Preparation of silk fibroin/hyaluronic acid composite hydrogel based on thiol-ene click chemistry. / 基于巯基-çƒ¯ç‚¹å‡»åŒ–å­¦åˆ¶å¤‡ä¸ç´ è›‹ç™½/é€æ˜Žè´¨é ¸å¤åˆæ°´å‡èƒ¶.

OBJECTIVES: To design and prepare silk fibroin/hyaluronic acid composite hydrogel. METHODS: The thiol modified silk fibroin and the double-bond modified hyaluronic acid were rapidly cured into gels through thiol-ene click polymerization under ultraviolet light condition. The grafting rate of modified silk fibroin and hyaluronic acid was characterized by 1H NMR spectroscopy; the gel point and the internal microstructure of hydrogels were characterized by rheological test and scanning electron microscopy; the mechanical properties were characterized by compression test; the swelling rate and degradation rate were determined by mass method. The hydrogel was co-cultured with the cells, the cytotoxicity was measured by the lactate dehydrogenase method, the cell adhesion was measured by the float count method, and the cell growth and differentiation on the surface of the gel were observed by scanning electron microscope and fluorescence microscope. RESULTS: The functional group substitution degrees of modified silk fibroin and hyaluronic acid were 17.99% and 48.03%, respectively. The prepared silk fibroin/hyaluronic acid composite hydrogel had a gel point of 40-60 s and had a porous structure inside the gel. The compressive strength was as high as 450 kPa and it would not break after ten cycles. The water absorption capacity of the composite hydrogel was 4-10 times of its own weight. Degradation experiments showed that the hydrogel was biodegradable, and the degradation rate reached 28%-42% after 35 d. The cell biology experiments showed that the cytotoxicity of the composite gel was low, the cell adhesion was good, and the growth and differentiation of the cells on the surface of the gel were good. CONCLUSIONS: The photocurable silk fibroin/hyaluronic acid composite hydrogel can form a gel quickly, and has excellent mechanical properties, adjustable swelling rate and degradation degree, good biocompatibility, so it has promising application prospects in biomedicine.

Controllable Large-Scale Transfection of Primary Mammalian Cardiomyocytes on a Nanochannel Array Platform.

While electroporation has been widely used as a physical method for gene transfection in vitro and in vivo, its application in gene therapy of cardiovascular cells remains challenging. Due to the high concentration of ion-transport proteins in the sarcolemma, conventional electroporation of primary cardiomyocytes tends to cause ion-channel activation and abnormal ion flux, resulting in low transfection efficiency and high mortality. In this work, a high-throughput nanoelectroporation technique based on a nanochannel array platform is reported, which enables massively parallel delivery of genetic cargo (microRNA, plasmids) into mouse primary cardiomyocytes in a controllable, highly efficient, and benign manner. A simple "dipping-trap" approach was implemented to precisely position a large number of cells on the nanoelectroporation platform. With dosage control, our device precisely titrates the level of miR-29, a potential therapeutic agent for cardiac fibrosis, and determines the minimum concentration of miR-29 causing side effects in mouse primary cardiomyocytes. Moreover, the dose-dependent effect of miR-29 on mitochondrial potential and homeostasis is monitored. Altogether, our nanochannel array platform provides efficient trapping and transfection of primary mouse cardiomyocyte, which can improve the quality control for future microRNA therapy in heart diseases.

Metal-polyphenol networks-modified tantalum plate for craniomaxillofacial reconstruction.

Using three-dimensional (3D) printing technology to make the porous tantalum plate and modify its surface. The physicochemical properties, cytocompatibility, antioxidant capacity, and histocompatibility of the modified materials were evaluated to prepare for the repair of craniomaxillofacial bone defects. The porous tantalum plates were 3D printed by selective laser melting technology. Tantalum plates were surface modified with a metal polyphenol network. The surface-modified plates were analyzed for cytocompatibility using thiazolyl blue tetrazolium bromide and live/dead cell staining. The antioxidant capacity of the surface-modified plates was assessed by measuring the levels of intracellular reactive oxygen species, reduced glutathione, superoxide dismutase, and malondialdehyde. The histocompatibility of the plates was evaluated by animal experiments. The results obtained that the tantalum plates with uniform small pores exhibited a high mechanical strength. The surface-modified plates had much better hydrophilicity. In vitro cell experiments showed that the surface-modified plates had higher cytocompatibility and antioxidant capacity than blank tantalum plates. Through subcutaneous implantation in rabbits, the surface-modified plates demonstrated good histocompatibility. Hence, surface-modified tantalum plates had the potential to be used as an implant material for the treatment of craniomaxillofacial bone defects.

More than just a beer - Brewers' spent grain, spent hops, and spent yeast as potential functional fillers for polymer composites.

Beer is among the most popular beverages in the world, with the production distributed uniformly between the biggest continents, so the utilization of brewing by-products is essential on a global scale. Among their potential recipients, the plastics industry offers extensive range of potential products. Herein, the presented study investigated the application of currently underutilized solid brewing by-products (brewers' spent grain, spent hops, spent yeast) as fillers for highly-filled poly(ε-caprolactone)-based composites, providing the first direct connection between spent hops or spent yeast and the polymer composites. Comprehensive by-product characterization revealed differences in chemical composition. The elemental C:O ratio, protein content, and Trolox equivalent antioxidant capacity varied from 1.40 to 1.89, 12.9 to 32.4 wt%, and 2.41 to 10.24 mg/g, respectively, which was mirrored in the composites' structure and performance. Morphological analysis pointed to the composition-driven hydrophilicity gap limiting interfacial adhesion for high shares of brewers' spent grain and spent hops, due to high hydrophilicity induced by carbohydrate content. Phytochemicals and other components of applied by-products stimulated composites' oxidative resistance, shifting oxidation onset temperature from 261 °C for matrix over 360 °C for high spent yeast shares. Simultaneously, spent yeast also provided compatibilizing effects for poly(ε-caprolactone)-based composites, reducing complex viscosity compared to other fillers and indicating its highest affinity to poly(ε-caprolactone)due to the lowest hydrophilicity gap. The presented results indicate that the proper selection of brewing by-products and adjustment of their shares creates an exciting possibility of engineering composites' structure and performance, which can be transferred to other polymers differing with hydrophilicity.

Biomimetic Polyphenolic Scaffolds with Antioxidative Abilities for Improved Bone Regeneration.

Bone defects have a severe impact on the health and lives of patients due to their long-lasting and difficult-to-treat features. Recent studies have shown that there are complex microenvironments, including excessive production of reactive oxygen species. Herein, a surface functionalization strategy using metal-polyphenolic networks was used, which was found to be beneficial in restoring oxidative balance and enhancing osseointegration. The surface properties, biocompatibility, intracellular ROS scavenging, and osseointegration capacity were evaluated, and the therapeutic effects were confirmed using a skull defect model. This approach has great potential to improve complex microenvironments and enhance the efficiency of bone tissue regeneration.

Polysaccharide-based biomaterials in a journey from 3D to 4D printing.

3D printing is a state-of-the-art technology for the fabrication of biomaterials with myriad applications in translational medicine. After stimuli-responsive properties were introduced to 3D printing (known as 4D printing), intelligent biomaterials with shape configuration time-dependent character have been developed. Polysaccharides are biodegradable polymers sensitive to several physical, chemical, and biological stimuli, suited for 3D and 4D printing. On the other hand, engineering of mechanical strength and printability of polysaccharide-based scaffolds along with their aneural, avascular, and poor metabolic characteristics need to be optimized varying printing parameters. Multiple disciplines such as biomedicine, chemistry, materials, and computer sciences should be integrated to achieve multipurpose printable biomaterials. In this work, 3D and 4D printing technologies are briefly compared, summarizing the literature on biomaterials engineering though printing techniques, and highlighting different challenges associated with 3D/4D printing, as well as the role of polysaccharides in the technological shift from 3D to 4D printing for translational medicine.

Research Progress in Energy Based on Polyphosphazene Materials in the Past Ten Years.

With the rapid development of electronic devices, the corresponding energy storage equipment has also been continuously developed. As important components, including electrodes and diaphragms, in energy storage device and energy storage and conversion devices, they all face huge challenges. Polyphosphazene polymers are widely used in various fields, such as biomedicine, energy storage, etc., due to their unique properties. Due to its unique design variability, adjustable characteristics and high chemical stability, they can solve many related problems of energy storage equipment. They are expected to become a new generation of energy materials. This article briefly introduces the research progress in energy based on polyphosphazene materials in the past ten years, on topics such as fuel cells, solar cells, lithium batteries and supercapacitors, etc. The main focus of this work is on the defects of different types of batteries. Scholars have introduced different functional group modification that solves the corresponding problem, thus increasing the battery performance.

The Injected Foaming Study of Polypropylene/Multiwall Carbon Nanotube Composite with In Situ Fibrillation Reinforcement.

This paper explored the injection foaming process of in situ fibrillation reinforced polypropylene composites. Using polypropylene (PP) as the continuous phase, polytetrafluoroethylene (PTFE) as the dispersed phase, multi-wall carbon nanotubes (MWCNTs) as the conductive filler, and PP grafted with maleic anhydride (PP-g-MA) as the compatibilizer, a MWCNTs/PP-g-MA masterbatch was prepared by using a solution blending method. Then, a lightweight, conductive PP/PTFE/MWCNTs composite foam was prepared by means of extruder granulation and supercritical nitrogen (ScN2) injection foaming. The composite foams were studied in terms of rheology, morphological, foaming behavior and mechanical properties. The results proved that the in situ fibrillation of PTFE can have a remarkable effect on melt strength and viscoelasticity, thus improving the foaming performance; we found that PP/3% PTFE showed excellent performance. Meanwhile, the addition of MWCNTs endows the material with conductive properties, and the conductivity reached was 2.73 × 10-5 S/m with the addition of 0.2 wt% MWCNTs. This study's findings are expected to be applied in the lightweight, antistatic and high-performance automotive industry.

Polysaccharide-based nanocomposites for biomedical applications: a critical review.

Polysaccharides (PSA) have taken specific position among biomaterials for advanced applications in medicine. Nevertheless, poor mechanical properties are known as the main drawback of PSA, which highlights the need for PSA modification. Nanocomposites PSA (NPSA) are a class of biomaterials widely used as biomedical platforms, but despite their importance and worldwide use, they have not been reviewed. Herein, we critically reviewed the application of NPSA by categorizing them into generic and advanced application realms. First, the application of NPSA as drug and gene delivery systems, along with their role in the field as an antibacterial platform and hemostasis agent is discussed. Then, applications of NPSA for skin, bone, nerve, and cartilage tissue engineering are highlighted, followed by cell encapsulation and more critically cancer diagnosis and treatment potentials. In particular, three features of investigations are devoted to cancer therapy, i.e., radiotherapy, immunotherapy, and photothermal therapy, are comprehensively reviewed and discussed. Since this field is at an early stage of maturity, some other aspects such as bioimaging and biosensing are reviewed in order to give an idea of potential applications of NPSA for future developments, providing support for clinical applications. It is well-documented that using nanoparticles/nanomaterials above a critical concentration brings about concerns of toxicity; thus, their effect on cellular interactions would become critical. We compared nanoparticles used in the fabrication of NPSA in terms of toxicity mechanism to shed more light on future challenging aspects of NPSA development. Indeed, the neutralization mechanisms underlying the cytotoxicity of nanomaterials, which are expected to be induced by PSA introduction, should be taken into account for future investigations.

Recent advances in biofluid detection with micro/nanostructured bioelectronic devices.

Most biofluids contain a wide variety of biochemical components that are closely related to human health. Analyzing biofluids, such as sweat and tears, may deepen our understanding in pathophysiologic conditions associated with human body, while providing a variety of useful information for the diagnosis and treatment of disorders and disease. Emerging classes of micro/nanostructured bioelectronic devices for biofluid detection represent a recent breakthrough development of critical importance in this context, including traditional biosensors (TBS) and micro/nanostructured biosensors (MNBS). Related biosensors are not restricted to flexible and wearable devices; solid devices are also involved here. This article is a timely overview of recent technical advances in this field, with an emphasis on the new insights of constituent materials, design architectures and detection methods of MNBS that support the necessary levels of biocompatibility, device functionality, and stable operation for component analysis. An additional section discusses and analyzes the existing challenges, possible solutions and future development of MNBS for detecting biofluids.

A CRISPR/Cas13a-powered catalytic electrochemical biosensor for successive and highly sensitive RNA diagnostics.

Rapid and specific quantitation of a variety of RNAs with low expression levels in early-stage cancer is highly desirable but remains a challenge. Here, we present a dual signal amplification strategy consisting of the CRISPR/Cas13a system and a catalytic hairpin DNA circuit (CHDC), integrated on a reusable electrochemical biosensor for rapid and accurate detection of RNAs. Signal amplification is accomplished through the unique combination of the CRISPR/Cas13a system with CHDC, achieving a limit of detection of 50 aM within a readout time of 6 min and an overall process time of 36 min, using a measuring volume of 10 µL. Enzymatic regeneration of the sensor surface and ratiometric correction of background signal allow up to 37 sequential RNA quantifications by square-wave voltammetry on a single biosensor chip without loss of sensitivity. The reusable biosensor platform could selectively (specificity = 0.952) and sensitively (sensitivity = 0.900) identify low expression RNA targets in human serum, distinguishing early-stage patients (n = 20) suffering from non-small-cell lung carcinoma (NSCLC) from healthy subjects (n = 30) and patients with benign lung disease (n = 12). Measurement of six NSCLC-related RNAs (miR-17, miR-155, TTF-1 mRNA, miR-19b, miR-210 and EGFR mRNA) shows the ability of the electrochemical CRISPR/CHDC system to be a fast, low-cost and highly accurate tool for early cancer diagnostics.

Rotational Molding of Linear Low-Density Polyethylene Composites Filled with Wheat Bran.

Application of lignocellulosic fillers in the manufacturing of wood polymer composites (WPCs) is a very popular trend of research, however it is still rarely observed in the case of rotational molding. The present study aimed to analyze the impact of wheat bran content (from 2.5 wt.% to 20 wt.%) on the performance of rotationally-molded composites based on a linear low-density polyethylene (LLDPE) matrix. Microscopic structure (scanning electron microscopy), as well as physico-mechanical (density, porosity, tensile performance, hardness, rebound resilience, dynamic mechanical analysis), rheological (oscillatory rheometry) and thermo-mechanical (Vicat softening temperature) properties of composites were investigated. Incorporation of 2.5 wt.% and 5 wt.% of wheat bran did not cause significant deterioration of the mechanical performance of the material, despite the presence of 'pin-holes' at the surface. Values of tensile strength and rebound resilience were maintained at a very similar level, while hardness was slightly decreased, which was associated with the porosity of the structure. Higher loadings resulted in the deterioration of mechanical performance, which was also expressed by the noticeable rise of the adhesion factor. For lower loadings of filler did not affect the rheological properties. However, composites with 10wt.% and 20 wt.% also showed behavior suitable for rotational molding. The presented results indicate that the manufacturing of thin-walled products based on wood polymer composites via rotational molding should be considered a very interesting direction of research.

Intravesical Hydrogels as Drug Reservoirs.

The complex environment in the bladder weakens the efficacy of intravesical therapy. Hydrogel-based drug delivery systems are poised to revolutionize the delivery of therapeutic agents to bladder lesion sites. This forum article highlights the prospective applications of hydrogels as drug reservoirs in treating chronic bladder diseases.

Fabrication of bimodal open-porous poly (butylene succinate)/cellulose nanocrystals composite scaffolds for tissue engineering application.

The design of porous tissue engineering scaffold with multiscale open-pore architecture (i.e., bimodal structure) promotes cell attachment and growth, which facilitates nutrient and oxygen diffusion. In this study, a porous poly (butylene succinate) (PBS)/cellulose nanocrystals (CNCs) composite scaffold with a well-defined controllable bimodal open-pore interconnected structure was successfully fabricated. The bimodal open-porous scaffold architecture was designed by synergistic control of temperature variation and a two-step depressurization in a supercritical carbon dioxide (Sc-CO2) foaming process. The microstructure and properties of the bimodal open-porous PBS/CNCs scaffold, such as morphology, open porosity, hydrophilic and degradation performance, and mechanical compression properties, were analyzed. In the experiments, the scaffold with unimodal pore structure was used for comparison. The results showed that the bimodal open-porous PBS5 scaffold displayed a well-defined bimodal open-pore structure composed of large pore (~68.9 µm in diameter) and small pore (~11.0 µm in diameter), with a high open porosity (~95.2%). In addition, the scaffolds exhibited good mechanical compressive properties (compressive strength of 2.76 MPa at 50% strain), hydrophilicity (water contact angle of 71.7 °C) and in vitro degradation rate. Moreover, in vitro biocompatibility was determined with NIH-3T3 fibroblast cells using MTT assay and live/dead cell viability assay. Results indicated that the obtained bimodal open-porous scaffolds had a good biocompatibility and the viability of cells grown on the scaffolds reached up to 98% after 7th day of culture. Therefore, our work provides new insights into the use of biodegradable polymeric composite scaffolds with bimodal open-pore structure and balanced properties in tissue engineering.

Enhanced osseointegration of double network hydrogels via calcium polyphosphate incorporation for bone regeneration.

To overcome the low mechanical strength and difficult bonding of hydrogels to bones which are the major limitations of hydrogels used in bone-regeneration, a new type of calcium polyphosphate incorporated into bioinspired alginate/polyacrylic acid (CPP/PAA-Alg) hybrid double network (DN) hydrogel with both high strength and enhanced osseointergration was prepared by a two-step polymerization with alginate and polyacrylic acid for bone regeneration. The morphology, mechanical properties, swelling, biocompatibility, osseointegration and osteogenic ability of this CPP/PAA-Alg DN hydrogel were investigated. The results show that CPP/PAA-Alg DN hydrogel with highly porous microstructure possesses high water absorption capacity and highly strength properties which meet the requirements of bone repairing. The results of in vitro studies revealed that the CPP/PAA-Alg DN hydrogels can support the spread of cells and promote the cell proliferation. Animal studies demonstrated that the CPP incorporated would enhance the osseointegration of DN hydrogel with host bone at an early stage after implantation to accelerate the regeneration of bone. This research may provide a new way to develop biocompatible biomaterials with high mechanical strength and good osseointegration to meet the needs of bone regeneration.

Fabrication of Poly(butylene succinate)/Carbon Black Nanocomposite Foams with Good Electrical Conductivity and High Strength by a Supercritical CO2 Foaming Process.

Lightweight, high-strength and electrically conductive poly(butylene succinate) (PBS)/ carbon black (CB) nanocomposite foams with a density of 0.107-0.344 g/cm3 were successfully fabricated by a solid-state supercritical CO2 (ScCO2) foaming process. The morphology, thermal and dynamic mechanical properties, and rheological behavior of the PBS/CB nanocomposites were studied. The results indicate that the CB nanofiller was well dispersed in the PBS matrix and the presence of a proper CB nanofiller can accelerate the rate of crystallization, improve the thermal stability, enhance the stiffness, and increase the complex viscosity of PBS/CB nanocomposites. These improved properties were found to play an important role in the foaming process. The results from foaming experiments showed that the PBS/CB nanocomposite foams had a much smaller cell size, a higher cell density, and a more uniform cell morphology as compared to neat PBS foams. Furthermore, the PBS/CB nanocomposite foams also possessed low density (0.107-0.344 g/cm3), good electrical conductivity (~0.45 S/cm at 1.87 vol % CB loading), and improved compressive strength (108% increase), which enables them to be used as lightweight and high-strength functional materials.

Preparation, Properties, and Applications of Graphene-Based Hydrogels.

As a new carbon-based nanomaterial, graphene has exhibited unique advantages in significantly improving the combination properties of traditional polymer hydrogels. The specific properties of graphene, such as high electrical conductivity, high thermal conductivity and excellent mechanical properties, have made graphene not only a gelator to self-assemble into the graphene-based hydrogels (GBH) with extraordinary electromechanical performance, but also a filler to blend with small molecules and macromolecules for the preparation of multifunctional GBH. It fully exploits the practical applications of traditional hydrogels. This review summarizes the preparation methods, properties, and the applications of GBH. Further developments and challenges of GBH are also prospected.

Synthesis of DOPO-HQ-functionalized graphene oxide as a novel and efficient flame retardant and its application on polylactic acid: Thermal property, flame retardancy, and mechanical performance.

The fabrication of biodegradable polymer nanocomposites with improved flame retardancy has been an urgent task in practical because of the huge benefits of biodegradable polymers. In this work, 10-(2,5-dihydroxyl phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ)-functionalized graphene oxide (GO) (FGO-HQ) was used as a novel and highly efficient flame retardant (FR) to improve the flame retardancy of polylactide (PLA) nanocomposites. Contributed by the bi-phase flame retardant action, including the physical barrier char in solid phase and the decreased flammable volatiles in gas phase, the resultant PLA/FGO-HQ nanocomposites presented excellent flame resistance at the loading of 6 wt% FR: UL-94 reached V-0 rating; peak heat release rate (PHRR) and total heat release (THR) decreased by 24.0% and 43.0%, respectively; smoke production rate (SPR) and total smoke release (TSR) decreased by 46% and 83%, respectively. For further confirming its flame-resistance mechanism, thermogravimetric analysis/infrared spectrometry (TG-IR) and Fourier transform infrared spectra (FT-IR), scanning electron microscope (SEM), and Raman spectroscopy were employed. Results indicated that the incorporation of FGO-HQ can effectively reduce the evaporation of flammable gaseous product in gas phase through quenching free radicals. Meanwhile, graphitized carbons are formed in the residual char and PLA/FGO-HQ sample can achieve a good thermal stability in the combustion with phosphorus-containing compounds and aromatic structure in the solid phase. Furthermore, the tensile strength of PLA nanocomposites presented good mechanical properties with the addition of FR as well. These results suggested that the incorporation of FGO-HQ FR not only improve the flame retardancy and thermal stability of biodegradable polymer nanocomposites but also without sacrificing their mechanical properties.

Patchable micro/nanodevices interacting with skin.

Patchable devices that interface with the skin across a wide range of size scales, from cellular level down to molecular level, become increasingly attractive in biomedical research. These devices hold the potential for diagnostic and therapeutic functions with exceptional spatiotemporal precision, continuity, and convenience. Further, they afford new opportunities to integrate cloud-based technology and artificial intelligence for a smarter healthcare system. This article reviews recent advances in materials design and assembly techniques for fabricating various patchable devices, with focuses on electrical, thermal, mechanical, and chemical biosensors as well as transdermal gene and drug delivery platforms. A concluding discussion provides perspectives for future developments and outlooks in clinical applications.

Morphological Structure, Rheological Behavior, Mechanical Properties and Sound Insulation Performance of Thermoplastic Rubber Composites Reinforced by Different Inorganic Fillers.

The application area of a sound insulation material is highly dependent on the technology adopted for its processing. In this study, thermoplastic rubber (TPR, polypropylene/ethylene propylene diene monomer) composites were simply prepared via an extrusion method. Two microscale particles, CaCO3 and hollow glass microspheres (HGW) were chosen to not only enhance the sound insulation but also reinforced the mechanical properties. Meanwhile, the processing capability of composites was confirmed. SEM images showed that the CaCO3 was uniformly dispersed in TPR matrix with ~3 µm scale aggregates, while the HGM was slightly aggregated to ~13 µm scale. The heterogeneous dispersion of micro-scale fillers strongly affected the sound transmission loss (STL) value of composites. The STL values of TPR composites with 40 wt % CaCO3 and 20 wt % HGM composites were about 12 dB and 7 dB higher than that of pure TPR sample, respectively. The improved sound insulation performances of the composites have been attributed to the enhanced reflection and dissipate sound energy in the heterogeneous composite. Moreover, the mechanical properties were also enhanced. The discontinued sound impedance and reinforced stiffness were considered as crucial for the sound insulation.