Article
Materials Science, Paper & Wood
Darren H. Brouwer, Janelle G. Mikolajewski
Summary: Solid-state 13C nuclear magnetic resonance (NMR) spectroscopy is an important tool for identifying different forms of cellulose. In this paper, the authors show that the secondary crystalline form in bacterial cellulose differs from the I beta allomorph found in tunicate cellulose, based on their analysis of 1D and 2D NMR spectra.
Article
Chemistry, Physical
Clayton J. Dahlman, Rhys M. Kennard, Piotr Paluch, Naveen R. Venkatesan, Michael L. Chabinyc, G. N. Manjunatha Reddy
Summary: Layered hybrid organic-inorganic perovskites, such as the lead halide Ruddlesden-Popper (RP) series, exhibit tunable optoelectronic properties due to dynamic interactions between the ionic perovskite substructure and organic spacer cations. Solid-state NMR spectroscopy was used to characterize the static and dynamic structures of linear alkylammonium and aromatic spacers in lead iodide RP phases, revealing different site-specific rigidity trends for short and long spacers. The study highlights the interplay between spacer interactions with lead iodide octahedra and van der Waals forces in contributing to a variety of site-specific dynamics and structural distortions at intermediate time scales.
CHEMISTRY OF MATERIALS
(2021)
Review
Chemistry, Multidisciplinary
Igor d'Anciaes Almeida Silva, Ettore Bartalucci, Carsten Bolm, Thomas Wiegand
Summary: Recent studies have shown that mechanochemical strategies are beneficial for directed conversions of organic compounds. However, finding new reactions has been challenging due to the lack of mechanistic understanding of mechanochemical reaction events. Spectroscopic techniques play a crucial role in addressing these questions. In this overview, the opportunities and challenges of solid-state nuclear magnetic resonance (NMR) spectroscopy in the field of organic mechanochemistry are discussed. The strengths of solid-state NMR in ex situ structure characterization, differentiating polymorphs, NMR-crystallographic structure-determination protocols, and detecting weak noncovalent interactions in molecular-recognition events using proton-detected solid-state NMR experiments at fast MAS frequencies are highlighted.
ADVANCED MATERIALS
(2023)
Article
Engineering, Biomedical
Yannick Coppel, Yann Prigent, Genevieve Gregoire
Summary: This study introduces a set of solid state NMR experiments for characterizing the main components of human dentin, focusing on the H-1 signals of water molecules, HPO42-, and OH- groups. By utilizing sample modifications, hydrogen signals of these species can be distinguished, providing valuable structural and dynamic information for biomaterials.
ACTA BIOMATERIALIA
(2021)
Article
Chemistry, Physical
Yifei Xu, Lina Gao, Qianqian Liu, Qian Liu, Zerui Chen, Wei Zhao, Xueqian Kong, Hao Bin Wu
Summary: Metal-organic frameworks have been developed as solid electrolytes for Li batteries. A study demonstrates metal-organic solid electrolytes with superionic conductivity by grafting hemilabile anionic chains in the pore channels of an Al-based metal-organic framework. The solid electrolyte shows excellent stability and enables remarkable rate performance in Li batteries.
ENERGY STORAGE MATERIALS
(2023)
Article
Dentistry, Oral Surgery & Medicine
Yannick Coppel, Karim Nasr, Yann Prigent, Genevieve Gregoire
Summary: This study investigated the chemical and structural changes in dentin during the application of a mild universal adhesive. It was found that the etch-and-rinse mode led to a decrease in inorganic apatite and a reorganization of the mineral phase, while the self-etch mode formed a low amount of adhesive phosphate monoesters calcium salt. The adhesive had a similar interaction with dentin collagen in both modes, but the presence of isopropanol as the solvent significantly reduced the amount of free water molecules without significant changes in collagen structure.
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.
Review
Chemistry, Inorganic & Nuclear
Yao Fu, Hanxi Guan, Jinglin Yin, Xueqian Kong
Summary: Molecular motions in MOFs involve various phenomena such as gas sorption, linker rotation, ion diffusion, and chemical reactions. SSNMR is a unique tool that can capture dynamic pictures across a wide range of time scales to understand these motional processes. Different SSNMR strategies are required to accurately characterize molecular motions in MOFs based on their different motion regimes.
COORDINATION CHEMISTRY REVIEWS
(2021)
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)
Article
Chemistry, Multidisciplinary
Xue Li, Marianna Porcino, Jingwen Qiu, Doru Constantin, Charlotte Martineau-Corcos, Ruxandra Gref
Summary: Recent development of nanoscale metal-organic frameworks with versatile coatings has attracted attention in nanomedicine field. The preparation of core-shell MIL-100(Al) nanoMOFs for delivering the anticancer drug DOX and the affinity of the coatings for both DOX and MOF cores were demonstrated. Solid state nuclear magnetic resonance experiments were used to gain understanding on the interactions in the core-shell system.
Article
Chemistry, Multidisciplinary
David S. Hughes, Ann L. Bingham, Michael B. Hursthouse, Terry L. Threlfall, Andrew D. Bond
Summary: This article describes the patterns of N-HMIDLINE HORIZONTAL ELLIPSISO and N-HMIDLINE HORIZONTAL ELLIPSISN hydrogen bonds in a set of 101 crystal structures containing sulfathiazole. The topologies of the hydrogen bond motifs are analyzed, and the structures are compared using both topological analysis and node shape comparison. The article presents examples of topological similarity between multi-component structures and the sulfathiazole polymorphs, as well as cases where structures show geometrical similarity but have different hydrogen-bond schemes. The uncertainties and ambiguities inherent in tolerance-based methods for comparing molecular crystal structures are highlighted.
Article
Multidisciplinary Sciences
Jonathan M. Chan, Avram C. Kordon, Ruimeng Zhang, Muzhou Wang
Summary: This study visualized single-bottlebrush chains using single-molecule localization microscopy to study their conformations in a polymer melt, revealing that bottlebrushes are significantly more rigid in the solid state compared to in solution, and the scaling relationships between persistence length and side chain length deviate from theory predictions. The findings provide insights into polymer science and pave the way for answering unresolved questions in the field.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Chemistry, Physical
Kasper P. van der Zwan, Wiebke Riedel, Fabien Aussenac, Christian Reiter, Klaus Kreger, Hans-Werner Schmidt, Thomas Risse, Torsten Gutmann, Juergen Senker
Summary: The study demonstrates the efficiency of dynamic nuclear polarization (DNP) enhanced F-19 MAS NMR spectroscopy for detecting fluorinated target molecules without F-19-containing solvents and matrices via F-19-F-19 spin diffusion. Direct polarization transfer over distances up to at least 20 A can achieve substantial enhancements, enabling spatial spectral editing in crowded spectra. The technique of exciting F-19 via DNP and transferring polarization to other heteronuclei within close proximity is expected to become more important in the future for NMR spectroscopy.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Inorganic & Nuclear
Debapriya Gupta, Ankit Kumar Gaur, Deepanshu Chauhan, Sandeep Kumar Thakur, Vaitheesh Jeyapalan, Sanjay Singh, Gopalan Rajaraman, Sugumar Venkataramani
Summary: A new class of photoactive and chelating ligands incorporating arylazo-3,5-dimethylpyrazole units has been designed and synthesized. These ligands directly coordinate as neutral N-donor ligands and form tri- and tetra-dentate chelating ligands when complexed with transition metal ions. The ligands and their complexes exhibit excellent forward and reverse photoisomerization properties, as well as intriguing photochromism.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Tao Wang, Alejandro Berdonces-Layunta, Niklas Friedrich, Manuel Vilas-Varela, Jan Patrick Calupitan, Jose Ignacio Pascual, Diego Pena, David Casanova, Martina Corso, Dimas G. de Oteyza
Summary: This study successfully synthesized nitrogen-doped triangulene and characterized its electronic properties through experimental and theoretical calculations. It was demonstrated that nitrogen-doped triangulene exhibits an open-shell triplet ground state on Au(111) surface and a closed-shell character on Ag(111) surface.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tomasz Pawlak, Isaac Sudgen, Grzegorz Bujacz, Dinu Iuga, Steven P. Brown, Marek J. Potrzebowski
Summary: This work presents the X-ray diffraction crystal structure and spectral properties of a new, room-temperature polymorph of teriflunomide for the first time, along with insights into the thermal transitions and torsional angle differences between the low-temperature and room-temperature structures. The study demonstrates the combination of experiments, such as DSC, X-ray diffraction, and MAS NMR, with DFT calculations to probe and understand the solid-state landscape, particularly the role of dynamics, in pharmaceutical molecules.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Biochemistry & Molecular Biology
Rosalie Cresswell, Ray Dupree, Steven P. Brown, Caroline S. Pereira, Munir S. Skaf, Mathias Sorieul, Paul Dupree, Stefan Hill
Summary: Water plays a critical role at the hemicellulose-cellulose interface in the molecular architecture of softwood secondary cell walls. After dehydration, molecular shrinkage occurs and the original conformation is not fully recovered upon rehydration. These irreversible nanostructural changes provide a basis for understanding and enhancing the properties of wood-based materials.
Article
Chemistry, Physical
Patrick M. J. Szell, Sten O. Nilsson Lill, Helen Blade, Steven P. Brown, Leslie P. Hughes
Summary: NMR crystallography is a powerful tool for structural characterization and crystal structure verification, but faces challenges in terms of consistency, workflow, and understanding of experimental solid-state NMR and calculations. Fully parameterized scripts have been developed to improve efficiency, robustness, and workflow, aiding in DFT calculations, result extraction & visualization, and crystallographic modelling. These tools aim to facilitate NMR crystallography and harmonize the process across users.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2021)
Article
Chemistry, Multidisciplinary
Aneesa J. Al-Ani, Patrick M. J. Szell, Zainab Rehman, Helen Blade, Helen P. Wheatcroft, Leslie P. Hughes, Steven P. Brown, Chick C. Wilson
Summary: This study presents the crystal structure of salbutamol oxalate and investigates its crystallographic disorder using X-ray crystallography and solid-state NMR. The study reveals that the chiral center of salbutamol is disordered over two positions and the tert-butyl group is rotating rapidly. The impact of crystallization conditions on the disorder is also explored.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Biochemistry & Molecular Biology
Li Yu, Yoshihisa Yoshimi, Rosalie Cresswell, Raymond Wightman, Jan J. Lyczakowski, Louis F. L. Wilson, Konan Ishida, Katherine Stott, Xiaolan Yu, Stephan Charalambous, Joel Wurman-Rodrich, Oliver M. Terrett, Steven P. Brown, Ray Dupree, Henry Temple, Kristian B. R. M. Krogh, Paul Dupree
Summary: Patterned beta-galactoglucomannan (beta-GGM) is widespread in eudicot primary cell walls and exhibits similarities to xyloglucan (XyG). This study demonstrates a related role of beta-GGM and XyG in primary cell walls, opening avenues for further research on their functions.
Article
Chemistry, Physical
Parth Raval, Julien Trebose, Tomasz Pawlak, Yusuke Nishiyama, Steven P. Brown, G. N. Manjunatha Reddy
Summary: Analysis of short-to-intermediate range intermolecular interactions provides a valuable approach to understanding the solid-state organization of small molecules and materials. A combination of 2D NMR spectroscopy techniques allows for the detection of intermolecular distances, particularly when low-gamma quadrupolar nuclei are involved. The presented experiment demonstrates the applicability of the HMQC-SD-RFDR approach in detecting medium-range proximities in molecular solids.
SOLID STATE NUCLEAR MAGNETIC RESONANCE
(2022)
Article
Chemistry, Physical
Patrick M. J. Szell, Zainab Rehman, Ben P. Tatman, Leslie P. Hughes, Helen Blade, Steven P. Brown
Summary: Crystallographic disorder can have negative effects on the stability and manufacturing control of active pharmaceutical ingredients. Solid-state NMR is a useful technique for studying crystallographic disorder. This study used high-field Cl-35 solid-state NMR to characterize the disorder in duloxetine hydrochloride, promethazine hydrochloride, and trifluoperazine dihydrochloride. The results showed that higher magnetic fields were beneficial for resolving the disorder in some compounds.
Article
Biochemistry & Molecular Biology
Awatif Alruwaili, Goran M. M. Rashid, Victoria Sodre, James Mason, Zainab Rehman, Anjali K. Menakath, David Cheung, Steven P. Brown, Timothy D. H. Bugg
Summary: The breakdown pathways of lignin by soil microbes have the potential to be used for developing new routes for the production of renewable chemicals, but remain incompletely understood. By feeding β-C-13-labelled DHP lignin to Rhodococcus jostii RHA1, it was found that C-13 label was incorporated into metabolites such as oxalic acid, 4-hydroxyphenylacetic acid, and 4-hydroxy-3-methoxyphenylacetic acid, confirming their origin from lignin breakdown. The identification of glycolate oxidase enzyme and its role in the production of oxalic acid and 4-hydroxybenzoylformic acid provides insights into the pathways involved in lignin degradation.
RSC CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Physical
Ben P. Tatman, W. Trent Franks, Steven P. Brown, Jozef R. Lewandowski
Summary: Solid-state nuclear spin diffusion is a coherent and reversible process transferring spin order through dipolar couplings. Understanding how increased H-1 resolution affects spin diffusion is crucial for interpreting common experiments in solid-state nuclear magnetic resonance. A low-order correlation in Liouville space model based on Dumez et al.'s work has been developed to investigate the coherent contributions to spin diffusion under fast magic-angle spinning (MAS). The model considers resonance-offset dependence and the inclusion of chemical shifts in spin diffusion modeling.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Biochemical Research Methods
Ben P. Tatman, Haritosh Modha, Steven P. Brown
Summary: This study compares the effectiveness of two classes of recoupling schemes for restoring the 1H -14N dipolar coupling. The TRAPDOR method shows better sensitivity, but is sensitive to the 14N transmitter offset.
JOURNAL OF MAGNETIC RESONANCE
(2023)
Article
Chemistry, Medicinal
Zainab Rehman, W. Trent Franks, Bao Nguyen, Heather Frericks Schmidt, Garry Scrivens, Steven P. Brown
Summary: Lorlatinib is an active pharmaceutical ingredient used to treat lung cancer. This study presents the NMR crystallography analysis of Lorlatinib, combining single-crystal X-ray diffraction structure determination, solid-state NMR, and NMR chemical shift calculation. The crystal structure of Lorlatinib is described, including the presence of intermolecular hydrogen bonds. The study also demonstrates the resolution enhancement in MAS NMR at a higher Larmor frequency.
JOURNAL OF PHARMACEUTICAL SCIENCES
(2023)
Correction
Chemistry, Physical
Jacqueline Tognetti, W. Trent Franks, Jozef R. Lewandowski, Steven P. Brown
Summary: This study focuses on optimizing H-1 PMLG homonuclear decoupling at 60 kHz MAS to enable N-15-H-1 through-bond heteronuclear correlation solid-state NMR spectroscopy.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Jacqueline Tognetti, W. Trent Franks, Jozef R. Lewandowski, Steven P. Brown
Summary: This study demonstrates enhanced decoupling in H-1 magic-angle spinning solid-state NMR, as well as good performance of windowed decoupling in H-1 spin-echo experiments. The findings have implications for N-15-H-1 cross polarization experiments.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Patrick M. J. Szell, Jozef R. Lewandowski, Helen Blade, Leslie P. Hughes, Sten O. Nilsson Lill, Steven P. Brown
Summary: The study revealed that the dynamics in the crystalline form of efavirenz are significant, whereas the dynamics in its cocrystals with l-proline are constrained, with the cyclopropyl group being the most constrained due to a more favorable crystal packing in the cocrystals.
