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)
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
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
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
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
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
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
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
David C. Grills, Sergei Lymar
Summary: This study investigated the equilibrium between a solvent cavity-localized electron and a dimeric solvent anion in acetonitrile using pulse radiolysis. Quantifying the radiation yield of the solvated electron revealed important insights and resolved controversies surrounding the properties of the solvated electron in acetonitrile.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Inorganic & Nuclear
Matthias Haemmer, Jakoah Brgoch, Philip Netzsch, Henning A. Hoeppe
Summary: Three new members in the Bi2O3-SO3-H2O system have been identified and characterized by single crystal X-ray diffraction and Rietveld refinement. The structures, optical properties, and thermal properties of these compounds have been investigated, along with the influence of the Bi3+ lone pair effect on their properties.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Jacy K. K. Conrad, Stephen P. P. Mezyk, Liam H. H. Isherwood, Aliaksandr Baidak, Corey D. D. Pilgrim, Daniel Whittaker, Robin M. M. Orr, Simon M. M. Pimblott, Gregory P. P. Horne
Summary: This study presents a comprehensive computer model to describe the radiolytic and hydrolytic degradation of AHA in aqueous sodium nitrate and nitric acid solutions. The model accurately predicts the yields of the major degradation products of AHA by comparing with experimental data.
Article
Chemistry, Multidisciplinary
Mengyu Gao, Yoonjae Park, Jianbo Jin, Peng-Cheng Chen, Hannah Devyldere, Yao Yang, Chengyu Song, Zhenni Lin, Qiuchen Zhao, Martin Siron, Mary C. Scott, David T. Limmer, Peidong Yang
Summary: Halide perovskite is a unique dynamical system with complex structural and chemical processes, but its intrinsic instability makes real-time investigation challenging. However, our research reveals that atomically thin carbon materials can stabilize ultrathin halide perovskite nanostructures and enable atomic-level visualization of their movement. Protected by carbon shells, these structures maintain their integrity under high electron dose rate and exhibit unusual dynamical behaviors. Our work provides a new method to protect beam-sensitive materials and study structure dynamics of nanomaterials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Gregory P. Horne, Brian M. Rotermund, Travis S. Grimes, Joseph M. Sperling, David S. Meeker, Peter R. Zalupski, Nicholas Beck, Zachary K. Huffman, Daniela Gomez Martinez, Andrew Beshay, Dean R. Peterman, Bobby H. Layne, Jason Johnson, Andrew R. Cook, Thomas E. Albrecht-Schonzart, Stephen P. Mezyk
Summary: This study investigates the radiation-induced redox chemistry of berkelium and californium ions in acidic aqueous solutions. It reveals that these ions prefer to adopt divalent states and exhibits fast reactivity in reduction by hydrated electron and hydrogen atom, as well as in oxidation by hydroxyl and nitrate radicals. The absorption spectra of transient Cf(II), Cf(IV), and Bk(IV) are also reported. Overall, this research highlights the complex and intrinsic late actinide radiation-induced redox chemistry.
INORGANIC CHEMISTRY
(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
Nanoscience & Nanotechnology
Yukun Zhang, Chong Chen, Zhengfei Chen, Tongtong Zhang, Yunlong Wang, Shuiyan Cao, Jun Ma
Summary: In this study, MXene-reinforced composite coatings were fabricated using an efficient, ambient, and solvent-free electron beam (EB) curing technology for metal anticorrosion. The dispersion of MXene nanoflakes was dramatically improved by modifying with PDMS-OH, which enhanced water resistance. The controllable irradiation-induced polymerization resulted in a unique high-density cross-linked network, providing a large physical barrier against corrosive media. The newly developed APU-PDMS@MX1 coatings exhibited excellent corrosion resistance with a protection efficiency of 99.9957%.
ACS APPLIED MATERIALS & INTERFACES
(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
Nuclear Science & Technology
Li-Heng Zhou, Shui-Yan Cao, Tao Sun, Yun-Long Wang, Jun Ma
Summary: Considering the importance of low-energy electrons (LEEs; 0-20 eV) in radiobiology, this study investigates the potential of gold nanoparticles (AuNPs) as high-flux LEE emitters under sub-keV electron irradiation. A track-structure Monte Carlo simulation code based on the dielectric theory is developed to accurately simulate the electron transport in gold. The code is validated using secondary electron yield and backscattering coefficient, and also verified for energy deposition calculations using the Geant4 toolkit. This code development lays the foundation for future studies on the role of AuNPs in targeted radionuclide radiotherapy.
NUCLEAR SCIENCE AND TECHNIQUES
(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
Materials Science, Multidisciplinary
Xianmei Chen, Zhihao Wang, Mingshuo Tang, Zhiwei He, Miao Yu, Tianran Yu, Jian Cai, Hanayxam Emer, Jun Ma, Yunlong Wang
Summary: Rewritable photonic crystal (PC) paper has the potential to significantly reduce forest resource consumption in the printing industry, being both environmentally friendly and efficient. A novel rewritable PC paper compatible with pin-printing is presented in this study, enabling high-resolution printing and water-erasable information. The PC paper has the capability of multicolor printing with a precision finer than 100 μm and has potential applications in office papers, smart price tags, and anti-counterfeiting labels.
ADVANCED ENGINEERING MATERIALS
(2023)
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, Applied
Tongtong Zhang, Yukun Zhang, Chong Chen, Yukun Tian, Yunlong Wang, Shuiyan Cao, Jun Ma
Summary: In this study, a SiO2-graphene oxide filled silane-treated resin (SiO2-GO/HEP) coating was successfully fabricated using electron beam (EB) curing technology, which exhibited a protection efficiency of nearly 99.995% and a complete curing time of less than 1 minute. Compared with conventional UV curing, the EB curing significantly reduced the current density and water absorption rate.
PROGRESS IN ORGANIC COATINGS
(2023)
Article
Multidisciplinary Sciences
Changjiang Hu, Zhiwen Jiang, Qunyan Wu, Shuiyan Cao, Qiuhao Li, Chong Chen, Liyong Yuan, Yunlong Wang, Wenyun Yang, Jinbo Yang, Jing Peng, Weiqun Shi, Maolin Zhai, Mehran Mostafavi, Jun Ma
Summary: The efficient and selective production of CH3OH from CO2 and water using renewable X/gamma-rays or accelerated electrons is challenging but promising for a carbon-neutral economy. In this study, atomic Cu-Ni dual-metal sites embedded in a metal-organic framework are shown to enable efficient CH3OH production (around 98%) over multiple irradiated cycles. The use of practical electron-beam irradiation and a cost-effective hydroxyl radical scavenger promotes CH3OH production rate to 0.27 mmol g(-1) min(-1). Time-resolved experiments and calculations reveal the direct generation of CO2 center dot-. radical anions via aqueous electrons attachment and cascade hydrogenation steps. This study highlights a radiolytic route for producing CH3OH from CO2 feedstock and introduces a desirable atomic structure to enhance performance.
NATURE COMMUNICATIONS
(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.
