Article
Chemistry, Organic
Lei Pan, Macy M. Deckert, Maria Victoria Cooke, Annika R. Bleeke, Sebastien Laulhe
Summary: We have successfully synthesized aryl boronic esters and aryl phosphonate esters using visible-light as a promoter, without the presence of transition metals or photoredox catalysts. This transformation occurs at room temperature with sodium hydride as a nonnucleophilic base and displays functional group tolerance for anilines, amides, and esters. UV-vis spectroscopy, radical trapping experiments, and computational (TD-DFT) calculations support the hypothesis of an electron-donor-acceptor (EDA) complex formed between solvent anions and aryl halides as the key species responsible for the reaction.
Article
Energy & Fuels
Pawanpreet Kaur, Harish Kumar Chopra
Summary: Supported ionic liquids (SILs), immobilized ILs onto solid support materials, have shown advantages over pure ILs in various applications. In this study, new SILs were synthesized by immobilizing S-alkyl/aryl-substituted 2-mercaptobenzothiazolium-based ILs onto MCM-41 silica support. The synthesized SILs were characterized, and their performance in removing sulfur-containing aromatic species from gasoline was investigated. MCM-41@[S-BzBTh][Cl] showed excellent sulfur removal efficiency from model gasoline.
Article
Chemistry, Medicinal
Nishad Thamban Chandrika, Emily K. Dennis, Katelyn R. Brubaker, Stefan Kwiatkowski, David S. Watt, Sylvie Garneau-Tsodikova
Summary: Fluorinated aryl- and heteroaryl-substituted monohydrazones demonstrate excellent broad-spectrum activity against various fungal strains, including clinically relevant Candida auris strains. These compounds exhibit fungicidal activity with low hemolysis and no mammalian cell cytotoxicity, prevent biofilm formation, and do not induce resistance in C. auris over multiple passages.
Article
Chemistry, Organic
Clement Gommenginger, Yongxiang Zheng, Daniele Maccarone, Ilaria Ciofini, Laurence Miesch
Summary: Upon treatment with TBAF, CF3-substituted N-allenamides were transformed into γ-sultams. Addition of acetic acid to the ammonium salt yielded cyclic sulfonamides bearing an ene-gem-difluorinated tether, while TBAF alone provided the corresponding trifluorinated ethyl sultams. A combined experimental and computational mechanistic study suggested that this transformation involves a 5-endo-dig cyclization on the ene-ynamide generated in situ.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Polymer Science
Karl M. Mukeba, Ketki E. Shelar, Behzad Faradizaji, Eugene B. Caldona, Charles U. Pittman, Dennis W. Smith
Summary: Perfluorocyclohexene (PFCH) undergoes step-growth polymerization and copolymerization with variable sulfone and polyaromatic containing bisphenols in the presence of triethyl amine under mild conditions affording a new class of semi-fluorinated poly(aryl ether sulfone)s. The copolymers exhibit tough, creaseable films with high transparency and variable refractive indices. The PFCH vinylene ether groups provide controllable branch sites and can be further functionalized or cross-linked.
Article
Chemistry, Multidisciplinary
Jun Zhang, Zhanying Chen, Yan Zhang, Shengyi Dong, Yufang Chen, Shiguo Zhang
Summary: By introducing alkoxy moieties into poly(ionic liquid)s, highly efficient adhesives with strong hydrogen bonding interactions can be designed, exhibiting excellent adhesive properties on various substrates. Furthermore, photosensitive or electronically conductive composite adhesives can be fabricated by utilizing the compatibility between ionic liquids and carbon nanotubes or silver nanofibers.
ADVANCED MATERIALS
(2021)
Article
Chemistry, Physical
Christopher M. Burba, Kylie Feightner, Ming Liu, Ayman Hawari
Summary: The synthesis and properties of Solvate ionic liquids (SIL) depend on delicate interactions between cations, solvents, and anions. Fluorinated solvents have different charge distributions and impact SIL. This study found that partially substituting solvent TEG leads to a decrease in ionic conductivity and an increase in ionically-bound species. Additionally, the competition between FTEG and TEG for coordinating Li+ ions enhances conductivity.
Article
Polymer Science
Zhaoyang Wang, Bo Jiang, Yunhe Zhang, Xuefeng Li, Yongpeng Wang, Yingshuang Shang, Haibo Zhang
Summary: In this study, a series of cross-linked fluorinated poly(aryl ether)s films were prepared and their thermal, mechanical, and dielectric properties were compared. The polymeric films showed remarkable dielectric properties with a low dielectric constant and dissipation factor. These films also demonstrated excellent mechanical properties and performed well at high frequencies. The results suggest that these polymeric films have great potential for applications in high-speed communication.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
M. Trinidad Martin, Mario Marin, Celia Maya, Auxiliadora Prieto, M. Carmen Nicasio
Summary: This study describes a new Ni-catalyzed C-S cross-coupling reaction that efficiently couples a wide range of (hetero)aryl halides, including challenging aryl chlorides, with various aromatic and aliphatic thiols. Additionally, it was found that aryl and alkenyl tosylates can also serve as competent electrophilic partners in the reaction.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Swati J. N. Dixit, Sajeev Chacko, Biswajit Manna, Neeraj Agarwal
Summary: In this work, perylene diimide (PDI)-based materials with different aryl substituents were synthesized to understand the electron transfer dynamics. The effect of solvents on the electronic properties was studied, and CBZ-N-Ph-PDI showed significant solvent-dependent behavior. Ultrafast dynamics studies revealed fast electron transfer only in CBZ-N-Ph-PDI. DFT calculations and photophysical data confirmed the possibility of intramolecular electron transfer in CBZ-N-Ph-PDI.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Multidisciplinary
Ali Monfared, Gholamhossein Khalili
Summary: A facile synthesis method for the preparation of 1,3-difunctionalized 2-sulfonamidopropane derivatives is described, which involves the reaction of N-(2,3-dibromopropyl)-aryl(alkyl)sulfonamide with substituted thiourea or oxime derivatives in the presence of MeONa without a catalyst.
MONATSHEFTE FUR CHEMIE
(2023)
Article
Biochemistry & Molecular Biology
Ainka T. Brown, Nadale K. Downer-Riley
Summary: 2-Substituted benzo- and naphthothiazoles have been efficiently synthesized using mild conditions and non-toxic reagents. The reactions exhibit good yields, making them suitable for large-scale preparations.
Article
Polymer Science
Qingze Jiao, Na Li, Pei Zhang, Shanshan Wang, Yun Zhao, Caihong Feng, Yuzhen Lv
Summary: A novel bisphenol monomer was synthesized and used to prepare two aromatic poly(aryl ether ketone)s. These polymers exhibit high thermal stability, improved solubility, and low dielectric constants, making them suitable for various applications including telecommunications.
POLYMER SCIENCE SERIES B
(2021)
Article
Polymer Science
Da-lin Dong, Yue-zhen Bing, Xi-gao Jiang
Summary: The preparation of fluorine-substituted poly(aryl ether ketone) at low temperature is significant in both scientific research and industrial production. The introduction of fluorine atoms can optimize the properties of the polymer, but also affects its molecular structure and thermal properties. Fluorine-substituted poly(aryl ether ketone) has potential for further functionalization.
ACTA POLYMERICA SINICA
(2022)
Article
Polymer Science
Yung-Chung Chen, Yu-Yang Su, Sheng-Chieh Lin
Summary: A series of fluorinated aromatic poly(ether imide)s (PEIs) with bulky fluorene bis(ether anhydride) and various fluorinated diamines were synthesized. The resulting PEIs showed good solubility in organic solvents and exhibited colorless and transparent films with excellent thermal stability and mechanical properties. Moreover, the fluorinated PEIs had low dielectric constant and water uptake, making them promising candidates for high-performance films.
IRANIAN POLYMER JOURNAL
(2023)
Article
Electrochemistry
Ryoichi Tatara, Yosuke Ugata, Shuhei Miyazaki, Natsuki Kishida, Shohei Sasagawa, Kazuhide Ueno, Seiji Tsuzuki, Masayoshi Watanabe, Kaoru Dokko
Summary: Highly concentrated Li salt/aprotic solvent solutions have potential as electrolytes for next-generation batteries. This study investigated the phase behavior, solvate structures, and Li+ transport properties of binary mixtures containing lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and various sul-fones. It was found that the [LiTFSA]/[sulfone] = 1/2 mixtures, except for the MSL system, remained in a liquid state at room temperature, allowing for a systematic comparison of Li+ transport properties in highly concentrated electrolytes. The results showed that sulfone solvents with compact molecular sizes and low energy barriers of conformational change are favorable for enhancing Li+ ion transport in the electrolytes.
Article
Chemistry, Multidisciplinary
Zachary T. Gossage, Nanako Ito, Tomooki Hosaka, Ryoichi Tatara, Shinichi Komaba
Summary: This study provides a deeper understanding of the solid-electrolyte interphase (SEI) that occurs in highly concentrated water-insalt electrolytes (WISEs). The research shows that SEI in aqueous batteries exhibits similar passivating structures and slow electron transfer rates to that found in lithium-ion batteries. Additionally, the properties of SEI change when the electrolyte becomes more concentrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Alayna M. Johnson, Jeremiah A. Johnson
Summary: Bifunctional silyl ether (BSE)-containing high-density polyethylene (HDPE)-like materials have been synthesized under mild polymerization and hydrogenation conditions. Both the concentration of BSEs in the polymer chain and the silicon steric bulk can be tuned to yield materials with HDPE-like thermomechanical properties. The materials undergo two distinct deconstruction pathways and can be recycled without compromising their mechanical strength.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Electrochemistry
Yuki Fujii, Ryoichi Tatara, Daisuke Igarashi, Tomooki Hosaka, Rena Takaishi, Eisuke Shiiyama, Takashi Matsuyama, Shinichi Komaba
Summary: In this study, the diluted-electrode method is used to estimate the sodium-ion insertion kinetics of a hard carbon electrode. By adding inert nickel particles to dilute the hard carbon powder electrode, the concentration of hard carbon can be adjusted while maintaining the composite electrode structure. The highly diluted electrode shows a 10 times higher sodium-ion insertion rate compared to the undiluted electrode, attributed to the alleviation of sodium-ion depletion and insignificant concentration polarization under dilute conditions. The study reveals the high inherent kinetics of sodium-ion insertion into hard carbon, providing a basis for the development of high-power sodium-ion batteries.
Article
Chemistry, Physical
Shogo Yamazaki, Ryoichi Tatara, Hironori Mizuta, Kei Kawano, Satoshi Yasuno, Shinichi Komaba
Summary: Silicon is a promising anode material for lithium-ion batteries, but its large volume fluctuation during charge-discharge cycling leads to significant capacity decay. In this study, the cycling performance of silicon-based composite electrodes was investigated under different cutoff voltages, and the degradation of the electrolyte and electrodes was analyzed. The results showed that the consumption of the electrolyte additive, FEC, led to decreased discharge capacity at high delithiation cutoff voltages. Additionally, the presence of Li metal in the cell also contributed to FEC consumption. These findings provide insights into the degradation mechanisms of Si-based electrodes and can guide the development of Si-based electrodes for lithium-ion batteries.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Michael A. Stolberg, Benjamin A. Paren, Pablo A. Leon, Christopher M. Brown, Gavin Winter, Kiarash Gordiz, Alberto Concellon, Rafael Gomez-Bombarelli, Yang Shao-Horn, Jeremiah A. Johnson
Summary: Solid polymer electrolytes have the potential to enable safer and more energy-dense batteries. This study investigates the impact of anion dissociation energy on ion conduction in solid polymer electrolytes. The researchers developed ionenes with various cations and found that the addition of a cation-coordinating solvent greatly enhanced ionic conductivity without disrupting the lamellar structure. This work demonstrates that molecular design can facilitate significant improvements in ion conduction in solid polymer electrolytes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Nanoscience & Nanotechnology
Motohiro Kosugi, Ryoichi Tatara, Yuki Fujii, Shinichi Komaba
Summary: A phenothiazine-based electropolymerized layer deposited on sucrose-derived carbon was utilized to develop a formate (HCOO-) bioanode, which synergistically catalyzed the oxidation of the coenzyme (NADH) and fuel (HCOO-) to achieve efficient electron transfer. The replacement of carbon nanotubes with water-dispersible sucrose-derived carbon as the electrode base allowed the fabrication of a surfactant-free bioanode. The study also demonstrated the potential of formic acid as a fuel and possibilities for the application of carbon materials in bioanodes.
ACS APPLIED BIO MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Tomooki Hosaka, Tatsuo Matsuyama, Ryoichi Tatara, Zachary T. T. Gossage, Shinichi Komaba
Summary: In the pursuit of long-life K-ion batteries, half-cell measurements using highly reactive K metal counter electrodes have been a standard practice. However, electrolyte decomposition by K metal has been found to impact electrode performance. This study systematically explored K metal-treated electrolytes and identified the formation of different decomposition products, which had positive or negative effects on electrode performance.
Article
Polymer Science
Tetsu Ouchi, Wencong Wang, Brooke E. E. Silverstein, Jeremiah A. A. Johnson, Stephen L. L. Craig
Summary: The influence of strand length on deformation and tension in a polymer network was studied using mechanophore force probes. It was found that the critical strain at which measurable mechanochromism is observed is correlated with the strain hardening of the matrix, but independent of the molecular length of the probes. The rate of decoloration during relaxation of the network was found to depend on the relaxing strain, indicating the effect of residual tension on the reversion reaction.
Article
Chemistry, Multidisciplinary
Keith E. L. Husted, Abraham Herzog-Arbeitman, Denise Kleinschmidt, Wenxu Zhang, Zehao Sun, Alyssa J. Fielitz, An N. Le, Mingjiang Zhong, Jeremiah A. Johnson
Summary: Based on experimental results from a library of 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, a versatile backbone-pendant sequence-control strategy is discovered, which provides a simple method for precisely controlling the thermomechanical and morphological properties of graft copolymers. Small structural variations of pendant groups in small-molecule comonomers have significant impacts on various properties of silicone-based graft copolymers, resulting in a wide range of designable materials properties. This study reveals a new pendant-group-mediated self-assembly strategy that simplifies graft copolymer synthesis and enables the development of a diverse family of silicone-based materials with tailored performance specifications.
ACS CENTRAL SCIENCE
(2023)
Article
Materials Science, Multidisciplinary
Shogo Yamazaki, Ryoichi Tatara, Hironori Mizuta, Kei Kawano, Satoshi Yasuno, Shinichi Komaba
Summary: SiO has been extensively studied as a high-capacity negative electrode material for lithium-ion batteries (LIBs), but battery performance degradation caused by volume change hinders its practical application. To mitigate volume change degradation, partially neutralized cross-linked sodium polyacrylate (CLPA) binders were used to fabricate carbon-coated SiO (SiO@C) composite electrodes. New CLPA-based polymers with different amounts of a flexible additive were synthesized to provide flexibility to the SiO composite layer. Maturation treatment improved the electrochemical properties, mechanical properties, and passivation of the SiO@C composite electrodes.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Organic
Landon J. Kilgallon, Yang Shao-Horn, Jeremiah A. Johnson
Summary: A simple and scalable method for synthesizing DMTMSA and other trifluoromethanesulfonamide solvents is described. No specialized glassware is needed, and water is used as the solvent with an ice bath for cooling. The optimized process is highly efficient and reduces waste.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daisuke Igarashi, Ryoichi Tatara, Ryusei Fujimoto, Tomooki Hosaka, Shinichi Komaba
Summary: In this study, the electrochemical insertion and extraction of rubidium ions into and from graphite and carbonaceous materials was achieved. It was found that graphite undergoes a phase transition and forms a stage-1 RbC8 structure in non-aqueous electrolytes. Similar behavior was observed with other alkali metals.
Article
Chemistry, Physical
Daisuke Igarashi, Yoko Tanaka, Kei Kubota, Ryoichi Tatara, Hayato Maejima, Tomooki Hosaka, Shinichi Komaba
Summary: By optimizing the ZnO-template of hard carbon material, capacity and energy density of Na-ion batteries can be improved, and it shows good performance in sodium-ion and potassium-ion storage.
ADVANCED ENERGY MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Daisuke Igarashi, Ryoichi Tatara, Ryusei Fujimoto, Tomooki Hosaka, Shinichi Komaba
Summary: The reversible insertion of rubidium into carbonaceous materials, such as graphite, was achieved in this study. The chemical compositions of rubidiated graphite were determined at each step of the electrochemical reduction process, and it was found that rubidium underwent a phase transition from RbC8 to RbC36, with RbC24 as an intermediate. Rubidium was also found to be reversibly inserted into both graphitizable and non-graphitizable carbons.
