Exploring the Adaptability of 4D Printed Shape Memory Polymer Featuring Dynamic Covalent Bonds.

4D printing (4DP) of high-performance shape memory polymers (SMPs), particularly using digital light processing (DLP), has garnered intense global attention due to its capability for rapid and high-precision fabrication of complex configurations, meeting diverse application requirements. However, the development of high-performance dynamic shape memory polymers (DSMPs) for DLP printing remains a significant challenge due to the inherent incompatibilities between the photopolymerization process and the curing/polymerization of high-strength polymers. Here, a mechanically robust DSMP compatible is developed with DLP printing, which incorporates dynamic covalent bonds of imine linking polyimide rigid segments, exhibiting remarkable mechanical performance (tensile strength ≈41.7 MPa, modulus ≈1.63 GPa) and thermal stability (Tg ∼ 113 °C, Td ∼ 208 °C). More importantly, benefiting from the solid-state plasticity conferred by dynamic covalent bonds, 4D printed structures demonstrate rapid network adaptiveness, enabling effortless realization of reconfiguration, self-healing, and recycling. Meanwhile, the extensive π-π conjugated structures bestow DSMP with an intrinsic photothermal effect, allowing controllable morphing of the 4D configuration through dual-mode triggering. This work not only greatly enriches the application scope of high-performance personalized configurations but also provides a reliable approach to addressing environmental pollution and energy crises.

Improved Tribological Performance of MOF@MXene/PI under High Temperature.

High-temperature-resistant and self-lubricating polymer composites with long life and high reliability are increasingly indispensable in the aerospace field. Herein, ZIF-67 grown on the MXene lamella was successfully prepared, and ZIF-67@MXene/PI composites with a regular layered structure were obtained by a hot-pressing three-dimensional network aerogel. It was revealed that incorporating ZIF-67@MXene into PI dramatically reduced the friction and abrasion with elevated temperatures. Largely, aerogel walls always paralleled the sliding direction by compressing, providing a significant antifriction effect. More notably, the presence of a vigorous tribofilm composed of a PI matrix and a diamond-type lattice MOF-modified MXene provided rolling and sliding interface friction under high temperatures, simultaneously. In addition, the uniform tribofilm with a thickness of about 200 nm can effectively avoid the direct contact of the friction pair during the sliding process. Hence, the combination of the constructed multiscale nanocomposites and nanostructured tribofilm with outstanding tribological performance endow the material potentially useful in reducing energy consumption, thus addressing the energy wastage problem caused by friction.

Solvent Content Controlling Strategy for Cocrystallizable Polyesters Enables a Stress-Free Two-Way Shape Memory Effect with Wider Service Temperatures.

It is challenging to enhance the stress-free two-way shape memory (stress-free TWSM) effect to obtain a wide range of response temperatures. Herein, a polycaprolactone (PCL)/poly(ω-pentadecalactone) (PPDL) is photocured under UV light irradiation in the solvent of 1,1,2-trichloroethane (TCA), to obtain a series of cross-linked polyesters (CPES). Controlling solvent content (SC) which is removed after the polymerization allows the yielded CPES to perform a regulatable thermodynamic and stress-free TWSM properties. High SC is beneficial to reduce the degree of chain overlap (C/C* ) of PPDL chain segments in the PCL-based CPES network, then causes the cocrystallization of PCL and PPDL and yielding an additional melting-transitions (Tm ). An enhanced stress-free TWSM is obtained in high SC samples (CPES-15-90), reflected in the attainment of a wide range of response temperature, which means a wider service temperature. The enhancement is reflected in higher reversible strain of high SC samples compared with the samples prepared with low SC when varying high trigger temperature (Thigh ). Even at high Thigh , the high SC sample still has reversible strain. Therefore, controlling SC strategy for photocuring copolyester not only provides a new preparation approach for high-performance shape memory (SM) polymers, but also offers new condensed polymer structure to explore.

Strengthening-Durable Trade-Off and Self-Healing, Recyclable Shape Memory Polyurethanes Enabled by Dynamic Boron-Urethane Bonds.

Addressing the demand for integrating strength and durability reinforcement in shape memory polyurethane (SMPU) for diverse applications remains a significant challenge. Here a series of SMPUs with ultra-high strength, self-healing and recyclability, and excellent shape memory properties through introducing dynamic boron-urethane bonds are synthesized. The introducing of boric acid (BA) to polyurethane leading to the formation of dynamic covalent bonds (DCB) boron-urethane, that confer a robust cross-linking structure on the SMPUs led to the formation of ordered stable hydrogen-bonding network within the SMPUs. The flexible crosslinking with DCB represents a novel strategy for balancing the trade-off between strength and durability, with their strengths reaching up to 82.2 MPa while also addressing the issue of durability in prolonged usage through the provision of self-healing and recyclability. The self-healing and recyclability of SMPU are demonstrated through rapid dynamic exchange reaction of boron-urethane bonds, systematically investigated by dynamic mechanical analysis (DMA). This study sheds light on the essential role of such PU with self-healing and recyclability, contributing to the extension of the PU's service life. The findings of this work provide a general strategy for overcoming traditional trade-offs in preparing SMPUs with both high strength and good durability.

A Biocompatible 4D Printing Shape Memory Polymer as Emerging Strategy for Fabrication of Deployable Medical Devices.

The rapid development of 4D printing provides a potential strategy for the fabrication of deployable medical devices (DMD). The minimally invasive surgery to implant the DMD into the body is critical, 4D printing DMD allows the well-defined device to be implanted with a high-compacted shape and transformed into their designed shape to meet the requirement. Herein, a 4D printing tissue engineering material is developed with excellent biocompatibility and shape memory effect based on the photocrosslinked polycaprolactone (PCL). The fast thiol-acrylate click reaction is applied for photocrosslinking of the acrylates capped star polymer (s-PCL-MA) with poly-thiols, that enable the 3D printing for the DMD fabrication. The cell viability, erythrocyte hemolysis, and platelet adhesion results indicate the excellent biocompatibility of the 4D printing polymer, especially the biological subcutaneous implantation results confirm the promote tissue growth and good histocompatibility. A 4D printing stent with deformable shape and recovery at a temperature close to human body temperature demonstrated the potential application as DMD. In addition, the everolimus is loaded to the polymer (ps1-PCL) through host-guest coordination with ß-cyclodextrin as the core of the star polymer, which shows sustained drug release and improved body's inflammatory response.

4D Printing of Shape Memory Vascular Stent Based on ßCD-g-Polycaprolactone.

The 4D-printing technology is applied to fabricate a shape memory peripheral stent with good biocompatibility, which sustains long-term drug release. The star polymer s-PCL is prepared by ring opening polymerization of ε-caprolactone with the -OH of ß-cyclodextrin (ßCD) as initiator, and then the s-PCL is modified with acrylate endgroup which allows the polymerization under UV light to form the crosslinking network c-PCL. Attributed to the feature of the high crosslinked structure and chemical nature of polycaprolactone (PCL) and ßCD, the composite exhibits appropriate tensile strength and sufficient elasticity and bursting pressure, and it is comparable with great saphenous vein in human body. The radial support of the 4D-printed stent is 0.56 ± 0.11 N and is equivalent to that of commercial stent. The cell adhesion and proliferation results show a good biocompatibility of the stent with human umbilical vein endothelial cells. Due to the presence of ßCD, the wettability and biocompatibility of the materials are improved, and the sustained paclitaxel release based on the host-guest complexion shows the potential of the drug-loaded stent for long-term release. This study provides a new strategy to solve the urgent need of small-diameter scaffolds to treat critical limb ischemia.

Activation of HIF-1α and its downstream targets in rat hippocampus after long-term simulated microgravity exposure.

Microgravity has many detrimental impact on brain functions, however the underlying mechanism remain unclear. In present study, 28 days of tail-suspension (30°) was used to simulate microgravity in rats. We showed that oxidative stress in hippocampus was increased after 28 days of simulated microgravity in consideration of the decreased expression of NF-E2-related factor 2 (Nrf2) and the declined activities of total superoxide dismutase (T-SOD), CuZn-SOD, glutathione peroxidase (GSH-PX) and total antioxidant capacity (T-AOC). Using RNA-seq, we further investigated the effect of simulated microgravity on the expression of genes in hippocampus, and 849 genes were found to be differentially expressed. According to pathway analysis, the differentially expressed genes involved in cytoskeleton, metabolism, immunity, transcription regulation, etc. It is interesting to note that the differentially expressed genes were involved in hypoxia-associated pathway. In agreement with this, the expression of hypoxia induced factor-1α (HIF-1α), the master regulator of oxygen homeostasis, was significantly increased. Meanwhile, HIF-2α, a HIF-1α paralog, was elevated compared with the control group. The expression of pyruvate dehydrogenase kinase 1 (PDK1), lactate dehydrogenase A (LDHA) and vascular endothelial growth factor (VEGF), three well-defined downstream targets of HIF-1α, were up-regulated in hippocampus after 28 days of simulated microgravity exposure. Additionally, brain oxygen saturation (SO2) and blood flow analyzed by the tissue oxygen analysis system were also significantly reduced. These findings indicate that simulated microgravity might cause an alteration in oxygen homeostasis, providing novel insight into better understanding of how simulated microgravity affects the function of hippocampus and a new direction to the development of countermeasure for brain dysfunction during spaceflight (actual microgravity).

Familial progressive hyperpigmentation: A family resurvey and ultrastructural skin investigation.

Familial progressive hyperpigmentation (FPH) is an autosomal dominant genodermatosis characterized by hyperpigmented patches that increase in size and number with age. Since its initial description in an African-American family in 1971, only a few cases of FPH have been documented. A three-generation family with FPH in central China has also been reported. Here, we resurveyed that Chinese FPH family for a few unusual features including delayed age of onset and noninvolvement of ocular and oral mucosae. Electron microscopic examination of skin from the proband of the family showed that there were more melanosomes in lesional keratinocytes than in perilesional keratinocytes. Additionally, a large number of nonmembrane-bound melanosome complexes were observed in the keratinocytes of hyperpigmented areas, whereas all of the melanosomes were dispersed in the keratinocytes of normally pigmented areas.

Intramuscular injection of mechano growth factor E domain peptide regulated expression of memory-related sod, miR-134 and miR-125b-3p in rat hippocampus under simulated weightlessness.

OBJECTIVE: To investigate the expression of memory-related antioxidant genes and miRNAs under simulated weightlessness and the regulation of mechano growth factor (MGF) E domain, the peptide preventing nerve damage. RESULTS: Igf-iea and mgf mRNA levels, expression of antioxidant genes sod1 and sod2 and levels of miR-134 and miR-125b-3p increased in rat hippocampus after 14 days tail suspension to simulate weightlessness which was inhibited with intramuscular injection of E domain peptide. Therefore, administration of MGF E domain peptide could reverse increased expressions of memory-related igf-iea, mgf, sod1, sod2, miR-134 and miR-125b-3p in rat hippocampus under simulated weightlessness. CONCLUSIONS: MGF may regulate the redox state and miRNA-targeted NR-CREB signaling, and intramuscular injection may be the alternative administration because of its safety, convenience and ability to pass through the blood brain barrier.

Controllable fabrication of CoNi bimetallic alloy for high-performance electromagnetic wave absorption.

With the coming era of artificial intelligence (AI) dominated by high-tech electronics, developing high-performance microwave absorption materials (MAMs) is imperative to solve the problem of increasing electromagnetic inference and pollution. Herein, a metal-organic framework (MOF)-derived CoNi bimetallic alloy (CoNi/C) with an irregular rod-like structure is prepared by a thermal reduction method. Introducing the CoNi alloy facilitates the balance between conduction loss and polarization loss and forms good impedance matching, leading to excellent microwave absorption performance. Interestingly, the optimization of absorption performance can be further achieved by controllably modulating the molar ratio of Co and Ni (Co2+/Ni2+). As expected, the obtained CoNi/C delivers excellent microwave absorption performance with a minimum reflection loss (RLmin) of -50.80 dB at 10.40 GHz and an effective absorption bandwidth (EAB) of 3.28 GHz (8.91-12.19 GHz) with a filler loading of 50 wt% at 2.0 mm. In addition, the CoNi/C can reach a maximum EAB of 4.77 GHz (12.99-17.76 GHz) at a low thickness of 1.5 mm, spanning nearly the entire Ku band. The CoNi3/C also exhibits an impressive RLmin of -44.84 dB at 3.28 GHz in the S band. This work offers a novel strategy to modulate the magnetic/electric properties of MOF-derived MAMs.

Ultratough Supramolecular Polyurethane Featuring an Interwoven Network with Recyclability, Ideal Self-Healing and Editable Shape Memory Properties.

Developing multifunctional polymers with excellent mechanical properties, outstanding shape memory characteristics, and good self-healing properties is a formidable challenge. Inspired by the woven cross-linking strategy, a series of supramolecular polyurethane (PU) with an interwoven network structure composed of covalent and supramolecular cross-linking nodes have been successfully synthesized by introducing the ureido-pyrimidinone (UPy) motifs into the PU skeleton. The best-performing sample exhibited ultrahigh strength (∼77.2 MPa) and toughness (∼312.7 MJ m-3), along with an ideal self-healing efficiency (up to 90.8% for 6 h) and satisfactory temperature-responsive shape memory effect (shape recovery rates up to 96.9%). Furthermore, it ensured recyclability. These favorable properties are mainly ascribed to the effective dissipation of strain energy due to the disassembly and reconfiguration of supramolecular nodes (i.e., quadruple hydrogen bonds (H-bonds) between UPy units), as well as the covalent cross-linking nodes that maintain the integrity of the polymer network structure. Thus, our work provides a universal strategy that breaks through the traditional contradictions and paves the way for the commercialization of high-performance multifunctional PU elastomers.

Tribological Properties of Polyimide Composites Modified with Diamondoid Metal-Organic Frameworks.

In this work, diamondoid metal-organic frameworks (MOFs) were efficiently prepared by sonochemical synthesis and grown on polyimide (PI), aiming to improve the anti-wear performance of the PI matrix. By introducing MOFs into the PI matrix, the free movement of PI molecular chains were restricted, and its hardness and elastic modulus were improved. It was found that the wear rate of the 3 wt.% MOFs/PI composites was reduced by 72.6% compared to pure PI at a load of 4 N after tribological testing by using a ball-on-disk tribometer. This can be attributed to the excellent load-bearing and shear resistance of the fourfold-interpenetrated diamondoid networks, in which the transition metal elements can favor the formation of transfer films. It is worth noting that the 3 wt.% MOFs/PI composites still exhibited great tribological properties under high loads or high speeds. The findings of the present study indicate that diamondoid metal-organic frameworks can be used as efficient modifiers to enhance the tribological properties of PI.

Tribological and Mechanochemical Properties of Nanoparticle-Filled Polytetrafluoroethylene Composites under Different Loads.

For the tribological properties of nanoparticle-modified PTFE, a more comprehensive study has been conducted, but there is still some room for research on tribology behavior, tribofilm formation and structure evolution of polytetrafluoroethylene (PTFE) filled with α-Al2O3 and SiO2 nanoparticles during sliding against steel counterparts under different loads. At the same time, it establishes the linkage and mechanism between the maintenance of mechanical strength and the tribological application of polymers in service and provides corresponding scientific data and theoretical guidance for the long-lasting application of polymer lubrication materials. It is found that both composites exhibit good wear resistance across the pressure of 1 MPa to 10 MPa, with the α-Al2O3/PTFE composite demonstrating better performance stability compared to the SiO2/PTFE composite. The high wear resistance is attributed to the formation of tribofilms at the friction interface. For the α-Al2O3/PTFE, an island-like tribofilm is formed with a thickness ranging from 100 to 200 nm, while the tribofilm of the SiO2/PTFE composite is thinner, measuring approximately 50 to 100 nm, and manifests a striped pattern. The chemical composition, both at the surface and subsurface levels, as well as the morphology of the tribofilms, were studied using FTIR spectrometry, X-ray photoelectron spectroscopy (XPS), and FIB-TEM. It is found that the difference in thickness and microstructure of the tribofilms for the two composites is mainly due to the tribochemistry of the nanoparticles. The α-Al2O3 nanoparticle plays a "cohesion" role during the formation of the tribofilm, which facilitates the formation of a thicker, more uniform, and stronger adhered tribofilm on the metallic counterpart, making it more robust against higher shear stress.

Zinc gluconate improves atopic dermatitis by modulating CXCL10 release of keratinocytes via PPARα activation.

Atopic dermatitis (AD) is a chronic inflammatory skin condition with complex causes involving immune factors. The presence of essential trace elements that support immune system function can influence the development of this condition. This study investigated how serum trace elements impact the pathogenesis of atopic dermatitis. Upon analyzing serum microelements in AD patients and control subjects, it was observed that patients with AD had notably lower zinc levels. Genomic analysis of AD skin revealed distinct gene expression patterns, specifically the increased expression of CXCL10 in the epidermis. The heightened levels of CXCL10 in AD skin lesions were found to correlate with reduced serum zinc levels. Treatment with zinc gluconate showed reduced chemotactic response and CXCL10 release, suggesting its potential to regulate CXCL10 expression of keratinocytes in AD. The mechanism behind this involved the downregulation of STAT phosphorylation through activating PPARα. In the AD-like dermatitis mouse model, zinc gluconate therapy decreased serum IgE levels, alleviated skin lesion severity, reduced skin thickness, and lowered CXCL10 expression, demonstrating its efficacy in managing AD-like skin conditions. These findings indicate that zinc gluconate can reduce inflammation in keratinocytes by activating PPARα, inhibiting STAT signaling, and decreasing CXCL10 release, thus highlighting its potential as a therapeutic target for AD.

Super-Durable, Tough Shape-Memory Polymeric Materials Woven from Interlocking Rigid-Flexible Chains.

Developing advanced engineering polymers that combine high strength and toughness represents not only a necessary path to excellence but also a major technical challenge. Here for the first time a rigid-flexible interlocking polymer (RFIP) is reported featuring remarkable mechanical properties, consisting of flexible polyurethane (PU) and rigid polyimide (PI) chains cleverly woven together around the copper(I) ions center. By rationally weaving PI, PU chains, and copper(I) ions, RFIP exhibits ultra-high strength (twice that of unwoven polymers, 91.4 ± 3.3 MPa), toughness (448.0 ± 14.2 MJ m-3), fatigue resistance (recoverable after 10 000 cyclic stretches), and shape memory properties. Simulation results and characterization analysis together support the correlation between microstructure and macroscopic features, confirming the greater cohesive energy of the interwoven network and providing insights into strengthening toughening mechanisms. The essence of weaving on the atomic and molecular levels is fused to obtain brilliant and valuable mechanical properties, opening new perspectives in designing robust and stable polymers.

Flexible Cages Enable Robust Supramolecular Elastomers.

Advances in modern industrial technology continue to place stricter demands on engineering polymeric materials, but simultaneously possessing superior strength and toughness remains a daunting challenge. Herein, a pioneering flexible cage-reinforced supramolecular elastomer (CSE) is reported that exhibits superb robustness, tear resistance, anti-fatigue, and shape memory properties, achieved by innovatively introducing organic imide cages (OICs) into supramolecular networks. Intriguingly, extremely small amounts of OICs make the elastomer stronger, significantly improving mechanical strength (85.0 MPa; ≈10-fold increase) and toughness (418.4 MJ m-3; ≈7-fold increase). Significantly, the cooperative effect of gradient hydrogen bonds and OICs is experimentally and theoretically demonstrated as flexible nodes, enabling more robust supramolecular networks. In short, the proposed strengthening strategy of adding flexible cages effectively balances the inherent conflict between material strength and toughness, and the prepared CSEs are anticipated to be served in large-scale devices such as TBMs in the future.

Tribological Behavior of Cotton Fabric/Phenolic Resin Laminated Composites Reinforced with Two-Dimensional Materials.

In this study, cotton fabric-reinforced phenolic resin (CPF) composites were modified by adding four two-dimensional fillers: graphitic carbon nitride (g-C3N4), graphite (Gr), molybdenum disulfide (MoS2), and hexagonal boron nitride (h-BN). The tribological properties of these modified materials were investigated under dry friction and water lubrication conditions. The CPF/Gr composite exhibits significantly better tribological performance than the other three filler-modified CPF composites under dry friction, with a 24% reduction in friction coefficient and a 78% reduction in wear rate compared to the unmodified CPF composite. Under water lubrication conditions, all four fillers did not significantly alter the friction coefficient of the CPF composites. However, except for an excessive amount of Gr, the other three fillers can reduce the wear rate. Particularly in the case of 10% MoS2 content, the wear rate decreased by 56%. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were employed for the analysis of the morphology and composition of the transfer films. Additionally, molecular dynamics (MD) simulations were conducted to investigate the adsorption effects of CPF/Gr and CPF/MoS2 composites on the counterpart surface under both dry friction and water lubrication conditions. The difference in the adsorption capacity of CPF/Gr and CPF/MoS2 composites on the counterpart, as well as the resulting formation of transfer films, accounts for the variation in tribological behavior between CPF/Gr and CPF/MoS2 composites. By combining the lubrication properties of MoS2 and Gr under dry friction and water lubrication conditions and using them as co-fillers, we can achieve a synergistic lubrication effect.

A stretchable, mechanically robust polymer exhibiting shape-memory-assisted self-healing and clustering-triggered emission.

Self-healing and recyclable polymer materials are being developed through extensive investigations on noncovalent bond interactions. However, they typically exhibit inferior mechanical properties. Therefore, the present study is aimed at synthesizing a polyurethane-urea elastomer with excellent mechanical properties and shape-memory-assisted self-healing behavior. In particular, the introduction of coordination and hydrogen bonds into elastomer leads to the optimal elastomer exhibiting good mechanical properties (strength, 76.37 MPa; elongation at break, 839.10%; toughness, 308.63 MJ m-3) owing to the phased energy dissipation mechanism involving various supramolecular interactions. The elastomer also demonstrates shape-memory properties, whereby the shape recovery force that brings damaged surfaces closer and facilitates self-healing. Surprisingly, all specimens exhibite clustering-triggered emission, with cyan fluorescence is observed under ultraviolet light. The strategy reported herein for developing multifunctional materials with good mechanical properties can be leveraged to yield stimulus-responsive polymers and smart seals.

Exosomal miRNAs in autoimmune skin diseases.

Exosomes, bilaterally phospholipid-coated small vesicles, are produced and released by nearly all cells, which comprise diverse biological macromolecules, including proteins, DNA, RNA, and others, that participate in the regulation of their biological functions. An increasing number of studies have revealed that the contents of exosomes, particularly microRNA(miRNA), play a significant role in the pathogenesis of various diseases, including autoimmune skin diseases. MiRNA is a class of single-stranded non-coding RNA molecules that possess approximately 22 nucleotides in length with the capability of binding to the untranslated as well as coding regions of target mRNA to regulate gene expression precisely at the post-transcriptional level. Various exosomal miRNAs have been found to be significantly expressed in some autoimmune skin diseases and involved in the pathogenesis of conditions via regulating the secretion of crucial pathogenic cytokines and the direction of immune cell differentiation. Thus, exosomal miRNAs might be promising biomarkers for monitoring disease progression, relapse and reflection to treatment based on their functions and changes. This review summarized the current studies on exosomal miRNAs in several common autoimmune skin diseases, aiming to dissect the underlying mechanism from a new perspective, seek novel biomarkers for disease monitoring and lay the foundation for developing innovative target therapy in the future.

Mechanically Ultra-Robust Elastomers Integrating Self-Healing and Recycling Properties Enable Information Encryption and Hierarchical Decryption.

Developing high-performance elastomers with distinctive features opens up new vistas and exciting possibilities for information encryption but remains a daunting challenge. To surmount this difficulty, an unprecedented synthetic approach, "modular molecular engineering", was proposed to develop tailor-made advanced elastomers. The customized hydrophobic poly(urea-urethane) (HPUU-R) elastomer perfectly integrated ultrahigh tensile strength (∼75.3 MPa), extraordinary toughness (∼292.5 MJ m-3), satisfactory room-temperature healing, high transparency, puncture-, scratch-, and water-resistance; and miraculously, its 0.20 g film could lift objects over 100 000 times its weight without rupture. Intriguingly, we unexpectedly discovered that the elastomers fluoresce brightly at the optimal excitation wavelength attributed to the "clusterization-triggered emission". Based on the gradient hydrophobicity and fluorescent properties of HPUU-R, a hierarchical information encryption/decryption mode was innovatively established. Using high-performance HPUU-R as a double encryption platform makes the information highly stable and persistent, thus providing a stronger guarantee for the encrypted information. More attractively, given the impressive recyclability and self-healing of HPUU-R, information encryption can be realized by using recycled elastomers, injecting new vitality into green and sustainable development.