Article
Multidisciplinary Sciences
Alexander Klein, Petra Rovo, Varun V. Sakhrani, Yangyang Wang, Jacob B. Holmes, Viktoriia Liu, Patricia Skowronek, Laura Kukuk, Suresh K. Vasa, Peter Guentert, Leonard J. Mueller, Rasmus Linser
Summary: NMR chemical shifts provide detailed information on the chemical properties of molecules. This study demonstrates the use of higher-dimensional, proton-detected, solid-state NMR to assign a large protein, tryptophan synthase, and characterize its chemical properties and relaxation. The results suggest a connection between active-site chemistry, electrostatic environment, and catalytically important dynamics.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Madhusudan Chaudhary, Arkadii Pominov, Dundappa Mumbaraddi, Bryce Allen, Jan Meyer, Anna Maria Kirchberger, Guy M. Bernard, Tom Nilges, Arthur Mar, Vladimir K. Michaelis
Summary: Sodium-containing chalcogenide materials are being used as solid electrolytes in inexpensive all-solid-state sodium-ion batteries due to their high ionic conductivity, abundance, and structural variability. The solid solution Na3PS4-xSex shows promise as a solid electrolyte for sodium-ion batteries, with its structure transforming from tetragonal to cubic with increasing substitution of S by Se. Na-23 NMR experiments reveal that the quadrupolar lineshapes are influenced by sodium ion dynamics, and the activation energies decrease with increased Se content.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Physical
Berislav Peric, Natalija Pantalon Juraj, Gabor Szalontai, Suzana R. Velickovic, Filip M. Veljkovic, Drazen Vikic-Topic, Srecko I. Kirin
Summary: p-Disubstituted phenyldiketopiperazines 1, 2, and 3 were synthesized and characterized using NMR and IR spectroscopy. Their identity was confirmed by ESI-MS and HRMS spectrometry. X-ray single crystal structures revealed different crystallization spaces for the compounds.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Physical
Gholamhossein Mohammadnezhad, Hossein Farrokhpour, Helmar Gorls, Winfried Plass
Summary: Enol-imine and keto-amine tautomerism in carbohydrate-derived Schiffbases were studied using theoretical calculation, NMR spectroscopy, and crystallography. The stability of different tautomers was found to be influenced by the electronic properties of the substituents, with electron-releasing groups increasing the energy difference between keto and enol forms. Methanol was also found to play a role in stabilizing the tautomers, with the position and nature of the substitution influencing its participation.
JOURNAL OF MOLECULAR STRUCTURE
(2021)
Article
Chemistry, Multidisciplinary
Federica Bravetti, Simone Bordignon, Edith Alig, Daniel Eisenbeil, Lothar Fink, Carlo Nervi, Roberto Gobetto, Martin U. Schmidt, Michele R. Chierotti
Summary: CSP-NMRX is a powerful method for crystal structure prediction that utilizes NMR information to reduce computational resources and improve efficiency. It was successfully applied to predict the crystal packing of three known phases of mebendazole, demonstrating its effectiveness in utilizing NMR data for structure determination.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Crystallography
Edi Topic, Vladimir Damjanovic, Katarina Piculjan, Visnja Vrdoljak, Mirta Rubcic
Summary: A series of aryl-functionalized alkyl dihydrazones were synthesized and characterized in terms of structure and properties. The compounds showed good thermal stability and antibacterial activity.
Article
Chemistry, Physical
Robert Calaminus, Sascha Harm, Douglas H. Fabini, Lucas G. Balzat, Anna-Katharina Hatz, Viola Duppel, Igor Moudrakovski, Bettina V. Lotsch
Summary: This study presents a novel approach to improve the ionic conductivities of thiophosphate solid electrolytes (SEs) through in situ formation of hybrid SEs. The experimental results show that the ionic conductivity can reach up to 7 mS cm(-1), exceeding that of the original SEs and simple mixtures.
CHEMISTRY OF MATERIALS
(2022)
Article
Biochemistry & Molecular Biology
Martin Dracinsky
Summary: This study thoroughly analyzes the large deviations in predicted hydrogen and carbon chemical shifts of a series of solid pyridinium fumarates. The influence of geometry optimization protocol and computational level on the accuracy of predicted chemical shifts is investigated, with improvements suggested for proton chemical-shift predictions through the use of computationally demanding hybrid functional for geometry optimization.
Article
Chemistry, Physical
Chanaprom Cholsuk, Sujin Suwanna, Tobias Vogl
Summary: A solid-state quantum emitter is an essential component in optical quantum technologies, and its wavelength should be compatible with other components in a quantum network. This study uses density functional theory (DFT) to calculate the complete optical fingerprints of quantum emitters in hexagonal boron nitride. The results suggest that multiple optical properties should be considered when comparing simulations to experiments, rather than relying solely on the zero-phonon line energy. In addition, this approach helps predict the suitability of using these emitters in specific quantum applications, providing a recipe for classifying and generating universal quantum emitters in future hybrid quantum networks.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Tomasz Pawlak, Malgorzata Szczesio, Marek J. Potrzebowski
Summary: This study reports a structural investigation of AND-1184, including the differences in structural characteristics and dynamic behaviors between MBS and MBSHCl. Solid-state NMR study combined with quantum-chemical calculations successfully assigned all C-13 and most H-1 signals.
Article
Chemistry, Physical
Mehrnaz Khalaji, Piotr Paluch, Marek J. Potrzebowski, Marta K. Dudek
Summary: Many solids crystallize as microcrystalline powders, making it difficult to use single crystal X-Ray diffraction for structural elucidation. This study demonstrates a possible approach to overcome the obstacles in using high-resolution solid-state NMR and crystal structure prediction calculations. The results provide reliable molecular arrangements even for molecules with significant conformational freedom.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2022)
Article
Chemistry, Physical
Benedikt Soeldner, Kristof Grohe, Peter Neidig, Jelena Auch, Sebastian Blach, Alexander Klein, Suresh K. Vasa, Lars V. Schaefer, Rasmus Linser
Summary: Understanding macromolecular function, interactions, and stability requires detailed assessment of conformational ensembles. Limited by the qualitative or low abundance of solid-state nuclear magnetic resonance internuclear distance information, accurately elucidating the spatial dynamics of solid proteins at physiological temperatures is challenging. However, this study demonstrates unprecedented access to abundant proton-proton internuclear distances, enabling accurate molecular dynamics simulations and providing atomic-level spatial details of conformational dynamics in various biomolecular systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Biochemistry & Molecular Biology
Vitaly Volkov, Alexander Chernyak, Nikita A. Slesarenko, Irina A. Avilova
Summary: This review focuses on the progress of solvation and mobility studies in solid electrolyte, particularly ion-exchange membranes and composite materials, using NMR techniques. The applications of various NMR techniques are discussed, and comparisons are made between diffusion coefficients and ionic conductivity data. The microscopic mechanism of ionic transfer is also explored.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Physical
Brijith Thomas, Boyce S. Chang, Julia J. Chang, Martin Thuo, Aaron J. Rossini
Summary: This study successfully determined the molecular structures of self-assembled, one-dimensional metal coordination polymers using advanced solid-state NMR spectroscopy, powder X-ray diffraction, and quantum chemical calculations. The research protocol was validated on a known structure and applied to determine the crystal structures of previously unknown coordination polymers. The obtained structures were confirmed by comparing experimental and simulated patterns and were found to be energetically stable according to density functional theory calculations.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Amy Woods-Ryan, Cheryl L. Doherty, Aurora J. Cruz-Cabeza
Summary: This article revisits tautomeric polymorphs in the Cambridge Structural Database (CSD) and compares them with other polymorphs related by proton transfer. The study finds that tautomeric polymorphs are more prevalent in pharmaceuticals than in common organic compounds. Additionally, it identifies different categories of polymorphs related by proton transfer, with tautomeric polymorphs being the most common and multi-zwitterionic polymorphs being the rarest.
Article
Chemistry, Multidisciplinary
Manuel Yanez, Filiberto Ortiz-Chi, Gabriel Merino, Ibon Alkorta
Summary: The interaction between ammonia and Be-n clusters (n < 1-10) was investigated using density functional theory and ab initio calculations. The results show that regardless of the cluster size, the ammonia structure and the Be cluster structure are not preserved due to the dissociation of N-H bonds and the migration of hydrogen atoms towards available Be atoms. This migration leads to the formation of stable Be-H bonds and enhances the strength of Be-N bonds. The most stable complex is formed with the beryllium trimer, which contains three N-Be and three Be-H bonds.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
M. Merced Montero-Campillo, Ibon Alkorta, Otilia Mo, Jose Elguero, Manuel Yanez
Summary: The structures, bonding, and stability of (MF2)(m):(M ' F-3)(n) (M = Be, Mg; M ' = B, Al; m = 0,1,2; n = 0,1,2) clusters were studied. Replacing first-row elements with second-row elements led to changes in bonding enthalpies and the formation of more stable structures in trimers and tetramers. The electronic environment around each monomer did not significantly change with the nature of the monomers or the size of the cluster. It was found that the stability of larger clusters can be predicted based on the values obtained for smaller ones.
Article
Chemistry, Multidisciplinary
M. Carmen Torralba, Carla I. Nieto, Rosa M. Claramunt, Jose Elguero
Summary: Here, we conducted a comprehensive crystallographic study on three series of N1-aryl substituted-2-pyrazolines, with the aryl groups being 4-nitrophenyl, 2,4-dinitrophenyl, and 2,4,6-trinitrophenyl. We described the structural features and analyzed the influence of the substituents on the molecular structures. The presence of both enantiomers was observed in compounds with stereogenic centers, and the molecular packings in all series followed different patterns of intermolecular interactions.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Paul L. A. Popelier, Ibon Alkorta
Summary: The aim of this study is to experimentally connect the interatomic exchange-correlation energy with the energy decomposition method IQA. The nuclear magnetic resonance (NMR) J-coupling constant 3J(H,H ') is identified as a suitable experimental quantity due to its strong correlation with QTAIM's delocalization index (DI). By investigating the correlations between 3J(H,H ') and a relevant dihedral angle in several compounds, it is concluded that the inter-hydrogen exchange-correlation energy Vxc(H,H ') shows the best agreement with experiment, especially when multiplied with the internuclear distance RHH '.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Editorial Material
Chemistry, Physical
Ibon Alkorta, John M. C. Plane, Jose Elguero, Juan Z. Davalos, A. Ulises Acuna, Alfonso Saiz-Lopez
Summary: In this study, the authors address the argument raised in a previous comment regarding the energy of the NO3 radical and its impact on the reaction profiles of the NO3 radical with various compounds. They used 49 DFT functionals to obtain the optimized geometry of the NO3 radical and compared the results from different functionals. The thermodynamic values of three reactions were calculated using the functionals with smaller errors and compared with experimental data. The authors also recalculated the barriers of the reactions using these functionals and observed a difference of 10.5 kJ mol(-1) compared to the results obtained with the M08HX functional.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Ibon Alkorta, Anthony Legon
Summary: The reduced nucleophilicities of axially symmetric molecules B were determined using the equation D-e/sigma(min) = N-B/sigma(min)) E-XY = (sic)E-XY. Graphs of D-e/sigma(min) versus E-XY for different groups of B showed straight lines through the origin, indicating a common (reduced) nucleophilicity for each group.
Article
Chemistry, Physical
Marta Delgado Gomez, Marco Marazzi, Jose Elguero, Maxime Ferrer, Ibon Alkorta
Summary: Theoretical chemistry was used to design a system based on ammonia boranes catalyzed by pyrazoles for the production of dihydrogen as clean fuel. The reactivity of ammonia borane and cyclotriborazane with different pyrazole catalysts was investigated. The results suggest a catalytic cycle in which ammonia borane can store and produce dihydrogen and amino borane, and amino borane can trimerize to produce cyclotriborazane that can also generate dihydrogen. This study proposes a progress in using environmentally sustainable (metal free) catalysts to efficiently extract dihydrogen from small B-N bonded molecules.
Article
Engineering, Chemical
Eduardo J. Cueto-Diaz, Alberto Castro Muniz, Fabian Suarez Garcia, Ibon Alkorta, Maria Pilar Valles Gonzalez, Eva Mateo-Marti
Summary: Carbon dioxide solid sorbents produced from mesoporous functionalized silica microparticles (SBA-15) were theoretically studied using density functional theory and empirically evaluated for their CO2 adsorption capacity. Different types of organosilyl groups were tested, and SBA-15 bearing (3-aminopropyl)triethoxysilane (APTES) showed significant enhancement in CO2 adsorption compared to pristine SBA-15. The maximum adsorption capacity under conditions relevant to CO2 capture was increased from 0.34 mmol/g (SBA-15) to 1.15 mmol/g (SBA-15@NH2).
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Physical
Ibon Alkorta, Anthony Legon
Summary: The strength of binding in hydrogen-bonded complex B & BULL;& BULL;& BULL;HX can be determined by measuring the equilibrium dissociation energy D(e) and through properties of components B and HX. By comparing calculated D(e) values with those obtained from the proposed equation, it is shown that the equation leads to accurate results in general.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Multidisciplinary Sciences
Maxime Ferrer, Ibon Alkorta, Jose Elguero, Josep M. Oliva-Enrich
Summary: The reactivity of B3P3-doped hexa-cata-hexabenzocoronene (B3P3-NG) towards carbon dioxide was studied. It was found that the compound can capture multiple CO2 molecules due to its poly-cyclic Frustrated Lewis Pair system.
SCIENTIFIC REPORTS
(2023)
Article
Chemistry, Multidisciplinary
Ibon Alkorta, Jose Elguero
Summary: This work theoretically examines the migration of borane groups between nitrogen atoms of pyrazolyl rings. BH2 pyrazol-1-yl derivatives were used as a model to study the effects of substituents on the pyrazole ring. The interacting quantum atoms methodology was employed to analyze the energy partitioning and mutual interaction between pyrazole and BH2 group.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Carlos Martin-Fernandez, Maxime Ferrer, Ibon Alkorta, M. Merced Montero-Campillo, Jose Elguero, Marcos Mandado
Summary: Multiply charged complexes bound by noncovalent interactions have been studied in organic and main group inorganic systems. In this work, we investigate similar complexes in organometallic systems containing transition metals and provide insights into their existence. Our results reveal that carboxylic acid-containing dimers are more strongly bonded and have higher barriers to dissociation compared to amide ones, and cationic complexes are more stable than anionic ones. Additionally, we report a symmetric proton transfer in the metastable phase.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Maxime Ferrer, Ibon Alkorta, Jose Elguero, Josep M. Oliva-Enrich
Summary: A theoretical study was conducted to investigate the reaction between several borataacenes and CO2. The study explored the influence of a counterion, cation complexation, and solvent effects. The computational results successfully predicted the observed syn/anti selectivity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Biochemistry & Molecular Biology
Otilia Mo, M. Merced Montero-Campillo, Manuel Yanez, Ibon Alkorta, Jose Elguero
Summary: In this study, the common bonding patterns in pure and mixed clusters of beryllium and magnesium derivatives were explored using chemical bonding tools. The results showed interesting differences in stability sequences between hydrides and fluorides/chlorides in dimers. Additionally, trimers exhibited peculiarities associated with compact trigonal cyclic structures competing in stability with more conventional hexagonal and linear forms. This study provides insights into previously unexplored structures.
Article
Chemistry, Physical
Ibon Alkorta, Anthony Legon
Summary: In this study, the nucleophilicities of methane, ethane, cyclopropane, ethyne, and ethene acting as Lewis bases were determined through experimental and computational methods. The inductive effect of the methyl group when ethyne is methylated was also investigated.
CHEMICAL PHYSICS LETTERS
(2023)
