Review
Chemistry, Inorganic & Nuclear
Isaac F. Leach, Remco W. A. Havenith, Johannes E. M. N. Klein
Summary: This paper presents a computational analysis of the challenging oxidation state assignment of the formal Cu(III) complex [Cu(CF3)(4)](1-). A quasi-d(10) perspective of the metal center is proposed, and the implications for understanding reactions with oxidation state changes are discussed.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Natercia F. Bras, Salavat S. Ashirbaev, Hendrik Zipse
Summary: This study explores the mechanism of covalent binding between baicalein and human amyloid proteins, revealing how it inhibits fibril aggregation and deposition. The reaction with pentylamine generates regioselectively C6-substituted products, supporting baicalein's anti-amyloid activity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jesus M. Dones, Nile S. Abularrage, Namrata Khanal, Brian Gold, Ronald T. Raines
Summary: The study integrated two strategies to optimize alkynyl reagents for achieving high reaction rates. Computational analysis indicated that aryl substitution could be beneficial for increasing reactivity. Experimental results showed that interactions between the new reagents and amino dipolarophile contribute to enhanced reaction efficiency.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Mikhail S. Kuklin, Kim Eklund, Jarno Linnera, Artturi Ropponen, Nikolas Tolvanen, Antti J. Karttunen
Summary: In this study, the structural properties, magnetic ground states, and fundamental electronic properties of 100 binary d-metal oxides were systematically investigated using hybrid density functional methods and localized basis sets. The PBE0 hybrid functional method was found to accurately describe the structural properties of most d-metal oxides, except for molecular oxides with weak intermolecular forces. A database of optimized geometries and magnetic ground states was provided for future studies on the more complex properties of binary d-metal oxides.
Article
Chemistry, Multidisciplinary
Jeffrey Seeman
Summary: This article introduces the sharing of the 1981 Nobel Prize in Chemistry by Kenichi Fukui and Roald Hoffmann for their contributions to the theories of chemical reactions. It also discusses Fukui's personality, professional style, teaching methods, and flexibility in both behavior and scientific research. Finally, it lists Fukui's key awards.
Article
Chemistry, Multidisciplinary
Bo Chen, K. N. Houk, Roberto Cammi
Summary: This study reports on the thermal dimerization of 1,3-cyclohexadiene at different pressures, and analyzes the activation enthalpies and activation volumes of different reaction pathways through quantum chemical calculations. The results show that under high pressure, the reduction of reaction barriers is more significant in concerted reactions compared to stepwise reactions, and the transition state of the [6+4]-ene reaction shifts towards the reactant. The computed results agree well with experimental data, confirming the existence of competing mechanisms in the thermal dimerization of 1,3-cyclohexadiene.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jeffrey Seeman
Summary: Fukui's paper, published in 1964, was a precursor to his award-winning publication that explained the mechanism of the Diels-Alder reaction using frontier molecular orbital theory. It laid the foundation for pericyclic reactions and was in line with the research by Woodward and Hoffmann.
Review
Chemistry, Physical
Alina F. Sattarova, Yulia N. Biglova, Akhat G. Mustafin
Summary: This review highlights the essential role of quantum chemistry in interpreting experimental measurements of fullerene and its derivatives, focusing on a wide range of molecular properties. The use of density functional theory and computational studies demonstrate the promising prospects of quantum-chemical calculations in various fields of fullerene chemistry, such as geometric parameters, electronic structures, and reaction mechanisms. Potential readers are provided with a wealth of references for further exploration of computational approaches in this area.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jeffrey Seeman
Summary: This article introduces Kenichi Fukui's contributions and his involvement in various areas of chemical research. His frontier molecular orbital theory provided an explanation for the mechanism of the Diels-Alder reaction, and his research preceded Woodward and Hoffmann's studies on orbital symmetry to some extent.
Article
Physics, Multidisciplinary
Yijian Zou, Shengqi Sang, Timothy H. Hsieh
Summary: We analyze the effect of decoherence, modeled by local quantum channels, on quantum critical states and find universal properties of entanglement in resulting mixed states. We define a renormalization group flow between quantum channels and relate the subleading logarithmic scaling of subsystem entropy to correlation functions in conformal field theory. We also show that the subsystem entanglement negativity can exhibit different scaling behaviors based on the renormalization group flow. Our results are important for understanding quantum critical states in noisy quantum simulators.
PHYSICAL REVIEW LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Qiyuan Zhao, Dylan M. Anstine, Olexandr Isayev, Brett M. Savoie
Summary: The emergence of & UDelta;-learning models provides a versatile route to accelerate high-level energy evaluations. However, these models are unable to predict reaction properties that require both high-level geometry and energy evaluation. This study introduces a & UDelta;(2)-learning model that predicts high-level activation energies based on low-level critical-point geometries. The model demonstrates excellent performance on unseen reactions and shows near chemical accuracy, making it an efficient strategy for accelerating chemical reaction characterization.
Article
Multidisciplinary Sciences
Jie Han, Siyuan Liu, Huanan Wang, Jie Wang, Hui Qian, Zhiming Li, Shengming Ma, Junliang Zhang
Summary: The 13-H elimination is a crucial step in the carbon-palladium bond quenching for the Heck reaction and has been a challenge to control enantioselectivity. Here, we developed a concise and efficient method to construct chiral allenes from fully substituted enol triflates through enantioselective 13-H elimination of alkenyl palladium species under mild conditions. The identified Xu-Phos catalysts play a crucial role in chemoselectivity and enantioselectivity. Multiple linear regression analysis shows the significance of steric effect on enantioselectivity. DFT calculations propose an intramolecular base-assisted deprotonation mechanism for this progress, and energy decomposition analysis suggests that the difference in electrostatic energy of the transition states dominates the stereoselectivity.
Article
Chemistry, Multidisciplinary
Philippe A. Peixoto, Mourad El Assal, Isabelle Chataigner, Frederic Castet, Anaelle Cornu, Romain Coffinier, Cyril Bosset, Denis Deffieux, Laurent Pouysegu, Stephane Quideau
Summary: Many natural products are derived from enzymatic dearomative oxygenation of 2-alkylphenolic precursors into 6-alkyl-6-hydroxycyclohexa-2,4-dienones, which cyclodimerize via a bispericyclic Diels-Alder reaction. The involvement of catalytic or dirigent proteins in this process is still a question, but the cyclodimerization of ortho-quinols can be chemically reproduced in the laboratory with the same level of regioselectivity and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Thomas Eckert, Jan von Cosel, Benedict Kamps, Hans-Christian Siebert, Ruiyan Zhang, Ning Zhang, Konstantinos Gousias, Athanasios K. Petridis, Dimitrios Kanakis, Konstantin Falahati
Summary: The collagen-integrin interactions are mediated by the Mg2+ cation, but experiments have shown that Co2+ cations can form stable complexes for such interactions. Studying the impact of these cations in cell-culture experiments is essential, especially in the context of tissue repair and neuro-oncology. This research opens up new possibilities for understanding the interactions of integrins with heavy-metal ions at the sub-atomic level and their potential applications in tumor tissues.
FRONTIERS IN MOLECULAR BIOSCIENCES
(2021)
Article
Chemistry, Multidisciplinary
Anthony R. Izzotti, James L. Gleason
Summary: The previously proposed edge-to-face cycloaddition mechanism was found to be not a concerted process. At low temperature, a mixture of cis and trans cycloadducts as well as other cycloadducts was observed. Upon warming to room temperature, the mixture of products converted to trans cycloadducts. The formation of cis cycloadducts was confirmed by additional studies.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
