Article
Chemistry, Multidisciplinary
Anna G. Scott, Diogo Alves Galico, Isabel Bogacz, Paul H. Oyala, Junko Yano, Elizaveta A. Suturina, Muralee Murugesu, Theodor Agapie
Summary: Atomically defined large metal clusters have significant applications in new reaction development and the synthesis of materials with tailored properties. In this study, a new class of Fe clusters, Tp*4W4Fe13S12, with M-M bonds is reported, which has only been observed in main group and late metal chemistry. The Fe-13 core of this cluster exhibits a large spin ground state of S=13 and can undergo significant rearrangements through small molecule activations involving the transfer of up to 12 electrons.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Environmental
Fansong Liu, Qiujing Xu, Huizhi Liang, Haiying Wang, Cheng Zhong, Xiaobo Min, Liyuan Zhang
Summary: Stabilization of arsenic sulfur slag is crucial to prevent environmental pollution, but the molecular understanding of its stability is lacking, hindering the development of effective solutions. By studying the structure-stability relationship of As-S slag, the most stable structure was identified and a successful excess-S-based hydrothermal method was proposed to promote stabilization. This method significantly reduced the arsenic concentration in the leaching test, demonstrating its effectiveness compared to other methods.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Inorganic & Nuclear
Zhilin Guo, Maolin You, Yi-Fei Deng, Qiang Liu, Yin-Shan Meng, Zoe Pikramenou, Yuan-Zhu Zhang
Summary: The study successfully obtained two Fe(ii) grid-like complexes using a coordination-driven supramolecular assembly strategy, demonstrating spin-crossover behavior in azido-bridged complexes. By substitution of the ligand, the complex showed a synergistic effect between spin-crossover behavior and luminescence.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Arup Sarkar, Matthew R. Hermes, Christopher J. Cramer, John S. Anderson, Laura Gagliardi
Summary: This study uses electronic structure calculations and theoretical inference to explain the temperature dependence of spin-crossover (SCO) behavior in the dimeric triple-decker Cr(II) complex. The findings suggest that variations in antiferromagnetic interactions and ligand-field effects play significant roles in influencing the SCO behavior of this complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Sebastian Ovalle, Cecile Malardier-Jugroot
Summary: Simultaneous prediction of the geometries, spin states, and binding energies of iron porphyrins using DFT methods is challenging. In this study, six functionals and three basis sets were tested, and the B97D functional with basis set A was found to provide accurate geometries, correct spin states, and good binding energies for the heme model. This study provides valuable information for selecting suitable DFT methods for studying small iron porphyrins and their interaction with oxygen.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Brian A. Finney, Sabyasachi Roy Chowdhury, Clara Kirkvold, Bess Vlaisavljevich
Summary: By using fully internally contracted (FIC)-CASPT2 analytical gradients, geometry optimizations of spin-crossover complexes have been reported. The study shows that a wave function-based level of theory can be used to optimize the geometries of metal complexes in reasonable times and enable treatment of the molecular geometry and electronic structure of the complexes at the same level of theory. Good overall agreement between DFT and CASPT2 was observed, especially for larger complexes with moderate sized basis sets. Based on efficiency, the recommendation is to use the (10e,12o) active space for convergence to a minimum structure.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Energy & Fuels
Lu Liu, Guangcai Shao, Peng Gong, Zhiwei Wu, Jiaming Chu, Yangang Hu, Junfeng Wang, Shuang Wang, Chenghang Zheng, Xiang Gao, Nathalie De Geyter, Rino Morent
Summary: The study investigates the influence of steps on a CaO surface on the adsorption of SO3 molecules, finding that steps with O and Ca atoms at the edges are the most stable and best suited for SO3 adsorption. Using density function theory calculations, it is shown that SO3 binds to OCaO sites and forms weak bonds with Ca and OSO3 atoms, with the highest adsorption energy observed at edge sites.
Article
Materials Science, Multidisciplinary
Thilini K. Ekanayaka, Okten Ungor, Yuchen Hu, Esha Mishra, Jared P. Phillips, Ashley S. Dale, Saeed Yazdani, Ping Wang, Kayleigh A. McElveen, M. Zaid Zaz, Jian Zhang, Alpha T. N'Diaye, Christoph Klewe, Padraic Shafer, Rebecca Y. Lai, Robert Streubel, Ruihua Cheng, Michael Shatruk, Peter A. Dowben
Summary: Modifications driven by TCNQ affect the spin state configuration and electric conductivity of [Fe(3-bpp)2](TCNQ)2 and [Fe{H2B(pz)2}2(bipy)] and TCNQ mixtures. The addition of TCNQ increases the conductivity and carrier lifetimes of [Fe{H2B(pz)2}2(bipy)]. TCNQ also enhances the transistor carrier mobility of [Fe{H2B(pz)2}2(bipy)] thin films grown using DMF.
MATERIALS CHEMISTRY AND PHYSICS
(2023)
Article
Quantum Science & Technology
Ruslan N. Tazhigulov, Shi-Ning Sun, Reza Haghshenas, Huanchen Zhai, Adrian T. K. Tan, Nicholas C. Rubin, Ryan Babbush, Austin J. Minnich, Garnet Kin-Lic Chan
Summary: This study simulates the correlated electronic structure of complex molecules and materials using Google's Sycamore architecture quantum processor. By simplifying the electronic structure into suitable models and employing error mitigation and simulated data, the research team achieves meaningful results with a certain level of resource usage.
Article
Chemistry, Physical
Justin K. Kirkland, Jyothish Joy, Brooke L. Small, Julie A. Leseberg, Steven M. Bischof, Michael S. Webster-Gardiner, Daniel H. Ess
Summary: Through density functional theory and metadynamics calculations, our study on the aldehyde retro-hydroformylation pathway using cyclopentadienyl phosphine-type Ir(III) catalysts has revealed two surprising and unique aspects of catalysis: (1) The turnover of the catalytic cycle is determined by the rate of singlet-triplet spin state crossover; and (2) During catalysis, after C-H bond activation, a transient Ir-III-H intermediate undergoes intramolecular proton transfer to give a dearomatized η(4)-Cp-H diene ligand. These mechanistic insights provide a foundation for the design of novel retro-hydroformylation molecular catalysts.
Article
Chemistry, Inorganic & Nuclear
Barbora Brachnakova, Jan Moncol, Jan Pavlik, Ivan Salitros, Sebastien Bonhommeau, Francisco Javier Valverde-Munoz, Lionel Salmon, Gabor Molnar, Lucie Routaboul, Azzedine Bousseksou
Summary: The synthesis and characterization of three Hofmann-like metal-organic frameworks with photoisomerizable guest molecules were conducted, revealing the significant influence of different guest molecules and conformations on magnetic and photomagnetic behaviors of the framework. Additionally, the hinderance of photoisomerization of guest molecules by the framework was observed.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Inorganic & Nuclear
Ryohei Akiyoshi, Ryo Ohtani, Leonard F. Lindoy, Shinya Hayami
Summary: Soft materials such as polymers, liquid crystals, and colloids exhibit unique functionalities derived from their non-rigid structures. Soft metal complexes with long alkyl chains show synergy between structural dynamics and electron dynamics. This review focuses on spin crossover behaviors associated with structural phase transitions in soft metal complexes, including liquid crystal transitions. Fabrication of soft materials based on spin crossover complexes is also discussed.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Multidisciplinary
Yasuhiro Ohk
Summary: Transition metal cluster complexes, particularly those containing iron and sulfur, are used as catalysts for the biological reduction of inert small molecules such as N2 and CO2. The structures of these biological clusters are complicated and the protein backbones around the clusters often play important roles in catalysis, hence reproducing or mimicking the enzymatic functions with synthetic cluster complexes remains a challenge. This account reviews recent studies on iron-containing biomimetic cluster complexes and their potential utility in catalytic reduction of inert small molecules.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Inorganic & Nuclear
Daniel Vidal, Jordi Cirera, Jordi Ribas-Arino
Summary: By studying a dataset of 24 different Fe(iii) hexacoordinated complexes, it was demonstrated that the B3LYP* functional is accurate in predicting spin-state energy gaps and distinguishing spin states of Fe(iii) complexes across a range of temperatures. This suggests that B3LYP* is a reliable method for screening new spin-crossover systems with tailored properties.
DALTON TRANSACTIONS
(2021)
Article
Materials Science, Multidisciplinary
Daniel Mejia-Rodriguez, Angel Albavera-Mata, Eric Fonseca, Dian-Teng Chen, H-p. Cheng, Richard G. G. Hennig, S. B. Trickey
Summary: Current spin-crossover (SCO) energy calculations lack automated screening methods and the combination of constraint-based, non-empirical density functional approximation (DFA) and well-defined semi-empirical corrections are not suitable for high-throughput screening. Generalized gradient approximation (GGA) DFA with a Hubbard -U correction (DFT + U) provides lower-cost alternatives, but it fails to give accurate delta E-HL values for [Mn(taa)] without degrading molecular structure or property predictions.
COMPUTATIONAL MATERIALS SCIENCE
(2022)
Article
Biochemistry & Molecular Biology
Murilo Hoias Teixeira, Guilherme Menegon Arantes
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2019)
Article
Chemistry, Medicinal
Andre A. O. Reis, Raphael S. R. Sayegh, Sandro R. Marana, Guilherme M. Arantes
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2020)
Article
Chemistry, Medicinal
Murilo H. Teixeira, Felipe Curtolo, Sofia R. G. Camilo, Martin J. Field, Peng Zheng, Hongbin Li, Guilherme M. Arantes
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2020)
Article
Chemistry, Medicinal
Sofia R. G. Camilo, Felipe Curtolo, Vanesa V. Galassi, Guilherme M. Arantes
Summary: This study investigates the electron-proton adiabaticity of the initial reaction catalyzed in the Q site of cytochrome bc(1) using a combination of molecular dynamics simulations, electronic-structure calculations, and semiclassical tunneling theory. The results demonstrate that the reaction is electronic nonadiabatic and proton tunneling is faster than mixing of electronic configurations, providing insights into the formalism for calculating vibronic couplings and kinetic parameters in similar PCET reactions.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2021)
Article
Biochemistry & Molecular Biology
Cameron Van Cleave, Jordan T. Koehn, Caroline Simoes Pereira, Allison A. Haase, Benjamin J. Peters, Seth W. Croslow, Kyle G. McLaughlin, Katarina R. Werst, Audra L. Goach, Dean C. Crick, Guilherme Menegon Arantes, Debbie C. Crans
Summary: The location and conformation of truncated menaquinones in model membrane environments are influenced by the environment, but their association with phospholipids remains unchanged under physiological conditions regardless of side chain length.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Multidisciplinary Sciences
Guodong Yuan, Felipe Curtolo, Yibing Deng, Tao Wu, Fang Tian, Qun Ma, Yutong Liu, Jinglin Zuo, Guilherme Menegon Arantes, Peng Zheng
Summary: MT is a metal-bound protein that plays essential roles in metal homeostasis and heavy metal detoxification. It contains dynamic polynuclear metal clusters with multiple conformational states, contributing to its diverse cellular functions as a metal-carrier protein.
Article
Multidisciplinary Sciences
Injae Chung, John J. Wright, Hannah R. Bridges, Bozhidar S. Ivanov, Olivier Biner, Caroline S. Pereira, Guilherme M. Arantes, Judy Hirst
Summary: In this study, the authors reconstitute mammalian complex I and use cryo-EM and molecular dynamics simulations to investigate the binding and structural changes of Q(10) in the complex. The findings provide insights into the mechanism of Q(10) reduction and substrate binding in complex I.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Felipe Curtolo, Guilherme M. Arantes
Summary: Flavins play important roles as redox cofactors and chromophores in flavoenzymes. Understanding their properties is crucial for modeling flavin reactivity. In this study, high-level electronic-structure methods were used to investigate the ground-state properties of lumiflavins in different oxidation and charge states. The results show that M06-2X is the most accurate functional for most properties, except gas-phase basicity. Additionally, the presence of noncanonical protonation states adds complexity to modeling flavins. These findings will guide future computational studies of flavoproteins and flavin chemistry.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Meeting Abstract
Biochemistry & Molecular Biology
Injae Chung, John J. Wright, Hannah R. Bridges, Bozhidar S. Ivanov, Olivier Biner, Caroline S. Pereira, Guilherme M. Arantes, Judy Hirst
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
(2022)
Article
Chemistry, Medicinal
Felipe Curtolo, Guilherme M. Arantes
Summary: The interconversion between fumarate and succinate is vital for energy metabolism in organisms and is catalyzed by fumarate reductases and succinate dehydrogenases. These flavoenzymes play important roles in biomedical and biotechnological fields. The understanding of their catalytic mechanisms is valuable for further research and applications.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2023)
Article
Multidisciplinary Sciences
Caroline S. Pereira, Murilo H. Teixeira, David A. Russell, Judy Hirst, Guilherme M. Arantes
Summary: Respiratory complex I is an important cellular energy transducer in mitochondria. This study investigates the inhibition of complex I by rotenone and reveals the importance of ligand flexibility and conformer interconversion for efficient binding. Understanding the mechanism of rotenone action has implications for designing synthetic derivatives and further elucidating the catalytic mechanism of complex I.
SCIENTIFIC REPORTS
(2023)
Article
Cardiac & Cardiovascular Systems
Ligia A. Kiyuna, Darlan S. Candido, Luiz R. G. Bechara, Itamar C. G. Jesus, Lisley S. Ramalho, Barbara Krum, Ruda P. Albuquerque, Juliane C. Campos, Luiz H. M. Bozi, Vanessa O. Zambelli, Ariane N. Alves, Nicolas Campolo, Mauricio Mastrogiovanni, Silvina Bartesaghi, Alejandro Leyva, Rosario Duran, Rafael Radi, Guilherme M. Arantes, Edecio Cunha-Neto, Marcelo A. Mori, Che-Hong Chen, Wenjin Yang, Daria Mochly-Rosen, Ian J. MacRae, Ludmila R. P. Ferreira, Julio C. B. Ferreira
Summary: This study investigates the mechanisms and potential treatment for the deleterious effects of 4-hydroxynonenal (4-HNE) in heart failure. The results show that 4-HNE inhibits Dicer, which impairs miRNA processing. Boosting 4-HNE clearance through pharmacological activation of aldehyde dehydrogenase 2 (ALDH2) restores Dicer activity and miRNA biogenesis, offering a potential treatment for heart failure patients.
EUROPEAN HEART JOURNAL
(2023)
Article
Chemistry, Medicinal
Felipe Curtolo, Guilherme M. Arantes
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2020)
Article
Biology
M. S. Baptista, M. J. M. Alves, G. M. Arantesc, H. A. Armelin, O. Augusto, R. L. Baldini, D. S. Basseres, E. J. H. Bechara, A. Bruni-Cardoso, H. Chaimovichm, P. Colepicolo Neto, W. Collie, I. M. Cuccovia, A. M. Da-Silva, P. Di Mascio, S. C. Farahm, C. Ferreira, F. L. Forti, R. J. Giordano, S. L. Gomes, F. J. Gueiros Fllho, N. C. Hoch, C. T. Hotta, L. Labriola, C. Lameu, M. T. Machini, B. Malnic, S. R. Marana, M. H. G. Medeiros, F. C. Meotti, S. Miyamoto, C. C. Oliveira, N. C. Souza-Pinto, E. M. Reis, G. E. Ronsein, R. K. Salinas, D. Schechtman, S. Schreier, J. C. Setubal, M. C. Sogayar, G. M. Souza, W. R. Terra, D. R. Truzzi, H. Ulrich, S. Verjovski-Almeida, F. Winck, B. Zingales, A. J. Kowaltowski
BRAZILIAN JOURNAL OF MEDICAL AND BIOLOGICAL RESEARCH
(2019)
Article
Chemistry, Multidisciplinary
Murilo Hoias Teixeira, Guilherme Menegon Arantes
