Article
Chemistry, Multidisciplinary
Chao Zhou, Qi-Chao Gan, Tai-Ping Zhou, Tao Lei, Chen Ye, Xiao-Jun He, Bin Chen, Heng Lu, Qian Wan, Rong-Zhen Liao, Chen-Ho Tung, Li-Zhu Wu
Summary: This study reports the first regioselective heteroarylation of indole through a radical-radical cross-coupling using visible-light irradiation. Spectroscopic and computational studies show that the hydrogen-bonding interaction between an organic base and its conjugated acid plays a crucial role in determining the reaction pathway, resulting in regioselective formation of C-3 and N-1 heteroarylation of indoles. This methodology has great potential in large-scale synthesis and late-stage derivatization of bioactive compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yusuke Yoneda, S. Jimena Mora, James Shee, Brian L. Wadsworth, Eric A. Arsenault, Diptarka Hait, Gerdenis Kodis, Devens Gust, Gary F. Moore, Ana L. Moore, Martin Head-Gordon, Thomas A. Moore, Graham R. Fleming
Summary: This study investigates the photoinduced PCET dynamics of a biomimetic model system using various spectroscopic techniques and computational methods, providing insights into the complex dynamics and synergistic motions involved in the process. Specifically, the evolution of the 2DEV line shape, sensitive to the mixing of vibronic states, is interpreted through accurate computational modeling of the charge separated state, revealing a gradual change in electron density distribution associated with a dihedral twist occurring on a 120 fs time scale.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Tomohiro Kikuchi, Keiji Yamada, Takeshi Yasui, Yoshihiko Yamamoto
Summary: The metal-free ring expansion of cyclopropanols with a styrene moiety was achieved through a proton-coupled electron transfer enabled by an organic photoredox catalyst. Variants of 1-tetralone and 1-benzosuberone with a substituent at the benzylic position were selectively obtained through the regioselective ring closure of alkyl radical intermediates, depending on the substitution pattern of the alkene moiety.
Article
Chemistry, Multidisciplinary
Clorice R. Reinhardt, Elvira R. Sayfutyarova, Jiayun Zhong, Sharon Hammes-Schiffer
Summary: Ribonucleotide reductase (RNR) is an essential enzyme in DNA synthesis, with the active form of E. coli Ia RNR consisting of two subunits, alpha and beta, involved in a series of proton-coupled electron transfer (PCET) reactions. Quantum mechanical/molecular mechanical simulations suggest thermodynamically favored forward radical transfer in the pre-turnover state and backward radical transfer in the post-turnover state between Y731 and Y730. The simulations also propose that E623 plays a key role in influencing the directionality of PCET and predict the impact of mutation of E623 on catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Wencong Sun, Dong Yao, Yuehua Tai, Li Zhou, Wenxue Tian, Min Yang, Chunxiang Li
Summary: Polyoxometalates (POMs) can effectively catalyze the electrocatalytic CO2 reduction reaction (CO2RR) through multistep proton-coupled electron transfer (PCET) processes. In this study, a combination of commercial indium electrodes with Keggin-type POMs (PVnMo(12-n)O40)(n+3)- (n = 1, 2, 3) achieved a Faradaic efficiency toward ethanol of 93.4% at -0.3V (vs. RHE). The PCET processes in POMs activated CO2 molecules and caused the oxidation of the electrode, resulting in the loss of active sites. The addition of POM electrolyte additives regulated the interface microenvironment and improved CO2RR performance.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Review
Chemistry, Physical
Feng Zhu, Wenbin Zhang, Jiao Xun, Bi-Jun Geng, Qing-Man Liang, Yang Yang
Summary: This review focuses on the effects of proton donor/acceptor on several typical electrocatalytical reactions, including species, concentration, pKa, and steric hindrance. Specifically, the proton transfer pathway arising from ligand design strategy of molecular catalysts and modification of electrode-electrolyte interface is presented.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Nanoscience & Nanotechnology
Yuanfeng Gao, Qingyu Xue, Jiayuan Li, Mingkai Zhang, Yuanyuan Ma, Yongquan Qu
Summary: Coupling acid-electrolyte proton exchange membrane fuel cells with cathodic hydrogenation shows potential in energy and chemical industry. The use of phytate coordination on Cu surface enhances the kinetic of proton adsorption/activation and hydrogenation activity. This work provides a promising approach to integrate electricity generation and chemical production.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Multidisciplinary Sciences
Zhongneng Zhou, Zijing Chen, Xiu-Wen Kang, Yalin Zhou, Bingyao Wang, Siwei Tang, Shuhua Zou, Yifei Zhang, Qiaoyu Hu, Fang Bai, Bei Ding, Dongping Zhong
Summary: In this study, the photocycle of the FMN-Gln-Tyr motif in the BLUF domain of OaPAC was investigated using computational simulations. The results show that forward PCET is concerted, while only the wild-type protein proceeds with an ultrafast reverse PCET process.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Engineering, Environmental
Fan Nie, Wenyue Xu, Di Zhang, Junwei Wang, Ruixue Zhang, Xiaojie Fang, Yaxin Wang
Summary: In this study, a visible-light-driven catalyst FeS2@Mo2C/PMS was prepared by band regulation and surface interface structural modifications under the nanoconfinement effect. The catalyst exhibited high efficiency in activating peroxymonosulfate (PMS) for degradation of Azo dyes. The presence of stable S-Mo bonds in the FeS2@Mo2C Schottky junctions and the acceleration of electron transfer and hole oxidation in FeS2 contributed to the enhanced catalytic performance. The mesoporous catalysts prepared through nanoconfinement effect exhibited excellent removal efficiency for target pollutants.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2022)
Article
Chemistry, Physical
Pinit Ariyageadsakul, Kyoung Koo Baeck
Summary: The charge-transfer excited state of NH3Cl can undergo a typical proton-coupled electron transfer process through proton transfer and electron transfer. The study reveals that the branching ratio is influenced by the vibration levels of the initial precursor anion and the isotope substitution of the connecting H atom.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Biswajit Mondal, Soumitra Dinda, Neeta Karjule, Sanjit Mondal, Alagar Raja Kottaichamy, Michael Volokh, Menny Shalom
Summary: Electrolysis of water is a sustainable method to produce clean hydrogen, but it requires a high applied potential due to the pH-dependency of the hydrogen and oxygen evolution reactions. By combining proton-coupled electron transfer and single-electron transfer processes, we have achieved hydrogen production from water at low cell potentials by pH adjustment.
Article
Chemistry, Physical
Zhaosheng Liu, Shuai Zhong, Xiaochen Ji, Guo-Jun Deng, Huawen Huang
Summary: A visible light-induced photocatalytic system was developed to enable intramolecular hydroarylation of N-arylacrylamides with high 5-exo-trig selectivity through proton-coupled electron transfer (PCET). This mild protocol provides a straightforward entry to structurally valuable oxindoles and complements previously established 6-endo-trig cyclization by photochemical triplet energy transfer (TET).
Article
Chemistry, Multidisciplinary
Xiao-Dong Yang, Jun-Hao Zhou, Jing-Wang Cui, Jie Yang, Hong-Peng Jia, Jian-Ke Sun, Jie Zhang
Summary: Multiple charge separation was achieved through a proton-coupled electron transfer reaction in an organic cocrystal. The adjustable electronic energy levels of the donor and acceptor, controlled by thermal-induced proton migration, resulted in distinct optical absorption behaviors and color changes. The charge-separated states exhibited a longer lifetime due to the coplanarity and pi-pi interaction of the electron acceptors, and the enhanced absorption towards longer wavelengths allowed for near-infrared photothermal conversion for imaging and bacterial inhibition, controllable by the degree of proton migration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Belinda Pettersson Rimgard, Zhen Tao, Giovanny A. Parada, Laura F. Cotter, Sharon Hammes-Schiffer, James M. Mayer, Leif Hammarstrom
Summary: In this study, a photochemical mechanism termed proton-coupled energy transfer (PCEnT) was experimentally discovered and theoretically analyzed. Anthracene-phenol-pyridine triads were found to undergo a local excited state and emit fluorescence through singlet-singlet energy transfer, despite the lack of spectral overlap. Theoretical calculations also indicated negligible charge transfer between the anthracene and phenol-pyridine units. These findings suggest the relevance of PCEnT in biological systems and future photonic devices.
Article
Nanoscience & Nanotechnology
Damiano Genovese, Andrea Baschieri, Danilo Vona, Ruxandra Elena Baboi, Fabio Mollica, Luca Prodi, Riccardo Amorati, Nelsi Zaccheroni
Summary: Nitroxides are an important class of radical trapping antioxidants with promising biological activities due to their ability to scavenge peroxyl radicals. The reaction rate constants of TEMPO derivatives with peroxyl radicals were measured, showing a good Marcus relationship between log (k(inh)) and E degrees. The use of nitroxide derivatives in developing novel nanoantioxidants was discussed, highlighting the importance of choosing the best linkage group and the regeneration cycle in determining the duration of inhibition.
ACS APPLIED MATERIALS & INTERFACES
(2021)
