Extremely Robust and Multifunctional Nanocomposite Fibers for Strain‐Unperturbed Textile Electronics

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(15)

Published: Jan. 20, 2023

Textile electronics are needed that can achieve strain-unaltered performance when they undergo irregular and repeated strain deformation. Such textile require advanced fibers simultaneously have high functionalities extreme robustness as fabric materials. Current synthetic nanocomposite based on inorganic matrix remarkable but often suffer from low poor tolerance against crack formation. Here, we present a design for high-performance multifunctional fiber is mechanically electrically robust, which was realized by crosslinking titanium carbide (MXene) nanosheets with slide-ring polyrotaxane to form an internal mechanically-interlocked network. This featured distinct strain-hardening mechanical behavior exceptional load-bearing capability (toughness approaching 60 MJ m-3 ductility over 27%). It retained 100% of its after cyclic loading. Moreover, the electrical conductivity (>1.1 × 105 S m-1 ) electrochemical (>360 F cm-3 be well subjecting extensive (>25% strain) long-term (10 000 cycles) dimensional changes. superior allowed fabrication into various robust wearable devices, such textile-based electromechanical sensors strain-unalterable sensing fiber-shaped supercapacitors invariant 10 loading cycles.

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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Mechanical Stretch α‐Cyclodextrin Pseudopolyrotaxane Elastomer with Reversible Phosphorescence Behavior

Advanced Science, Journal Year: 2024, Volume and Issue: 11(14)

Published: Feb. 4, 2024

Abstract Polyethylene glycol chains in two terminals of the naphthalene functional group are threaded into α‐cyclodextrin cavities to form pseudopolyrotaxane (NPR), which not only effectively induces phosphorescence by cyclodextrin macrocycle confinement, but also provides interfacial hydrogen bonding assembly function between polyhydroxy groups and waterborne polyurethane (WPU) construct elastomers. The introduction NPR endows elastomer with enhanced mechanical properties excellent room temperature phosphorescent (RTP) emission (phosphorescence remains water, acid, alkali, organic solvents, even at 160 °C high temperatures). Especially, reversible mechanically responsive behavior intensity increased three times under 200% strain) can be observed stretch recover process, owing strain‐induced microstructural changes further inhibiting non‐radiative transition vibration NPR. Therefore, changing supramolecular elastomers through stretching a new approach for luminescent materials.

Language: Английский

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Oligo[2]catenane That Is Robust at Both the Microscopic and Macroscopic Scales

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 9011 - 9020

Published: April 13, 2023

Polycatenanes are extremely attractive topological architectures on account of their high degrees conformational freedom and multiple motion patterns the mechanically interlocked macrocycles. However, exploitation these peculiar structural dynamic characteristics to develop robust catenane materials is still a challenging goal. Herein, we synthesize an oligo[2]catenane that showcases properties at both microscopic macroscopic scales. The key feature design controlling force-bearing points metal-coordinated core [2]catenane moiety able maximize energy dissipation via dissociation metal-coordination bonds then activation sequential intramolecular motions circumrotation, translation, elongation under external force. As such, level, single-molecule force spectroscopy measurement exhibits rupture in reaches record 588 ± 233 pN. At our manifests itself as toughest material ever reported (15.2 vs 2.43 MJ/m3). These fundamental findings not only deepen understanding structure-property relationship poly[2]catenanes with full set features but also provide guiding principle fabricate high-performance materials.

Language: Английский

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Photoresponsive Rotaxane-Branched Dendrimers: From Nanoscale Dimension Modulation to Macroscopic Soft Actuators

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14498 - 14509

Published: June 16, 2023

Aiming at the construction of novel soft actuators through amplified motions molecular machines nanoscale, design and synthesis a new family photoresponsive rotaxane-branched dendrimers an efficient controllable divergent approach was successfully realized for first time. In third-generation dendrimers, up to 21 azobenzene-based rotaxane units located each branch, thus making them successful light-control integrated artificial machines. Notably, upon alternative irradiation with UV visible light, photoisomerization azobenzene stoppers leads collective precisely arranged units, resulting in reversible dimension modulation integrating solution. Moreover, macroscopic were further constructed based on these which revealed fast shape transformation behaviors actuating speed 21.2 ± 0.2° s-1 ultraviolet irradiation. More importantly, resultant could produce mechanical work light control that has been employed weight-lifting cargo transporting, laying foundation toward smart materials can perform programmed events.

Language: Английский

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Mechanically interlocked [an]daisy chain networks

Chem, Journal Year: 2023, Volume and Issue: 9(8), P. 2206 - 2221

Published: May 4, 2023

Language: Английский

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Doubly Threaded Slide-Ring Polycatenane Networks

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12315 - 12323

Published: May 25, 2023

Crosslinking in polymer networks leads to intrinsic structural inhomogeneities that result brittle materials. Replacing fixed covalent crosslinks with mobile ones mechanically interlocked polymers (MIPs), such as slide-ring (SRNs) which are formed when chains threaded through crosslinked rings, can lead tougher, more robust networks. An alternative class of MIPs is the polycatenane network (PCN), replaced rings introduce unusual catenane’s mobility elements (elongation, rotation, and twisting) connections between chains. A (SR-PCN), doubly embedded a network, combines features both SRNs PCNs, where catenated ring slide along backbone two limits bonding (covalent interlocked). This work explores using metal ion-templated pseudo[3]rotaxane (P3R) crosslinker, combined crosslinker chain extender, access catalyst-free nitrile-oxide/alkyne cycloaddition polymerization was used vary ratio P3R yield series SR-PCNs amount crosslinking units. Studies on their mechanical properties show ions fix leading similar behavior PEG gels. Removal ion frees resulting high-frequency transition attributed additional relaxation while also increasing rate poroelastic draining at longer timescales.

Language: Английский

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Enhancing the Toughness and Strength of Polymers Using Mechanically Interlocked Hydrogen Bonds

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 1109 - 1121

Published: Dec. 23, 2023

The energy dissipative features of hydrogen bonds under conditions mechanical strain have provided an ongoing incentive to explore bonding units for the purpose controlling and customizing properties polymeric materials. However, there remains a need bond that (1) possess directionality, (2) provide selectivity, (3) dissipate effectively, (4) can be incorporated readily into materials regulate their properties. Here, we report mechanically interlocked incorporate multiple within [2]catenane structure. conformational flexibility associated spatial folding characteristics allow molecular scale motion external stress, while structure serves as pivot maintains directionality selectivity resultant units. When polymers, these motifs serve strengthen toughen resulting This study not only presents novel unit creating with improved but also underscores unique opportunities structures may across diverse range applications.

Language: Английский

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The Green Box: Selenoviologen-Based Tetracationic Cyclophane for Electrochromism, Host–Guest Interactions, and Visible-Light Photocatalysis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 9118 - 9128

Published: April 4, 2023

The novel selenoviologen-based tetracationic cyclophanes (green boxes 3 and 5) with rigid electron-deficient cavities are synthesized via SN2 reactions in two steps. green exhibit good redox properties, narrow energy gaps, strong absorption the visible range (370-470 nm), especially for box 5 containing selenoviologen (SeV2+) units. Meanwhile, femtosecond transient (fs-TA) reveals that have a stabilized dicationic biradical, high efficiency of intramolecular charge transfer (ICT), long-lived separation state due to formation cyclophane structure. Based on excellent photophysical applied electrochromic devices (ECDs) visible-light-driven hydrogen production H2 generation rate (34 μmol/h), turnover number (203), apparent quantum yield (5.33 × 10-2). In addition, host-guest recognitions demonstrated between electron-rich guests (e.g., G1:1-naphthol G2:platinum(II)-tethered naphthalene) MeCN through C-H···π π···π interactions. As one-component system, complexes box⊃G2 successfully visible-light photocatalytic electron (IET) platinum(II) G2 SeV2+ box, which provides simplified system solar conversion.

Language: Английский

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Sacrificial Mechanical Bond is as Effective as a Sacrificial Covalent Bond in Increasing Cross-Linked Polymer Toughness

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23794 - 23801

Published: Oct. 18, 2023

Sacrificial chemical bonds have been used effectively to increase the toughness of elastomers because such dissociate at forces significantly below fracture limit primary load-bearing bonds, thereby dissipating local stress. This approach owes much its success ability adjust threshold force which sacrificial fail desired rate, for example, by selecting either covalent or noncovalent bonds. Here, we report experimental and computational evidence that a mechanical bond, responsible structural integrity rotaxane catenane, increases elastomer's strain, stress, energy as bond comparable mechanochemical dissociation kinetics. We synthesized studied 6 polyacrylates cross-linked difluorenylsuccinonitrile (DFSN), is an established mechanochromic moiety; [2]rotaxane, whose stopper allows wheel dethread on same subsecond time scale DFSN dissociates when under tensile 1.5-2 nN; structurally homologous [2]rotaxane with bulkier stable >5.5 similarly stoppered [3]rotaxanes containing in their axles; control polymer aliphatic nonsacrificial cross-links. Our data suggest dethreading without failure any may be important, hitherto unrecognized, contributor some rotaxane-cross-linked polymers provide mechanism material behavior independently response networks, due distinct relationships between structure reactivity.

Language: Английский

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