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
Chemistry, Physical
Sunandita Paul, Vamsee K. Voora, Jyotishman Dasgupta
Summary: In this study, the excited state dynamics of a redox-active TTF radical cation and its corresponding dimethyl-derivative inside a confined supramolecular cavity were investigated. It was found that upon photoexcitation, these reactive intermediates quickly de-excite to the hot ground state, inhibiting further oxidation reactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(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, 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, 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, Multidisciplinary
Debojyoti Roy, Sunandita Paul, Jyotishman Dasgupta
Summary: Ultrafast C-H bond activation and functionalization in confinement using visible light is demonstrated for the first time on poly-aromatic hydrocarbons (PAH) using an all-organic cationic nanocage. This transition metal-free method allows the formation of oxidized photoproducts with high selectivity through host-guest charge transfer. The mechanism involves sequential electron transfer and proton transfer steps with a timescale of a few hundred picoseconds.
CHEMICAL COMMUNICATIONS
(2023)
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
Polymer Science
Xiaoguang Qiao, Liang Qiao, Mengjie Zhou, Xi Zhang, Ge Shi, Yanjie He, Elodie Bourgeat-Lami, Xinchang Pang
Summary: This study demonstrates the efficient utilization of carbon quantum dots as a green photocatalyst in miniemulsion atom transfer radical polymerization. The heterogeneous photocatalytic system shows high reaction rates and excellent temporal control, and can be extended to other aqueous dispersion RDRP systems.
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
Electrochemistry
Jean-Francois Longevial, Iryna Knysh, Shaymaa Al Shehimy, Lhoussain Khrouz, Aramugam Pandurangan, Simon Pascal, Gabriel Canard, Christophe Bucher, Denis Jacquemin, Olivier Siri
Summary: Researchers have synthesized and characterized the soluble 6,13-dipivaloyl-5,14-dihydro-5,7,12,14-tetraazapentacene and its aromatic counterpart. Using complementary chemical, (spectro)-electrochemical, theoretical, and spectroscopic techniques, all the intermediates generated during the electrochemical processes of these compounds were fully characterized. The results demonstrate the ambipolar redox behavior of 6,13-dipivaloyl-5,14-dihydro-5,7,12,14-tetraazapentacene, leading to drastic color changes through proton-coupled electron transfer in a totally reversible fashion.
ELECTROCHIMICA ACTA
(2023)
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
Gaoyuan Zhao, Juncheng Li, Ting Wang
Summary: The development of visible-light-induced photoacid catalyzed glycosylation using eosin Y and PhSSPh catalyst system was reported, demonstrating a broad substrate scope and mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Mohd Taher, Basudev Maity, Taiki Nakane, Satoshi Abe, Takafumi Ueno, Shyamalava Mazumdar
Summary: The study shows that mutations at the core of the ferritin nanocage can impact the uptake of IrCp*, with mutation of Arg52 by His leading to a significant increase in uptake. Additionally, the ferritin variants were found to exhibit high activity and enantioselectivity in catalyzing transfer hydrogenation reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Shreetama Karmakar, Abhinandan Ambastha, Ajay Jha, Aditya Dharmadhikari, Jayashree Dharmadhikari, Ravindra Venkatramani, Jyotishman Dasgupta
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Chemistry, Multidisciplinary
Hong-Guang Duan, Vandana Tiwari, Ajay Jha, Golibjon R. Berdiyorov, Alexey Akimov, Oriol Vendrell, Pabitra K. Nayak, Henry J. Snaith, Michael Thorwart, Zheng Li, Mohamed E. Madjet, R. J. Dwayne Miller
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Multidisciplinary Sciences
Hong-Guang Duan, Ajay Jha, Xin Li, Vandana Tiwari, Hanyang Ye, Pabitra K. Nayak, Xiao-Lei Zhu, Zheng Li, Todd J. Martinez, Michael Thorwart, R. J. Dwayne Miller
Article
Chemistry, Physical
Ajay Jha, Kaustubh R. Mote, Suman Chandra, Perunthiruthy K. Madhu, Jyotishman Dasgupta
Summary: The research demonstrates the rapid charge transfer process in host-guest supramolecular assemblies, supported by transient spectroscopy and EPR studies, showing efficient charge separation and long-lived charge in COF assemblies, paving the way for COF-based photocatalytic reaction centers.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Nanoscience & Nanotechnology
Yan Yan, Cheng Liu, Yi Yang, Guoxiang Hu, Vandana Tiwari, De-en Jiang, Wei Peng, Ajay Jha, Hong-Guang Duan, Friedjof Tellkamp, Yong Ding, Weidong Shi, Shouqi Yuan, Dwayne Miller, Wanhong Ma, Jincai Zhao
Summary: The study uncovers the issue of acidic protons residue in TiO2 ETL prepared with commercially available TiO2 nanocrystal paste, and proposes a straightforward deprotonation approach to eliminate this issue. This method significantly enhances the performance and stability of perovskite solar cells.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Rahul Gera, Huib J. Bakker, Ricardo Franklin-Mergarejo, Uriel N. Morzan, Gabriele Falciani, Luca Bergamasco, Jan Versluis, Indraneel Sen, Silvia Dante, Eliodoro Chiavazzo, Ali A. Hassanali
Summary: This study investigates the properties of the water and surfactant C12E6 interface, finding that the addition of C12E6 near the critical micelle concentration enhances hydrogen bond strength and alters the orientation of water molecules. This leads to the formation of a broad interface with a large electric field, potentially opening up new possibilities for designing catalytic and light-harvesting systems at the water-surfactant-air interface.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Wei Weng, Alexander B. Weberg, Rahul Gera, Neil C. Tomson, Jessica M. Anna
Summary: The study investigates the impact of ligand structural variation on the ultrafast dynamics of copper coordination complexes, revealing that an increase in phenyl groups leads to a broader frequency distribution and more accessible configurations for the azide group.
JOURNAL OF PHYSICAL CHEMISTRY B
(2021)
Article
Chemistry, Physical
Rahul Gera, Carolyn J. Moll, Aditi Bhattacherjee, Huib J. Bakker
Summary: Using HD-VSFG, we investigated the molecular-scale structure of the Reline surface. As the water content increased, we observed a gradual depletion of urea from the surface, enhanced alignment of choline cations, and surface speciation of ChCl.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Multidisciplinary Sciences
Hong-Guang Duan, Ajay Jha, Lipeng Chen, Vandana Tiwari, Richard J. Cogdell, Khuram Ashraf, Valentyn I. Prokhorenko, Michael Thorwart, R. J. Dwanye Miller
Summary: Scientists have discovered that electronic coherence in light harvesting can be prolonged at extremely low temperatures, increasing the stability of the process against fragile quantum effects.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Multidisciplinary Sciences
Jianwei Shen, Ajay Jha, Meng Lv, Guanyu Jiang, Qixu Zhao, Zihui Liu, Jinquan Chen, Yan Yang, Haitao Sun, Hong-Guang Duan, Zhenrong Sun
Summary: Merocyanine dyes are of great interest due to their nonlinear optical properties and solvatochromism. In this study, the excited state dynamics of a merocyanine dye known as HB194 were investigated, revealing solvent-dependent charge transfer dynamics. The excited state decays in different solvents showed multi-exponential components, with polar solvents inducing conformationally relaxed intramolecular charge transfer states and nonpolar solvents exhibiting solvent-stabilized ICT states. An anomalously red-shifted emission was observed in ethylene glycol, which was attributed to the presence of molecular dimers. This work emphasizes the importance of gaining molecular-level insight into system-solvent interactions for designing next-generation merocyanine-based solvatochromic dyes.
SCIENTIFIC REPORTS
(2022)
Article
Chemistry, Physical
Sanghamitra Sengupta, Rahul Gera, Colin Egan, Uriel N. Morzan, Jan Versluis, Ali Hassanali, Huib J. Bakker
Summary: The interfacial vibrational footprints of SDS and C12E6 binary mixture were investigated using HDVSFG. The presence of C12E6 enhances the effect of SDS on the orientation of interfacial water molecules, contrary to the predictions of the traditional Langmuir adsorption model. Molecular dynamics simulations also support this observation.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Xia-Ping Fu, Yizhi Yuan, Ajay Jha, Nikita Levin, Jack Ren, Dimitrios Mamalis, Shabaz Mohammed, Benjamin G. Davis, Andrew M. Giltrap
Summary: Chemical post-translational methods allow editing of proteins without genetic intervention. A light-mediated desulfurative method can generate site-selectively edited proteins with full retention of native stereochemistry from a natural amino acid precursor. This methodology has great potential in exploring protein side-chain diversity and function and constructing useful bioconjugates.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Hyein Hwang, Vandana Tiwari, Hong-Guang Duan, Simon F. Bittmann, Friedjof Tellkamp, Ajay Jha, R. J. Dwayne Miller
Summary: In this paper, a general method based on spatial confinement is presented to grow thin single organic crystals with large area. Using 1,5-dihydroxyanthraquinone as an example, the protocol for optically characterizing structural dynamics is provided, enabling proper assignments using diffraction methods.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Gourab Chatterjee, Ajay Jha, Alejandro Blanco-Gonzalez, Vandana Tiwari, Madushanka Manathunga, Hong-Guang Duan, Friedjof Tellkamp, Valentyn Prokhorenko, Nicolas Ferre, Jyotishman Dasgupta, Massimo Olivucci, R. J. Dwayne Miller
Summary: This study reveals the importance of the concerted interplay between nuclear and electronic motions in molecules in solution for chemical reactions. By experiment and simulation, we find that vibrational excitation plays a key role in modulating the charge-density distribution, and demonstrate the significance of molecular geometries in energy transfer.
Article
Chemistry, Physical
Rahul Gera, Jyotishman Dasgupta
Summary: The study focuses on photoexciting charge transfer transitions arising from host-guest interactions in a confined environment, and the investigation of heterogeneity of guest orientations and ensuing charge transfer dynamics, highlighting challenges for using molecular cages as photocatalytic reaction vessels.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
