Pyridine Isomer Effects in the Framework of Phase‐Separated Vitrimer‐Like Materials Operated with Trans‐N‐Alkylation Bond Exchange of Quaternized Pyridines DOI Open Access

Maho Suzuki,

Mikihiro Hayashi

Macromolecular Chemistry and Physics, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Abstract Pyridine groups are known to form various types of bonds, including hydrogen, ionic, and coordination bonds. Another distinctive feature pyridine is the presence structural isomers. The effects isomers have been investigated, particularly for ortho‐ para‐ substituted pyridines, in relation their bond formation abilities interaction energies, which ultimately influence macroscopic physical properties. In this study, on quaternization bonds newly explored, based original design vitrimer‐like materials. polymer component a poly(acrylate) random copolymer containing , meta‐ side groups, cross‐linked by diiodo molecules through quaternized pyridines self‐aggregate into nano‐domains, exchange occurs via trans‐ N ‐alkylation an inter‐domain manner. differences related properties samples with three distinct isomers, creep stress relaxation behaviors materials investigated. Overall, study offers new insights isomer provides fresh perspective tuning bond‐exchangeable

Language: Английский

Structural Rheology in the Development and Study of Complex Polymer Materials DOI Open Access
Sergey O. Ilyin

Polymers, Journal Year: 2024, Volume and Issue: 16(17), P. 2458 - 2458

Published: Aug. 29, 2024

The progress in polymer science and nanotechnology yields new colloidal macromolecular objects their combinations, which can be defined as complex materials. complexity may include a complicated composition architecture of chains, specific intermolecular interactions, an unusual phase behavior, structure multi-component polymer-containing material. Determination relation between the material, properties its constituent elements, rheological material whole is subject structural rheology—a valuable tool for development study novel This work summarizes author’s structural–rheological studies materials determining conditions rheo-manifestations micro- nanostructuring. chemical chains role structuring via block segregation cooperative hydrogen bonds melt solutions considered using tri- multiblock styrene/isoprene vinyl acetate/vinyl alcohol copolymers. Specific molecular interactions are analyzed cellulose; acetate butyrate; gelatin/carrageenan combination; different acrylonitrile, oxadiazole, benzimidazole A homogeneous result from conformational transition, mesophase formation, or association caused by chain inter- supramolecular which, however, masked entanglements when behavior. heterogeneous formation implies microscopic separation upon non-solvent addition, temperature change, intense shear up to macroscopic decomposition. polymer/particle have been examined polyethylene oxide solutions, polyisobutylene melts, cellulose gels containing solid particles nature, demonstrating competition entanglements, interparticle adsorption governing properties. Complex has long-chain branched polybutylene-adipate-terephthalate cross-linked sodium hyaluronate hydrogels, asphaltene linear/highly-branched polydimethylsiloxane blends, showing that branching raises viscosity elasticity limited miscibility with linear isomonomer chains. Finally, some examples composite adhesives, membranes, greases structured polymeric functional presented demonstration performance

Language: Английский

Citations

16
Thermoswitchable catalysis to inhibit and promote plastic flow in vitrimers DOI Creative Commons
Filip Van Lijsebetten, Stephan Maes, Johan M. Winne

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(19), P. 7061 - 7071

Published: Jan. 1, 2024

Acid-base catalysis is a common strategy to induce covalent bond exchanges in dynamic polymer networks. Strong acids or strong bases can promote rapid network rearrangements, and are simultaneously preferred catalysts for chemical reactions where maximum efficiency at the lowest possible temperature aimed for. However, within context of networks, incorporation highly active negatively affect longer term application potential. Network dynamicity diminish through catalyst ageing quenching may prematurely activate exchanges, leading dimensional instability thus low creep resistance Herein, we present several examples explicitly explored weak (carboxylic acids) as using vinylogous urethanes (VU) well-understood protic acid catalysed vitrimer chemistry. Surprisingly, have found that sought-after long-term stability offered by does not necessarily bring lower activity high temperature. In fact, show remarkable thermoswitchable catalytic behaviour, going from an inactive hydrogen bonded state matrix protonated, with profound impact on reactivity rheology. Carboxylic different electronic steric environments clear trends their fine-tuning resulted most thermally responsive VU vitrimers studied date. Our findings point out choice design only poorly informed performance more traditional (in solvent), tailored holds great promise field vitrimers.

Language: Английский

Citations

10
Dynamic crosslinking of thermoplastics via perfluorophenyl nitrene C–H insertion to form recyclable thermosets DOI

Zhi Yuan Lee,

Sirin Kamarulzaman,

Rizqullah Rasyiddin

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102479 - 102479

Published: March 1, 2025

Language: Английский

Citations

2
Molecular Simulation of Covalent Adaptable Networks and Vitrimers: A Review DOI Open Access
Argyrios Karatrantos, Olivier Couture,

Channya Hesse

et al.

Polymers, Journal Year: 2024, Volume and Issue: 16(10), P. 1373 - 1373

Published: May 11, 2024

Covalent adaptable networks and vitrimers are novel polymers with dynamic reversible bond exchange reactions for crosslinks, enabling them to modulate their properties between those of thermoplastics thermosets. They have been gathering interest as materials recycling self-healing properties. In this review, we discuss different molecular simulation efforts that used over the last decade investigate understand nanoscale behaviors covalent vitrimers. particular, dynamics, Monte Carlo, a hybrid dynamics Carlo approaches model reaction, which is main mechanism since it controls both mechanical rheological behaviors. The techniques presented yield sufficient results structure well responses such networks. benefits each method highlighted. use other tools theoretical models machine learning has included. We noticed, amongst most prominent results, stress relaxes reaction happens, at temperatures higher than glass transition temperature, better more BERs observed. lifetime crosslinks follows, moderate high temperatures, an Arrhenius-like temperature dependence. note modeling certain like melt viscosity topology freezing according behavior ruled by either Williams–Landel–Ferry equation or Arrhenius equation. Discrepancies in dissociative associative discussed. conclude stating material parameters atomistic factors, nanoscale, not yet taken into account lacking current literature.

Language: Английский

Citations

8
Temperature-Dependent Fracture Toughness of Epoxy Vitrimers DOI

Yuxiang Sun,

Xudong Wang, Yi Zhao

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Vitrimer, a class of covalent dynamic networks, is promising for polymeric applications requiring reshaping, recycling, and self-healing. The bonds in vitrimer can be reversibly broken reformed under thermal actuation. This work investigates the effects temperature on fracture toughness soft epoxy vitrimers. We measured above topology freezing temperature. Elevated temperatures reduce both stretch toughness, while they linearly increase modulus. Given invariant cross-linking density, dependence attributed to sensitivity bond-exchange reactions. extend Lake–Thomas theory by incorporating kinetic bond scission elucidate such Unlike conventional elastomers with threshold decreased at elevated temperatures, our indicates continuous decrease until approximating zero value, aligning unique viscous behavior

Language: Английский

Citations

1
Microstructure and Viscoelasticity of Oppositely Charged Ionomer Blend Melts DOI Creative Commons

Chia-Chi Tsai,

Jie Xu, Cassie Duclos

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

Language: Английский

Citations

1
Epoxy-Based Vitrimers for Sustainable Infrastructure: Emphasizing Recycling and Self-Healing Properties DOI Open Access

Myung Kue Lee,

Min Ook Kim,

T. Clive Lee

et al.

Polymers, Journal Year: 2025, Volume and Issue: 17(3), P. 373 - 373

Published: Jan. 30, 2025

Epoxy-based vitrimers represent a paradigm shift in material science, offering an unprecedented combination of mechanical robustness, environmental sustainability, and reconfigurability. These dynamic polymer systems utilize associative covalent bonds (DCBs) such as transesterification to blend the structural integrity thermosets with recyclability self-healing properties thermoplastics. This unique makes ideal candidates for high-performance applications industries civil engineering, where durability, repairability, compatibility are critical. vitrimers, particular, exhibit exceptional capabilities, allowing them autonomously repair microcracks damage, restoring under appropriate stimuli heat or light. Their further aligns global sustainability goals by reducing waste lifecycle costs. Recent advancements have also integrated bio-based feedstocks scalable manufacturing methods, enhancing feasibility these materials industrial applications. review explores underlying mechanisms, recycling processes, emerging role epoxy-based engineering. Challenges related scalability, optimization, regulatory acceptance discussed, focus on their potential drive sustainable innovation infrastructure materials.

Language: Английский

Citations

1
Molecularly Engineered Artificial Solid Electrolyte Interphase with Tailored Lithiophilicity and Solvent‐Phobicity for Stable Lithium Metal Batteries DOI Open Access

Yeong Hun Jeong,

Gwangbin Won,

Seunghyeon Kim

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 16, 2025

Lithium (Li) metal is recognized as a promising anode material for rechargeable batteries primarily due to its high specific capacity and energy density. However, major challenge persists in uncontrolled Li electrodeposition irregular solid electrolyte interphase (SEI) formation during cycling, leading premature cell failure safety hazards. Herein, an artificial SEI presented with tailored lithiophilicity solvent-phobicity address these critical issues. As model system the SEI, series of polyethyleneimine (PEI) substituted by 1,2-epoxyhexane (EH) (PEI-EH) introduced, consisting lithiophilic, nitrogen-rich PEI, which promotes ion solvation regulates uniform flux. The abundant amine groups PEI are partially solvent-phobic hexyl reduce swelling prevent solvent decomposition. By systematically modulating physical properties PEI-EH, including polarity mechanical characteristics, optimized protective layer that effectively suppresses dendrite growth identified. This study highlights importance molecular engineering design SEIs achieving dendrite-free, long-lasting batteries.

Language: Английский

Citations

1
Inflammation modulates lymph node biomechanics in a sex-dependent manner DOI Creative Commons

Ann Ramirez,

Vedanth Sriram,

Yassmin Abbouchi

et al.

bioRxiv (Cold Spring Harbor Laboratory), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Lymph nodes are highly specialized immune organs that orchestrate the adaptive response. In lymph nodes, naïve B and T lymphocytes encounter cognate antigens, sparking their activation response to foreign substances. grow in an challenge, at least part accommodate increased numbers of infiltrating proliferating lymphocytes. This behavior is supported by a robust three-dimensional network extracellular matrix (ECM) fibers fibroblastic reticular cells (FRCs). ECM FRCs work synergistically alternate stretching contractile forces between them allowing node maintain structural integrity during rapid tissue reconstruction. These changes ultimately alter material properties node, which can impact cell migration, proliferation, differentiation. Recent has investigated physiological implications changing microenvironment; however, biophysical these remain largely unexplored. Here, we use multiple particle tracking microrheology (MPT), minimally invasive nanoparticle-based technique investigate (elastic/loss moduli, microviscosity, pore size) post inflammatory stimulus. Our results highlight mechanical both initial phases acute upon resolution inflammation, topic relatively understudied. We show rich areas restructure independently, with zones remodeling significantly exhibiting nearly 3-fold higher elastic modulus. Additionally, for first time, biological sex modulates biomechanics inflammation: from female mice showed ∼20-fold increase loss moduli peak while male had ∼5-fold decrease moduli. appeared permanently remodel inflammation resulting maintenance overall modulus, returned untreated nodes. also found some biomechanical were correlated materials suggesting structure-function relationship. Overall, our studies provide key insights into how altered previously unstudied area, lay foundation relationships involved demonstrate analysis interstitial they vary stimuli.

Language: Английский

Citations

1
Linear Viscoelasticity of Polystyrene Vitrimers: Segmental Motions and the Slow Arrhenius Process DOI
Daniel Barzycki, Dana Ezzeddine, Sachin Shanbhag

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: April 4, 2025

Language: Английский

Citations

1