Article
Chemistry, Multidisciplinary
Ruixue Bai, Zhaoming Zhang, Weishuai Di, Xue Yang, Jun Zhao, Hao Ouyang, Guoquan Liu, Xinhai Zhang, Lin Cheng, Yi Cao, Wei Yu, Xuzhou Yan
Summary: A new type of mechanically stable [2]catenane materials were synthesized by controlling the force-bearing points on the metal-coordinated core. This study not only deepens our understanding on the structure-property relationship of poly[2]catenanes, but also provides a guiding principle for the fabrication of high-performance mechanically interlocked catenane materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hajime Iwamoto, Yuki Ishizu, Eietsu Hasegawa, Ryo Sekiya, Takeharu Haino
Summary: N-sulfonylated [3]catenanes, existing as two translational isomers, were synthesized. The X-ray crystal structure of the distal isomer revealed hydrogen bonds involving carboxylic acid moieties, which influenced the isomerization process as indicated by the thermodynamic parameters.
CHEMICAL COMMUNICATIONS
(2021)
Article
Polymer Science
Shilong Wu, Huanhuan Yang, Quan Chen
Summary: Molecular theories for dynamics of entangled polymers are based on the number of Kuhn segments per entanglement and the number of entanglements per chain. Linear viscoelasticity can be properly normalized, but normalization fails in the nonlinear extensional rheological properties. This study identifies a suitable model system with fixed parameters and finds that the degree of transient strain hardening during extensional flow increases with alkyl group size, attributed to weaker friction reduction when the main backbones are more separated.
Article
Chemistry, Multidisciplinary
Hirotake Yato, Kota Oto, Akinori Takasu, Masahiro Higuchi
Summary: By using NHCtBu as catalyst, the polymerization of ethyl sorbate can be achieved, and after complete monomer consumption, a second addition of monomer can result in the formation of a polycatenane structure.
Article
Mechanics
Lilian Lin, Young Lee, Heon E. Park
Summary: Biodegradable plastics, despite their potential in reducing plastic pollution, are not widely recycled due to their ability to decompose. It is important to develop recyclable biodegradable plastics. A study on cutlery made of PLA and talc revealed that while recycling may reduce mechanical strength, it has minimal impact on the product.
Article
Chemistry, Multidisciplinary
Andrei S. Baluna, Albano Galan, David A. . Leigh, Gareth D. Smith, Justin T. J. Spence, Daniel J. Tetlow, Inigo J. Vitorica-Yrezabal, Min Zhang
Summary: We repeated the earliest claimed catenane synthesis reported by Wasserman over 60 years ago to investigate the formation of mechanically interlocked rings through a nontemplate, statistical synthesis. Using modern synthetic methods, we reconstructed Wasserman's deuterium-labeled macrocycle and other building blocks on a scale necessary to generate approximately 1 mg of catenane. We employed advanced spectroscopic and chemical techniques to detect, isolate, and prove the structure of a putative [2]catenane consisting of a 34-membered cyclic hydrocarbon mechanically linked with a 34-membered cyclic alpha-hydroxyketone.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Ceramics
O. N. Koroleva, V. A. Bychinsky, A. A. Tupitcyn
Summary: This study utilized a Gibbs energy minimisation approach to investigate silicate melts of various systems and compositions, including single and mixed alkali systems. The correspondence of the developed models with actual systems was verified by comparing the results with experimental data, establishing the limits of their applicability.
JOURNAL OF NON-CRYSTALLINE SOLIDS
(2021)
Article
Materials Science, Ceramics
Sun Yong Kwon, Reghan J. Hill, In-Ho Jung
Summary: A general multi-ion diffusion model for liquid slag in silicate melts was developed by combining tracer diffusivities of ions and chemical potentials from thermodynamic database. The model successfully simulated liquid-junction diffusion and dissolution of solid particles in the system. It can be expanded to multicomponent systems for applications in various high temperature processes.
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Gui-Yuan Wu, Hong-Juan Zhu, Fang-Fang Pan, Xiao-Wei Sheng, Ming-Rui Zhang, Xianyi Zhang, Guangxin Yao, Hang Qu, Zhou Lu
Summary: Transition metal-mediated templating and self-assembly have been utilized to construct bimetallic [3]catenane and [4]catenane molecules, characterized by NMR, mass spectrometry, and theoretical calculations. Additionally, the formation of tubular structures through stacking of individual [3]catenane molecules driven by strong pi-pi interactions was observed.
FRONTIERS IN CHEMISTRY
(2021)
Article
Chemistry, Physical
M. K. Glagolev, A. A. Glagoleva, V. V. Vasilevskaya
Summary: Through molecular dynamics simulation, the process of microphase separation in diblock helix-coil copolymer melts was studied. The resulting microstructures were examined, showing differences in the helix-coil copolymers compared to classic coil-coil copolymer blends.
Article
Polymer Science
Naoki Ando, Shuntaro Uenuma, Hideaki Yokoyama, Kohzo Ito
Summary: In this study, we investigated the disassembly mechanism of a pseudo-polyrotaxane nanosheet (PPRNS) upon heating. The results showed that the PPRNS exhibited structural changes in two temperature ranges due to the anisotropy of the topological constraint.
Article
Biochemistry & Molecular Biology
Katarzyna Biniek-Antosiak, Magdalena Bejger, Joanna Sliwiak, Daniel Baranowski, Ahmed S. A. Mohammed, Dmitri I. I. Svergun, Wojciech Rypniewski
Summary: Chitin degradation involves the important step of deacetylation. The analysis of a deacetylase from the extremophile Pyrococcus chitonophagus reveals that it is a hexameric, zinc-containing metalloenzyme with high structural stability and specific catalytic activity. This study provides important insights into the enzymatic mechanism of chitin degradation.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Geochemistry & Geophysics
Weiran Li, Fidel Costa, Clive Oppenheimer, Kazuhide Nagashima
Summary: Apatite can incorporate volatile and trace elements, providing important information about pre-eruptive processes in magma. This study presents a comprehensive dataset for the partitioning of volatiles and trace elements between fluorapatite and phonolitic melts, and proposes a lattice-strain model for estimating these partitioning relations under different conditions. The study also develops a new oxybarometer and reveals the reequilibration of hydrogen in melt inclusions, which has implications for magma properties and volcanic behavior. Furthermore, the findings have broad applications in the study of magma differentiation and ore formation involving fluorapatite.
CONTRIBUTIONS TO MINERALOGY AND PETROLOGY
(2023)
Article
Polymer Science
Panagiotis A. Klonos, Lazaros Papadopoulos, Maria Kasimatis, Hermis Iatrou, Apostolos Kyritsis, Dimitrios N. Bikiaris
Summary: In this study, five poly(n-alkylene succinate)s were synthesized via multi-step polycondensation methods and investigated from the perspectives of structure, crystallinity, and molecular mobility. Lower n values were found to result in stronger structure/crystal memory and higher crystalline fraction, while the polymer chain length directly affected the nucleation rate. The molecular dynamics mapping of these polyesters revealed accelerated segmental dynamics with increasing n and reduced cooperativity, with spatial confinement imposed on the amorphous polymer by distributed crystallites as n increased. These findings suggest potential for tuning final polymer properties related to crystallization for future biomedical, packaging, and other applications.
Article
Crystallography
Chang Liu, Jinglong Liang, Hui Li, Hongyan Yan, Sijia Zheng, Weigang Cao, Le Wang
Summary: The electrochemical reduction process of ZnFe2O4 in NaCl-CaCl2 melts is studied, showing that Fe3+ and Zn2+ are reduced in different steps. Higher temperature facilitates the diffusion of oxygen ions and increases the deoxidation rate, while the gradual increase of voltage impacts the reduction process of ZnFe2O4.
Correction
Polymer Science
James H. Lettow, Richard Y. Kaplan, Paul F. Nealey, Stuart J. Rowan
Editorial Material
Chemistry, Multidisciplinary
Krishna N. Ganesh, Marc Hillmyer, David Kaplan, Sebastien Lecommandoux, Jodie L. Lutkenhaus, Stuart Rowan, Kirk Schanze, Shu Wang, Deqing Zhang
Article
Chemistry, Multidisciplinary
Adarsh Suresh, Stuart J. Rowan, Chong Liu
Summary: Manufacturing low-density-high-strength carbon foams can benefit various industries. This study presents a method to create macroscale carbon foams with exceptional dimensional stability by pyrolysis of template-coating pairs. The resulting carbon foams exhibit remarkable dimensional stability and high specific strengths.
ADVANCED MATERIALS
(2023)
Editorial Material
Polymer Science
Stuart J. Rowan
Article
Chemistry, Multidisciplinary
Alex E. Crolais, Neil D. Dolinski, Nicholas R. Boynton, Julia M. Radhakrishnan, Scott A. Snyder, Stuart J. Rowan
Summary: A new series of catalyst-free, room-temperature dynamic thia-Michael acceptors bearing an isoxazolone motif were developed and utilized to access both dynamic covalent networks and linear polymers. By leveraging the generation of aromaticity upon thiol addition and tuning the electronic-withdrawing/donating nature of the acceptor at two different sites, a wide range of equilibrium constants were obtained. Integration into a ditopic isoxazolone-based Michael acceptor allowed access to both bulk dynamic networks and linear polymers with tailored thermomechanical properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Laura F. Hart, William R. Lenart, Jerald E. Hertzog, Jongwon Oh, Wilson R. Turner, Joseph M. Dennis, Stuart J. Rowan
Summary: Crosslinking in polymer networks leads to brittle materials, but using mobile crosslinks in mechanically interlocked polymers (MIPs) can result in tougher networks. This study explores the use of a metal ion-templated doubly threaded pseudo[3]-rotaxane (P3R) crosslinker to create slide-ring polycatenane networks (SR-PCNs) that combine the mobility features of SRNs and PCNs. Varying the ratio of P3R and covalent crosslinker allowed the researchers to create SR-PCNs with different amounts of interlocked crosslinking units. The mechanical properties of the networks were studied, showing that the metal ions fix the rings in the network and that the removal of the metal ions leads to increased relaxation and poroelastic draining.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Hongbo Feng, Chang-Geun Chae, Christopher Eom, Gordon S. W. Craig, Stuart J. Rowan, Paul F. Nealey
Summary: Modification of a block copolymer using click chemistry has been shown to effectively control the properties of the copolymer. This study focuses on the modification of a glycidyl methacrylate block with amine-epoxy click chemistry to generate a series of block-random copolymers. The dependence of the effective interaction parameter and surface energy difference on the ratio of the more polar amine is determined, and a lamellae-forming copolymer with sub-10 nm features and zero surface energy difference is demonstrated. Different morphologies can be achieved by adjusting the ratio of the polar amine using this method.
Article
Chemistry, Multidisciplinary
Chuqiao Chen, Michael van der Naald, Abhinendra Singh, Neil D. Dolinski, Grayson L. Jackson, Heinrich M. Jaeger, Stuart J. Rowan, Juan J. de Pablo
Summary: Suspensions of polymeric nano-and microparticles are fascinating stress-responsive material systems that display a diverse range of flow properties under shear. This study focuses on suspensions of micrometer-sized polymeric particles with accessible glass transition temperatures (Tg) and demonstrates that a dramatic and nonmonotonic change in shear thickening occurs as the suspensions transition through the particles' Tg. This strategy enables the in situ tuning of the system's ability to shear jam by varying the temperature relative to Tg and lays the groundwork for other types of stimuli-responsive jamming systems through polymer chemistry.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Hongbo Feng, Benjamin Kash, Soonmin Yim, Kushal Bagchi, Gordon S. W. Craig, Wen Chen, Stuart J. Rowan, Paul F. Nealey
Summary: By synthesizing block copolymers and random copolymers with specific composition ratios, two distinct wetting behaviors were demonstrated and explained.
Article
Polymer Science
Charlie A. Lindberg, Elina Ghimire, Chuqiao Chen, Sean Lee, Neil D. Dolinski, Joseph M. Dennis, Sihong Wang, Juan J. de Pablo, Stuart J. Rowan
Summary: Dynamic liquid crystal elastomers (LCEs) are polymer networks that combine liquid crystalline monomers and dynamic covalent bonds. The placement of the dynamic bonds within the network can be adjusted to tune stress relaxation times without affecting the characteristics of the LCEs.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Hojin Kim, Mike van der Naald, Neil D. Dolinski, Stuart J. Rowan, Heinrich M. Jaeger
Summary: Frictional network formation is a new paradigm for understanding non-Newtonian shear-thickening behavior in dense suspensions. This study investigates a friction that arises from dynamic chemical bridging of functionalized particle surfaces, leading to tunable rheopexy. By using thiol-functionalized particles suspended in ditopic polymers, dynamic covalent bonds can be formed through chemical reactions, resulting in sticky friction that mimics physical friction but is tunable.
Article
Chemistry, Organic
Jerald E. Hertzog, Guancen Liu, Benjamin W. Rawe, Vincent J. Maddi, Laura F. Hart, Jongwon Oh, Neil D. Dolinski, Stuart J. Rowan
Summary: Synthesizing stable doubly threaded [3]rotaxanes with large rings is a key challenge in interlocked chemistry. In this study, a series of doubly threaded [3]rotaxanes with different macrocycle sizes and stopper groups were synthesized and their kinetic stability was examined. The results show that the ring size greatly affects the stability of the rotaxanes, and the smaller stopper group has limited stabilizing effect. These findings lay the foundation for the synthesis of higher order doubly threaded interlocked architectures.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Marissa M. Tranquilli, Benjamin W. Rawe, Guancen Liu, Stuart J. Rowan
Summary: The main-chain poly[n]catenane, resembling a macroscopic chain-link structure, was synthesized using a metallosupramolecular polymer (MSP) template. Closure of the thread components resulted in a mixture of cyclic, linear, and branched poly[n]catenanes. The study investigated the effect of the thread-like monomer structure on the poly[n]catenane synthesis and demonstrated the selective synthesis of branched poly[n]catenanes by tailoring the monomer structure.
Review
Chemistry, Multidisciplinary
Guancen Liu, Phillip M. Rauscher, Benjamin W. Rawe, Marissa M. Tranquilli, Stuart J. Rowan
Summary: This article discusses the key factors of chemical composition and architecture that control the physical and material properties of polymers, with a specific focus on the unique structures of polycatenanes, their synthesis, properties, and simulation studies. Recent developments in the field are highlighted.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Jerald E. Hertzog, Vincent J. Maddi, Laura F. Hart, Benjamin W. Rawe, Phillip M. Rauscher, Katie M. Herbert, Eric P. Bruckner, Juan J. de Pablo, Stuart J. Rowan
Summary: Ring size is crucial for unique molecular motions in interlocked molecules. This study successfully synthesized doubly threaded [3]rotaxanes using a large macrocycle, demonstrating high yields via metal templating. The stopper group nature plays a critical role in accessing metastable rotaxanes with controllable degradation rates.