The nature of protons in ice VII up to 368°C and 16GPa was investigated with synchrotron near-infrared spectroscopy. The absorption band of the first OH stretching overtone mode divided into doublet peaks above 5GPa at room temperature, suggesting that proton tunneling occurs at the overtone level. As the temperature increased, the doublet peaks gradually reduced to a singlet. This result implies that thermally activated protons hop between the two potential minima along the oxygen-oxygen axis. A pressure-temperature diagram for the proton state was constructed from the changing band shape of the overtone mode.
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http://dx.doi.org/10.1016/j.saa.2014.06.024 | DOI Listing |
JACS Au
December 2024
Department of Chemistry, University of Antwerp, Antwerp 2020, Belgium.
Proton-coupled electron transfer (PCET) is a fundamental redox process and has clear advantages in selectively activating challenging C-H bonds in many biological processes. Intrigued by this activation process, we aimed to develop a facile PCET process in cancer cells by modulating proton tunneling. This approach should lead to the design of an alternative photodynamic therapy (PDT) that depletes the mitochondrial electron transport chain (ETC), the key redox regulator in cancer cells under hypoxia.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Univ Paris Est Creteil and Université Paris Cité, CNRS, LISA, F-94010 Créteil, France.
Large amplitude motions (LAMs), most notably represented by proton tunneling, mark a significant departure from small amplitude vibrations where protons merely oscillate around their equilibrium positions. These substantial displacements require tunneling through potential energy barriers, leading to splittings in, e.g.
View Article and Find Full Text PDFAdv Mater
December 2024
Physics of Energy Conversion and Storage, Department of Physics, Technical University of Munich, James-Franck-Straße 1, 85748, Garching, Germany.
Designing electrocatalysts with optimal activity and selectivity relies on a thorough understanding of the surface structure under reaction conditions. In this study, experimental and computational approaches are combined to elucidate reconstruction processes on low-index Pd surfaces during H-insertion following proton electroreduction. While electrochemical scanning tunneling microscopy clearly reveals pronounced surface roughening and morphological changes on Pd(111), Pd(110), and Pd(100) surfaces during cyclic voltammetry, a complementary analysis using inductively coupled plasma mass spectrometry excludes Pd dissolution as the primary cause of the observed restructuring.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
December 2024
Center for Ultrafast Science and Technology, School of Chemistry and Chemical Engineering, School of Physics and Astronomy, Zhang Jiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai 200240, China.
Photolyase and cryptochrome belong to a group of structurally similar flavoproteins but with two distinct functions of DNA repair as a photoenzyme and signal transduction as a photoreceptor, respectively, under blue-light illumination. Here, we studied a recently discovered bifunctional cryptochrome (CraCRY) with focus on its repair of UV-induced pyrimidine-pyrimidone (6-4) photoproduct (6-4PP). We used femtosecond spectroscopy and site-directed mutagenesis to map out the critical elementary steps by following the dynamics of initial reactants, various intermediates, and final products.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Chemical reactions are commonly described by the reactive flux transferring the population from reactants to products across a double-well free energy barrier. Dynamics often involves barrier recrossing and quantum effects like tunneling, zero-point energy motion, and interference, which traditional rate theories, such as transition-state theory, do not consider. In this study, we investigate the feasibility of simulating reaction dynamics using a parametrically driven bosonic superconducting Kerr-cat device.
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