Fabrication of a MXene-based shape-memory hydrogel and its application in the wound repair of skin.

Wound dressings can generally complete hemostasis and provide temporary protection after skin damage. Herein, a MXene-based hydrogel was prepared from MXene, gelatin, poly(ethylene glycol)diacrylate (PEGDA) and N,N'-methylenebis(acrylamide) (HEAA) to prepare wound-dressing hydrogels for skin repair. HEAA and PEGDA crosslink polymerization formed the first layer of the network. Hydrogen bonds between MXene, PHEAA, and gelatin formed the second layer of the network. To make the hydrogel more suitable for skin repair, the mechanical properties of the hybrid hydrogel were adjusted. The MXene-based hydrogel could recover its original shape in 16 s upon immersion in water or for a few minutes under light irradiation. The obtained hydrogel showed good photothermal properties upon light irradiation (808 nm, 1 W cm-2) for 20 s, and its temperature on the surface could reach 86.4 °C. Due to its good photothermal properties, this MXene-based hydrogel was suitable for skin repair.

Construction of Wash-Resistant Photonic Crystal-Coated Fabrics based on Hydrogen Bonds and a Dynamically Cross-Linking Double-Network Structure.

Structural coloration as the most possible way to realize the ecofriendly dying process for textiles or fabrics has attracted significant attention in the past decades. However, photonic crystals (PCs) are a typical example of materials with structural color usually located on the surface of the fabrics or textiles, which make them not stable when rubbed, bent, or washed due to the weak interaction between the PC coatings and fabrics. Here, double networks were constructed between the PC coatings and the fabrics for the first time via a hydrogen bond by introducing tannic acid (TA) and dynamic cross-linking with 2-formylphenylboronic acid to increase the wash resistance of the structural colored fabrics. On modifying the monodispersed SiO2 nanoparticles, poly(dimethylsiloxane), and the fabrics, the interaction between the PC coatings and the fabrics increased by the formation of double networks. The structural color, wash, and rub resistance of the PC-coated fabrics were systematically studied. The obtained fabrics with the TA content at 0.030% (SiDT30) showed the best wash and rub resistance. The construction of double networks not only improved the wash and rub resistance of PCs but also retained the bright structural color of the PC coatings, facilitating the practical application of structural coloration in the textile industry.

Structurally colored aramid fabric construction and its application as a recyclable photonic catalyst.

Structural colors can be used in fabric coloring due to their bright color and non-fading properties. However, it is still a challenge to construct structural color on high crystallinity, smooth surfaced and yellow colored aramid fabrics. Herein, for the first time, photonic crystals (PCs) with structural color were constructed on aramid fabrics by introducing dopamine to modify aramid fabrics and synthesizing monodisperse high refractive index zinc sulfide nanoparticles (ZnS). The influence of the PC coatings on the structural color, mechanical properties, and thermal stability of the structurally colored aramid fabrics or fibers was further investigated. Moreover, due to the excellent catalytic properties of ZnS and the slow photon effects of PCs, the structurally colored fabrics showed good photocatalytic properties, which will be beneficial in reusing the catalysts, which is crucial to their application in the coloring of fabrics but also facilitates the recycling of waste PC coated aramid fabrics.

Solvent Quality-Mediated Regioselective Modification of Gold Nanorods with Thiol-Terminated Polymers.

Modification of nanorods (NRs) with functional polymer ligands is of great significance to enhance their surface chemistry and prompt their applications in many fields (e.g., photothermal therapy, bioimaging, and catalysis). However, the regioselective modification of AuNRs still remains a great challenge. Herein, we introduce a facile yet versatile strategy to achieve the regioselective modification of AuNRs through a solvent quality-mediated strategy. By employing a poor solvent of the original ligand cetyltrimethylammonium bromide (CTAB) as the medium in the modification, polymer ligands would selectively graft onto the two ends of AuNRs, while polymer ligands would graft onto the entire surface when employing a good solvent. This strategy demonstrates good reproducibility and is applicable to both hydrophilic and hydrophobic polymer ligand modifications. Moreover, by combing our strategy with the preoccupation route, the two ends and sidewall of AuNRs modified by two different polymers form an "ABA"-type building block, which can further self-assemble into well-ordered superstructures. Our finding provides a new opportunity for multifunctionalization of NRs.

Metallosupramolecular Photonic Elastomers with Self-Healing Capability and Angle-Independent Color.

Photonic elastomers that can change colors like a chameleon have shown great promise in various applications. However, it still remains a challenge to produce artificial photonic elastomers with desired optical and mechanical properties. Here, the generation of metallosupramolecular polymer-based photonic elastomers with tunable mechanical strength, angle-independent structural color, and self-healing capability is reported. The photonic elastomers are prepared by incorporating isotropically arranged monodispersed SiO2 nanoparticles within a supramolecular elastomeric matrix based on metal coordination interaction between amino-terminated poly(dimethylsiloxane) and cerium trichloride. The photonic elastomers exhibit angle-independent structural colors, while Young's modulus and elongation at break of the as-formed photonic elastomers reach 0.24 MPa and 150%, respectively. The superior elasticity of photonic elastomers enables their chameleon-skin-like mechanochromic capability. Moreover, the photonic elastomers are capable of healing scratches or cuts to ensure sustainable optical and mechanical properties, which is crucial to their applications in wearable devices, optical coating, and visualized force sensing.

Regulating Block Copolymer Assembly Structures in Emulsion Droplets through Metal Ion Coordination.

In this report, we demonstrate the metal ion coordination-induced morphological transition of block copolymer assemblies under three-dimensional (3D) confinement. Polystyrene- block-poly(4-vinyl pyridine) (PS- b-P4VP) aggregates with various morphologies can be obtained by emulsion-solvent evaporation in the presence of metal ions (e.g., Pb(II) or Fe(III) ions) in the aqueous phase. Due to the coordination interaction between 4VP units and metal ions, the overall shape, internal structure, and surface composition of the particles can be tailored by varying the type and concentration of the metal ions. For example, when Pb(II) ions were employed, morphological transition of the assemblies occurred due to the formation of P4VP-Pb(II) complexes. More interestingly, when Fe(III) ions were added, hydrolysis of Fe(III) caused the reduction of the pH value of the aqueous phase, leading to the protonation of 4VP units. As a result, interfacial instability took place to trigger the splitting of emulsion droplets and then formation of nanosized micelles. Therefore, metal ion coordination is a facile strategy to tune the structure of assemblies under 3D confinement and offers an alternative approach for the design of organic-inorganic hybrid assemblies with well-tunable structures.

Responsive Photonic Hydrogel-Based Colorimetric Sensors for Detection of Aldehydes in Aqueous Solution.

In this work, we present a fast and efficient strategy for the preparation of responsive photonic hydrogels for aldehyde sensing by combining the self-assembly of monodisperse carbon-encapsulated Fe3O4 nanoparticles (NPs) and in situ photopolymerization of polyacrylamide (PAM) hydrogels. The responsive photonic hydrogels exhibit structural color variation after being treated with formaldehyde aqueous solution, which can be attributed to the chemical reaction between the amide groups in the hydrogels and the formaldehyde. We have also shown that the photonic hydrogels can be used to determine the concentration of formaldehyde and to differentiate aldehydes through a facile reflection spectra shift and color change. This study provides a facile strategy for the visualized determination of aldehyde in aqueous solution.

Emulsion Solvent Evaporation-Induced Self-Assembly of Block Copolymers Containing pH-Sensitive Block.

A simple yet efficient method is developed to manipulate the self-assembly of pH-sensitive block copolymers (BCPs) confined in emulsion droplets. Addition of acid induces significant variation in morphological transition (e.g., structure and surface composition changes) of the polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) assemblies, due to the hydrophobic-hydrophilic transition of the pH-sensitive P4VP block via protonation. In the case of pH > pKa(P4VP) (pKa (P4VP) = 4.8), the BCPs can self-assemble into pupa-like particles because of the nearly neutral wetting of PS and P4VP blocks at the oil/water interface. As expected, onion-like particles obtained when pH is slightly lower than pKa(P4VP) (e.g., pH = 3.00), due to the interfacial affinity to the weakly hydrophilic P4VP block. Interestingly, when pH was further decreased to ∼2.5, interfacial instability of the emulsion droplets was observed, and each emulsion droplet generated nanoscale assemblies including vesicles, worm-like and/or spherical micelles rather than a nanostructured microparticle. Furthermore, homopolymer with different molecular weights and addition ratio are employed to adjust the interactions among copolymer blocks. By this means, particles with hierarchical structures can be obtained. Moreover, owing to the kinetically controlled processing, we found that temperature and stirring speed, which can significantly affect the kinetics of the evaporation of organic solvent and the formation of particles, played a key role in the morphology of the assemblies. We believe that manipulation of the property for the aqueous phase is a promising strategy to rationally design and fabricate polymeric assemblies with desirable shapes and internal structures.

Particle-size dependent melt viscosity behavior and the properties of three-arm star polystyrene-Fe3O4 composites.

The melt viscosity of three-arm star polystyrene (S3PS)-Fe(3)O(4) nanoparticle composites was studied by means of rheological measurements. The arm molecular weight (M(a)) of S3PS (or radius gyration) and the particle size of Fe(3)O(4) (radius (R(p)): 3 nm and 44 nm) showed a strong influence on the melt viscosity behavior (at low shear frequencies) of S3PS-Fe(3)O(4) composites. The reinforcement (viscosity increase) was observed in the composites where the M(a) was higher than the M(c) of PS (M(c): the critical molecular weight for chain entanglement). For M(a) < M(c), when the size of Fe(3)O(4) nanoparticles was changed, the melt viscosity of the composites exhibited either plasticization (melt viscosity reduction) or reinforcement. When the content of Fe(3)O(4) was low (1 wt%), the transformation from plasticization to reinforcement behavior could be observed, which strongly depended on the size ratio of the radius of gyration (R(g)) of S3PS to the size of nanoparticles (R(p)). In addition, the magnetic properties and thermal stability of S3PS-Fe(3)O(4) composites were studied.

dependence of melt behavior of star polystyrene/POSS composites on the molecular weight of arm chains.

Rheological behavior of three-arm and six-arm star polystyrene (SPS) with a small amount of polyhedral oligosilsesquioxane (POSS) was studied. Both linear oscillatory frequency sweep and steady state shear results of SPS/POSS composites showed the reduction of melt viscosity in the unentangled SPS matrix and the increase of viscosity in the entangled SPS matrix. In particular, when molecular weight of the arm (Ma) of SPS was smaller than the critical molecular weight for entanglement (Mc) of PS, the melt viscosity of SPS/POSS composites with low content of POSS was lower than that of pure SPS. The abnormal phenomenon of reduced melt viscosity in SPS/POSS composites was in coincidence with the melt viscosity behavior of SPS/C60 composites reported in our previous work ( Soft Matter 2013 , 9 , 6282 - 6290 ), although the diameters of two nanoparticles and their interaction with SPS matrix were different. A possible mechanism behind the melt viscosity behavior was discussed. Furthermore, the time-temperature superposition principle (TTS) was applied in SPS and SPS/POSS composites. The Cox-Merz empirical relationship was verified to be valid for SPS/POSS composites when the content of POSS was low (1 wt %).

Controlled chain-scission of polybutadiene by the Schwartz hydrozirconation.

Controlled chain-scission of polybutadiene (PB), polyisoprene, and poly(styrene-co-butadiene), induced by bis(cyclopentadienyl) zirconium hydrochloride (Cp(2)ZrHCl), was revealed at room temperature. The chain-scission reaction of linear PB was studied by means of GPC, NMR spectroscopy, and MALDI-TOF-MS. It was confirmed that the molecular weights of degraded products were quasi-quantitatively controlled by Cp(2)ZrHCl loading, irrespective of the starting PB, whereas the microstructure of PB chains was crucial to the scission reaction. The hydrozirconation of model molecules indicated that the existence of an internal double bond in compounds with multiple double bonds was essential for chain cleavage. The chain-cleavage mechanism was proposed to involve hydrozirconation of internal double bonds in PB chains and ß-alkyl elimination. Furthermore, metallocene-catalyzed chain-scission by a chain-transfer reaction was developed. It is believed that the reported chain scission offers a promising pathway for end-group functionalization by chain cleavage and presents a new application of Schwartz's reagent.