Article
Biochemistry & Molecular Biology
Anna Helena Mazurek, Lukasz Szeleszczuk, Kostas Bethanis, Elias Christoforides, Marta Katarzyna Dudek, Monika Zielinska-Pisklak, Dariusz Maciej Pisklak
Summary: In this study, the host-guest inclusion complex between ss-CD and EST was prepared using four different methods, and the obtained samples were deeply characterized. The crystal structure of the complex was determined using SCXRD, which is the first solved crystal structure of an estrogen/CD complex to our knowledge. Periodic DFT calculations using GIPAW were found to be particularly helpful in analyzing disorder in the solid state and interpreting experimental NMR results. This study highlights the importance of a combined ssNMR/SCXRD approach to studying the structure of inclusion complexes formed by cyclodextrins.
Article
Chemistry, Multidisciplinary
Ayelen F. Crespi, Paula N. Zomero, Veronica M. Sanchez, Ana L. Perez, Carlos D. Brondino, Daniel Vega, Enrique Rodriguez-Castellon, Juan M. Lazaro-Martinez
Summary: This study describes the synthesis of two copper soluble complexes for the activation of hydrogen peroxide and the generation of reactive oxygen species. By combining various experimental and computational methods, the chemical structure of the ligands and metal ions was studied in detail. The results showed that the copper complexes were effective for the activation of H2O2 and only generated hydroxyl as the reactive oxygen species. These complexes can efficiently remove dyes.
Article
Chemistry, Multidisciplinary
Ettore Bartalucci, Alexander A. A. Malar, Anne Mehnert, Julius B. Kleine B. Buening, Lennart Guenzel, Maik Icker, Martin Boerner, Christian Wiebeler, Beat H. H. Meier, Stefan Grimme, Berthold Kersting, Thomas Wiegand
Summary: In this study, proton-detected solid-state Nuclear Magnetic Resonance (NMR) experiments were used to detect a single water molecule trapped in a lanthanide complex by analyzing three types of non-covalent interactions. The water proton resonances were detected at a chemical-shift value close to zero ppm, which was further confirmed by quantum-chemical calculations. Density Functional Theory calculations revealed the sensitivity of the proton chemical-shift value for hydrogen-pi interactions. This study highlights the importance of proton-detected solid-state NMR in probing weak non-covalent interactions in molecular recognition events in chemistry and biology.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Multidisciplinary
Yao Fu, Zhengzhong Kang, Weicheng Cao, Jinglin Yin, Yaoquan Tu, Jianhua Li, Hanxi Guan, Yiran Wang, Qi Wang, Xueqian Kong
Summary: Understanding drug-carrier interactions in metal-organic frameworks (MOFs) is crucial for designing drug-delivery systems. This study found that defects in MOFs play a key role in loading pharmaceuticals with phosphate or phosphonate groups, enhancing capacity due to Coulombic attraction. Solid-state NMR spectroscopy and molecular simulations were used to elucidate the mechanisms of drug-carrier interactions at defects.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiangsi Liu, Ziteng Liang, Yuxuan Xiang, Min Lin, Qi Li, Zigeng Liu, Guiming Zhong, Riqiang Fu, Yong Yang
Summary: The recent applications of solid-state nuclear magnetic resonance (ssNMR) and magnetic resonance imaging (MRI) techniques in Li/Na batteries are reviewed, emphasizing the importance of investigating battery materials structure, solid electrolyte interfaces, and in situ research.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Physical
Xin-Yuan Feng, Chun-Hai Wang, Haijun Pan, Zhilin Ji, Xiao-Ming Wang, Leiming Fang, Fa Luo
Summary: In this study, the crystal structure and ionic conductivity of the Li2+xC1-xBxO3 solid solution were investigated using experimental and theoretical methods. Multiple lithium sites were observed, and the migration pathways of lithium ions at different temperatures were explored.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Qianyi Yang, Fuqiang Lu, Yulin Liu, Yijie Zhang, Xiujuan Wang, Yuepeng Pang, Shiyou Zheng
Summary: The study reports the preparation of solid electrolytes with high Li-ion conductivity by nanoconfining Li-2(BH4)(NH2) in mesoporous silica molecular sieves using a melting-infiltration approach. The solid electrolyte exhibits excellent electrochemical stability, Li-ion conductivity, and cycling performance in Li|Li-2(BH4)(NH2)@SBA-15|TiS2 cells.
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
Energy & Fuels
Francesco Panattoni, Jonathan Mitchell, Edmund J. Fordham, Ravinath Kausik, Clare P. Grey, Pieter C. M. M. Magusin
Summary: The study utilized high-field, solid-state NMR methods to analyze kerogen isolates of different maturity levels, finding that the aromatic/aliphatic ratio of kerogen increases with maturity. This increase in ratio is reflected in the H-1 MAS NMR spectra by the intensity ratio of aliphatic-to-aromatic signals, suggesting a decrease in kerogen proton density during maturation.
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, Multidisciplinary
Naiara Leticia Marana, Mauro Francesco Sgroi, Lorenzo Maschio, Anna Maria Ferrari, Maddalena D'Amore, Silvia Casassa
Summary: The all-solid-state lithium-ion battery with a solid-state electrolyte offers increased safety and energy density. This study used density functional theory to investigate the surface properties of β-Li3PS4 and found that besides the (100) surface, other surfaces are also stable and can facilitate Li-ion migration.
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
Engineering, Environmental
Hiram Kwak, Daseul Han, Juhyoun Park, Kyung-Wan Nam, Hyungsub Kim, Jong Seok Kim, Yoon Seok Jung, Jun Pyo Son
Summary: Aliovalent-substituted Li2ZrCl6 with In3+ (or Sc3+) shows drastically increased Li+ conductivity, attributed to anisotropic lattice volume expansion and redistribution of Li in the lattice, leading to more favorable Li+ migration pathways in the (002) plane.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Christian Schroeder, Stacey Zones, Michael Ryan Hansen, Hubert Koller
Summary: The zeolite catalyst SSZ-42 exhibits a high abundance of hydrogen-bonded Bronsted acid sites, with the classification and diversity of hydrogen bonding affecting chemical shifts. The alignment of oxygen atoms is expected to impact their role in catalytic reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ander Orue, Juan Miguel Lopez del Amo, Frederic Aguesse, Montse Casas-Cabanas, Pedro Lopez-Aranguren
Summary: By using multi-walled carbon nanotubes in the design and optimization of composite electrodes, high-performance Li-metal solid-state cells were achieved with a capacity retention rate of 92% at high current densities, demonstrating great potential.
ENERGY STORAGE MATERIALS
(2023)
Article
Nanoscience & Nanotechnology
Gwenaelle Courbaron, Emmanuel Petit, Jon Serrano-Sevillano, Christine Labrugere-Sarroste, Jacob Olchowka, Dany Carlier, Nathalie Delpuech, Cyril Aymonier, Laurence Croguennec
Summary: Spinel LiNi0.5Mn1.5O4 (LNMO) is a promising candidate as the positive electrode material for the next generation of Li-ion technology and all-solid-state batteries. In this work, a simple and cheap process called supercritical fluid chemical deposition (SFCD) is used to modify the surface of LNMO with a homogeneous coating of Al2O3 type, leading to significantly improved performance compared to bare LNMO.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Nanoscience & Nanotechnology
Sona Valiyaveettil-SobhanRaj, Rosalia Cid, Travis Thompson, Francisco Bonilla, Gabriel A. Lopez, Frederic Aguesse, Montse Casas-Cabanas
Summary: Temperature-assisted densification methods are used to suppress resistive interfaces in oxide-based solid-state batteries. However, the chemical reactivity among different cathode components still poses a challenge. This study evaluates the impact of temperature and heating atmosphere on the LiNi0.6Mn0.2Co0.2O2 (NMC), Li1+xAlxTi2-xP3O12 (LATP), and Ketjenblack (KB) system. The results suggest that the heating atmosphere and reaction mechanism play a role in the degradation and capacity decay of the batteries.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Marine Reynaud, Jon Serrano-Sevillano, Montse Casas-Cabanas
Summary: Understanding and controlling structural defects in crystalline materials is crucial for exploring composition-structure-property relationships. Recent advancements in structural disorder characterization techniques provide valuable insights and tools for accurately analyzing microstructural complexity. Mastering these techniques offers great potential for designing improved materials.
CHEMISTRY OF MATERIALS
(2023)
Article
Electrochemistry
M. Enterria, R. Mysyk, L. Medinilla, S. Villar-Rodil, J. I. Paredes, I. Rincon, F. J. Fernandez-Carretero, K. Gomez, J. M. Lopez del Amo, N. Ortiz-Vitoriano
Summary: In order to overcome the challenges of Na-O2 batteries and develop cheap, metal-free, and abundant electrocatalysts, boron and nitrogen-functionalized graphene aerogels were explored. The results showed an improvement in cycling overpotential and coulombic efficiency with the functionalized graphene aerogels. However, the nitrogen-containing cathode exhibited a shorter cycle life and decreased charging stability. On the other hand, functionalization with boron-containing groups showed promise with minimized parasitic products and enhanced cell efficiency, resulting in a cycle life of 70 cycles.
ELECTROCHIMICA ACTA
(2023)
Article
Electrochemistry
Sona Valiyaveettil-SobhanRaj, Marina Enterria, Rosalia Cid, Damien Saurel, Gene Medard Nolis, Florencia Marchini, Travis Thompson, Frederic Aguesse, Montse Casas-Cabanas
Summary: One of the main challenges in oxide-based solid-state batteries is the densification of components to improve interfacial contact. The common method of co-sintering at high temperatures often leads to element inter-diffusion and degradation of cathode performance. This study evaluates the impact of different carbon grades on thermal response and chemical compatibility, showing that low surface area carbons are more suitable due to higher oxidation temperatures and lower reactivity.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
Article
Nanoscience & Nanotechnology
Pierre Ranque, Nicola Boaretto, Haritz Perez-Furundarena, Hugo Arrou-Vignod, Kerman Gomez Castresana, Francisco Javier Bonilla, Rosaliaa Cid, Juan Miguel Lopez del Amo, Michel Armand, Shanmukaraj Devaraj
Summary: Li metal secondary batteries are highly anticipated energy storage systems, but their instability with common Li-ion battery electrolytes can be alleviated by using a polymer electrolyte. Current trends focus on improving ionic conductivity, mechanical stability, and electrochemical stability. This study presents a multifunctional polysalt synthesized from sustainable materials, which shows high compatibility with Li metal and quasi-single-ion conducting property, making it suitable for high-voltage Li metal anode polymer batteries.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Pedram Ghorbanzade, Arianna Pesce, Kerman Gomez, Grazia Accardo, Shanmukaraj Devaraj, Pedro Lopez-Aranguren, Juan Miguel Lopez del Amo
Summary: In this study, the chemical evolution and phase transitions of LLZO during heat treatment were investigated using solid state NMR, Raman, and XRD diffraction techniques. The results showed that the activation energy for Li jumps decreased after heat treatment, indicating improved Li dynamics. Furthermore, the pretreatment of powders was found to be an effective method for obtaining garnet-rich composite electrolytes with better flexibility and garnet-polymer interphases, enhancing the prospects of this material for processing.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
A. G. Sabato, M. Nunez Eroles, S. Anelli, C. D. Sierra, J. C. Gonzalez-Rosillo, M. Torrell, A. Pesce, G. Accardo, M. Casas-Cabanas, P. Lopez-Aranguren, A. Morata, A. Tarancon
Summary: Additive manufacturing techniques with advanced functional materials are gaining attention in the field of all solid-state lithium batteries (ASSBs) for their potential to produce cheaper, safer, and customizable batteries with high energy density. This study explores the use of stereolithography (SLA) to fabricate complex-shaped Li1.5Al0.5Ge1.5P3O12 (LAGP) full-ceramic electrolytes. The printed electrolytes demonstrated comparable ionic conductivity to conventionally fabricated LAGP. Additionally, 3D printed LAGP membranes with increased interfacial area showed reduced area specific resistance. Symmetrical cells with LAGP printed electrolytes coated with a germanium protective interlayer exhibited stable cycling performance. This innovative approach opens up new possibilities for manufacturing full ceramic electrolytes with complex shapes for the next generation of ASSBs based on LAGP.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Electrochemistry
Ines Escher, Annica I. I. Freytag, Juan Miguel Lopez del Amo, Philipp Adelhelm
Summary: The possibility of co-intercalating sodium ions and glymes in graphite for use in sodium-ion batteries as negative electrode material needs further clarification regarding the storage mechanism and local interactions. Experiments using solid-state NMR provide insights into the storage mechanism depending on the state of charge and electrolyte solvent used, as well as information on sodium ion transport in the graphitic lattice. The inferior cycling performance of triglyme compared to diglyme and pentaglyme is reflected in the ss-NMR spectra, showing reduced mobility and stronger interactions between sodium ions, triglyme, and graphite.
BATTERIES & SUPERCAPS
(2023)
Article
Chemistry, Physical
Nahom Enkubahri Asres, Naiara Etxebarria, Iciar Monterrubio, Damien Saurel, Christian Fink Elkjaer, Montse Casas-Cabanas, Marine Reynaud, Marcus Fehse, Juan Miguel Lopez del Amo
Summary: In this study, Li-6, Li-7 solid state nuclear magnetic resonance (ssNMR) is used to characterize local disorder in LiNi0.5Mn1.5O4 spinel cathodes and understand their implications for the phase transformation mechanism during electrochemical cycling. The study demonstrates the high sensitivity of ssNMR in detecting transition metal order and disorder induced by stoichiometric variations. It also investigates the lithiation reaction mechanism of non-stoichiometric LNMO spinel cathode using Li-7 NMR and suggests that stoichiometrically induced transition metal disorder promotes a mixed solid solution and biphasic reaction mechanism.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Physical
Pierre L. Stigliano, Nagore Ortiz-Vitoriano, Lidia Medinilla, Jason E. Bara, Juan Miguel Lopez del Amo, Luis Lezama, Maria Forsyth, David Mecerreyes, Cristina Pozo-Gonzalo
Summary: This study investigates the use of a branched ether solvent, 1,2,3-trimethoxypropane (TMP), as an alternative electrolyte for sodium-air batteries (SABs). The addition of a co-solvent, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpyr][TFSI]), effectively limits the reactivity of TMP with sodium metal. The new cell design with a Na-beta-alumina disk for anode protection improves cell performance and achieves high discharge capacities. The findings highlight the potential of TMP as a base solvent and the importance of careful electrolyte composition design for greener and less toxic batteries.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Brigette Althea Fortuin, Jon Otegi, Juan Miguel Lopez del Amo, Sergio Rodriguez Pena, Leire Meabe, Hegoi Manzano, Maria Martinez-Ibanez, Javier Carrasco
Summary: Model validation is used to predict the ionic structure and dynamics of alternative alkali metal ions in solid polymer electrolytes. A comprehensive study based on molecular dynamics is conducted to understand the ion coordination and transport properties. This approach can be extended to predict the performance of different alkali metal-based solid polymer electrolytes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
