Article
Materials Science, Multidisciplinary
Ying Hou, Bei Nie
Summary: By in situ synthesis of an AgNO3 complex molecular cage, selective extraction of icosahedral C-60 has been achieved, resulting in exclusive C-60 organometallic microcrystals with a ratio of C-60/C-70 = 6/1. The method utilizes the intrinsic insolubility of C-60 against nonpolar solvents to separate it from homologues like C-70, showcasing decent specificity and efficiency. Structural characterizations and efficiency evaluations demonstrate the feasibility and advantages of this separation technique.
JOURNAL OF MATERIALS SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Samuel P. Jarvis, Hongqian Sang, Filipe Junqueira, Oliver Gordon, Jo E. A. Hodgkinson, Alex Saywell, Philipp Rahe, Salvatore Mamone, Simon Taylor, Adam Sweetman, Jeremy Leaf, David A. Duncan, Tien-Lin Lee, Pardeep K. Thakur, Gabriella Hoffman, Richard J. Whitby, Malcolm H. Levitt, Georg Held, Lev Kantorovich, Philip Moriarty, Robert G. Jones
Summary: The study showed that water (H2O) and hydrogen fluoride (HF) molecules encapsulated inside a C60 cage experience significant internal rotational motion and substantial intra-cage electrostatic interaction. Despite their off-center positions, these molecules do not affect the endofullerene's frontier orbitals.
COMMUNICATIONS CHEMISTRY
(2021)
Article
Engineering, Biomedical
Guanzhao Zhang, Hui Fang, Shuting Chang, Renzeng Chen, Lanlan Li, Danbo Wang, Yamei Liu, Ruyi Sun, Yingjie Zhao, Bo Li
Summary: A water-soluble cube-like supramolecular cage was constructed to encapsulate one fullerene C60 molecule, improving its water-solubility without altering its structure. The cage was effective in reducing reactive oxygen species in cardiomyocytes and demonstrated positive effects on myocardial ischemia-reperfusion injury in a mouse model. This study provides guidance for constructing water-soluble C60 and validates its importance in preventing oxidative stress-related cardiovascular injuries.
MATERIALS TODAY BIO
(2023)
Article
Chemistry, Physical
Aleksander Jaworski, Niklas Hedin
Summary: The study investigates the confinement effects of methane encapsulated in C-60 fullerene, using local energy decomposition analysis to provide insights into intermolecular interactions. The calculated stabilization energy of methane inside the fullerene was significantly higher than its latent heat of evaporation. Vibrational frequencies of the endohedral complex were found to be essentially silent due to the dielectric screening effect of C-60.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Physics, Nuclear
Tsutomu Ohtsuki, Riichi Kuwahara, Kaoru Ohno
Summary: The decay rate of 7Be electron capture in C70 and Be metal was measured and compared. The half-life of 7Be@C70 at room temperature and liquid helium temperature was found to be slightly shorter compared to that of 7Be in Be metal. The difference in the electron wave functions inside C70 and Be metal contributed to this discrepancy.
Article
Chemistry, Physical
E. Kwon, T. Matsukawa, A. Hoshikawa, T. Ishigaki, S. Aoyagi, K. Kawachi, Y. Kasama
Summary: A neutron diffraction study revealed that the nucleus of Li+ in a C60 fullerene is closer to the inner wall of the fullerene cage than the center of its electron density. Additionally, a hyperconjugation interaction was observed between the vacant Li+ orbital and the pi orbitals of the hexagonal moiety of the C60.
CHEMICAL PHYSICS LETTERS
(2022)
Article
Chemistry, Physical
Avik Ghosh, Soumadip Banerjee, Tanay Debnath, Abhijit K. Das
Summary: Mechanistic investigations using Density Functional Theory have revealed the detailed mechanism of the functionalization of three fullerene cages, including different ring fusions and the effect of Li+ encapsulation. The results provide guidance for further research in fullerene chemistry.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
SeyedAbdolreza Sadjadi, Quentin Andrew Parker
Summary: By combining two robust theoretical quantum chemistry calculation techniques, it is shown that highly ionized forms of C-60 fullerene can be achieved up to C-60 (26+) before coulomb explosion of the cage. These highly ionized forms exhibit comparable structural and bonding stability as the neutral fullerene, opening up new avenues for studying complex ion/molecule reactions and fragmentation products. This has implications in the emerging field of astrochemistry, offering additional pathways for spreading carbon throughout the universe.
FULLERENES NANOTUBES AND CARBON NANOSTRUCTURES
(2021)
Article
Chemistry, Physical
Yoji Horii, Hal Suzuki, Yuji Miyazaki, Motohiro Nakano, Shota Hasegawa, Yoshifumi Hashikawa, Yasujiro Murata
Summary: Low-temperature heat capacity analysis of an NO-encapsulated fullerene derivative revealed low-energy reorientational motions and strong magnetic anisotropy of the NO molecule, with only a small number of NO molecules participating. The paramagnetic nature of the NO molecules was confirmed even at 1 K. Ab-initio calculations showed that the magnetic properties of the NO unit are highly dependent on its surroundings, allowing for the estimation of the conformation of the fullerene cage.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
George Razvan Bacanu, Tanzeeha Jafari, Mohamed Aouane, Jyrki Rantaharju, Mark Walkey, Gabriela Hoffman, Anna Shugai, Urmas Nagel, Monica Jimenez-Ruiz, Anthony J. Horsewill, Stephane Rols, Toomas Room, Richard J. Whitby, Malcolm H. Levitt
Summary: This study utilizes terahertz spectroscopy and inelastic neutron scattering to determine the potential energy function for the nonbonded interaction between helium atoms and C-60 fullerene cages. The experimentally derived potential is compared to estimates from quantum chemistry calculations and sums of empirical two-body potentials.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Materials Science, Multidisciplinary
Giovanni Maria Matrone, Elizabeth Gutierrez-Meza, Alex H. Balzer, Aditi Khirbat, Artem Levitsky, Alexander B. Sieval, Gitti. L. Frey, Lee J. Richter, Carlos Silva, Natalie Stingelin
Summary: Polymer-based blend morphology in systems like organic photovoltaics typically deviates from equilibrium, impacting final device performance. By comparing different fullerenes with a specific polymer in blends, phase diagrams can provide insights into optoelectronic processes and structure-property relationships.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Physics, Multidisciplinary
Supriya K. Chaudhuri
Summary: The spectroscopic properties of He atom encapsulated under neutral and charged C-60 fullerene cage are studied here, revealing the influence of the overall charge of the fullerene cage on the properties of the encapsulated He atom.
CANADIAN JOURNAL OF PHYSICS
(2022)
Article
Chemistry, Physical
Tanzeeha Jafari, Anna Shugai, Urmas Nagel, George Razvan Bacanu, Mohamed Aouane, Monica Jimenez-Ruiz, Stephane Rols, Sally Bloodworth, Mark Walkey, Gabriela Hoffman, Richard J. Whitby, Malcolm H. Levitt, Toomas Room
Summary: We used THz and INS spectroscopies to study the interaction between an endohedral noble gas atom and the C-60 molecular cage. The THz absorption spectra of A@C-60 samples (A = Ar, Ne, Kr) were measured in the energy range from 0.6 to 75 meV for temperatures between 5 and 300 K. The INS measurements were carried out at liquid helium temperature in the energy transfer range from 0.78 to 54.6 meV. Using a spherical oscillator model, we showed that the change of the THz spectrum shape with temperature is caused by the anharmonicity of the potential function.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Christian Bengs, Mohamed Sabba, Malcolm H. Levitt
Summary: The Aharonov-Anandan phase is a contribution to the phase acquired by the cyclic evolution of a quantum state, which depends only on the geometric properties of its trajectory. We report the study and exploitation of the Aharonov-Anandan phase in homonuclear spin-1/2 pairs using nuclear magnetic resonance interferometry techniques. We introduce a new method for engineering effective zero-quantum Hamiltonians with an arbitrary phase in the transverse plane and demonstrate its applications in studying the geometric Aharonov-Anandan phase.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Eddy Dib, Svetlana Mintova, Georgi N. Vayssilov, Hristiyan A. Aleksandrov, Marina Carravetta
Summary: By using a combination of symmetry-based recoupling in 29Si NMR, spin dynamics-based simulations, and DFT-based theoretical calculations, we demonstrate how to characterize the 29Si NMR peaks of (Si-O-Si), Bronsted acid sites (Si-OH-Al), and silanols (Si-OH) in nanosized ZSM-5 zeolites. Theoretical calculations and experimental observations reveal significant differences in the chemical shift anisotropy for silicon nuclei close to aluminum (Q(4)(1Al)) compared to those which are not, allowing for clear assignment of Si-29 NMR peaks. The isotropic chemical shift alone cannot differentiate these differences.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Herbert Wakefield, Ilia Kevlishvili, Kelsie E. Wentz, Yunxin Yao, Tatiana B. Kouznetsova, Sophia J. Melvin, Em G. Ambrosius, Abraham Herzog-Arbeitman, Maxime A. Siegler, Jeremiah A. Johnson, Stephen L. Craig, Heather J. Kulik, Rebekka S. Klausen
Summary: The cis- and trans-isomers of a silacycloheptene were selectively synthesized using a silyl dianion, providing a novel method for studying strained cycloalkenes. Quantum chemical calculations and crystallographic signatures confirmed that the trans-isomer is more strained than the cis isomer. The trans-isomer also exhibited unique reactivity in ring-opening metathesis polymerization (ROMP) and showed increased molecular compliance compared to carbon-based analogues.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Johanna Rademacher, Elliott S. Reedy, Fabrizia Negri, Shamim Alom, Richard J. Whitby, Malcolm H. Levitt, Ewen K. Campbell
Summary: Gas-phase electronic spectra of H2O@C-60(+) and D2O@C-60(+) were obtained by one-photon dissociation of weakly bound helium complexes synthesised in a 3 K ion trap. The spectra showed rich structure with absorptions attributed to internal excitation of the encapsulated molecule during the C-60(+) electronic transition. The experimental data were supported by density functional theory calculations using the B3LYP functional and 6-31++G** basis set.
Article
Chemistry, Physical
Matthew E. Potter, Jonas Amsler, Lucas Spiske, Philipp N. Plessow, Theresah Asare, Marina Carravetta, Robert Raja, Paul A. Cox, Felix Studt, Lindsay-Marie Armstrong
Summary: Catalytic transformations are crucial for chemical technologies as we shift towards renewable bio-based systems. The dehydration of short-chain alcohols using solid acid catalysts is of interest to multiple industries. Microporous aluminophosphates, such as SAPO-34 and SAPO-5, show promising potential due to their size matching with alcohols and various framework topologies.
Article
Polymer Science
Haley K. Beech, Jeremiah A. Johnson, Bradley D. Olsen
Summary: Small angle neutron scattering was used to measure the single chain radii of gyration of end-linked polymer gels before and after cross-linking. The prestrain, which is the ratio of the average chain size in a cross-linked network to that of a free chain in solution, increased as gel synthesis concentration decreased near the overlap concentration. Dilute gels with higher loop fractions were found to be spatially homogeneous. The results provide a reference for network theories that rely on prestrain for the calculation of mechanical properties.
Article
Chemistry, Multidisciplinary
Nanami Takiguchi, Shohei Yamazaki, Michihisa Murata, Shintaro Kawano, Motohiro Shizuma, Masahiro Muraoka
Summary: A new method for the synthesis of degenerate [2]rotaxanes with two different amine stations is presented in this study. The addition of trifluoroacetic acid was found to initiate molecular shuttling, as revealed by variable-temperature H-1 NMR and rotating-frame nuclear Overhauser effect correlation spectroscopy experiments. The activation barrier for the motion remained constant even with different amines in the outer station. Conversely, the addition of camphorsulfonic acid caused rotational motion, as demonstrated by synthesizing a new [2]rotaxane without an outer station and examining its molecular behavior in the presence of acid.
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
Biochemical Research Methods
Uluk Rasulov, Anupama Acharya, Marina Carravetta, Guinevere Mathies, Ilya Kuprov
Summary: Response functions of resonant circuits create ringing artefacts if their input changes rapidly. This paper introduces the implementation and benchmarks of recent Lie-group methods that can efficiently simulate and optimize smooth control sequences.
JOURNAL OF MAGNETIC RESONANCE
(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
Chemistry, Physical
Mohamed Aouane, Jeff Armstrong, Mark Walkey, Gabriela Hoffman, George R. Bacanu, Richard J. Whitby, Malcolm H. Levitt, Stephane Rols
Summary: The confining potential of the He-3@C-60 endofullerene, which consists of a He-3 atom trapped inside a C-60 fullerene cage, is investigated using inelastic neutron scattering. The dynamical structure factor S(Q, omega), which provides information on energy and momentum transfers, is measured and simulated using a spherical anharmonic oscillator model, with good agreement between the experimental and simulated data sets.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
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
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)
