Article
Chemistry, Physical
Daniele Loco, Isabelle Chataigner, Jean-Philip Piquemal, Riccardo Spezia
Summary: Modeling chemical reactions using Quantum Chemistry is a widely used predictive strategy that complements experimental studies to understand reaction mechanisms. This research benchmarked various computational approaches for predicting energy barriers in six Diels-Alder reactions of increasing complexity. The results showed that using economical Density Functional Theory methods combined with empirical dispersion corrections can provide high-quality results with minimal computational effort. This simulation protocol opens new prospects for studying Diels-Alder reactions with explicit solvent using hybrid QM/MM molecular dynamics simulations.
Article
Chemistry, Multidisciplinary
Junjun Wang, Xin Huang, Honglin Zhang, Linqing Wang, Weijiu Huang, Shaofu Kuang, Fuxiang Huang
Summary: The study investigated the peeling process of coatings by using first-principles calculations to analyze the work of adhesion, interface energy, and electronic structure. Results showed that the diamond-Si interface exhibited better performance, while the Ti-Ti interface was most prone to deformation, and the Si-Ti interface was more likely to delaminate.
JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
(2021)
Article
Chemistry, Physical
Niklas Thoben, Tobias Kaper, Simon de Graaff, Luca Gerhards, Marc Schmidtmann, Thorsten Kluener, Rudiger Beckhaus, Sven Doye
Summary: Hybrid Density Functional Theory (DFT) calculations were used to investigate the multiple conformers of the insertion reactions of a methylenecyclopropane into the Ti-C bond of two differently α-substituted titanaaziridines. The calculations explained the experimentally observed differences in regioselectivity between catalytic hydroaminoalkylation reactions and corresponding stoichiometric reactions. The study also provided insights into the lack of reactivity of α-phenyl-substituted titanaaziridines and the diastereoselectivity of the reactions.
Article
Chemistry, Multidisciplinary
Cheng Xu, Zhen Ye, Li Xiang, Shuhan Yang, Qian Peng, Xuebing Leng, Yaofeng Chen
Summary: The synthesis of silacycle compounds, including the insertion of metal-substituted silylene fragments into the aromatic ring of naphthalene, is of both fundamental and application importance. This insertion is followed by interesting rearrangements to yield silaspiro-benzocycloheptenyl and cyclobutenosilaindan derivatives, with mechanistic aspects revealed through DFT investigations. Additionally, formed cyclobutenosilaindan potassium can readily react with various compounds to afford substituted cyclobutenosilaindans in high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Albert Artigas, Cristina Castanyer, Nil Roig, Agusti Lledo, Miquel Sola, Anna Pla-Quintana, Anna Roglans
Summary: A synthetic methodology for functionalizing C-60 and C-70 fullerenes by cascading reactions has been reported. The resulting polyheterocyclic fullerene adducts can be potentially used in organic and perovskite photovoltaic devices.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Biochemistry & Molecular Biology
Andi Liu, Yuanyuan Si, Shi-Hui Dong, Nilkamal Mahanta, Haley N. Penkala, Satish K. Nair, Douglas A. Mitchell
Summary: YcaO enzymes catalyze various post-translational modifications on peptide substrates, with thioamidation being one of them.
TfuA protein plays a crucial role in thioamidation by hydrolyzing thiocarboxylated ThiS to enhance the affinity of YcaO towards the thioamidation substrate.
NATURE CHEMICAL BIOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Maurizio Chiminelli, Andrea Serafino, Davide Ruggeri, Luciano Marchio, Franca Bigi, Raimondo Maggi, Max Malacria, Giovanni Maestri
Summary: Dearomative cycloadditions offer a powerful method to access a vast chemical space using simple and ubiquitous building blocks. However, the loss of aromaticity has limited their synthetic potential. We have devised a general intramolecular method that overcomes this limitation by photosensitizing allenamides. This visible-light-promoted process produces complex [2.2.2]-(hetero)-bicyclooctadienes at room temperature, potentially stabilizing transient (bi)radicals through naphthalene. The reaction is tolerant of various functional groups, making it suitable for a wide range of applications, including the synthesis of isoindoles and metal complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jacob S. Bestwick, David J. Jones, Helen E. Jones, Panagiotis G. Kalomenopoulos, Rafal Szabla, Andrew L. Lawrence
Summary: A biomimetic synthetic strategy was used to synthesize (+/-)-ulodione A and predict two potential natural products. Computational investigations into biosynthetic selectivity guided the chemical synthesis. This work demonstrates the importance of biosynthetic considerations in guiding efficient synthetic strategies and anticipating new natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Physics, Multidisciplinary
Tomasz Maciazek
Summary: The reduced density matrix functional theory is a powerful tool for studying properties of ground states of strongly interacting quantum many body systems, especially Bose-Einstein condensation and systems of strongly correlated electrons. It has been shown that the density functional in these systems exhibits a repulsive gradient, known as the Bose-Einstein condensation force, which is universal for different types of pair-interaction and non-homogeneous gases. The theory has also been extended to fermionic systems, showing the existence of a similar repulsive gradient in the fermionic RDMFT.
NEW JOURNAL OF PHYSICS
(2021)
Article
Nanoscience & Nanotechnology
Ignacio Romero-Muniz, Carlos Romero-Muniz, Isabel del Castillo-Velilla, Carlo Marini, Sofia Calero, Felix Zamora, Ana E. Platero-Prats
Summary: In this study, we identified the presence of node vacancies within MOF-808 that can be chemically modified using infrared spectroscopy experiments and first-principles calculations. We resolved the atomic structure of single metal sites incorporated into catechol groups postsynthetically using advanced synchrotron characterization tools. Furthermore, we demonstrated the catalytic activity of these modified MOF-808 materials for 1,3-dipolar cycloadditions.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Estefania del Horno, Jesus Jover, Miguel Mena, Adrian Perez-Redondo, Carlos Yelamos
Summary: Low-valent titanium species were prepared by reacting [TiCp*X-3] with LiEH4 or BH3(thf), and their structures were elucidated using experimental and theoretical methods. The compounds can be described as either titanium(II) or titanium(III) species, with specific molecular structures and interactions between the Ti-Ti bond and the Al atoms.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Estefania del Horno, Jesus Jover, Miguel Mena, Adrian Perez-Redondo, Carlos Yelamos
Summary: By reacting [TiCp*Cl-3] with magnesium, a trinuclear mixed-valence complex is formed, which can react with dinitrogen to produce a diamagnetic compound. The reaction process can potentially be used for cyclic ammonia synthesis under ambient conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
San Hua Lim, Chee Kok Poh
Summary: This study demonstrates that SiC monolayers are promising substrates for the development of highly stable single atom catalysts, with enhanced diffusion barrier energy and stability. These catalysts also show a significant reduction in activation barrier energy for CO oxidation.
Article
Food Science & Technology
Xiaopeng Qin, Linbo Li, Xiao Yu, Qianchun Deng, Qisen Xiang, Yingying Zhu
Summary: This study compared the composition and functionality of flaxseed protein isolate, globulin, and albumin fractions. The results showed that albumin had smaller particle size and better protein solubility, as well as more flexible conformation. It also exhibited excellent antioxidant and emulsifying properties. Therefore, modulating the retention of albumin fraction and specific phenolic acids can improve the techno-functionality of flaxseed protein.
Article
Chemistry, Physical
Hengquan Guo, Sung Gu Kang, Seung Geol Lee
Summary: This study investigates the possibility of 15 transition-metal (TM)-promoted (TM=Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, and Hg) and their hydrogen evolution reaction (HER) performance on two-dimensional titanium carbides (TiC2). The adsorption strength of TMs on TiC2 is found to be stronger than that on gamma-graphyne and weaker than that on Ti3C2. Among the fifteen investigated catalysts, Ru-TiC2, Ag-TiC2, Ir-TiC2, Au-TiC2, and Fe-TiC2 exhibit overpotentials of -0.18, -0.15, -0.18, -0.17, and -0.04 V, respectively. The Volmer-Tafel step is preferred on Fe-TiC2. This work suggests that Fe-TiC2 may be a superior HER electrocatalyst.
