Article
Chemistry, Physical
Jiawei Xue, Jun Bao
Summary: Photocatalysis is a promising technique for tackling the growing energy crisis and environmental issues, but faces challenges such as poor light absorption, fast charge recombination, and lack of active sites. The construction of heterojunction photocatalysts is a popular approach to address these issues. Understanding the interfacial charge transfer in heterojunction photocatalysts is crucial for designing high-performance photocatalysts.
SURFACES AND INTERFACES
(2021)
Review
Chemistry, Multidisciplinary
Ridwan Tobi Ayinla, Mehrdad Shiri, Bo Song, Mahesh Gangishetty, Kun Wang
Summary: Integrating efforts from various fields, single-molecule electronics has made remarkable progress with the development of single-molecule junction techniques. While the electrical properties of covalent molecules have been extensively studied, the impact of non-covalent interactions has gained increasing attention recently. Understanding both covalent and non-covalent interactions is crucial for expanding the functionality and scalability of molecular-scale devices. This review surveys the advances in probing how non-covalent interactions affect electron transmission through single molecules, focusing on key interactions such as π-π stacking, hydrogen bonding, and charge transfer complexation.
MATERIALS CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
J. T. Kohn, N. Gildemeister, S. Grimme, D. Fazzi, A. Hansen
Summary: Designing organic semiconductors for practical applications requires understanding charge transfer mechanisms. This study used a semiempirical quantum mechanical method combined with a non-self-consistent density matrix tight-binding potential to evaluate charge transfer integrals. The results showed that the method consistently performs well for calculating coupling integrals with reasonable accuracy at low computational cost.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Engineering, Environmental
Hanyu Tang, Zhaoyong Bian, Yiyin Peng, Shunlin Li, Hui Wang
Summary: The research focuses on stepwise hydrogenation dechlorination of chlorinated alkenes, using a low-cost Fe-Ni/rGO/Ni foam cathode to achieve high removal rates of trichloroethylene (TCE) above 78.0% over 8 cycles, with a maximum EHDC efficiency of 86.1%. Calculations using density functional theory (DFT) suggest that the 4-Cl and 5-Cl of TCE are expected to be removed first during the stepwise cleavage process on the Fe-Ni/rGO/Ni foam.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Spectroscopy
Li Xu, Yin Li, Peixin Jing, Guohao Xu, Qi Zhou, Yingxiang Cai, Xiaohua Deng
Summary: Co-crystallization is an effective strategy to improve drug properties, but the thermodynamic backgrounds, particularly lattice vibrations, are not fully understood. In this study, terahertz spectroscopy was used to characterize indomethacin cocrystals formed with nicotinamide and saccharin. DFT calculations with constrained unit cell showed better agreement with experimental results, and the thermodynamic contributions from lattice vibrations to cocrystal formations were evaluated, revealing the importance of vibrational energy in the formation process.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2021)
Article
Engineering, Environmental
Frank Leresche, Elena A. Vialykh, Fernando L. Rosario-Ortiz
Summary: This study calculated the UV-vis spectra of DOM model compounds using time-dependent density functional theory and successfully re-created the exponential shape of DOM absorption spectra by summing individual spectra. The effects of borohydride reduction on DOM absorbance spectra were accurately predicted, with a larger decrease in absorbance at longer wavelengths. Additionally, intra-molecular charge-transfer interactions were found to contribute to DOM absorption, while inter-molecular interactions were deemed less likely to play a role.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
M. A. Orekhov
Summary: This paper demonstrates that the Li-molecule pair model provides incorrect results for some solvents in simulating the reduction process of Li-ion batteries. By using the constrained density functional theory (CDFT) to place the additional electron on the molecule, the suggested approach improves the agreement with experimental data and can be used for computational screening of solvents.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Zachary R. Mansley, Ryan J. Paull, Louisa Savereide, Scott Tatro, Emily P. Greenstein, Abha Gosavi, Emily Cheng, Jianguo Wen, Kenneth R. Poeppelmeier, Justin M. Notestein, Laurence D. Marks
Summary: In this study, the use of structurally similar LnScO(3) nanoparticles as supports reveals that NdScO3 support material exhibits higher activation energy and slower rate in CO oxidation, which is attributed to differences in CO2 binding strength to the support surface.
Article
Chemistry, Multidisciplinary
Thi Le Anh Nguyen, Thi Hoai Nam Doan, Dinh Hieu Truong, Nguyen Thi Ai Nhung, Duong Tuan Quang, Dorra Khiri, Sonia Taamalli, Florent Louis, Abderrahman El Bakali, Duy Quang Dao
Summary: The antioxidant and UV absorption activities of three aaptamine derivatives were theoretically studied, showing their potential applications in pharmaceuticals and cosmetics as sunscreen and antioxidant ingredients.
Article
Multidisciplinary Sciences
Iris K. M. Yu, Fuli Deng, Xi Chen, Guanhua Cheng, Yue Liu, Wei Zhang, Johannes A. Lercher
Summary: This study investigates the influence of hydronium ions on the rate constant in aqueous-phase Pd-catalyzed furfural hydrogenation reactions. The results indicate that the strength of hydrogen binding on Pd is a decisive factor in the hydrogenation kinetics, while furfural adsorption on Pd is not affected by pH.
NATURE COMMUNICATIONS
(2022)
Article
Environmental Sciences
Bingqing Wang, Baohua An, Zhi Su, Laicai Li, Yong Liu
Summary: The study investigated the efficiency and products of nitrate or nitrite reduction by CO2 center dot- radical, proposing a novel strategy for rapid reduction of nitrate into N-2 with high efficiency and selectivity using CO2 center dot- radical.
Article
Chemistry, Multidisciplinary
Yangyang Lu, Chen Xiao, Yilong Jiang, Chuan Tang, Lei Chen, Junhui Sun, Linmao Qian
Summary: This study investigates the nanoscale wear process between silicon and silicon dioxide through experiments and calculations. The results show that the wear rate of silicon in ambient air increases exponentially with stress and does not follow the classical Archard's law. Atomic-level wear model calculations reveal that mechanical stress linearly drives electron transfer, activating the sequential formation and rupture of interfacial bonds in the atomistic wear process. This work is important for understanding and controlling wear and manufacturing of material surfaces.
Article
Engineering, Environmental
Jimmy Murillo-Gelvez, Kevin Hickey, Dominic M. Di Toro, Herbert E. Allen, Richard F. Carbonaro, Pei C. Chiu
Summary: This study measured the reduction rates of munition constituents and their surrogates in reducing environments. It was found that all of them can be reduced by hydroquinones. By developing a linear free energy relationship model, the reaction rate constants were successfully predicted, which is crucial for predicting the fate and half-lives of munition constituents in reducing environments.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Multidisciplinary Sciences
Courtney E. Wise, Anastasia E. Ledinina, David W. Mulder, Katherine J. Chou, John W. Peters, Paul W. King, Carolyn E. Lubner
Summary: Electron bifurcation is an energy-conserving process widely utilized in biochemistry, which generates high-energy products from substrates with lower reducing potential. The energetic challenge of the first bifurcation event, with a thermodynamically uphill step, is resolved by elucidating the unusually low two-electron potential of the bifurcating flavin.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Chidera C. Nnadiekwe, Ahmed Nada, Ismail Abdulazeez, Mohammad R. Imam, Muhammad Ramzan Saeed Ashraf Janjua, Abdulaziz A. Al-Saadi
Summary: The ability to tune the structural properties of dendrimers with respect to size, polarity, and terminal functionalities makes them highly attractive for potential biological and catalytic applications. The synthesized Janus (J) and Twin (T) benzamide-based branched structures were characterized using spectroscopic and theoretical techniques, revealing the orientation of aliphatic chains and linkage configurations. UV-Vis spectra showed consistent absorption around 290 nm, with assigned prominent bands correlating with the molecules' structural and electronic aspects.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Aishik Bhattacharya, Arnab Kumar Nath, Arnab Ghatak, Abhijit Nayek, Souvik Dinda, Rajat Saha, Somdatta Ghosh Dey, Abhishek Dey
Summary: The reduction of SO2 by iron(II) tetraphenylporphyrin has been demonstrated, generating an intermediate [Fe-III-SO](+) species which releases SO. The SO obtained from the chemical reduction of SO2 can be evidenced in the form of a cheletropic adduct of butadiene resulting in an organic sulfoxide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Samir Chattopadhyay, Soumya Samanta, Ankita Sarkar, Aishik Bhattacharya, Suman Patra, Abhishek Dey
Summary: In-operando spectroscopic observation using SERRS-RDE is crucial for studying the mechanism of electrocatalytic reactions. However, current technology is limited to oxygen reduction reactions due to stability issues. This study presents a second-generation SERRS-RDE setup using Ag nanostructure-modified graphite electrode, which overcomes the stability issues and allows observation of intermediates in other reactions.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Abhishek Dey
Summary: Reducing CO2 selectively to a specific C1 product is challenging due to similar thermodynamic reduction potentials for different CO2 reductions. Inspired by nickel CO dehydrogenase (Ni-CODH), the use of bimetallic iron porphyrins bridged by a urea moiety enables fast and selective reduction of CO2 to CO. The mechanism appears to mimic Ni-CODH, where one metal binds and reduces CO2 while the other stabilizes the reduced species and facilitates C-O bond cleavage.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bohee Kim, Magdalene T. T. Brueggemeyer, Wesley J. J. Transue, Younwoo Park, Jaeheung Cho, Maxime A. A. Siegler, Edward I. I. Solomon, Kenneth D. D. Karlin
Summary: Lytic polysaccharide monooxygenases are important in converting biomass to biofuel, and recent studies show that their peroxygenase activity using H2O2 as an oxidant is more important than their monooxygenase functionality. New insights into this activity have been described, including ligand-substrate hydroxylation and Fenton-type chemistry reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sarmistha Bhunia, Arnab Ghatak, Atanu Rana, Abhishek Dey
Summary: Iron porphyrins with one or four tertiary amine groups in their second sphere show higher rates and selectivity in the electrochemical O2 reduction reaction (ORR) compared to iron tetraphenylporphyrin lacking these amines. The presence of these amine groups leads to protonation and lower overpotentials, enhancing the ORR rate. Heterogeneous aqueous conditions reveal changes in the rate-determining step (rds) of the ORR depending on the number of amine groups, with cleavage of the O-O bond being the rds in the presence of one amine group, while proton-coupled reduction becomes the rds with four amine groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Aleksandra Wandzilak, Katarzyna Grubel, Kazimer L. Skubi, Sean F. Mcwilliams, Dimitrios Bessas, Atanu Rana, Stefan Hugenbruch, Abhishek Dey, Patrick L. Holland, Serena Debeer
Summary: This study successfully elucidated the characteristics and mechanism of the intermediate species during the cleavage of the strong triple bond of N2 by Diketiminate-supported iron complexes, using a range of spectroscopic techniques and computational models.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jeffrey T. T. Babicz Jr, Melanie S. Rogers, Dory E. DeWeese, Kyle D. Sutherlin, Rahul Banerjee, Lars H. Bottger, Yoshitaka Yoda, Nobumoto Nagasawa, Makina Saito, Shinji Kitao, Masayuki Kurokuzu, Yasuhiro Kobayashi, Kenji Tamasaku, Makoto Seto, John D. Lipscomb, Edward I. Solomon
Summary: The extradiol dioxygenases and intradiol dioxygenases play a crucial role in the carbon cycle by catalyzing oxidative aromatic ring cleavage. This study investigates the mechanisms behind their regiospecificity in cleavage, using EDO and IDO enzymes as models. The results reveal the structural and electronic properties of key intermediates and propose a viable mechanism for intradiol cleavage.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Augustin Braun, Leland B. Gee, Michael W. Mara, Ethan A. Hill, Thomas Kroll, Dennis Nordlund, Dimosthenis Sokaras, Pieter Glatzel, Britt Hedman, Keith O. Hodgson, A. S. Borovik, Michael L. Baker, Edward I. Solomon
Summary: Fe K-edge XAS is widely used for studying high-valent iron intermediates in catalysts. The 4p-mixing into the 3d orbitals complicates the analysis, but understanding it correctly enables deeper insights into the structure and reactivity. This study reveals that the loss of inversion in the equatorial plane leads to 4p mixing into the 3dx2-y2,xy orbitals, providing structural insights for distinguishing 6- vs 5-coordinate active sites. Furthermore, the study investigates the electronic structure of Fe(IV)=O active sites and their reactivity selectivity through O K-edge XAS.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Casey Van Stappen, Huiguang Dai, Anex Jose, Shiliang Tian, Edward I. Solomon, Yi Lu
Summary: This research investigates the influence of the primary and secondary coordination sphere on CuII-catalyzed S-nitrosylation. The study reveals that kinetic competency is correlated with Cu-S bond strength, Cu spin localization, and relative S(p(s)) vs S(p(p)) contributions to the ground state.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hyeongtaek Lim, Magdalene T. Brueggemeyer, Wesley J. Transue, Katlyn K. Meier, Stephen M. Jones, Thomas Kroll, Dimosthenis Sokaras, Bradley Kelemen, Britt Hedman, Keith O. Hodgson, Edward I. Solomon
Summary: This study investigates the electronic structure of the d(10) Cu(I) active site in LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the required 3d/p mixing for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, particularly the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H2O2 O-O bond and understand the activation of the geometric and electronic structure of the Cu(I)-LPMO site for rapid reactivity with H2O2.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Asmita Singha, Alina Sekretareva, Lizhi Tao, Hyeongtaek Lim, Yang Ha, Augustin Braun, Stephen M. Jones, Britt Hedman, Keith O. Hodgson, R. David Britt, Daniel J. Kosman, Edward I. Solomon
Summary: In multicopper oxidases (MCOs), the T1 Cu accepts electrons from the substrate and transfers them to the TNC, reducing O-2 to H2O. The literature fails to explain the wide range of T1 potentials in MCOs, ranging from 340 to 780 mV. This study focuses on the difference in potential of the T1 center in Fet3p and Trametes versicolor laccase (TvL) that have the same ligand set, and reveals that second-sphere H-bonding interactions and carboxylate residues significantly lower the T1 potential.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Paramita Saha, Sudip Barman, Sk Amanullah, Abhishek Dey
Summary: Nitric oxide (NO) is a key intermediate in the nitrogen cycle, but there are limited molecular catalysts for its transformation. Heme nitrosyls, particularly the ferrous nitrosyl species, play important roles in the reduction of NO2 (-) to NH4 (+). This study investigates the effect of substituents on iron porphyrins on the reduction of NO, and demonstrates that the presence of -COOEt groups can shift the potential for electrochemical NO reduction, making it more physiologically relevant.
Article
Chemistry, Multidisciplinary
Ankita Sarkar, Snehadri Bhakta, Samir Chattopadhyay, Abhishek Dey
Summary: Heme nitrite reductases play a key role in the global nitrogen cycle by reducing NO2- to NO or NH4+. The presence of arginine residues in the second sphere of these enzymes is proposed to assist in substrate binding and provide protons for the reaction. This study investigates the role of guanidine arm attached to a synthetic ferrous porphyrin in reducing NO2-, and suggests that rapid re-protonation of arginine residues may trigger NO dissociation from the ferric nitrosyl species.
Article
Chemistry, Multidisciplinary
Soumya Samanta, Srijan Sengupta, Saptarshi Biswas, Sucheta Ghosh, Sudip Barman, Abhishek Dey
Summary: Heme dioxygenases play a crucial role in the biosynthesis of important biomolecules. In this study, the catalytic function of a ferrous heme dioxygen adduct was investigated using in situ resonance Raman spectroscopy. The results showed the accumulation of different species during the electrochemical ORR catalysis, mimicking the reaction of heme dioxygenases. This study provides important insights into the mechanism of biological catalysts and can inspire the design of more efficient artificial catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Sandipan Jana, Puja De, Chinmay Dey, Somdatta Ghosh Dey, Abhishek Dey, Sayam Sen Gupta
Summary: This study reports a synthetic iron complex that mimics cytochrome P450 in water using H2O2 as the oxidant. It shows high selectivity in oxidizing unactivated C-H bonds in small organic molecules, with predictable stereoretention and moderate to high yields. The reactivity of this iron complex in water is about 300 times higher than in organic solvents.