Engineering Tough Supramolecular Hydrogels with Structured Micropillars for Tunable Wetting and Adhesion Properties.

Soft-lithography is widely used to fabricate microstructured surfaces on plastics and elastomers for designable physical properties such as wetting and adhesions. However, it remains a big challenge to construct high-aspect-ratio microstructures on the surface of hydrogels due to the difficulty in demolding from the gel with low strength and stiffness. Demonstrated here is the engineering of tough hydrogels by soft-lithography to form well-defined micropillars. The mechanical properties of poly(acrylamide-co-methacrylic acid) hydrogels with dense hydrogen-bond associations severely depend on temperature, with Young's modulus increasing from 8.1 MPa at 15 °C to 821.8 MPa at -30 °C, enabling easy demolding at low temperatures. Arrays of micropillars are maintained on the surface of the gel, and can be used at room temperature when the gel restores soft and stretchable. The hydrogel also exhibits good shape-memory property, favoring tailoring the morphology with a switchable tilt angle of micropillars. Consequently, the hydrogel shows tunable wetting and adhesion properties, as manifested by varying contact angles and adhesion strengths. These surface properties can also be tuned by geometry and arrangement of micropillars. This facile strategy by harnessing tunable viscoelasticity of supramolecular hydrogels should be applicable to other soft materials, and broaden their applications in biomedical and engineering fields.

Network pharmacological investigation into the mechanism of Kaixinsan powder for the treatment of depression.

Kaixinsan powder (KXS), a classic prescription of traditional Chinese Medicine (TCM), is widely used in the treatment of depression, but its mechanism remains unclear. The network pharmacology method was used to constructe the "herb-component-target" network, and elucidated KXS potential mechanisms of action in the treatment of depression. Moreover, molecular docking was applied to valid the important interactions between the ingredients and the target protein. The "herb-component-target" network indicated that the ingredients of Girinimbin, Gomisin B and Asarone, and the protein targets of ESR, AR and NR3C1 mostly contribute to the antidepressant effect of KXS. KEGG pathway analysis highlighted the most significant pathways associated with depression treatment, including neuroactive ligand-receptor interaction pathway, serotonergic synapse pathway, PI3K-Akt signaling pathway and MAPK signaling pathway. Go enrichment analysis indicated that the mechanism of KXS in treating depression was involved in the biological process of GPCR signal transduction, hormone metabolism and nerve cell apoptosis. Moreover, molecular docking results showed that Polygalaxanthone III, Girinimbine and Pachymic acid performed greater binding ability with key antidepressant target 5-HTR. In conclusion, this study preliminarily revealed key active components in KXS, including Gomisin B, Asarone, Ginsenoside Rg1, Polygalaxanthone III and Pachymic acid, could interact with multiple targets (5-HTR, DR, ADRA, AR, ESR, NR3C1) and modulate the activation of multiple pathways (Neuroactive ligand -receptor interaction pathway, serotonergic synapse pathway, PI3K-Akt signaling pathway and MAPK signaling pathway).

Healable, Recyclable, and Multifunctional Soft Electronics Based on Biopolymer Hydrogel and Patterned Liquid Metal.

Recent years have witnessed the rapid development of sustainable materials. Along this line, developing biodegradable or recyclable soft electronics is challenging yet important due to their versatile applications in biomedical devices, soft robots, and wearables. Although some degradable bulk hydrogels are directly used as the soft electronics, the sensing performances are usually limited due to the absence of distributed conducting circuits. Here, sustainable hydrogel-based soft electronics (HSE) are reported that integrate sensing elements and patterned liquid metal (LM) in the gelatin-alginate hybrid hydrogel. The biopolymer hydrogel is transparent, robust, resilient, and recyclable. The HSE is multifunctional; it can sense strain, temperature, heart rate (electrocardiogram), and pH. The strain sensing is sufficiently sensitive to detect a human pulse. In addition, the device serves as a model system for iontophoretic drug delivery by using patterned LM as the soft conductor and electrode. Noncontact detection of nearby objects is also achieved based on electrostatic-field-induced voltage. The LM and biopolymer hydrogel are healable, recyclable, and degradable, favoring sustainable applications and reconstruction of the device with new functions. Such HSE with multiple functions and favorable attributes should open opportunities in next-generation electronic skins and hydrogel machines.

[Occurrence of Atmospheric (Micro)plastics and the Characteristics of the Plastic Associated Biofilms in the Coastal Zone of Dalian in Summer and Autumn].

Microplastics have been considered emerging pollutants that are widely distributed in the water, soil, and atmospheric environment. Compared with the research breadth and depth of microplastics in marine and terrestrial environments, the study of atmospheric microplastics is still in its infancy. At present, there are few studies on microplastics in the atmospheric environment, and the understanding of their pollution characteristics and potential risks remains insufficient. In this study, the occurrence characteristics of atmospheric (micro)plastics were investigated in the coastal zone of Dalian in summer and autumn. The bacterial community structures and functions of plastic-associated biofilms in the coastal zone of Dalian in summer and autumn were also studied. The results of this study showed that the dominant type of atmospheric microplastics in Dalian was fiber, and the main colors of atmospheric microplastics were transparent, blue, and black. The dominant particle size range of the atmospheric microplastics was less than 1 mm, and the polymer compositions were mainly polyethylene terephthalate, cellophane, and ethylene-propylene-diene terpolymer (>90%). Obvious weathering characteristics and biofilm formation could be observed on the surface of atmospheric microplastics. Proteobacteria, Cyanobacteria, and Actinobacteria were the dominant bacterial phyla that colonized on the surface of atmospheric plastic debris in the coastal zone of Dalian in summer and autumn. The results from the prediction of gene function showed that several functional genes that are closely related to human diseases exist in the epiphytic biofilms of atmospheric plastic debris. The results of this study can provide a scientific basis for the environmental and health risk assessment of atmospheric microplastics and their associated biofilms.

Photoregulated Gradient Structure and Programmable Mechanical Performances of Tough Hydrogels with a Hydrogen-Bond Network.

Gradient materials exist widely in natural living organisms, affording fascinating biological and mechanical properties. However, the synthetic gradient hydrogels are usually mechanically weak or only have relatively simple gradient structures. Here, we report on tough nanocomposite hydrogels with designable gradient network structure and mechanical properties by a facile post-photoregulation strategy. Poly(1-vinylimidazole-co-methacrylic acid) hydrogels containing gold nanorods (AuNRs) are in a glassy state and show typical yielding and forced elastic deformation at room temperature. The gel slightly contracts its volume when the temperature is above the glass-transition temperature that results in a collapse of the chain segments and formation of denser intra- and interchain hydrogen bonds. Consequently, the mechanical properties of the gels are enhanced, when the temperature returns to room temperature. The mechanical performances of hydrogels can also be locally tuned by near-infrared light irradiation due to the photothermal effect of AuNRs. Hydrogels with arbitrary two-dimensional gradients can be facilely developed by site-specific photoirradiation. The treated and untreated regions with different stiffness and yielding stress possess construct behaviors in stretching or twisting deformations. A locally reinforced hydrogel with the kirigami structure becomes notch-insensitive and exhibits improved strength and stretchability because the treated regions ahead the cuts have better resistance to crack advancement. These tough hydrogels with programmable gradient structure and mechanics should find applications as structural elements, biological devices, etc.

Photodirected Morphing Structures of Nanocomposite Shape Memory Hydrogel with High Stiffness and Toughness.

Shape memory hydrogels have drawn increasing attention in recent years. Practical applications require these hydrogels to have good mechanical properties as well as contactless stimulations to trigger the shape deformations. Here we report a stiff and tough shape memory hydrogel that can transform to various configurations sequentially by phototriggered site-specific deformations. Response of the shape memory hydrogel to near-infrared (NIR) light irradiation was achieved by incorporating gold nanorods (AuNRs) into the glassy gel matrix of poly(methacrylic acid-co-methacrylamide) without compromising the excellent mechanical properties. Owing to the photothermal effect of the AuNRs, the localized temperature rise led to a dramatic decrease in Young's modulus (from 200 to 2 MPa) of the prestretched hydrogel and bending deformation with a programmable direction and amplitude. More complex three-dimensional configurations can be obtained by multidirectional prestretching and shape memorizing the individual parts of the nanocomposite hydrogel. Furthermore, the AuNRs embedded in the gel were aligned along the prestretching direction, leading to anisotropic plasmon resonance. These photomediated programmable deformations of tough shape memory hydrogels should find applications in the biomedical and engineering fields.

Spin-coating-assisted fabrication of ultrathin physical hydrogel films with high toughness and fast response.

Hydrogel films have promising applications in medical dressings, flexible electronics, etc. However, it is challenging to fabricate ultrathin hydrogel films with high toughness and controllable thickness. Here, we report a facile approach to prepare tough physical hydrogel films by spin-coating of a poly(acrylic acid-co-acrylamide) (P(AAc-co-AAm)) solution and subsequent gelation in FeCl3 solution to form carboxyl-Fe3+ coordination complexes. The thickness of the obtained gel films, ranging from several to hundreds of micrometers, was easily tunable by adjusting the spin conditions and polymer concentration. The thus obtained hydrogel films showed excellent mechanical properties, with tensile breaking strengths of 0.6-14.5 MPa, breaking strains of 140-840%, Young's moduli of 0.1-61.7 MPa, and tearing fracture energies of 300-1300 J m-2. Based on this approach, responsive tough hydrogel films can also be prepared by spin-coating of a poly(acrylic acid-co-N-isopropylacrylamide) (P(AAc-co-NIPAm)) solution. The obtained gel films showed a fast response (<60 s) and a large output force (∼0.2 MPa) triggered by a concentrated saline solution, making them an ideal material in the design of chemomechanical devices. Furthermore, a bilayer hydrogel film was fabricated by two-step spin-coating of P(AAc-co-NIPAm) and P(AAc-co-AAm) solutions, which showed reversible bending deformation under external stimuli. This simple yet effective approach should be applicable to other systems to prepare versatile hydrogel films with tunable thickness and promising applications in diverse areas.

[Mesenchymal stem cells release membrane microparticles in the process of apoptosis].

Though mesenchymal stem cells (MSC) have been clinically used to repair a variety of damaged tissues, the underlying mechanisms remain elusively as the majority of the ex vivo expanded MSC die shortly after transplantation. To explore the mechanism in which the death cells play tissue repair effect, apoptosis of rat bone marrow MSC was induced by culturing cells in the conditions of hypoxia or/and serum-free medium, and the subcellular structures in the supernatants were analyzed. The results showed that apoptosis occurred in the presence of either hypoxia or serum-free condition as well, and the apoptotic proportion reached up to (17.44 ± 2.15) after the cells were treated by hypoxia plus serum free culture for 72 hours. The flow cytometric analysis of the sub-cellular substances harvested by ultracentrifugation of the supernatants found that the MSC released substantial amount of membrane microparticles into the supernatants, which expressed CD29, CD44A and Annexin-V-binding phosphatidylserine. It is concluded that the MSC can release membrane microparticles after induction, the amount of these membrane microparticles was around 15-fold of the parent cell numbers. The membrane microparticles is the mediators in the cross-talk between the transplanted cells and their surrounding tissues. This study provides some novel information for the mechanisms of MSC therapy.