Article
Chemistry, Physical
Benjamin W. J. Chen
Summary: In this review, computational methods for predicting kinetic and equilibrium isotope effects in heterogeneous catalysis are discussed. The influence of the catalytic environment and the potential pitfalls in isotope studies are also explored. Possible future applications of isotope effects and the promising synergies between experiments and computations are highlighted throughout the review.
CATALYSIS COMMUNICATIONS
(2023)
Article
Physics, Multidisciplinary
Mohammed Alghadeer, Abdulaziz Al-Aswad, Fahhad H. Alharbi
Summary: A highly accurate predictive model was developed using Machine Learning to estimate one-dimensional kinetic energy density functionals, showing better accuracy than standard KEDF. The statistical training approach suggested the reliability of the model for large-scale orbital free density functional theory calculations.
Review
Materials Science, Coatings & Films
Raymond T. Tung
Summary: For many decades, the mystery surrounding the formation mechanism of the Schottky barrier height (SBH) was dominated by the concept of Fermi-level pinning (FLP). However, experimental research on polycrystalline metal-semiconductor interfaces revealed insensitivity of the SBH to metal work function, leading to a shift in understanding and the proposal of new theories.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2021)
Article
Chemistry, Multidisciplinary
Raphael Robidas, Claude Y. Legault
Summary: A mechanism is proposed to explain the formation of benzobicyclo[3.2.0]heptane derivatives from 1,7-enyne derivatives bearing a terminal cyclopropane, which has been previously reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Ronen Kruchinin, Oswaldo Dieguez
Summary: In this article, density-functional theory calculations are used to study the energetics of CO2 reduction to methane via the Sabatier reaction on sulfur-based transition-metal dichalcogenides (TMDs) with non-, Ni- and Cu-doping. It is found that sulfur-based TMDs with Ni/Cu doping exhibit better indicators for catalytic performance of the CO2 reduction reaction compared to non-doped and doped TMDs without active sites. Furthermore, the role of the chalcogen and dopant atoms in influencing bonding strength and type is found to have a much bigger influence on the reaction than the transition metal.
Article
Chemistry, Physical
Aishanee Sur, Nicholas B. Jernigan, David C. Powers
Summary: The development of homogeneous catalysis is supported by various kinetics experiments. Metal-organic frameworks have gained attention as platforms for site-isolated catalysis. Evaluating the origin of catalytic activity in MOF-promoted reactions is still limited.
Article
Physics, Multidisciplinary
Subrata Jana, Sushant Kumar Behera, Szymon Smiga, Lucian A. Constantin, Prasanjit Samal
Summary: The importance of the Pauli kinetic energy enhancement factor alpha in constructing meta-GGA exchange-correlation energy functionals is discussed, along with the proposal of the MGGAC functional and its revised correlation energy. The successful implication of the alpha ingredient leads to significant improvements in solid structural and energetic properties, demonstrating usefulness in addressing current challenging solid-state problems.
NEW JOURNAL OF PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Gal Schwartz, Uri Hananel, Liat Avram, Amir Goldbourt, Gil Markovich
Summary: The mechanisms of nucleation and growth of europium-doped terbium phosphate nanocrystals under acidic conditions were studied using kinetic isotope effects and luminescence intensity monitoring. Delayed nucleation was observed, which was attributed to the formation of pre-nucleation clusters or polymers of the lanthanide and phosphate ions. The results suggest that the pre-nucleation and nanocrystal growth processes have similar chemical properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
R. Remme, T. Kaczun, M. Scheurer, A. Dreuw, F. A. Hamprecht
Summary: Orbital-free density functional theory (OF-DFT) is a promising method for computing ground state molecular properties at minimal cost. In this study, we propose a deep neural network architecture called KineticNet to learn the kinetic energy functional from ground truth provided by the more expensive Kohn-Sham density functional theory. KineticNet achieves chemical accuracy for learned functionals across different input densities and geometries of small molecules, and even demonstrates OF-DFT density optimization with chemical accuracy for two-electron systems.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Die Bai, Man Li, Rong-Zhen Liao
Summary: The merging of transition-metal-catalyzed C-H bond activation with electro-oxidation has become a promising approach for oxidative C-H bond functionalization. However, the specific effects of electro-oxidation on the reaction mechanism of transition-metal catalysis have rarely been studied. In this computational study, the rhodium-catalyzed electrochemical C-H phosphorylation of 2-phenylpyridine by diphenylphosphine oxide was investigated to reveal the mechanistic details. The calculations showed that C-H activation prefers to occur at the Rh(III) state, P-H activation at the Rh(IV) state, and reductive elimination at the Rh(V) state. The mechanistic insights obtained from this study are valuable for understanding transition-metal-catalyzed electro-oxidative C-H bond functionalization.
Article
Chemistry, Physical
Elias Polak, Tanguy Englert, Martin J. Gander, Tomasz A. Wesolowski
Summary: A general formalism is proposed to construct a symmetric version for evaluating the energy expression of the asymmetric part. This approach is applied to construct a symmetrized non-additive kinetic energy (NAKE) potential, leading to consistent energy evaluation. The new symmetrized energy expression shows superior performance in evaluating interaction energy.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Pharmacology & Pharmacy
Ivona Jasprica, Petar Horvat, Katarina Zrnc, Karl J. Bonney, Vidar Bjornstad, Lucija Hok, Robert Vianello, Nikola Bregovic, Josip Pozar, Katarina Leko, Vladislav Tomisic, Ernest Mestrovic
Summary: The discovery of cephalosporin and its improved stability in aqueous solution, as well as enhanced activity against penicillin-resistant organisms, were important advancements in beta-lactam antibiotics. This study investigated the degradation rates and mechanisms of ceftriaxone at therapeutic concentration in different water environments. Unique degradation products were observed, and the comparison between H2O and D2O provided valuable insight into the initial degradation. The effect of protium to deuterium isotope change on degradation kinetics was evaluated using HPLC analysis and H-1 NMR spectroscopy, and computational analysis offered molecular insight and explained the stabilizing effect of D2O.
EUROPEAN JOURNAL OF PHARMACEUTICAL SCIENCES
(2023)
Article
Chemistry, Physical
Priti Singh, Amrita Gogoi, Qurat Ul Aien, Mudit Dixit
Summary: The conversion of methane in shale gas reserves to high-value chemicals has gained significant interest, but it is still not commercially viable. Metal oxides, specifically gamma-Al2O3 clusters, have been studied for their ability to activate the C-H bonds of methane. This research investigates the C-H activation of methane on both pristine and doped gamma-Al2O3 clusters using density functional theory (DFT) calculations. The results show that the polar pathway is preferred energetically over the radical pathway, and the metal dopants, particularly gallium, greatly improve the catalytic activity.
Article
Chemistry, Multidisciplinary
Alexander G. Sturm, Uhut S. Karaca, Myron Heinz, Thorsten Felder, Kenrick M. Lewis, Norbert Auner, Max C. Holthausen
Summary: In this study, an energetically and environmentally benign synthetic protocol for the highly selective conversion of SiCl4 to HSiCl3 was reported. The protocol utilized organohydridosilanes as recyclable hydrogen transfer reagents and onium chlorides as efficient catalysts. This same protocol was also used for the quantitative conversion of higher oligosilane residues generated from Siemens processes.
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
Chemistry, Multidisciplinary
Daniel B. Larsen, Allan R. Petersen, Johannes R. Dethlefsen, Ayele Teshome, Peter Fristrup
CHEMISTRY-A EUROPEAN JOURNAL
(2016)
Article
Chemistry, Multidisciplinary
S. Tolborg, S. Meier, I. Sadaba, S. G. Elliot, S. K. Kristensen, S. Saravanamurugan, A. Riisager, P. Fristrup, T. Skrydstrup, E. Taarning
Article
Biochemical Research Methods
Maria Ejlersen, Niels Johan Christensen, Kasper K. Sorensen, Knud J. Jensen, Jesper Wengel, Chenguang Lou
BIOCONJUGATE CHEMISTRY
(2018)
Article
Biochemical Research Methods
Mads Ostergaard, Niels Johan Christensen, Christian T. Hjuler, Knud J. Jensen, Mikkel B. Thygesen
BIOCONJUGATE CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Chenguang Lou, Josephine Tuborg Boesen, Niels Johan Christensen, Kasper K. Sorensen, Peter W. Thulstrup, Martin Nors Pedersen, Ernest Giralt, Knud J. Jensen, Jesper Wengel
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Multidisciplinary
Ria K. Balogh, Bela Gyurcsik, Mikael Jensen, Peter W. Thulstrup, Ulli Koster, Niels Johan Christensen, Frederik J. Morch, Marianne L. Jensen, Attila Jancso, Lars Hemmingsen
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Adriano Aloisi, Niels Johan Christensen, Kasper K. Sorensen, Chloe Guilbaud-Chereau, Knud J. Jensen, Alberto Bianco
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Reka Geczy, Niels Johan Christensen, Kim K. Rasmussen, Ildiko Kalomista, Manish K. Tiwari, Pratik Shah, Seong Wook Yang, Morten J. Bjerrum, Peter W. Thulstrup
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Mathias B. Danielsen, Niels Johan Christensen, Per T. Jorgensen, Knud J. Jensen, Jesper Wengel, Chenguang Lou
Summary: Cationic moieties attached to oligonucleotides increased binding affinity and stability, with the 2'-amino-LNA analogue carrying a triaminated linker showing the most pronounced effect. Molecular modeling revealed salt-bridge formation between positively charged polyamine moieties and the dsDNA targets, resulting in the observed triplex stabilization. All investigated monomers showed increased resistance against 3'-nucleolytic digestion.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemical Research Methods
Niels Johan Christensen, Samuel Demharter, Meera Machado, Lykke Pedersen, Marco Salvatore, Valdemar Stentoft-Hansen, Miquel Triana Iglesias
Summary: We applied a novel symbolic regression algorithm, QLattice, on clinical omics datasets and generated parsimonious high-performing models that can predict disease outcomes and reveal putative disease mechanisms. These biomarker signatures have high predictive power and simplicity, making them attractive tools for high-stakes applications in healthcare.
Article
Biochemistry & Molecular Biology
Ria K. Balogh, Bela Gyurcsik, Mikael Jensen, Peter W. Thulstrup, Ulli Koester, Niels Johan Christensen, Marianne L. Jensen, Eva Hunyadi-Gulyas, Lars Hemmingsen, Attila Jancso
Summary: The C-terminal fragment of Escherichia coli CueR affects the binding affinity of Ag-I to CueR, possibly by stabilizing the metal site. This finding provides an important example of how amino acid residues can influence the properties of metal binding sites.
Article
Biochemical Research Methods
Shunliang Wu, Mads Ostergaard, Freja Fredholt, Niels Johan Christensen, Kasper K. Sorensen, Narendra K. Mishra, Hanne M. Nielsen, Knud J. Jensen
Summary: Chemical modification of peptides and proteins, such as PEGylation and lipidation, can create new conjugates with different properties. However, these conjugates are often not responsive to stimuli. This study reports the Ca2+-responsive properties of conjugates of oligogalacturonic acids (OGAs), derived from plant pectin. The self-assembly of OGA conjugates was studied and found to depend on OGA sequence length, as well as Zn2+ and Ca2+ concentrations.
BIOCONJUGATE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Narendra Kumar Mishra, Mads Ostergaard, Soren Roi Midtgaard, Sophie S. Strindberg, Stefan Winkler, Shunliang Wu, Thomas Just Sorensen, Tue Hassenkam, Jens-Christian N. Poulsen, Leila Lo Leggio, Hanne Morck Nielsen, Lise Arleth, Niels Johan Christensen, Peter W. Thulstrup, Knud J. Jensen
Summary: Metal ion-induced self-assembly of a human insulin analog modified with a tridentate chelator resulted in unique oligomerization in solution, with Fe2+ producing small discrete assemblies and Eu3+ forming large fractal assemblies. Spectroscopic analysis confirmed binding of both metal ions to the chelator, and emission lifetime experiments revealed distinct coordination geometries. The insulin analog maintained receptor affinity and exhibited extended blood glucose lowering and plasma concentration, indicating its potential for therapeutic applications.
Article
Chemistry, Multidisciplinary
Chenguang Lou, Niels Johan Christensen, Manuel C. Martos-Maldonado, Soren Roi Midtgaard, Maria Ejlersen, Peter W. Thulstrup, Kasper K. Sorensen, Knud J. Jensen, Jesper Wengel
CHEMISTRY-A EUROPEAN JOURNAL
(2017)
Article
Biochemical Research Methods
Chenguang Lou, Simone V. Samuelsen, Niels Johan Christensen, Birte Vester, Jesper Wengel
BIOCONJUGATE CHEMISTRY
(2017)