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The growing concern regarding widespread plastic pollution has propelled the development of sustainable self-healing plastics. Although considerable efforts have been dedicated to fabricating self-healing plastics, achieving rapid healing at room temperature is extremely challenging. Herein, we have developed an ultra-fast-healing glassy polyurethane (UGPU) by designing a hyperbranched molecular structure with a high density of multiple hydrogen bonds (H-bonds) on compliant acyclic heterochains and introducing trace water to form water bridge across the fractured surfaces. The compliant acyclic heterochains allow the dense multiple hydrogen bonds to form a frozen network, enabling tensile strength of up to 70 MPa and storage modulus of 2.5 GPa. The hyperbranched structure can drive the reorganization of the H-bonding network through the high mobility of the branched chains and terminals, thereby leading to self-healing ability at room temperature. Intriguingly, the presence of trace water vapor facilitates the formation of activated layers and the rearrangement of networks across the fractured UGPU sections, thereby enabling ultra-fast self-healing at room temperature. Consequently, the restored tensile strength after healing for 1 minute achieves a historic-record of 26.4 MPa. Furthermore, the high transparency (>90%) and ultra-fast healing property of UGPU make it an excellent candidate for advanced optical and structural materials.
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Adding small molecular plasticizers is the most common route to tailor the stretchability of poly(vinyl alcohol) (PVA). However, how the plasticization along with the nature of the plasticizer governs the structural homogeneity during stretching remains an open question to answer. Herein, two representative plasticizers, glycerol (GLY) and water, are chosen to endow the PVA films with ductility. It is found that large strain cavitations cause obvious stress whitening in the PVA/H2 O films; on the contrary, most of the PVA/GLY films maintain transparent undergoing tensile deformation. Through a combination of experimental inspections and molecular dynamic simulation, it is revealed that partial water molecules that behave as free water will aggregate into microdomains, which serve as mechanical defects responsible for yielding voids. Whereas, the GLY plasticizer homogeneously disperses at a molecular level and interacts with PVA chains through strong hydrogen bonds. More interestingly, it is illustrated that the dispersion and bound states of plasticizers are closely related to the mechanical character of the plasticized PVA films. These findings offer new insight into the working mechanism of plasticization on the structural stability during stretching, and guide the design of PVA/plasticizer system to obtain excellent comprehensive mechanics.
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Alcohol Polivinílico , Agua , Alcohol Polivinílico/química , Agua/química , Plastificantes/química , Glicerol , Resistencia a la TracciónRESUMEN
BACKGROUND: Amarogentin (AMA) is a secoiridoid glycoside extracted from Swertia and Gentiana roots and exhibits many biological effects such as antioxidative, anti-inflammatory, and antitumor activities. Atopic dermatitis (AD) is a chronic inflammatory skin disease caused by disorders in the regulation of multiple inflammatory cytokines. No effective cure has been found for AD now. METHODS: We constructed the HaCat and splenocyte model and tested the inhibitory effect of AMA on IL-4, IL-6, and IL-13 secretions using enzyme-linked immunosorbent assay (ELISA). The AD mouse model was constructed and treated with AMA, the severity of skin lesions was observed, epidermal tissue was collected, and epidermal thickness and mast cell infiltration were observed using hematoxylin and eosin and toluidine blue staining, respectively. The expression of kallikrein-related peptidase 7 (KLK7) and filaggrin (FLG) was detected using immunostaining and Western blot analysis. The mRNA expression of KLK7 and FLG was detected using quantitative polymerase chain reaction (qPCR). Blood immunoglobulin E (IgE) secretion was detected. RESULTS: AMA inhibited IL-6 secreted by tumor necrosis factor (TNF)-α-induced HaCaT cells and reduced IL-4 and IL-13 secreted by phytohemagglutinin (PHA)-induced primary cells in the mice spleen. It was found that the treatment of AMA with 2,4-dinitrochlorobenzene-induced AD-like mice could promote the recovery of dermatitis, reduce the score of dermatitis severity and the scratching frequency, treat the skin lesions, reduce the epidermal thickness, decrease the infiltration of mast cells, reduce the IgE level in serum, decrease the expression levels of AD-related cytokines, increase protein and mRNA expression of FLG, and reduce the protein and mRNA expression of KLK7 in the skin tissues of AD-like mice. CONCLUSION: In conclusion, AMA inhibits inflammatory response at the cellular level, and AMA reduces the validation response of specific dermatitis mice, relieves pruritus, and repairs the damaged skin barrier.
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Dermatitis Atópica , Animales , Ratones , Humanos , Dermatitis Atópica/inducido químicamente , Dermatitis Atópica/tratamiento farmacológico , Dermatitis Atópica/metabolismo , Dinitroclorobenceno/efectos adversos , Interleucina-13/efectos adversos , Interleucina-6/efectos adversos , Células HaCaT/metabolismo , Células HaCaT/patología , Interleucina-4/efectos adversos , Citocinas/genética , Citocinas/metabolismo , Factor de Necrosis Tumoral alfa/metabolismo , Antiinflamatorios/efectos adversos , Inmunoglobulina E/efectos adversos , ARN Mensajero/efectos adversosRESUMEN
Boron nitride nanosheets (BNNSs) are regarded as promising two-dimensional materials in thermally conductive yet electrically insulating applications. Attributed to the strong interlayer "lip-lip" interactions in bulk hexagonal boron nitride (h-BN), high-efficiency exfoliation and scalable fabrication of BNNSs via the top-down strategies remain formidable challenges. Herein, an interesting observation is manifested that gallium-based liquid metal (LM) forming robust coordination interactions with h-BN helps reduce the lip-lip interlayer interactions and thus facilitates successful exfoliation under intense shearing force. For example, employing the ball-milling technique, the BNNS yield can increase to 41.21% with the assistance of LM at only 2 h milling time. Its exfoliation efficiency (yield/time) reaches as high as 26.72%/h, more than 2-fold that of other previously reported methods, including sonication and other ball-milling methods. Moreover, the exfoliated BNNSs are still found to be highly electrically insulating with a band gap of 4.65 eV, showing prospective potential in thermally conductive yet electrical insulating applications. As a proof of concept, a microwave-transparent heat spreader (cellulose nanofiber/BNNSs) is fabricated and verified for applications in high-frequency thermal-management fields.
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Concentration-dependent phase transitions in concentrated solutions have remained speculation due to the serious impediment of macromolecule dynamics by intensive topological entanglement or intermolecular interaction as well as the absence of powerful tool for detecting changes in chain or segment movement. Herein, taking a general polymer, namely, poly(vinyl alcohol) (PVA), as an example, a water-soluble fluorescent molecule with aggregation-induced emission (AIE) is introduced into the PVA solutions as a chain dynamics indicator to investigate phase transitions at high concentrations through in situ monitoring of the solvent evaporation process. Two turning points of fluorescent intensity are observed for the first time at mean concentrations of â¼25% and â¼45%, corresponding to the gelation and amorphous-to-crystalline transitions, respectively. Our work offers a fundamental insight into the physical nature of concentrate-dependent nonequilibrium transitions and develops a reliable and sensitive approach based on the AIE phenomenon for following high-concentration-triggered property changes of a polymer solution.
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Polímeros , Alcohol Polivinílico , Fluorescencia , Polímeros/química , Alcohol Polivinílico/química , Agua/química , Solventes , ColorantesRESUMEN
Phase change materials (PCMs) are expected to achieve dual-mode thermal management for heating and cooling Li-ion batteries (LIBs) according to real-time thermal conditions, guaranteeing the reliable operation of LIBs in both cold and hot environments. Herein, we report a liquid metal (LM) modified polyethylene glycol/LM/boron nitride PCM, capable of dual-mode thermal managing the LIBs through photothermal effect and passive thermal conduction. Its geometrical conformation and thermal pathways fabricated through ice-template strategy are conformable to the LIB's structure and heat-conduction characteristic. Typically, soft and deformable LMs are modified on the boron nitride surface, serving as thermal bridges to reduce the contact thermal resistance among adjacent fillers to realize high thermal conductivity of 8.8 and 7.6 W m-1 K-1 in the vertical and in-plane directions, respectively. In addition, LM with excellent photothermal performance provides the PCM with efficient battery heating capability if employing a controllable lighting system. As a proof-of-concept, this PCM is manifested to heat battery to an appropriate temperature range in a cold environment and lower the working temperature of the LIBs by more than 10 °C at high charging/discharging rate, opening opportunities for LIBs with durable working performance and evitable risk of thermal runaway.