Autonomous Supramolecular Interface Self-Healing Monitored by Restoration of UV/Vis Absorption Spectra of Self-Assembled Thiazole Layers

Longevity of complex organic devices critically depends on the supramolecular integrity of the constituting layers and interfaces. Because the latter are soft matter, they can structurally respond to perturbation of their supramolecular structure by relaxing back to a thermodynamically favorable state. To use this response for self-healing of optoelectronically active layers and particularly interfaces, the degraded dyes in these layers need to be exchanged with non-degraded ones. Here, we present a dye layer interfaced between a solid surface and a dye reservoir that autonomously self-heals after photo-degradation of single molecules to restore its optical function. Surface sensitive in situ photothermal deflection spectroscopy reveals that this supramolecular self-healing approach critically depends on the thermodynamic stability of the layer, the chemical change of the dye upon degradation, and the medium dissolving the degraded dye and providing the reservoir dyes. Hence, the interplay of these parameters is key to successfully using this supramolecular self-healing approach to thin layers and interfaces in organic device for increased sustainability of organic optoelectronics and related fields.     

Photomechanics of liquid-crystalline elastomers and other polymers

Muscle is a transducer that can convert chemical energy into mechanical motion. To construct artificial muscles, it is desirable to use soft materials with high mechanical flexibility and durability rather than hard materials such as metals. For effective muscle-like actuation, materials with stratified structures and high molecular orders are necessary. Liquid-crystalline elastomers (LCEs) are superior soft materials that possess both the order of liquid crystals and the elasticity of elastomers (as they contain polymer networks). With the aid of LCEs, it is possible to convert small amounts of external energy into macroscopic amounts of mechanical energy. In this Review, we focus on light as an energy source and describe the recent progress in the area of soft materials that can convert light energy into mechanical energy directly (photomechanical effect), especially the photomechanical effects of LCEs with a view to applications for light-driven LCE actuators.     

The remarkable role of hydrogen bond,halogen, and solvent effect on self-healing supramolecular gel

Self-healing supramolecular gels of low-molecular-weight (LMW) molecules are smart soft materials; however, the development of self-healing LMW gelator is still a challenging task because of the lack of in-depth studies about self-healing mechanisms of LMW gels and the solvent effect on gel properties. Therefore, herein a different perspective was used to study a family of D-gluconic acetal-based gelators with variable structural fragments in 14 different solvents, and a more detailed understanding of self-assembly and self-healing mechanism of supramolecular gels was attained. Based on the critical gelation concentration, phase transition temperature, and rheological data, A8 bearing an amide group in side chain and two chlorine atoms linked to benzene ring was found to be an outstanding gelator, which could form gels with good self-healing ability in a variety of solvents. Interestingly, A8 gel formed in n-BuOH demonstrates high transparency, good mechanical strength, self-supporting behavior, and great self-healing ability from mechanical damage. Based on the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and theoretical calculation analysis, the self-assembly and self-healing mechanisms of A8 gel were proposed, indicating that a combination of hydrogen bonding and halogen effect was responsible for the efficient self-healing behavior of supramolecular gel. Furthermore, the analysis of solvent parameters indicated that the dispersion force of solvent favored gelators to self-assemble, hydrogen bonding donor ability of solvent mainly affected the formation of one-dimensional assembly, and hydrogen bonding receptor ability and polarity of solvent mainly influenced the supramolecular interactions among assemblies, significantly intervening the self-healing ability of gels. Overall, this study provides a new perspective to the understanding of gelator structure–property correlation in solvents and sheds light for future development of self-healing supramolecular gels.     

Supramolecular polymeric hydrogels

The supramolecular crosslinking of polymer chains in water by specific, directional and dynamic non-covalent interactions has led to the development of novel supramolecular polymeric hydrogels. These aqueous polymeric networks constitute an interesting class of soft materials exhibiting attractive properties such as stimuli-responsiveness and self-healing arising from their dynamic behaviour and that are crucial for a wide variety of emerging applications. We present here a critical review summarising the formation of dynamic polymeric networks through specific non-covalent interactions, with a particular emphasis on those systems based on host-guest complex formation, as well as the characterisation of their physical characteristics. Aqueous supramolecular chemistry has unlocked a versatile toolbox for the design and fine-tuning of the material properties of these hydrogels (264 references).     

A Novel Side-Chain Liquid Crystal Elastomer Exhibiting Anomalous Reversible Shape Change

Liquid crystalline elastomers (LCEs) have been actively investigated as stimuli-controlled actuators and soft robots. The basis of these applications is the ability of LCEs to undergo a reversible shape change upon a liquid crystalline (LC)-isotropic phase transition. Herein, we report the synthesis of a novel LCE based on a side-chain liquid crystalline polymer (SCLCP). In contrast to known LCEs, this LCE exhibits a striking anomalous shape change. Subjecting a mechanically stretched monodomain strip to LC-disorder phase transition, both the length and width of the strip contract in isotropic phase, and both elongate in LC phase. This thermally induced behaviour is the result of a subtle interplay between the relaxation of polymer main chain oriented along the stretching direction and the disordering of side-group mesogens oriented perpendicularly to the stretching direction. This finding points out potential design of LCEs of this peculiar type and possible applications to exploit.     

Toughening a Self-Healable Supramolecular Polymer by Ionic Cluster-Enhanced Iron-Carboxylate Complexes

Supramolecular polymers that can heal themselves automatically usually exhibit weakness in mechanical toughness and stretchability. Here we exploit a toughening strategy for a dynamic dry supramolecular network by introducing ionic cluster-enhanced iron-carboxylate complexes. The resulting dry supramolecular network simultaneous exhibits tough mechanical strength, high stretchability, self-healing ability, and processability at room temperature. The excellent performance of these distinct supramolecular polymers is attributed to the hierarchical existence of four types of dynamic combinations in the high-density dry network, including dynamic covalent disulfide bonds, noncovalent H-bonds, iron-carboxylate complexes and ionic clustering interactions. The extremely facile preparation method of this self-healing polymer offers prospects for high-performance low-cost material among others for coatings and wearable devices.     

A Novel Side‐Chain Liquid Crystal Elastomer Exhibiting Anomalous Reversible Shape Change

Liquid crystalline elastomers (LCEs) have been actively investigated as stimuli‐controlled actuators and soft robots. The basis of these applications is the ability of LCEs to undergo a reversible shape change upon a liquid crystalline (LC)‐isotropic phase transition. Herein, we report the synthesis of a novel LCE based on a side‐chain liquid crystalline polymer (SCLCP). In contrast to known LCEs, this LCE exhibits a striking anomalous shape change. Subjecting a mechanically stretched monodomain strip to LC‐disorder phase transition, both the length and width of the strip contract in isotropic phase, and both elongate in LC phase. This thermally induced behaviour is the result of a subtle interplay between the relaxation of polymer main chain oriented along the stretching direction and the disordering of side‐group mesogens oriented perpendicularly to the stretching direction. This finding points out potential design of LCEs of this peculiar type and possible applications to exploit.     

Tough Double Metal-ion Cross-linked Elastomers with Temperature-adaptable Self-healing and Luminescence Properties

Smart materials with a combination of tough solid-like properties, fast self-healing and optical responsiveness are of interests for the development of new soft machines and wearable electronics. In this work, tough physically cross-linked elastomers that show high mechanical strength, intriguing temperature-adaptable self-healing and fluorochromic response properties are designed using aluminum(Al) and fluorescent europium(Eu) ions as cross-linkers. The ionic Al-COOH binding is incorporated to construct the strong polymer network which mainly contributes to the mechanical robustness of the elastomer consisting of two interpenetrated networks. The Eu-iminodiacetate(IDA) coordination is mainly used to build the weaker but more dynamic network which dominate the elasticity, self-healing and luminescence of the elastomer.Moderate Eu~(3+) and Al~(3+) contents give these supramolecular elastomers high toughness. The temperature-sensitive Eu-IDA coordination enables tunable self-healing rate and efficiency along with fast Eu-centered "ON/OFF" switchable red emission. The mechanical, self-healing and luminescence properties of these elastomers can be adjusted by tuning the ratio of the two types of metal ions. This elastomer is potentially applicable for biosensors, wearable optoelectronics and anticounterfeiting materials.     

PREFACE

正We are delighted to present this special-themed issue of the Chinese Journal of Polymer Science(CJPS) devoted to the recent advances in self-healing polymeric materials. Selfhealing has been recognized as one of the most attractive topics for advanced polymers in the past few years, enabling their reworkability, durability and reliability.     

Liquid crystal elastomer actuators: Synthesis,alignment, and applications

Liquid crystal elastomers (LCEs) are a unique class of materials which combine rubber elasticity with the orientational order of liquid crystals. This combination can lead to materials with unique properties such as thermal actuation, anisotropic swelling, and soft elasticity. As such, LCEs are a promising class of materials for applications requiring stimulus response. These unique features and the recent developments of the LCE chemistry and processing will be discussed in this review. First, we emphasize several different synthetic pathways in conjunction with the alignment techniques utilized to obtain monodomain LCEs. We then identify the synthesis and alignment techniques used to synthesis LCE‐based composites. Finally, we discuss how these materials are used as actuators and sensors. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 395–411     

Fluorous tagging of DABCO through halogen bonding: recyclable catalyst for the Morita-Baylis-Hillman reaction

The halogen-bonded adduct between DABCO and two molecules of perfluorooctyl iodide (DABCO·(C(8)F(17)I)(2)) acts as a recyclable organocatalyst for the Morita-Baylis-Hillman reaction. This "supramolecular fluorous catalyst" is readily accessible and can be recovered by simple precipitation/filtration.     

Photoresponsive iodine-bonded liquid crystals based on azopyridine derivatives with a low phase-transition temperature

Halogen bonding interactions in the formation of liquid crystalline phases have been recognised in recent years. Here, we report a novel series of iodine-bonded liquid crystals using 1,2-diiodotetrafluorobenzene (1,2-DITFB) and azopyridine derivatives (AnAzPy), showing a smectic A phase and concurrent photoresponsive behaviour. These were characterised by using a polarising optical microscope, differential scanning calorimetry and UV-vis absorption spectroscopy. The formation of iodine bonding in the complexes was confirmed by X-ray photoelectron spectroscopy and Raman spectroscopy. Importantly, these iodine-bonded complexes demonstrated a low liquid crystal temperature range (30–50°C) among those reported for photoresponsive halogen-bonded liquid crystals. The molar ratio of the iodine-bonded donor and acceptor was 1:1 upon the self-assembly of the supramolecular complex molecule, as indicated by 1D-WAXD experiments of mixed samples of 1,2-DITFB and AnAzPy with different molar ratios. This study offers a new family of photoresponsive halogen-bonded liquid crystals and broadens the potential applications in their associated systems.     

One-Step Manufacturing of Supramolecular Liquid-Crystal Elastomers by Stress-Induced Alignment and Hydrogen Bond Exchange

Liquid-crystal elastomers (LCEs) capable of performing large and reversible deformation in response to an external stimulus are an important class of soft actuators. However, their manufacturing process typically involves a multistep approach that requires harsh conditions. For the very first time, LCEs with customized geometries that can be manufactured by a rapid one-step approach at room temperature are developed. The LCEs are hydrogen bond (H-bond) crosslinked main chain polymers comprising flexible short side chains. Applying a stretching/shear force to the LCE can simultaneously induce mesogen alignment and H-bond exchange, allowing for the formation of well-aligned LCE networks stabilized by H-bonds. Based on this working principle, soft actuators in fibers and 2D/3D objects can be manufactured by mechanical stretching or melt extrusion within a short time (e.g. <1 min). These actuators can perform reversible macroscopic motions with large, controlled deformations up to 38 %. The dynamic nature of H-bonds also provides the actuators with reprocessability and reprogrammability. Thus, this work opens the way for the one-step and custom manufacturing of soft actuators.     

Physical chemistry of supramolecular polymer networks

Supramolecular polymer networks are three-dimensional structures of crosslinked macromolecules connected by transient, non-covalent bonds; they are a fascinating class of soft materials, exhibiting properties such as stimuli-responsiveness, self-healing, and shape-memory. This critical review summarizes the current state of the art in the physical-chemical characterization of supramolecular networks and relates this knowledge to that about classical, covalently jointed and crosslinked networks. We present a separate focus on the formation, the structure, the dynamics, and the mechanics of both permanent chemical and transient supramolecular networks. Particular emphasis is placed on features such as the formation and the effect of network inhomogeneities, the manifestation of the crosslink relaxation dynamics in the macroscopic sample behavior, and the applicability of concepts developed for classical polymer melts, solutions, and networks such as the reptation model and the principle of time-temperature superposition (263 references).     

An Injectable and Antifouling Supramolecular Polymer Hydrogel with Microenvironment-Regulatory Function to Prevent Peritendinous Adhesion and Promote Tendon Repair

The imbalance of extrinsic and intrinsic healing of tendon is thought to be the main cause of peritendinous adhesions. In this work, an injectable supramolecular poly(N-(2-hydroxypropyl) acrylamide) (PHPAm) hydrogel is prepared merely via side chain hydrogen-bonding crosslinks. This PHPAm exhibits good antifouling and self-healing properties. The supramolecular hydrogel simultaneously loaded with Prussian blue (PB) nanoparticles and platelet lysate (PL) is explored as a functional physical barrier, which can significantly resist the adhesion of fibrin and fibroblasts, attenuate the local inflammatory response, and enhance the tenocytes activity, thus balancing extrinsic and intrinsic healing. The PHPAm hydrogel is shown to prevent peritendinous adhesions considerably by inhibiting NF-κB inflammatory pathway and TGF-β1/Smad3-mediated fibrosis pathway, thereby significantly improving tendon repair by releasing bioactive factors to regulate the tenocytes behavior. This work provides a new strategy for developing physical barriers to prevent peritendinous adhesions and promote tissue repair effectively.     

Two-dimensional self-healing hydrogen-bond-based supramolecular polymer film

A monolayer hydrogen-bond-based supramolecular polymer (HSP) film has self-healing properties at the two-dimensional limit after destroyed by tip of atomic force microscopy and it can also modify the SiO₂ dielectric for copper phthalocyanine field effect transistor with improved mobility.     

葫芦[n]脲超分子水凝胶的研究进展

超分子化学的发展一直是众多研究者所关注的一大热点,葫芦[n]脲作为第四代大环主体分子,拓宽了超分子化学领域的发展.水凝胶是一种具有可拉伸性、生物相容性、环境响应性等多种优异性能的软材料.人们充分利用葫芦[n]脲优异的分子识别能力和配位能力,研究出了一系列具有特殊功能的超分子水凝胶材料.本文在结合葫芦[n]脲特点的基础上...     

Supramolecular concepts and new techniques in mechanochemistry: cocrystals, cages, rotaxanes, open metal-organic frameworks

Mechanochemical reactions effected by milling or grinding are an attractive means to conduct chemical reactions dependent on molecular recognition and to systematically explore different modes of molecular self-assembly. The natural relationship between milling mechanochemistry and supramolecular chemistry arises primarily from the ability to avoid bulk solvent, which simultaneously avoids limitations of solution-based chemistry, such as solubility, solvent complexation, or solvolysis, and makes the resulting process highly environmentally friendly. This tutorial review highlights the use of mechanochemistry for the synthesis of supramolecular targets in the solid state, such as molecular hydrogen- or halogen-bonded complexes, molecular and supramolecular cages, open frameworks and interlocked architectures. It is also demonstrated that the molecular self-assembly phenomena that are well-established in solution chemistry, such as reversible binding through covalent or non-covalent bonds, thermodynamic equilibration and structure templating, are also accessible in milling mechanochemistry through recently developed highly efficient methodologies such as liquid-assisted grinding (LAG) or ion- and liquid-assisted grinding (ILAG). Also highlighted are the new opportunities arising from the marriage of concepts of supramolecular and mechanochemical synthesis, including organocatalysis, deracemisation and discovery of new molecular recognition motifs.     

Stimuli-responsive supramolecular polymeric materials

Supramolecular materials, dynamic materials by nature, are defined as materials whose components are bridged via reversible connections and undergo spontaneous and continuous assembly/disassembly processes under specific conditions. On account of the dynamic and reversible nature of noncovalent interactions, supramolecular polymers have the ability to adapt to their environment and possess a wide range of intriguing properties, such as degradability, shape-memory, and self-healing, making them unique candidates for supramolecular materials. In this critical review, we address recent developments in supramolecular polymeric materials, which can respond to appropriate external stimuli at the fundamental level due to the existence of noncovalent interactions of the building blocks.     

Self-healing and shape memory functions exhibited by supramolecular liquid-crystalline networks formed by combination of hydrogen bonding interactions and coordination bonding

We here report a new approach to develop self-healing shape memory supramolecular liquid-crystalline (LC) networks through self-assembly of molecular building blocks via combination of hydrogen bonding and coordination bonding. We have designed and synthesized supramolecular LC polymers and networks based on the complexation of a forklike mesogenic ligand with Ag⁺ ions and carboxylic acids. Unidirectionally aligned fibers and free-standing films forming layered LC nanostructures have been obtained for the supramolecular LC networks. We have found that hybrid supramolecular LC networks formed through metal–ligand interactions and hydrogen bonding exhibit both self-healing properties and shape memory functions, while hydrogen-bonded LC networks only show self-healing properties. The combination of hydrogen bonds and metal–ligand interactions allows the tuning of intermolecular interactions and self-assembled structures, leading to the formation of the dynamic supramolecular LC materials. The new material design presented here has potential for the development of smart LC materials and functional LC membranes with tunable responsiveness.

New supramolecular hybrid liquid-crystalline networks exhibiting self-healing and shape memory properties are developed by self-assembly of small components through hydrogen bonding interactions and coordination bonding.