Irradiation of a liquid solution generates solvated electrons and radiolysis products, which can lead to material deposition or etching. The chemical environment dictates the dominant reactions. Radiolysis-induced reactions in salt solutions have substantially different results in pure water versus water-ammonia, which extends the lifetime of solvated electrons. We investigate the interplay between transport and solution chemistry via the example of solid silver formation from e-beam irradiation of silver nitrate solutions in water and water-ammonia. The addition of ammonia results in the formation of a secondary ring-shaped deposit tens of micrometers in diameter (formed over tens of seconds) around the primary point of deposition (formed over milliseconds). Simulations uncover the relative importance of oxidizing and reducing reactions and transport effects. Our explanation of this behavior involves mechanisms beyond ammonia’s role in extending solvated electron lifetimes.
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http://dx.doi.org/10.1126/sciadv.abj8751 | DOI Listing |
Comput Biol Med
January 2025
Faculty of Chemistry, University of Science (Vietnam National University, Hanoi), 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Viet Nam; VNU University of Education, Vietnam National University, Hanoi, 144 Xuan Thuy, Cau Giay, Ha Noi, Viet Nam.
α-d-Glucose-conjugated thioureas 8a-w of substituted 4,6-diaryl-2-aminopyrimindines were designed, synthesized, and screened for their antidiabetic inhibitory activity. The thioureas with the strongest potential inhibitory activity included 8f (IC = 11.32 ± 0.
View Article and Find Full Text PDFInt J Mol Sci
January 2025
Trento Institute for Fundamental Physics and Application, TIFPA, 38123 Povo, Italy.
Among the most investigated hypotheses for a radiobiological explanation of the mechanism behind the FLASH effect in ultra-high dose rate radiotherapy, intertrack recombination between particle tracks arriving at a close spatiotemporal distance has been suggested. In the present work, we examine these conditions for different beam qualities and energies, defining the limits of both space and time where a non-negligible chemical effect is expected. To this purpose the TRAX-CHEM chemical track structure Monte Carlo code has been extended to handle several particle tracks at the same time, separated by pre-defined spatial and temporal distances.
View Article and Find Full Text PDFNat Phys
November 2024
Laboratory of Physical Chemistry, ETH Zürich, Zurich, Switzerland.
A dynamical rearrangement in the electronic structure of a molecule can be driven by different phenomena, including nuclear motion, electronic coherence or electron correlation. Recording such electronic dynamics and identifying its fate in an aqueous solution has remained a challenge. Here, we reveal the electronic dynamics induced by electronic relaxation through conical intersections in both isolated and solvated pyrazine molecules using X-ray spectroscopy.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Theoretical simulations of electron detachment processes are vital for understanding chemical redox reactions, semiconductor and electrochemical properties, and high-energy radiation damage. However, accurate calculations of ionized electronic states are very challenging due to their open-shell nature, importance of electron correlation effects, and strong interactions with chemical environment. In this work, we present an efficient approach based on algebraic diagrammatic construction theory with polarizable embedding that allows to accurately simulate ionized electronic states in condensed-phase or biochemical environments (PE-IP-ADC).
View Article and Find Full Text PDFAcc Chem Res
January 2025
Centre for Computational Chemistry, School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom.
ConspectusPhotochemical reactions have always been the source of a great deal of mystery. While classified as a type of chemical reaction, no doubts are allowed that the general tenets of ground-state chemistry do not directly apply to photochemical reactions. For a typical chemical reaction, understanding the critical points of the ground-state potential (free) energy surface and embedding them in a thermodynamics framework is often enough to infer reaction yields or characteristic time scales.
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