Mechanically Interlocked Vitrimers

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(2), P. 872 - 882

Published: Dec. 21, 2021

Mechanically interlocked networks (MINs) have emerged as an encouraging platform for the development of mechanically robust yet adaptive materials. However, difficulty in reversibly breaking mechanical bonds poses a real challenge to MINs customizable and sustainable Herein, we couple vitrimer chemistry with structures generate new class MINs─referred vitrimers (MIVs)─to address challenge. Specifically, prepared acetoacetate-decorated [2]rotaxane that undergoes catalyst-free condensation reaction two commercially available multiamine monomers furnish MIVs. Compared control whose wheels are nonslidable under applied force, our MIVs slidable motifs showcase enhanced performance including Young's modulus (18.5 ± 0.9 vs 1.0 0.1 MPa), toughness (3.7 MJ/m3), damping capacity (98% 72%). The structural basis behind unique property profiles is demonstrated be force-induced host-guest dissociation consequential intramolecular sliding along axles. peculiar behaviors represent consecutive energy dissipation mechanism, which provides complement other pathways mainly depend on sacrificial bonds. Moreover, by virtue vinylogous urethanes, impart reprocessability chemical recyclability MINs, thereby empowering reconfiguration without Finally, it disclosed motions [2]rotaxanes could accelerate dynamic exchange urethane via loosening network, suggestive synergistic effect between dual entities.

Language: Английский

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Highly Damping and Self‐Healable Ionic Elastomer from Dynamic Phase Separation of Sticky Fluorinated Polymers

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(10)

Published: Jan. 20, 2023

Shock-induced low-frequency vibration damage is extremely harmful to bionic soft robots and machines that may incur the malfunction of fragile electronic elements. However, current skin-like self-healable ionic elastomers as artificial sensing protecting layer still lack ability dampen vibrations, due their almost opposite design for molecular frictions material's elasticity. Inspired by two-phase structure adipose tissue (the natural damping skin layer), here, a highly elastomer with energy-dissipating nanophases embedded in an elastic matrix introduced, which formed polymerization-induced dynamic phase separation sticky fluorinated copolymers presence lithium salts. Such supramolecular decouples functions into two distinct phases, thus reconciles few intriguing properties including conductivity, high stretchability, softness, strain-stiffening, recovery, room-temperature self-healability, recyclability, most importantly, record-high capacity at human motion frequency range (loss factor tan δ > 1 0.1-50 Hz). This study opens door syntheses high-performance skins robust protective applications electronics robotics.

Language: Английский

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Mechanically interlocked polymers based on rotaxanes

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(16), P. 7046 - 7065

Published: Jan. 1, 2022

The nature of mechanically interlocked molecules (MIMs) has continued to encourage researchers design and construct a variety high-performance materials. Introducing structures into polymers led novel polymeric materials, called (MIPs). Rotaxane-based MIPs are an important class, where the characteristic retains high degree structural freedom mobility their components, such as rotation sliding motions rotaxane units. Therefore, these MIP materials known possess unique set properties, including mechanical robustness, adaptability responsiveness, which endow them with potential applications in many emerging fields, protective intelligent actuators, mechanisorption. In this review, we outline synthetic strategies, structure-property relationships, application explorations various polyrotaxanes, linear polyrotaxane networks, dendrimers.

Language: Английский

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Design of self-healing and self-restoring materials utilizing reversible and movable crosslinks

NPG Asia Materials, Journal Year: 2022, Volume and Issue: 14(1)

Published: Feb. 18, 2022

Abstract Self-healing materials have attracted attention due to their ability regain structure and function after damage. In recent years, significant progress has been made in achieving various functions through supramolecular chemistry. This review describes an overview of the strategies used prepare self-healing self-restoring utilizing reversible movable crosslinks. Reversible crosslinks, consisting noncovalent bonds, can reversibly undergo repeated cleavage reformation. Therefore, be achieved by effectively regenerating crosslinks between polymeric chains. exploit many kinds dynamic covalent bonds such as hydrogen metal coordination ionic interactions, π–π stacking, van der Waals forces, hydrophobic interactions. Movable exhibit properties. Self-restoring original shape mechanical properties a cycle loading unloading external stress. consist polymer chains that penetrate macrocyclic units sliding motion along addition, multiple cross-links produce synergistic effects simultaneously achieve high toughness effective self-healing. We believe will play substantial role realizing sustainable society.

Language: Английский

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Mechanically interlocked networks cross-linked by a molecular necklace

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: March 16, 2022

Molecular necklaces have attracted much research attention due to their unique topological structures. Although numerous molecular with exquisite structures been constructed, it remains a major challenge exploit the functions and applications associated fascinating architectural dynamic characteristics. Herein, we report class of mechanically interlocked networks (MINs) cross-linked by necklace, in which multiple crown ethers are threaded on hexagonal metallacyclic framework furnish cross-linker delicate The necklace possesses peculiar advantages: multivalent interactions rigid metallacycle guarantee robust features MINs while motion dissociation bring notable mechanical adaptivity. Moreover, could respond stimuli K+ Br-, lead dethreading ether even complete decomposition respectively, showing abundant active properties. These findings demonstrate untapped potential as cross-linkers open door extend advanced intelligent supramolecular materials.

Language: Английский

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Strong, Supertough and Self‐Healing Biomimetic Layered Nanocomposites Enabled by Reversible Interfacial Polymer Chain Sliding

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 3, 2023

Despite the remarkable progress in ultrastrong mechanical laminate materials, simultaneous achievement of toughness, stretchability and self-healing properties biomimetic layered nanocomposites remains a great challenge due to intrinsic limitations their hard essences lack effective stress transfer at organic-inorganic fragile boundary. Here, an ultratough nanocomposite is prepared by constructing chain-sliding cross-linking interface between sulfonated graphene nanosheets polyurethane layers based on ring molecules sliding linear polymer chains release stresses. Unlike traditional supramolecular bonding toughening with limited spacing, our strategy enables interfacial molecular reversible slippage when inorganic bear stretching force, providing sufficient interlayer spatial distance for relative dissipate more energy. The resulting laminates exhibit strong strength (22.33 MPa), supertoughness (219.08 MJ m-3 ), ultrahigh (>1900 %) ability (99.7 %), which far surpass most reported synthetic natural materials. Moreover, fabricated proof-of-concept electronic skin shows excellent flexibility, sensitivity healability human physiological signals monitoring. This breaks through that are intrinsically stiff opens up functional application flexible devices.

Language: Английский

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Advanced supramolecular design for direct ink writing of soft materials

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(5), P. 1614 - 1649

Published: Jan. 1, 2023

This review draws connections between top-down direct-ink-writing and bottom-up supramolecular designs. Examples of supramolecularly designed viscoelastic inks perspectives using motifs for 3D printing have been discussed.

Language: Английский

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Mechanically Interlocked Polymers with Dense Mechanical Bonds

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(6), P. 992 - 1006

Published: Feb. 28, 2024

ConspectusMechanically interlocked polymers (MIPs) such as polyrotaxanes and polycatenanes are polymer architectures that incorporate mechanical bonds, which represent a compelling frontier in science. MIPs with cross-linked structures known mechanically networks (MINs) widely utilized materials Leveraging the motion of MINs hold potential for achieving combination robustness dynamicity. Currently, reported predominantly consist discrete bonds cross-linking points, exemplified by well-known slide-ring rotaxane/catenane polymers. The these points facilitates redistribution tension throughout network, effectively preventing stress concentration thereby enhancing material toughness. In instances, impact can be likened to adage "small things make big difference", whereby limited number substantially elevate performance conventional addition there is another type MIN their principal parts chains composed dense bonds. Within MINs, generally serve repeating units, unique properties stem from integrating amplifying function large amount Consequently, tend reflect intrinsic polymers, making exploration critical comprehensive understanding MIPs. Nevertheless, investigations into featuring remain relatively scarce.This Account presents overview our investigation insights First, we delve synthetic strategies employed prepare while critically evaluating advantages limitations. Through meticulous control core interlocking step, three distinct have emerged: followed polymerization, supramolecular polymerization interlocking, dynamic interlocking. Furthermore, underscore structure–property relationships macroscopic originate countless microscopic motions phenomenon define an integration amplification mechanism. Our has revealed detailed characteristics bulk materials, encompassing quantification activation energy, discrimination varying distances, elucidation recovery process. Additionally, elucidated influence on respective materials. Moreover, explored applications leveraging exceptional These include toughness engineering adaptive multifunctional aerogels, mitigating Li protrusion interfacial layers lithium-ion batteries. Finally, offer personal perspectives promises, opportunities, key challenges future development underscoring transformative advancements this burgeoning field.

Language: Английский

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An NIR Discrete Metallacycle Constructed from Perylene Bisimide and Tetraphenylethylene Fluorophores for Imaging‐Guided Cancer Radio‐Chemotherapy

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(7)

Published: Nov. 25, 2021

To promote the clinical theranostic performances of platinum-based anticancer drugs, imaging capability is urgently desired, and their chemotherapeutic efficacy needs to be upgraded. Herein, a metallacycle (M) developed for imaging-guided cancer radio-chemotherapy using perylene bisimide fluorophore (PPy) tetraphenylethylene-based di-Pt(II) organometallic precursor (TPE-Pt) as building blocks. The formation this discrete supramolecular coordination complex facilitates encapsulation M by glutathione (GSH)-responsive amphiphilic block copolymer prepare M-loaded nanoparticles (MNPs). TPE-Pt acts drug also an excellent radiosensitizer, thus incorporating radiotherapy into nanomedicine accelerate therapeutic overcome resistance. NIR-emission PPy employed detect intracellular delivery tissue distribution MNPs in real time. In vitro vivo investigations demonstrate combining chemotherapy radiotherapy; administration effectively inhibits tumor growth greatly extends survival rate cisplatin-resistant A2780CIS-tumor-bearing mice. Guided fluorescence imaging, precisely carried out, which boosting outcomes minimizing undesired side effects. success system brings new hope nanomedicines potential translations.

Language: Английский

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Amplification of integrated microscopic motions of high-density [2]rotaxanes in mechanically interlocked networks

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 4, 2022

Abstract Integrating individual microscopic motion to perform tasks in macroscopic sale is common living organisms. However, developing artificial materials which molecular-level motions could be amplified behave macroscopically still challenging. Herein, we present a class of mechanically interlocked networks (MINs) carrying densely rotaxanated backbones as model system understand mechanical properties stemmed from the integration and amplification intramolecular embedded [2]rotaxane motifs. On one hand, bonds introduces original dangling chains into network, synergy numerous such leads an expansion entire imparting good stretchability puncture resistance MINs. other dissociation host−guest recognition subsequent sliding represent peculiar energy dissipation pathway, whose result bulk with favorable toughness damping capacity. Thereinto, develop continuous stress-relaxation method elucidate units, contributes understanding relationship between cumulative performance.

Language: Английский

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