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.

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.

Robust Fabrication of Fluorescent Cellulosic Materials via Hantzsch Reaction.

Hantzsch reaction is one of the typical multicomponent reactions (MCRs), and it is employed herein to endow cellulosic materials with fluorescent properties. For example, acetoacetyl (ACAC)-bearing cotton fabric prepared via transesterification with tert-butyl acetoacetate is subjected to an aqueous Hantzsch reaction with formaldehyde and ammonium acetate at ambient temperature. A strong fluorescent emission around 460 nm is achieved within 10 min. XPS, fluorescent spectroscopy, and elemental analysis are used to confirm the presence of 1,4-dihydropyridine (DHP) rings on the surface of the fabric. TGA, SEM, XRD, and mechanical testing results show that the modification process has minimum impact on intrinsic properties of the fabric. The strategy is also shown to be generally applicable to various forms of cellulosic materials and different aldehydes. This fast and simple approach enriches the application of MCR in modification of cellulose and cellulose derivatives.

Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties.

Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature.

Covalent layer-by-layer assembly of redox-active polymer multilayers.

Poly(ferrocenyl(3-bromopropyl)methylsilane) and poly(ethylene imine) are employed in a layer-by-layer deposition process to form covalently connected, redox-active multilayer thin films by means of an amine alkylation reaction. The stepwise buildup of these multilayers on silicon, ITO, and quartz substrates was monitored by UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), static contact angle measurements, surface plasmon resonance (SPR), atomic force microscopy, ellipsometry, and cyclic voltammetry, which provide evidence for a linear increase in multilayer thickness with the number of deposited bilayers. Upon oxidation and reduction, these covalently interconnected layers do not disassemble, in contrast to poly(ferrocenylsilane) (PFS) layers featuring similar backbone structures that are held together by electrostatic forces. The PFS/PEI multilayers are effective for the electrochemical sensing of ascorbic acid and hydrogen peroxide and show improved sensing performance at higher bilayer numbers. These covalently linked layers are readily derivatized further and can therefore be regarded as a versatile platform for creating robust, tailorable, redox-active interfaces with applications in sensing and biofuel cells.

Redox-active cross-linkable poly(ionic liquid)s.

The synthesis of a new class of cross-linkable redox-responsive poly(ferrocenylsilane)-based poly(ionic liquid)s (PFS-PILs) is reported. PFS-PILs self-cross-link at low concentrations into nanogels or form macroscopic hydrogel networks at higher concentrations. PFS-PILs proved to be efficient dispersants in the microemulsion polymerization of methyl methacrylate, producing stable PFS-poly(methyl methacrylate) latex suspensions.

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.

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.

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.

Probing the collapse dynamics of poly(N-isopropylacrylamide) brushes by AFM: effects of co-nonsolvency and grafting densities.

Collapse of poly(N-isopropylacrylamide) (PNIPAM) brushes in the mixed solvent system (water/methanol 50% v/v) is studied by in-situ atomic-force microscopy (AFM). PNIPAM brushes with three different grafting densities and similar chain lengths are synthesized via surface-initiated atom-transfer radical polymerization. By changing the solvent from water to a water/methanol (50% v/v) mixture, the polymer brushes switch from a swollen to collapsed state. AFM force measurements using a silica colloidal probe attached to the tip are employed to obtain the Young's moduli of the polymer brushes in different solvation states. The collapse dynamics of the brush is followed by monitoring the pull-off force (adherence) in situ. The modulus of the swollen high-density polymer brush is four times lower than that of the same brush in the collapsed state. It is shown that in the case of the high-density polymer brush with a thickness (t(in water) ) of 900 nm, the collapse takes place in a time scale of ~25 s, whereas the collapse occurs faster for the medium-density brush (t(in water) = 630 nm) and much more rapidly for the low-density brush (t(in water) = 80 nm). This difference in the response kinetics is primarily ascribed to the time needed for solvent exchange in the polymer brushes.

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.

Synthetic semicrystalline cellulose oligomers as efficient Pickering emulsion stabilizers.

Nanocellulose are promising Pickering emulsion stabilizers for being sustainable and non-toxic. In this work, semicrystalline cellulose oligomers (SCCO), which were synthesized from maltodextrin using cellobiose as primer by in vitro enzymatic biosystem, were exploited as stabilizers for oil-in-water Pickering emulsions. At first, the morphology, structure, thermal and rheological properties of SCCO suspensions were characterized, showing that SCCO had a sheet morphology and typical cellulose-Ⅱ structure with 56 % crystallinity. Then the kinetic stabilities of emulsions containing various amounts of SCCO were evaluated against external stress such as pH, ionic strength, and temperature. Noting that SCCO-Pickering emulsions exhibited excellent stabilities against changes in centrifugation, pH, ionic strengths, and temperatures, and it was also kinetically stable for up to 6 months. Both SCCO suspensions and their emulsions exhibited gel-like structures and shear-thinning behaviors. These results demonstrated great potential of SCCO to be applied as nanocellulosic emulsifiers in food, cosmetic and pharmaceutical industries.

Antibacterial thyme oil-loaded organo-hydrogels utilizing cellulose acetoacetate as reactive polymer emulsifier.

Organo-hydrogels are widely used in various fields, due to functional organic ingredients immobilized by the gel network or stored and protected by the gels. Herein, cellulose acetoacetate (CAA) served as reactive natural polymer emulsifier to stabilize thyme oil-in-water (O/W) emulsions. Hydroxypropyl chitosan (HPCS) was added to the continuous phase in emulsions to achieve the organo-hydrogel via the enamine bonds under mild conditions. The thyme@CAA emulsion with different loadings of the inner phase (up to 50%) displayed uniform droplets distribution (3-5 µm) and favorable stability. The organo-hydrogel was systematically analyzed by Fourier transform infrared spectroscopy, optical microscope, rheology analyses. The emulsion droplets evenly dispersed in the three-dimensional network. The modulus of organo-hydrogels depended on the viscosity of precursor emulsions and the crosslinking density. The resulting organo-hydrogel displayed favorable antibacterial activity against E. coli and S. aureus. CAA, as the reactive emulsifier and crosslinking agent, was a promising alternative candidate to fabricate a series of organo-hydrogel.

Antibacterial phase change microcapsules obtained with lignin as the Pickering stabilizer and the reducing agent for silver.

This paper provides a novel and facile method to synthesize antibacterial phase change microcapsules (microPCMs) decorated with silver particles, where lignin was acting as both the Pickering stabilizer and the reducing agent for silver. First lignin Pickering emulsions at various oil-to-water ratios and lignin loading were prepared. Then, n-eicosane encapsulated in polyurea (PU) shells was prepared via interfacial polymerization of isophorone diisocyanate (IPDI) and ethylene diamine/diethylene triamine (EDA/DETA) in a Pickering emulsion stabilized by lignin particles. The results showed that the lignin particles were embedded in the microPCMs shell. These lignin particles were utilized to reduce silver ions, resulting in silver particles decorated microPCMs (Ag/lignin microPCMs). The resulting Ag/lignin microPCMs exhibited a well-defined core-shell spherical morphology with high phase-transition enthalpy (177.6 J/g), high encapsulation efficiency (69.0%) and good thermal durability. As well, the Ag/lignin microPCMs presented good antibacterial activity, showing great potential in industrial applications such as biomedical, textile and construction areas.

Fabrication of lignin/poly(3-hydroxybutyrate) nanocomposites with enhanced properties via a Pickering emulsion approach.

The present-day world still demands for various commercially viable biosourced materials to replace the finite petroleum-derived polymers. Herein, lignin nanoparticles were homogeneously dispersed in the poly(3-hydroxybutyrate) (PHB) matrix via an economical, simple and environmentally friendly oil-in-water Pickering emulsion approach to form a nanocomposite with improved properties. The prepared lignin/PHB nanocomposites were investigated for their morphological, thermal, optical, rheological and mechanical properties. The lignin nanoparticles proved to be efficient nucleating agents for PHB in that they noticeably increased the crystallization rates of the polymer. PHB film containing 7% lignin demonstrated the optimum improvement in the tensile performance with 13.2% and 43.9% increase in tensile strength and Young's modulus, respectively. This upturn was ascribed to the uniform dispersion of the lignin nanoparticles and the formation of strong interfacial adhesion between the filler and the matrix due to hydrogen bonding interactions. Moreover, lower crystallinity, higher glass transition temperature, improved UV resistance/blocking and higher melt viscosity were achieved in the blends. The synergetic advancement in these properties may be of significant importance for the wider application of bio-sourced PHB in the packaging industry.

A naked-eye detection polyvinyl alcohol/cellulose-based pH sensor for intelligent packaging.

Naked-eye detection pH sensor is becoming a powerful tool in food safety monitoring. In this work, a pH sensor was developed by incorporating cellulose modified with acidochromic dye into polyvinyl alcohol (PVA). The results indicated that the dye (up to 170.4 µmol/g) was successfully anchored to cellulose. It was demonstrated that the addition of acidochromic regenerated cellulose (ARC) resulted in enhancement of tensile strength, elongation at break and maximum decomposition temperature by 44 %, 43.6 % and 11 °C, respectively. The pH sensor demonstrated that a visible color change from yellow to brick-red and to purple when placed in solutions of pH = 7, 10 and 12. The pH sensor showed excellent resistance to leaching under strong acidic and alkaline conditions. When applied to spoiled shrimp, an evident color change from yellow to brown was observed, suggesting it could serve as an easy-to-use, non-destructive visual indicator system for real-time food monitoring.

The fabrication of polylactide/cellulose nanocomposites with enhanced crystallization and mechanical properties.

Polylactide/cellulose nanocomposites were fabricated by blending of commercial polylactide (PLA) and modified cellulose nanocrystals (CNCs). Modified CNCs were prepared via the in situ polymerization of CNCs and L-lactic acid (CNCs-PLLA) or D-lactic acid (CNCs-PDLA). The actual occurrence of chemical bond between CNCs and PLA segment was confirmed by Fourier transform infrared, nuclear magnetic resonance, X-ray diffraction and solubility tests. Differential scanning calorimetry and X-ray diffraction characterization indicated that CNCs-PDLA better improved the crystallization ability of PLA matrix compared with CNCs-PLLA. Furthermore, compared with the neat PLA (60.0 MPa), the tensile strength of resulting nanocomposites showed an enhancement of up to 36% (81.65 MPa). And the nanocomposites with CNCs-PDLA exhibited both high crystallinity and improved mechanical properties.

Rheology of regenerated cellulose suspension and influence of sodium alginate.

Cellulosic colloidal suspensions present unique opportunities for rheological modification of complex fluids. In this work, the rheological behavior of regenerated cellulose (RC) suspensions, including their oscillating shear and time-dependent behavior, as well as yield stress, were studied. The rheological effects of sodium alginate's addition to aqueous RC solutions subject to shear flow were investigated. The results reveal that the RC suspension exhibited "gel-like" behavior and had a shear-thinning property. At increasing RC concentrations, the suspensions' yield stress and the extent of viscosity recovery after plastic deformation had both increased. The viscoelastic suspensions underwent a transition from "solid-like" to "liquid-like" behavior upon sodium alginate's inclusion. Sodium alginate was found to enhance RC suspensions' viscosity recoverability. Furthermore, with increasing concentrations of sodium alginate, the yield stress of RC suspension began to decrease and then vanished, occurring below the 1:1 RC: sodium alginate weight ratio with total solid content fixed at 1 wt%, due to RC's inability to form an extended network RC. This study yields insights into the rheology of RC suspensions and the influence of sodium alginate and supports both their usage as rheological modifies in applications such as coatings, drug delivery systems, and additive manufacturing techniques such as 3D printing.

Lignin assisted Pickering emulsion polymerization to microencapsulate 1-tetradecanol for thermal management.

This work explored the use of Pickering emulsion stabilized by lignin nanoparticles (LNPs) to microencapsulate 1-tetradecanol (TDA) via polymerization of acrylates for thermal management. The morphology and thermal performance of the resulting microcapsules were explored using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). A highest encapsulation ratio of 81.4% and melting enthalpy of 190 J/g could be achieved when the core/shell mass ratio was 2:1, and 10 wt% of the crosslinking monomer pentaerythritol tetraacrylate (PETRA) was used. Results of the leakage and accelerated thermal cycling tests showed that the microcapsules had good thermal and chemical stability. When the microcapsules were combined with gypsum, an effective thermal storage composite was obtained, showing good potential for thermal management in the construction field.

Durable and Effective Antibacterial Cotton Fabric Collaborated with Polypropylene Tissue Mesh for Abdominal Wall Defect Repair.

A feasible, efficient antibacterial and anti-infective mesh for clinical abdominal wall defect repair is significant, but challenging due to the complexity of the postoperative wound environment. Herein, a simple strategy was provided to construct woven cotton fabric modified with gentamicin (Gem) via the enamine bonds. The obtained cotton fabric possessed favorable antibacterial properties against E. coli and S. aureus with the bactericidal rate of over 99.99% and could be combined with a commercial polypropylene (PP) mesh to serve as a two-layer composite mesh for abdominal wall defect repair. The antibacterial cotton layer was systematically characterized by FTIR, XPS, SEM, EDS, and mechanical measurements. The C2C12 cells and human fibroblasts were employed to assess the cytocompatibility of the composite mesh in vitro. Furthermore, the rat abdominal wall defect model was used to evaluate the efficacy of antibacterial and anti-infection properties. It was demonstrated that the two-layer composite mesh possessed favorable biocompatibility and satisfactory anti-infection properties involved in abdominal wall defect repair. Therefore, this synergetic two-layer composite mesh would out-perform surgical PP meshes in preventing infectious complications.