Electrothermal Phase Change Composite with Flexibility over a Wide Temperature Range for Wearable Thermotherapy.

Flexible electrothermal composite phase change materials (PCMs) are promising candidates for portable thermotherapy. However, a great challenge remains to achieve high PCM loading while maintaining reasonable flexibility. Herein, the polypyrrole-decorated melamine foam (PPy@MF) was fabricated and thereafter applied to confine binary PCM mixtures composed of a high-enthalpy long-chain polyethylene glycol (PEG4000) and its short-chain homologue (PEG200) to make the novel PPy@MF-PEG4000+200 composite PCM. At a high loading of up to 74.1% PEG4000 and a high latent heat energy storage density of 150.1 J/g, the composite PCM remained flexible at temperature (-20 °C) far below its phase transition point thanks to the plasticine effect of PEG200. The composite also demonstrated good Joule heating performance, providing fast heating from 28 to 70 °C at low applied voltages (4.5-6.0 V). The energy could be stored efficiently and released to maintain the composites at the proper temperature. The electrothermal performance of the composite remained undisturbed during curved or repeated bending, showing good potential to be used for personal thermal management and thermotherapy.

A one-pot approach to prepare stretchable and conductive regenerated silk fibroin/CNT films as multifunctional sensors.

Silk fibroin (SF)-based materials are characterized by their outstanding biocompatibility and biodegradability and are considered as the most promising candidates for next-generation flexible electronics. In order to generate such devices, SF can be mixed with carbon nanotubes (CNTs) which feature excellent mechanical, electrical, and thermal properties. However, obtaining regenerated SF with homogeneous dispersion of CNTs in a sustainable manner represents a challenging task, mainly due to the difficulty in overcoming van der Waals forces and strong π-π interactions that hold together the CNT structure. In this study, a one-pot strategy for fabricating SF/CNT films is proposed by designing SF as a modifier of CNTs through non-covalent interactions with the assistance of aqueous phosphoric acid solution. Glycerol (GL) was introduced, endowing the SF/GL/CNT composite film with excellent flexibility and stretchability. The sustainable strategy greatly simplifies the preparation process, avoiding dialysis of SF and the use of artificial dispersants. The as-fabricated SF/GL/CNT films showed an excellent mechanical strength of 1.20 MPa and high sensitivity with a gauge factor of up to 13.7 toward tensile deformation. The composite films had a sensitive monitoring capability for small strains with detection limits as low as 1% and can be assembled into versatile sensors to detect human movement. Simultaneously, the composite films showed a superb thermosensitive capacity (1.64% °C-1), which satisfied the requirement of real-time and continuous skin temperature monitoring. We anticipate that the presented one-pot strategy and the prepared composite films could open a new avenue for forthcoming technologies for electronic skins, personal health monitoring, and wearable electronics.

High-tensile chitin films regenerated from cryogenic aqueous phosphoric acid.

The abuse of non-renewable fossil resources and the resulting plastic pollution have posed a great burden on the environment. Fortunately, renewable bio-macromolecules have shown great potential to replace synthetic plastics in fields ranging from biomedical applications, and energy storage to flexible electronics. However, the potential of recalcitrant polysaccharides, such as chitin, in the above-mentioned fields have not been fully exploited because of its poor processability, which is ultimately due to the lack of suitable, economical, and environmentally friendly solvent for it. Herein, we demonstrate an efficient and stable strategy for the fabrication of high-strength chitin films from concentrated chitin solutions in cryogenic 85 wt% aqueous phosphoric acid (aq. H3PO4). The regeneration conditions, including the nature of the coagulation bath and its temperature are important variables affecting the reassembly of chitin molecules and hence the structure and micromorphology of the films. Uniaxial orientation of the chitin molecules by applying tension to the RCh hydrogels further endows the films with enhanced mechanical properties of up to 235 MPa and 6.7 GPa in tensile strength and Young's modulus, respectively.

Highly stretchable porous regenerated silk fibroin film for enhanced wound healing.

Silk fibroin (SF) has received interest in tissue engineering owing to its biocompatibility, biodegradability, and favorable mechanical properties. However, the complex preparation, brittleness, and lack of pores in the structure of the silk fibroin film limit its application. Herein, we show that facile dissolution of SF in aqueous phosphoric acid followed by regeneration in aqueous ammonium sulfate ((NH4)2SO4) could afford highly stretchable films with nano-pores formed in the nonsolvent-induced phase separation process. The named phase separation, which determines the morphology and mechanical properties of the regeneration silk fibroin (RSF) films, is highly dependent on the (NH4)2SO4 concentration as well as the initial concentration of the SF solution. Therefore, the RSF films exhibit a tunable pore size ranging from 230 to 510 nm and excellent stretchability with tensile strain up to 143 ± 16%. Most interestingly, the RSF films were shown to support the proliferation of human skin fibroblasts in vitro as well as speed up full-thickness skin wound healing in a rat model. This work establishes an easy and feasible method to access porous RSF membranes that can be used for wound dressing in clinical settings.

Fabrication of Fe-BTC on aramid fabrics for repeated degradation of isoproturon.

Catalytic degradation is a promising and ideal technology in environmental remediation. Among them, catalytic oxidation and photocatalysis respectively based on catalysts and photocatalysts both trigger broad interests because of their high removal activity. However, the reusability of the powder catalysts still faces substantial challenges. Here, a simple strategy is proposed to load Fe-BTC catalyst on aramid fabrics (AF) to construct Fe-BTC MOF @ aramid fabric (Fe-BTC@AF) composite materials with layer-by-layer in situ self-assembly methods. The experimental results illustrated that 98% isoproturon could be removed by Fe-BTC@AF20 with oxidant H2O2, while the single Fe-BTC@AF20 could photo-degrade 99% isoproturon within 7 h. Meanwhile, it could sustain a high degradation rate of more than 80%, even if it had gone through 5 degradation cycles. Thus, the Fe-BTC@AF composite has a significant advantage in the recycling ability for degradation of isoproturon, which will have potential applications in the efficient removal of organic contaminants in water.

Composite hydrogel based oxidated sodium carboxymethyl cellulose and gelatin loaded carboxymethylated cotton fabric for hemostasis and infected wound treatment.

The fabric-based wound dressings are hard to maintain a moist environment for wound healing while the hemostatic property and gas permeability of some hydrogel-based wound dressings are not ideal. This study first put forward a strategy of checkerboard-pattern wound dressing: 1) preparing the base fabric with hemostatic property, 2) printing multifunctional hydrogels onto one side of the base fabric to form checkerboard patterns, 3) modifying the other side of the base fabric to be hydrophobic. In this manner, the composite dressing not only maintained the advantages of hydrogels, but also inherited good mechanical property, hemostatic property, and gas permeability from the base fabric. Here, the cotton fabric was carboxymethylated to be MCF. To obtain multifunctional hydrogel, sodium carboxymethylcellulose was oxidated to introduce aldehyde groups to form Schiff base with amino groups in gelatin, besides, dopamine and Ag nanoparticles were introduced to endow the hydrogel with antioxidant property and antibacterial activity. The multifunctional hydrogel was printed onto one side of MCF, subsequently, the deposition of paraffin made the other side of this dressing become hydrophobic. The good performance of the obtained dressing in hemostatic process and wound healing demonstrated its potential in the field of wound treatment.

Scalable Fabrication of Highly Breathable Cotton Textiles with Stable Fluorescent, Antibacterial, Hydrophobic, and UV-Blocking Performance.

Multifunctional cotton textiles that are highly breathable are desirable in a broad range of applications. However, it is still a big challenge to scale up production of such multifunctional cotton textiles. Herein, we developed a simple, scalable, and benign strategy to fabricate highly breathable multifunctional cotton textiles via mild surface modification. The 1,4-dihydropyridine (DHP) ring and gentamycin sulfate (GS) molecules were firmly attached to the cellulose chains under room temperature via a one-pot method. The resulting modified cotton textile showed integrated performances with bright fluorescence, good antibacterial behavior, hydrophobic behavior (contact angle of 134°), and UV-blocking (UPF being up to 69.2), which are very stable toward washing and various solvents. There is no obvious change in the whiteness, thermal stability, and mechanical performance of cotton fabrics after the surface modification. What's more, the air permeability of the modified cotton fabric was up to 31.3 (cm3/cm2)/s. This study not only focuses on the materials design and large-scale fabrication but also provides stable and multifunctional cotton textiles with broad application prospects for many fields.

A facile method for anti-cancer drug encapsulation into polymersomes with a core-satellite structure.

Polymersomes possess the self-assembly vesicular structure similar to liposomes. Although a variety of comparisons between polymersomes and liposomes in the aspects of physical properties, preparation and applications have been elaborated in many studies, few focus on their differences in drug encapsulation, delivery and release in vitro and in vivo. In the present work, we have provided a modified direct hydration method to encapsulate anti-cancer drug paclitaxel (PTX) into PEG-b-PCL constituted polymersomes (PTX@PS). In addition to advantages including narrow particle size distribution, high colloid stability and moderate drug-loading efficiency, we find that the loaded drug aggregate in small clusters and reside through the polymersome membrane, representing a unique core-satellite structure which might facilitate the sustained drug release. Compared with commercial liposomal PTX formulation (Lipusu®), PTX@PS exhibited superb tumor cell killing ability underlain by multiple pro-apoptotic mechanisms. Moreover, endocytic process of PTX@PS significantly inhibits drug transporter P-gp expression which could be largely activated by free drug diffusion. In glioma mice models, it has also confirmed that PTX@PS remarkably eradicate tumors, which renders polymersomes as a promising alternative to liposomes as drug carriers in clinic.

Lignocellulose Extraction from Sisal Fiber and Its Use in Green Emulsions: A Novel Method.

Regenerated lignocellulose nanofibrils (RLCNFs) have recently piqued the interest of researchers due to their widespread availability and ease of extraction. After dewaxing, we treated sisal fiber with alkali, followed by heating and agitation, to obtain RLCNFs, which were then vacuum oven-dried. We used a variety of characterization techniques, including XRD, SEM, and FT-IR, to assess the effects of the alkali treatment on the sisal fiber. Various characterizations demonstrate that lignocellulose fibrils have been successfully regenerated and contaminants have been removed. In addition, employing the RLCNFs as a stabilizer, stable Pickering emulsions were created. The effects of RLCNF concentration in the aqueous phase and water-to-oil volume ratio on stability were studied. The RLCNFs that have been produced show promise as a stabilizer in Pickering emulsions.

Morphology-Controlled Synthesis of Polyphosphazene-Based Micro- and Nano-Materials and Their Application as Flame Retardants.

Common flame retardants, such as halogen-based materials, are being phased-out owing to their harmful environmental and health effects. We prepared poly-(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (PZS) microspheres, nanotubes, capsicum-like nanotubes, and branched nanotubes as flame retardants. An increase in reaction temperature changed the morphology from nanotubes to microspheres. A PZS shape had a positive effect on the flame retardancy of polyethylene terephthalate (PET). The PZS with a capsicum-like nanotube morphology had the best flame retardancy, and the PET limiting oxygen index increased from 25.2% to 34.4%. The flame retardancy capability was followed by PZS microspheres (33.1%), branched nanotubes (32.8%), and nanotubes (32.5%). The capsicum-like nanotubes promote the formation of highly dense and continuous carbon layers, and they release a non-combustible gas (CO2). This study confirms polyphosphazene-based flame retardants as viable and environmentally-friendly alternatives to common flame retardants. It also presents a novel and facile design and synthesis of morphology-controlled nanomaterials with enhanced flame retardant properties.

Integrated Janus cellulosic composite with multiple thermal functions for personalized thermal management.

The effective integration of multiple thermal functions into one material is highly attractive in personal thermal management, taking the complex application environment into consideration. Herein, a multifunctional Janus cellulosic composite encompassing superior electrical heating, energy storage, thermal insulation, and infrared camouflage performance was firstly developed by integrating Janus cellulose nanofibers (CNF) aerogel, polypyrrole (PPy), and polyethylene glycol (PEG). In practice, the active heating-thermal regulation layer (PPy@CNFphilic-PEG) of multifunctional Janus cellulosic composite is faced inward to provide heating on-demand through the joint action of the electrically conductive PPy and thermally regulative PEG. The outward-facing hydrophobic aerogel layer (CNFphobic) serves as the thermal insulator, which simultaneously enables infrared camouflage by reducing heat loss to the environment via infrared radiation. This work presents an effective and facile strategy toward multifunctional Janus materials for efficient personal thermal management, showing great promise for potential applications, such as thermal comfort, infrared camouflage, and security protection.

Stimuli-Responsive Pickering Emulsions Regulated via Polymerization-Induced Self-Assembly Nanoparticles.

With the development of reversible deactivated radical polymerization techniques, polymerization-induced self-assembly (PISA) is emerging as a facile method to prepare block copolymer nanoparticles in situ with high concentrations, providing wide potential applications in different fields, including nanomedicine, coatings, nanomanufacture, and Pickering emulsions. Polymeric emulsifiers synthesized by PISA have many advantages comparing with conventional nanoparticle emulsifiers. The morphologies, size, and amphiphilicity can be readily regulated via the synthetic process, post-modification, and external stimuli. By introducing stimulus responsiveness into PISA nanoparticles, Pickering emulsions stabilized with these nanoparticles can be endowed with "smart" behaviors. The emulsions can be regulated in reversible emulsification and demulsification. In this review, the authors focus on recent progress on Pickering emulsions stabilized by PISA nanoparticles with stimuli-responsiveness. The factors affecting the stability of emulsions during emulsification and demulsification are discussed in details. Furthermore, some viewpoints for preparing stimuli-responsive emulsions and their applications in antibacterial agents, diphase reaction platforms, and multi-emulsions are discussed as well. Finally, the future developments and applications of stimuli-responsive Pickering emulsions stabilized by PISA nanoparticles are highlighted.

Quantitative analysis of factors determining the enzymatic degradation of poly(lactic acid).

The enzymatic degradation of poly(lactic acid) was catalyzed with Proteinase K and the effect of various factors on the rate of degradation was analyzed quantitatively with the help of appropriate kinetic models. The Michaelis-Menten model was modified for the purpose by considering the heterogeneous nature of the reaction and the denaturation of the enzyme. The results proved that Proteinase K degrades the polymer very efficiently. The rate of degradation increases considerably up to 0.1 mg/ml enzyme concentration, but remains constant at larger values. Temperature has an optimum at around 50 °C that is somewhat higher than the 37 °C extensively used in the literature as the most advantageous temperature. If degradation occurs in the same medium throughout the process, the formation of lactic acid results in the rapid decrease of pH and finally in the denaturation of the enzyme. The dropping of pH below 5 slows down and finally stops degradation completely. The daily change of the medium results in degradation with a constant rate and the entire amount of the polymer can be decomposed mainly into monomer or smaller oligomer fragments. Degradation rate decreases slightly with increasing molecular weight and increasing d-lactide content. The use of appropriate kinetic models allows quantitative analysis and the prediction of the rate of enzymatic degradation of PLA.

Cellulosic-Based Conductive Hydrogels for Electro-Active Tissues: A Review Summary.

The use of hydrogel in tissue engineering is not entirely new. In the last six decades, researchers have used hydrogel to develop artificial organs and tissue for the diagnosis of real-life problems and research purposes. Trial and error dominated the first forty years of tissue generation. Nowadays, biomaterials research is constantly progressing in the direction of new materials with expanded capabilities to better meet the current needs. Knowing the biological phenomenon at the interaction among materials and the human body has promoted the development of smart bio-inert and bio-active polymeric materials or devices as a result of vigorous and consistent research. Hydrogels can be tailored to contain properties such as softness, porosity, adequate strength, biodegradability, and a suitable surface for adhesion; they are ideal for use as a scaffold to provide support for cellular attachment and control tissue shapes. Perhaps electrical conductivity in hydrogel polymers promotes the interaction of electrical signals among artificial neurons and simulates the physiological microenvironment of electro-active tissues. This paper presents a review of the current state-of-the-art related to the complete process of conductive hydrogel manufacturing for tissue engineering from cellulosic materials. The essential properties required by hydrogel for electro-active-tissue regeneration are explored after a short overview of hydrogel classification and manufacturing methods. To prepare hydrogel from cellulose, the base material, cellulose, is first synthesized from plant fibers or generated from bacteria, fungi, or animals. The natural chemistry of cellulose and its derivatives in the fabrication of hydrogels is briefly discussed. Thereafter, the current scenario and latest developments of cellulose-based conductive hydrogels for tissue engineering are reviewed with an illustration from the literature. Finally, the pro and cons of conductive hydrogels for tissue engineering are indicated.

Antibacterial thyme oil-loaded zwitterionic emulsion hydrogels.

Emulsion hydrogels are structurally composite materials combining the advantages of emulsions and hydrogels with the ability to accommodate hydrophobic and hydrophilic components in one system. It is a promising strategy for the excellent encapsulation and delivery of many bioactive ingredients. In this work, the thyme oil-loaded zwitterionic emulsion hydrogels are constructed by the cellulose acetoacetate-horseradish peroxidase-hydrogen peroxide-initiated (CAA-HRP-H2O2-initiated) ternary enzyme-mediated polymerization of the thyme oil-in-water (O/W) emulsions stabilized by cellulose acetoacetate (CAA). CAA is the key component in the system, acting as the emulsifier and the polymerization mediator simultaneously. The formed zwitterionic poly(sulfobetaine methacrylate) (PSBMA) hydrogel network provides emulsion hydrogels with good hydration capacity and potential anti-fouling performance. The thyme oil-loaded zwitterionic emulsion hydrogels exhibit interconnected, uniform, and adjustable porous structures with tunable mechanical properties, antifouling performance, good biocompatibility, and excellent antibacterial activity against S. aureus and E. coli. These results all demonstrate that the ternary enzyme-mediated polymerization of zwitterionic monomers in the continuous phase of O/W emulsion templates is a facile and efficient strategy to encapsulate hydrophobic bioactive ingredients.

Comparison of the Rheological Properties and Structure of Fat Derivatives Generated via Different Mechanical Processing Techniques: Coleman Fat, Nanofat, and Stromal Vascular Fraction-Gel.

Importance: Coleman fat, nanofat, and stromal vascular fraction-gel (SVF-gel) are three widely used fat derivatives. However, their rheological properties and structure remain unknown. Objectives: To disclose the rheological properties and structure of three different fat derivatives. Design, Settings, and Participants: Fat tissues obtained from eight different donors were processed into three separate groups: Coleman fat, nanofat, and SVF-gel (n = 8); their viscoelastic properties and structure were determined. Intervention: Oscillation measurements were performed in the context of serrated 25-mm parallel-plate geometry with a 1.2-mm gap at 25°C. In addition, fat samples were fixed using a patented protocol and observed under scanning electron microscopy. Main Outcomes and Measures: Comparison of the viscoelastic properties, microstructure, and particle size. Results: At 0.77 Hz, the elastic modulus of SVF-gel, Coleman fat, and nanofat was 201.6 ± 0.74, 69.94 ± 15.61, and 34.89 ± 3.484 Pa, respectively; their viscosity was 44.06 ± 3.038, 15.37 ± 2.0380, and 7.516 ± 0.7250 mPa, respectively. The particle size of SVF-gel, Coleman fat, and nanofat was 106.0 ± 4.796, 86.93 ± 3.597, and 12.61 ± 7.603 µm, respectively. Conclusion and Relevance: Mechanical processing may impact graft efficacy. The characterization of the rheological properties and structure of different fat derivatives in this study may help surgeons select the better type of tissue for a given intervention; however, further studies are still required.

Mussel-inspired adhesive gelatin-polyacrylamide hydrogel wound dressing loaded with tetracycline hydrochloride to enhance complete skin regeneration.

Even though the global wound care market size was valued at USD 19.83 billion in 2020, it is still a challenge to develop a hydrogel-based wound dressing with a good mechanical property, adhesiveness and antibacterial property. This study established and validated a mussel-inspired adhesive hydrogel wound dressing with antibacterial activity by dispersing tetracycline hydrochloride into hydrogel based polydopamine, gelatin and polyacrylamide. A tough hydrogel with a fracture stress of 0.42 MPa was prepared by changing the contents of the gelatin and polyacrylamide. With the addition of polydopamine and tetracycline hydrochloride, the hydrogel was endowed with an adhesive property (with a tissue adhesive strength of 4.13 kPa) and antibacterial activity against both Escherichia coli and Staphylococcus aureus. Finally, a rat full-thickness skin defect wound model was used to evaluate the performance of the hydrogels in wound repair. The hydrogel group showed a significantly reduced wound area (95.72%) compared with the blank group (86.34%) on day 14. The hydrogel promoted the collagen deposition, weakened the inflammatory response and enhanced wound healing. Therefore, the hydrogel with multifunctional properties is a promising candidate for complete skin regeneration.

High-tensile regenerated cellulose films enabled by unexpected enhancement of cellulose dissolution in cryogenic aqueous phosphoric acid.

We have demonstrated, for the first time, high-efficient non-destructive and non-derivative dissolution of cellulose could be achieved in cryogenic aqueous phosphoric acid. Cellulose from different sources and of varying degree of polymerization from 200 (MCC) to 2200 (cotton fabric) could be dissolved completely to afford solutions containing 5 wt%-18 wt% cellulose, from which ultra-strong and tough cellulose films of tensile strength as high as 707 MPa could be obtained using water as the coagulant. These solutions can be stored at -18 °C for extended time without noticeable degradation while desired degree of polymerization is also attainable by tuning the storage conditions. The findings of this work call for renewal attention on phosphoric acid as a promising cellulose solvent for being non-toxic, non-volatile, easy to handle, and cost-effective.

Nanocellulose-mediated transparent high strength conductive hydrogel based on in-situ formed polypyrrole nanofibrils as a multimodal sensor.

A simple method was provided to prepare a transparent, highly conductive, mechanically reinforced, stretchable, and compressible hydrogel. In this system, pyrrole (Py) monomers were gently polymerized and uniformly deposited on the surface of cellulose nanofiber (CNF) via the improved in-situ polymerization. In the opaque PPy@CNF suspension, acrylamide monomers (AM) were dissolved and radical-polymerized to construct the PPy@CNF-PAM hydrogel with the in-situ formation of PPy nanofibrils in the presence of excess ammonium persulfate (APS). The in-situ formed PPy nanofibrils were well intertwined with the CNF and PAM chains, and a highly conductive path was established and permitted visible light to pass through. The amphipathic CNF took along and dispersed PPy aggregates well, and reinforced the hydrogel after formation of PPy nanofibrils. In view of the improved mechanical compressive, stretchable properties and excellent electrical conductivity (4.5 S/m), the resulting hydrogels could serve as a potential electrical device in a range of applications.

Facile biosynthesis of synthetic crystalline cellulose nanoribbon from maltodextrin through a minimized two-enzyme phosphorylase cascade and its application in emulsion.

Nanocellulose has many promising applications such as a green ingredient for Pickering emulsion. Traditional strategies to produce nanocellulose, which are acid or enzymatic hydrolysis and mechanical methods on natural complicated cellulose, are hard to control and can result in significant pollutants during the processes. Herein, we demonstrated a facile and sustainable method for the biocatalytic production of insoluble synthetic crystalline cellulose nanoribbon (CCNR) from cheap maltodextrin by coupling α-glucan phosphorylase (αGP) and cellodextrin phosphorylase (CDP) using cellobiose as a primer. And by optimizing the combination of different αGP and CDP, it turned out that the optimal enzyme combination is αGP from Thermotoga maritime and CDP from Clostridium thermocellum, in which CDP was attached to a family 9 cellulose-binding module. The product yield and degree of polymerization (DP) of insoluble synthetic CCNR was affected by the primer concentration at a fixed concentration of maltodextrin. After optimization of reaction conditions, the highest product yield of insoluble synthetic CCNR was 44.92 % and the highest DP of the insoluble synthetic CCNR was 24 from 50 g 1-1 maltodextrin. This insoluble synthetic CCNR can be used as a Pickering emulsions stabilizer, showing excellent emulsifiability. This study provides a promising alternative for cost-efficient production of insoluble synthetic CCNR which was used as a green emulsion stabilizer.