Review
Biochemistry & Molecular Biology
Philipp Innig Aguion, Alexander Marchanka
Summary: MAS ssNMR is an established tool for studying non-soluble or non-crystalline biomolecules, with significant progress in protein studies but challenges in RNA research. Resonance assignment is a critical step in NMR studies, determining the feasibility of structure determination. Recent research focuses on RNA resonance assignment methods and ssNMR secondary structure determination.
FRONTIERS IN MOLECULAR BIOSCIENCES
(2021)
Article
Chemistry, Physical
Tata Gopinath, Veliparambil S. Manu, Daniel K. Weber, Gianluigi Veglia
Summary: Solid-state NMR spectroscopy is a preferred method for analyzing the structural dynamics of challenging proteins. Researchers have developed a new approach (PHRONESIS) that allows for the simultaneous generation of multiple 3D H-1-detected ssNMR spectra, leading to significant advancements in structural analysis.
Article
Chemistry, Physical
Alexander A. Malar, Qiu Sun, Johannes Zehnder, Gerald Kehr, Gerhard Erker, Thomas Wiegand
Summary: Proton-detected solid-state NMR allows for atomic-level insight into solid-state reactions, such as heterogeneous catalysis, which is crucial for understanding chemical reaction mechanisms. This study introduces a phosphorus-31 radiofrequency channel in fast magic-angle spinning proton-detected solid-state NMR and demonstrates its application in characterizing PH-containing compounds from the chemistry of phosphane-borane frustrated Lewis pairs. The approach reveals important information on spatial proximity and chemical bonding within these compounds, and has the potential to greatly impact the structural characterization of hydrogen-activated phosphane/borane FLPs, heterogeneous catalysts, and solid-state reactions in general.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Isabella C. Felli, Roberta Pierattelli
Summary: Modern C-13 NMR has become a valuable tool for biomolecular applications, allowing for complete assignment of proteins and providing unique information. A wide range of NMR observables can be measured to characterize the structure and dynamics of proteins comprehensively.
Article
Biochemistry & Molecular Biology
Nghia Tuan Duong, Yoshitaka Aoyama, Katsumi Kawamoto, Toshio Yamazaki, Yusuke Nishiyama
Summary: MicroED is used to solve structures of sub-micrometer crystals, but the high R factor makes it difficult to locate hydrogens and assign nuclei with close atomic numbers. By combining microED and ssNMR experiments with spin dynamics numerical simulations, this study provides a method for natural abundance samples.
Review
Chemistry, Multidisciplinary
Isabella C. Felli, Roberta Pierattelli
Summary: Modern C-13 NMR has become a valuable tool for biomolecular applications, allowing for complete protein assignment and unique information for the study of various biomolecules. Its different properties compared to H-1 provide the rationale for experiments and their applications in structural and dynamic characterization.
Article
Chemistry, Physical
Alexey S. Kiryutin, Ivan V. Zhukov, Fabien Ferrage, Geoffrey Bodenhausen, Alexandra V. Yurkovskaya, Konstantin L. Ivanov
Summary: ZULF-TOCSY is a novel nuclear magnetic resonance method that achieves correlations between different nuclei by evenly distributing polarization, allowing for sequential assignments in peptides and other samples with natural isotopic abundance. This method provides a valuable alternative to traditional 2D experiments, such as HMBC, by offering more comprehensive spectral information.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Ivan Hung, Wenping Mao, Eric G. Keeler, Robert G. Griffin, Peter L. Gor'kov, Zhehong Gan
Summary: High sensitivity and resolution solid-state NMR methods are developed for selecting hydrogen-bonded N-15-O-17 pairs in peptides, aiding protein secondary and tertiary structure determination. Enhanced sensitivity is achieved through indirect H-1 detection under fast MAS and stronger relayed dipole couplings.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Philipp Innig Aguion, John Kirkpatrick, Teresa Carlomagno, Alexander Marchanka
Summary: Knowledge of RNA structure, whether in isolation or in complex, is crucial for understanding cellular processes. Solid-state NMR has been used to study high molecular-weight complexes, and recent developments in H-1 detection at fast MAS rates have overcome sensitivity and resolution limitations, allowing for more efficient analysis of RNA structures in protein-RNA complexes of any size.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Kerti Ausmees, Nele Reimets, Indrek Reile
Summary: Parahydrogen hyperpolarization is a promising tool for sensitively enhancing NMR metabolomics, allowing for resolution and quantification of low-abundance metabolites. The reliable identification of analytes producing parahydrogen hyperpolarized NMR signals currently requires the addition of internal standards, which can be laborious. This study demonstrates that generating libraries of hyperpolarized analyte signals, similar to regular NMR metabolomics, can address this limitation.
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
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
Materials Science, Ceramics
Alberto Isaac Ruiz, Encarnacion Reyes, Cristina Argiz, Miguel Angel de la Rubia, Amparo Moragues
Summary: This research investigates the influence of different nanomaterials on the structure of synthetic gels, showing that the incorporation of aluminum in the C-S-H gel can modify its structure. Mixtures with NS OX50 exhibit novel trends.
BOLETIN DE LA SOCIEDAD ESPANOLA DE CERAMICA Y VIDRIO
(2023)
Article
Materials Science, Paper & Wood
Darren H. Brouwer, Janelle G. Mikolajewski
Summary: A survey of literature on solid-state C-13 NMR spectra of native celluloses shows inconsistencies in reported C-13 chemical shifts for cellulose I alpha and I beta allomorphs. The correct chemical shifts are unclear due to variations of up to 2 ppm. Reliable experimental data is crucial for future work, such as quantum chemical calculations or identification of cellulose phases. By digitizing previous spectra and carefully considering referencing methods, it has been possible to establish a definitive set of correctly referenced C-13 chemical shifts for cellulose I alpha and I beta allomorphs. Additional evidence and new peak assignments were obtained through C-13 NMR experiments on a cellulose I alpha-rich sample. This work resolves inconsistencies and provides essential chemical shift data for future research.
Article
Biochemistry & Molecular Biology
Adilakshmi Dwarasala, Mehdi Rahimi, John L. Markley, Woonghee Lee
Summary: The interpretation of solid-state NMR (ssNMR) spectra is more difficult than that of solution NMR spectra due to heightened dipolar interactions in solids. However, ssNMR does not have the same molecular weight limitations as solution NMR. Recent advancements in ssNMR technology have allowed for the study of larger biomolecules, including membrane proteins. Despite these advancements, computational tools for analyzing complex ssNMR data from membrane proteins have not kept pace with those for solution NMR.
Article
Biochemistry & Molecular Biology
Yiling Xiao, Rupam Ghosh, Kendra K. Frederick
Summary: NMR techniques allow for determining protein structures labeled with isotopes, with both 10% DMSO and 15% glycerol proven to be appropriate cryoprotectants. However, DMSO did not improve the dispersion of AMUPol throughout the cellular biomass.
FRONTIERS IN MOLECULAR BIOSCIENCES
(2022)
Article
Biochemical Research Methods
Rupam Ghosh, Rania Dumarieh, Yiling Xiao, Kendra K. Frederick
Summary: Dynamic nuclear polarization (DNP) enhanced solid state NMR increases sensitivity, allowing detection of biomolecules at physiological concentrations. Reduction of AMUPol in lysed and intact HEK293 cells was investigated, showing first-order reduction kinetics by cell lysates and slightly faster reduction by intact cells. Independent reduction of the two nitroxide radicals of AMUPol leads to accumulation of the DNP-silent monoradical form. The addition of N-ethyl maleimide (NEM) inhibits AMUPol reduction but compromises cellular viability and does not improve DNP performance. Minimizing room temperature contact times with cellular constituents is the most effective strategy for achieving high DNP enhancements in in-cell NMR experiments.
JOURNAL OF MAGNETIC RESONANCE
(2022)
Article
Chemistry, Multidisciplinary
Ziqian Xue, Jia-Jia Zheng, Yusuke Nishiyama, Ming-Shui Yao, Yoshitaka Aoyama, Zeyu Fan, Ping Wang, Takashi Kajiwara, Yoshiki Kubota, Satoshi Horike, Ken-ichi Otake, Susumu Kitagawa
Summary: By manipulating the coordination geometries of metal centers, new porous coordination polymers (PCPs) with tunable structure and conductivity have been successfully achieved. These PCPs exhibit varying pore structures and conductivities, enabling modulated selectivity and sensitivity in gas sensing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kalipada Koner, Suvendu Karak, Yutaro Ogaeri, Yusuke Nishiyama, Rahul Banerjee
Summary: Covalent organic nanotubes (CONTs) are porous one-dimensional frameworks connected through imine bonds via Schiff base condensation. The presence of two amine groups at the ortho position in the structurally demanding tetraaminotriptycene (TAT) building block leads to multiple reaction pathways between the ditopic aldehyde and the tetratopic amine. The synthesis and characterization of CONT-1 monomers, including the conversion of imine to imidazole bonding and the structural connectivity of CONTs, are investigated using various experimental techniques.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemical Research Methods
Yutaro Ogaeri, Naoto Suzuki, Toshiro Fukami, Yusuke Nishiyama
Summary: The symmetry-based phase-modulated resonance-echo saturation-pulse double-resonance (PM-S-RESPDOR) method can efficiently and accurately measure the 1H-14N internuclear distances in rigid solids. The fraction curve, represented by (S0 - S')/S0, is derived from the PM-S-RESPDOR signal intensity with and without 14N PM saturation pulse, providing analytical equations for 1H-14N couplings. However, in multi-component systems commonly found in pharmaceutical applications, the limited 1H resolution at fast MAS may lead to the NH proton resonance not being well separated from other proton peaks. To address this issue, T-HMQC filtering is applied to suppress other 1H signals before conducting PM-S-RESPDOR experiments. The method is successfully demonstrated using the acetaminophen-oxalic acid (APAP-OXA) system. The analysis shows that the analytical equation can be safely applied in the analysis of T-HMQC filtered PM-S-RESPDOR experiments.
JOURNAL OF MAGNETIC RESONANCE
(2023)
Article
Chemistry, Physical
Haruki Sato, Koichiro Miyanishi, Makoto Negoro, Akinori Kagawa, Yusuke Nishiyama, Satoshi Horike, Koichi Nakamura, Munehiro Inukai
Summary: This study demonstrates the hyperpolarization of biomolecules in eutectic crystals using photoexcited triplet electrons at room temperature. The eutectic crystals, composed of benzoic acid doped with the polarization source and analyte domains, were prepared using a melting-quenching process. Solid-state NMR analysis elucidates spin diffusion between the benzoic acid and analyte domain, indicating the transfer of hyperpolarization from the benzoic acid domain to the analyte domain.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Kalipada Koner, Arnab Sadhukhan, Suvendu Karak, Himadri Sekhar Sasmal, Yutaro Ogaeri, Yusuke Nishiyama, Shuangjie Zhao, Miroslav Polozij, Agnieszka Kuc, Thomas Heine, Rahul Banerjee
Summary: Few-layer organic nanosheets are gaining attention as 2D materials due to their precise atomic connectivity and tailor-made pores. Most synthesis strategies rely on surface-assisted methods or top-down exfoliation, but a bottom-up approach with well-designed building blocks is more convenient for bulk-scale synthesis of 2D nanosheets. Crystalline covalent organic framework nanosheets were successfully synthesized by reacting tetratopic thianthrene tetraaldehyde (THT) and aliphatic diamines, with the bent geometry of thianthrene and flexible diamines contributing to nanosheet formation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Jaka Kragelj, Rania Dumarieh, Yiling Xiao, Kendra K. K. Frederick
Summary: Frozen proteins at cryogenic temperatures can provide detailed conformational restraints for DNP MAS NMR studies. Using peak shapes, conformational features of individual conformers in the ensemble can be assigned through simulation. This has important implications for studying proteins with intrinsically disordered regions in living cells.
Article
Chemistry, Physical
Hongyao Zhou, Shun Sato, Yusuke Nishiyama, Genki Hatakeyama, Xiaohan Wang, Yoichi Murakami, Teppei Yamada
Summary: Organic ionic plastic crystals (OIPCs) are a ductile soft material that can transform into a plastic phase at low temperature while maintaining a high melting point. This unique property is determined by the structure and distance of the composing ions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Shibani Mohata, Risov Das, Kalipada Koner, Mohd Riyaz, Kousik Das, Subhajit Chakraborty, Yutaro Ogaeri, Yusuke Nishiyama, Sebastian C. Peter, Rahul Banerjee
Summary: The conversion of CO2 to a carbonaceous product using photocatalysis is an important solution for reducing CO2 emissions and dependence on nonrenewable resources. However, developing a metal-free catalyst that is selective and efficient in CO2 reduction is challenging. In this study, a molecular engineering approach was used to design a photoactive polymer with high CO2 permeability and low water diffusivity, promoting CO2 transfer and suppressing the HER reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Biomaterials
Takashi Tanaka, Sakiko Hara, Hanan Hendawy, Hussein M. El-Husseiny, Ryo Tanaka, Tetsuo Asakura
Summary: The study found that transgenic SF coatings containing VEGF and REDV can accelerate endothelialization in vivo, while the effectiveness of YIGSR-containing transgenic SF coatings is lower.
Article
Chemistry, Multidisciplinary
Genki Hatakeyama, Hongyao Zhou, Takashi Kikuchi, Masaki Nishio, Kouki Oka, Masaaki Sadakiyo, Yusuke Nishiyama, Teppei Yamada
Summary: This manuscript reports a highly stable MOF with a cation exchange site synthesized by the reaction between zirconium and mellitic acid under a high concentration of ammonium cations (NH4+). The MOF has four free carboxyl groups, and one of the carboxyl groups acts as a monovalent ion-exchanging site with a high first association constant (pK(a1)). The MOF can reversibly exchange NH4+ with H+, Na+, and K+ cations, and its nanospace enables selective NH4+ recovery from aqueous mixtures, addressing the global nitrogen cycle problem. The proton conductivity of the MOF reaches 1.34 x 10(-3) S cm(-1) at 55 °C by ion exchange from NH4+ to H+.
Meeting Abstract
Biochemistry & Molecular Biology
Kendra Frederick, Yiling Xiao, Rupam Ghosh
Article
Chemistry, Multidisciplinary
Kyohei Nakano, Iat Wai Leong, Daisuke Hashizume, Kirill Bulgarevich, Kazuo Takimiya, Yusuke Nishiyama, Toshio Yamazaki, Keisuke Tajima
Summary: This study develops a new synthetic route to synthesize several new BIT derivatives. The properties of these derivatives are investigated experimentally and computationally, revealing rapid tautomerization in solution and solid state. It is also found that one of the derivatives exhibits good charge transport performance in an organic field effect transistor.
Article
Chemistry, Physical
Nghia Tuan Duong, Yusuke Nishiyama
Summary: This study presents a new experimental method for detecting proton and nitrogen correlations in solid-state nuclear magnetic resonance (NMR). This method is significant for the structural determination of biological and chemical systems.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
