakhmanov
Summary: The study revealed that the luminescence intensity of moving single-bubble sonoluminescence of Ce3+ in solutions of CeCl3 and (NH4)(2)Ce(NO3)(6) increases with the cerium ion concentration and saturates at a certain level. Additionally, sonophotoluminescence also contributes to the luminescence of Ce3+ at higher concentrations.
ULTRASONICS SONOCHEMISTRY
(2021)
Article
Engineering, Environmental
Benjamin D. Fennell, Douglas Fowler, Stephen P. Mezyk, Garrett McKay
Summary: Advanced reduction processes (ARP) have gained attention for PFAS treatment, but the effect of DOM on e(aq)(-) availability is not well understood.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Materials Science, Ceramics
Zhiping Zhang, Nan Zhang, Hongfei Liu
Summary: Orthorhombic Sc2Mo3O12 samples were synthesized via ethylene glycol (EG)-assisted hydrothermal reaction. The effects of hydrothermal temperature, hydrothermal time, and EG additive content on the preparation and negative thermal expansion (NTE) behavior of Sc2Mo3O12 samples were characterized. The results showed that flower-like Sc2Mo3O12 with uniform particle size can be obtained by using 60 ml EG at 120 degrees C for 2 h. Hydrothermal conditions and EG additive had significant influences on the growth and morphology of Sc2Mo3O12.
CERAMICS INTERNATIONAL
(2023)
Article
Biochemistry & Molecular Biology
Annalisa Masi, Amedeo Capobianco, Krzysztof Bobrowski, Andrea Peluso, Chryssostomos Chatgilialoglu
Summary: This study investigates the reaction of hydroxyl radicals and sulfate radical anions with a double-stranded oligodeoxynucleotide under anoxic conditions. The results suggest that the alternating GC sequences in the DNA structure allow for a new type of electron hole stabilization.
Article
Chemistry, Physical
Weikang Dai, Maoshuai Li, Jie Wei, Qi Yang, Yi Feng, Cheng Yang, Wanxin Yang, Mei-Yan Wang, Xinbin Ma
Summary: The paper investigates the dissociation and anion mechanism for formaldehyde hydroformylation using DFT calculation and experimental study. It finds that HCHO insertion into the Rh-H bond is the rate-controlling step in the dissociation mechanism, while the nucleophilic addition of HCHO to the HOCH2-Rh species is more energetically favorable in the anion mechanism. The research also suggests that the strong electron-donating ligand could lead to higher reactivity in the anion mechanism, providing insights for improving selectivity in the reaction.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Jianguo Yu, Zehui Yu, Yunling Jia, Ting Ran, Ming Song, Yanshuang Zhang, Qing Wang, Yuning Qu, Lili Wang
Summary: The performance of direct alcohol fuel cells is greatly affected by the phase and composition of the catalyst, necessitating the development of high-performance alcohol oxidation catalysts. In this study, PdCu core-shell nanoflowers were created for the first time using PVA preparation, resulting in a high electrochemically active surface area and a potent synergistic effect. The Cu@Pd22.3 catalyst exhibited 13 times higher catalytic performance than Pd/C in ethylene glycol oxidation reaction, offering an original method to improve the activity and endurance of polyol oxidation.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2023)
Article
Chemistry, Physical
John McGrady, Shinichi Yamashita, Sho Kano, Huilong Yang, Hiroaki Abe
Summary: The study found that the presence of oxides affects the decay behavior of hydrated electrons, with Fe2O3 slowing down the decay rate and ZrO2 increasing it, while Cr2O3 had negligible effect. The electron yield for all oxide/water mixtures was higher compared to pure water, indicating electron transfer from the oxides to the water.
RADIATION PHYSICS AND CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Kazuo Kobayashi, Jotaro Igarashi, Takahiro Kozawa
Summary: In this study, intramolecular electron transfer between FAD and haem b in FlavoHbs was investigated using pulse radiolysis. The results showed that the reduction of FlavoHb proceeded in two phases, with the slower phase attributed to intramolecular electron transfer from FAD to the haem iron. Additionally, the binding of azole compounds accelerated this process, indicating a conformational change.
Article
Chemistry, Physical
Sergey A. Denisov, Samuel Ward, Viacheslav Shcherbakov, Alexander D. Stark, Renata Kaczmarek, Ewa Radzikowska-Cieciura, Dipra Debnath, Taisiya Jacobs, Anil Kumar, Michael D. Sevilla, Pascal Pernot, Roman Dembinski, Mehran Mostafavi, Amitava Adhikary
Summary: This work demonstrates the importance of sulfur atom substitution in controlling charge transfer processes in DNA systems. Through a combination of synthesis, spectroscopic studies, and theoretical calculations, the researchers investigated the reactivity of a model compound and a nucleotide. They found that the formation of reactive intermediates and the subsequent charge transfer processes are highly dependent on the presence of sulfur atoms and the reaction conditions.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Astronomy & Astrophysics
N. Carrasco, J. Bourgalais, L. Vettier, P. Pernot, E. Giner, R. Spezia
Summary: The study shows that nitrogen in Titan's atmosphere can form nitrogen-rich organic compounds through reactions with radicals. These nitrogen-enriched organic compounds play an important role in explaining the high nitrogen content in Titan's organic matter. Moreover, the study highlights the significance of reactions between ions and radicals in astrochemistry.
ASTRONOMY & ASTROPHYSICS
(2022)
Article
Chemistry, Physical
Pascal Pernot
Summary: Uncertainty quantification in computational chemistry is still in its early stages, with very few methods providing confidence levels for predictions. The development of reliable uncertainty quantification methods is crucial for the confident use of computational chemistry in industrial processes.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Materials Science, Multidisciplinary
M. Trochet, F. Berthier, P. Pernot
Summary: Uncertainty propagation and sensitivity analysis are used to study the parameters of SMA-TB interatomic potentials in atomistic simulations of metals and alloys. By estimating initial probability distributions, we can determine the uncertainties and adjust physical properties using local and global Sobol sensitivity analysis methods.
COMPUTATIONAL MATERIALS SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Amel Zorai, Abdelhafid Souici, Diana Dragoe, Eric Riviere, Salim Ouhenia, Jacqueline Belloni, Mehran Mostafavi
Summary: The radiolytic method was used to synthesize ultrasmall cobalt ferrite nanoparticles with superparamagnetic properties. The properties of these nanoparticles were studied at increasing doses of irradiation. The analysis confirmed the formation of ultra-small cobalt ferrite nanoparticles (6-9 nm) in the cubic spinel structure, and their superparamagnetic properties were revealed through temperature-dependent magnetic measurements.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Engineering, Environmental
Zhiwen Jiang, Daniel Adjei, Sergey A. Denisov, Mehran Mostafavi, Jun Ma
Summary: This study used pulse radiolysis to investigate the reaction between the short-lived hydrated electron (eaq-) and short-chain PFAS, and discovered that radiolytic carbon dioxide radicals can selectively defluorinate PFBS, suggesting ionizing radiation as a versatile treatment technique.
ENVIRONMENTAL SCIENCE & TECHNOLOGY LETTERS
(2023)
Article
Chemistry, Physical
Daniel Adjei, Yahaira Reyes, Anil Kumar, Samuel Ward, Sergey A. Denisov, Moaadh Alahmadi, Michael D. Sevilla, Stanislaw F. Wnuk, Mehran Mostafavi, Amitava Adhikary
Summary: 5-AmdU has been used for DNA metabolic labeling and fluorescent imaging of live cells. It also shows significant radiosensitization in breast cancer cells through the formation of site-specific nitrogen-centered radicals. The study reveals that these radicals are not formed through the reduction of the azido group in 6-AmU. The formation of different nitrogen-centered radicals is controlled by thermodynamics and protonation from the surrounding water.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Multidisciplinary
Changjiang Hu, Liwei Cheng, Liheng Zhou, Zhiwen Jiang, Pingping Gan, Shuiyan Cao, Qiuhao Li, Chong Chen, Yunlong Wang, Mehran Mostafavi, Shuao Wang, Jun Ma
Summary: In this study, Zr/Hf-based nanoscale UiO-66 metal-organic frameworks were used as highly effective and stable radiation sensitizers for water splitting under gamma-ray irradiation. The unique structure of these frameworks allows for increased scattering between secondary electrons and water, resulting in enhanced H2 production. The use of a small quantity of UiO-66-Hf-OH achieves a gamma-rays-to-hydrogen conversion efficiency exceeding 10%, surpassing existing methods. This work demonstrates the feasibility and advantages of MOF-assisted radiolytic water splitting and offers a competitive method for creating a green H2 economy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Sarah Al Gharib, Pierre Archirel, Daniel Adjei, Jacqueline Belloni, Mehran Mostafavi
Summary: The oxidation mechanism of crocin, a major compound of saffron, by the free OH· radical was investigated using various techniques. The absorption spectra and reaction rate constants of the transient species were determined. The antioxidant properties of crocin were highlighted based on experimental and theoretical investigations.
Article
Chemistry, Physical
Qingde Chen, Sergey A. Denisov, Denis Dobrovolskii, Mehran Mostafavi
Summary: The decay kinetics of hydrated electrons in AOT-based ternary microemulsions were studied using picosecond pulse radiolysis and UV-vis spectroscopy. Two types of reactions, recombination at the water-oil interface and radical-radical reactions in the water pools, were observed. The size of water pools and the water-oil interface played important roles in the kinetics of the reactions.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Denis S. Dobrovolskii, Mehran Mostafavi, Sergey A. Denisov
Summary: The reactivity of electrons in the CO2-water system was studied using picosecond electron pulse radiolysis and UV-vis transient spectroscopy at different gas pressures and temperatures. The results showed a non-monotonic dependence of electron reactivity with CO2 concentration, which correlated with the changing molar concentration of CO2 in water under varying pressure.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Viacheslav Shcherbakov, Sergey A. Denisov, Mehran Mostafavi
Summary: In this study, the mechanism of dioxygen reduction catalysed by gold nanoparticles (AuNPs) using sodium ascorbate and hydroethidine as electron donors was investigated. The formation of ROS, such as O-2(-) and H2O2, was examined. The results showed that ROS are only formed as intermediates on the surface of nanoparticles and are catalytically reduced to water by AuNPs. This challenges the claim of ROS production in the presence of AuNPs often reported in literature. Additionally, AuNPs were found to catalyze the oxidation of electron donors in cells, leading to oxidative stress.
Article
Chemistry, Physical
Marija Knezevic, Vien-Duong Quach, Isabelle Lampre, Marie Erard, Pascal Pernot, David Berardan, Christophe Colbeau-Justin, Mohamed Nawfal Ghazzal
Summary: Adjusting the band gap energy of metal halide perovskites at room temperature through anion exchange leads to the formation of indirect excitons at the MHPs/TiO2 interface, resulting in slower charge-carrier relaxation and higher photocatalytic activity.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Andrew M. Teale, Trygve Helgaker, Andreas Savin, Carlo Adamo, Balint Aradi, Alexei Arbuznikov, Paul W. Ayers, Evert Jan Baerends, Vincenzo Barone, Patrizia Calaminici, Eric Cances, Emily A. Carter, Pratim Kumar Chattaraj, Henry Chermette, Ilaria Ciofini, T. Daniel Crawford, Frank De Proft, John F. Dobson, Claudia Draxl, Thomas Frauenheim, Emmanuel Fromager, Patricio Fuentealba, Laura Gagliardi, Giulia Galli, Jiali Gao, Paul Geerlings, Nikitas Gidopoulos, Peter M. W. Gill, Paola Gori-Giorgi, Andreas Gorling, Tim Gould, Stefan Grimme, Oleg Gritsenko, Hans Jorgen Aagaard Jensen, Erin R. Johnson, Robert O. Jones, Martin Kaupp, Andreas M. Koster, Leeor Kronik, Anna Krylov, Simen Kvaal, Andre Laestadius, Mel Levy, Mathieu Lewin, Shubin Liu, Pierre-Francois Loos, Neepa T. Maitra, Frank Neese, John P. Perdew, Katarzyna Pernal, Pascal Pernot, Piotr Piecuch, Elisa Rebolini, Lucia Reining, Pina Romaniello, Adrienn Ruzsinszky, Dennis R. Salahub, Matthias Scheffler, Peter Schwerdtfeger, Viktor N. Staroverov, Jianwei Sun, Erik Tellgren, David J. Tozer, Samuel B. Trickey, Carsten A. Ullrich, Alberto Vela, Giovanni Vignale, Tomasz A. Wesolowski, Xin Xu, Weitao Yang
Summary: This paper provides an informal review and discussion on the history, present status, and future of density-functional theory (DFT) by 70 workers in the field. The format of a roundtable discussion allowed participants to express their views through 302 individual contributions to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper offers a comprehensive snapshot of DFT in 2022.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Mathematics, Interdisciplinary Applications
Pascal Pernot, Andreas Savin
Summary: This article discusses the validation of calculation results by using different methods. However, when the methods are affected by the same errors, this approach fails. By using statistical methods, measures for reliability and similarity are defined, and the impact of result similarity on validating data is explored.