Multifunctional Hydrogels Based on Cellulose and Modified Lignin for Advanced Wounds Management.

Considering the complex process of wound healing, it is expected that an optimal wound dressing should be able to overcome the multiple obstacles that can be encountered in the wound healing process. An ideal dressing should be biocompatible, biodegradable and able to maintain moisture, as well as allow the removal of exudate, have antibacterial properties, protect the wound from pathogens and promote wound healing. Starting from this desideratum, we intended to design a multifunctional hydrogel that would present good biocompatibility, the ability to provide a favorable environment for wound healing, antibacterial properties, and also, the capacity to release drugs in a controlled manner. In the preparation of hydrogels, two natural polymers were used, cellulose (C) and chemically modified lignin (LE), which were chemically cross-linked in the presence of epichlorohydrin. The structural and morphological characterization of CLE hydrogels was performed by ATR-FTIR spectroscopy and scanning electron microscopy (SEM), respectively. In addition, the degree of swelling of CLE hydrogels, the incorporation/release kinetics of procaine hydrochloride (PrHy), and their cytotoxicity and antibacterial properties were investigated. The rheological characterization, mechanical properties and mucoadhesion assessment completed the study of CLE hydrogels. The obtained results show that CLE hydrogels have an increased degree of swelling compared to cellulose-based hydrogel, a better capacity to encapsulate PrHy and to control the release of the drug, as well as antibacterial properties and improved mucoadhesion. All these characteristics highlight that the addition of LE to the cellulose matrix has a positive impact on the properties of CLE hydrogels, confirming that these hydrogels can be considered as potential candidates for applications as oral wound dressings.

Correlation between Mechanical and Morphological Properties of Polyphenol-Laden Xanthan Gum/Poly(vinyl alcohol) Composite Cryogels.

This study aimed to evaluate the effect of the synthesis parameters and the incorporation of natural polyphenolic extract within hydrogel networks on the mechanical and morphological properties of physically cross-linked xanthan gum/poly(vinyl alcohol) (XG/PVA) composite hydrogels prepared by multiple cryo-structuration steps. In this context, the toughness, compressive strength, and viscoelasticity of polyphenol-loaded XG/PVA composite hydrogels in comparison with those of the neat polymer networks were investigated by uniaxial compression tests and steady and oscillatory measurements under small deformation conditions. The swelling behavior, the contact angle values, and the morphological features revealed by SEM and AFM analyses were well correlated with the uniaxial compression and rheological results. The compressive tests revealed an enhancement of the network rigidity by increasing the number of cryogenic cycles. On the other hand, tough and flexible polyphenol-loaded composite films were obtained for a weight ratio between XG and PVA of 1:1 and 10 v/v% polyphenol. The gel behavior was confirmed for all composite hydrogels, as the elastic modulus (G') was significantly greater than the viscous modulus (G″) for the entire frequency range.

Halogen-Free Waterborne Polymeric Hybrid Coatings for Improved Fire Retardancy of Textiles.

Wildfires are becoming more intense and more frequent, ravaging the habitations and ecosystems in their path. One solution to reducing the risk of damage to buildings and other structures during a fire event is the use of fire-retardant coatings that can stop or slow down the spread of flames, especially for textile materials. The present study focuses on the preparation and application of halogen-free boron/bentonite-based polymeric fire-retardant (FR) hybrid coating formulations for fabrics such as cotton (CO) and polyester (PE) fibers. For the preparation of FR composites, two types of boron derivatives, disodium octaborate and zinc borate, were used in combination with sodium bentonite. A styrene-acrylic copolymer was specifically synthesized and used as a coating binder for FR components to apply on fabrics. The properties of the synthesized copolymer and FR composites were characterized with a particle size analysis, FTIR spectroscopy, a dynamic mechanical thermal analysis (DMTA), and rheological measurements. The obtained hybrid composites based on styrene-acrylic copolymers and two different inorganic fillers were applied on cotton (CO) and polyester (PE) fabrics with a screen-printing technique, and the flame retardancy performance of the finished textile samples was investigated by means of flame spread and limit oxygen index (LOI) tests. The findings showed that the FR-composite-coated fabrics had higher LOI values and much decreased flame spread rates in comparison with uncoated ones. Among the boron derivatives, the composites prepared with disodium octaborate (FR-A) had much more pronounced LOI values and decreased flame spread behavior in comparison with the composite with zinc borate (FR-B). When compared to a commercial product, the FR-A composite, in conjunction with the specially synthesized polymer, demonstrated commendable fire retardancy performance and emerged as a promising candidate for a halogen-free waterborne fire-retardant coating for fabrics.

Influence of Gel Stage from Cellulose Dissolution in NaOH-Water System on the Performances of Cellulose Allomorphs-Based Hydrogels.

Novel hydrogels were prepared starting from different cellulose allomorphs (cellulose I, II, and III), through a swelling stage in 8.5% NaOH aqueous solution, followed by freezing at low temperature (−30 °C), for 24 h. After thawing at room temperature, the obtained gels were chemical cross-linked with epichlorohydrin (ECH), at 85 °C. The swelling degrees of the hydrogels were investigated, and a complex dependence on the type of the cellulose allomorph was found. Moreover, the gel stage has been shown to play a key role in the design of hydrogels with different performances, following the series: H-CII > H-CI > H-CIII. The correlations between the allomorph type and the morphological characteristics of hydrogels were established by scanning electron microscopy (SEM). The hydrogel H-CII showed the biggest homogeneous pores, while H-CIII had the most compacted pores network, with small interconnected pores. The rheological studies were performed in similar shear regimes, and a close correlation between the strength of the gel structure and the size of the gel fragments was observed. In the case of hydrogels, it has been shown that H-CII is softer, with a lower resistance of the hydrogel (G') above the oscillation frequencies tested, but it maintains its stable structure, while H-CIII has the highest modulus of storage and loss compared to H-CI and H-CII, having a stronger and more rigid structure. The X-ray diffraction (XRD) method showed that the crystalline organization of each type of allomorph possesses a distinctive diffraction pattern, and, in addition, the chemically cross-linking reaction has been proved by a strong decrease of the crystallinity. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy provided clear evidence of the chemical cross-linking of cellulose allomorphs with ECH, by the alteration of the crystal structure of cellulose allomorphs and by the formation of new ether bands.

The Effect of Different Soft Core/Hard Shell Ratios on the Coating Performance of Acrylic Copolymer Latexes.

Core-shell acrylic copolymer latexes containing bio resourced itaconic acid with different compositions in respect with the core and shell segments were synthesized, characterized, and applied as coating materials for leather. The purpose of the study was to evidence the high coating performance of the latexes when the ratio of the core/shell differed from 90/10 to 50/50 wt %. The copolymers were prepared via emulsion copolymerization technique and the products were isolated and characterized by means of structure identity, thermal behavior (DSC and DMTA), coating performance. The particle size of the latexes varied from 83 to 173 nm with the variation of the ratio of core/shell segments. The influence of the composition of soft part and hard part was highlighted in the thermal and coating properties. The optimal composition giving the best coating performance could be determined as DS 60/40. Further increase of the hard segment content, resulted in decreased emulsion stability and the coating performance on the leathers. The use of itaconic acid seemed to increase the emulsion stability as well the adhesion of the latexes to the substrate.

Alginate/poloxamer hydrogel obtained by thiol-acrylate photopolymerization for the alleviation of the inflammatory response of human keratinocytes.

Hydrogel-based wound dressings have been intensively studied as promising materials for wound healing and care. The mixed-mode thiol-acrylate photopolymerization is used in this paper for alginate/poloxamer hydrogels formation. First, the alginate was modified with thiol groups using the esterification reaction with cysteamine, and second, the terminal hydroxyl groups of poloxamer were esterified with acryloyl chloride to introduce polymerizable acrylate groups. Finally, the cross-linking reaction between the two macromers was performed to produce degradable alginate/poloxamer hydrogels. The optimum conditions for the photo-initiated reaction were studied in order to obtain high gel fractions. The resulting hydrogels have high swelling capacity in simulated physiological conditions, good elasticity and strength, and appropriate porosity, some of the physico-chemical properties required for their applications as wound dressings/patches. The biological assays show that the alginate/poloxamer hydrogels induce proliferation of human keratinocyte and have an anti-inflammatory effect on lipopolysaccharides (LPS)-activated keratinocytes by inhibiting the extracellular signal-regulated kinases (ERK)/ nuclear factor (NF)-kB/ tumor necrosis factor (TNF)-α signalling pathway. Taken together, the results showed that the chemical cross-linked alginate/poloxamer hydrogels may function as a dressing/patch applied directly on the skin lesion to heal the wound by reducing the exacerbated inflammation, the main cause of wound healing delay and local infection.

New composites based on starch/Ecoflex®/biomass wastes: Mechanical, thermal, morphological and antimicrobial properties.

Different biomass wastes were successfully blended with starch and Ecoflex® viz. poly(butylene adipate-co-terephthalate), without glycerol addition, to obtain biocomposite materials. The mechanical properties, as well as thermal and surface properties, of the developed composites were evaluated. It was found that the tensile strength and impact strength improved upon the addition of lignin, while the water uptake capacity decreased. The presence of 5% lignin determined an increase in tensile strength of 125.4% for materials comprising celery (CEL), 109.6% for materials comprising poplar seed hair fibers (PSH), 92.9% for materials comprising pomace (POM) and 127.7% for materials comprising Asclepias syriaca fibers (ASF), compared with a reference sample. The addition of lignin to all the formulations conferred good antimicrobial properties against different microorganisms, S. aureus and especially E. coli. The good mechanical properties, water resistance and antimicrobial activity against pathogens recommend these composites to be used in the manufacture of packaging materials.

Biocompatible Materials Based on Plasticized Poly(lactic acid), Chitosan and Rosemary Ethanolic Extract I. Effect of Chitosan on the Properties of Plasticized Poly(lactic acid) Materials.

The purpose of the present study is to develop new multifunctional environmentally friendly materials having applications both in medical and food packaging fields. New poly(lactic acid) (PLA)-based multifunctional materials containing additives derived from natural resources like chitosan (CS) and rosemary extract (R) were obtained by melt mixing. Each of the selected components has its own specific properties such as: PLA is a biodegradable thermoplastic aliphatic polyester derived from renewable biomass, heat-resistant, with mechanical properties close to those of polystyrene and polyethylene terephthalate, and CS offers good antimicrobial activity and biological functions, while R significantly improves antioxidative action necessary in all applications. A synergy of their combination, an optimum choice of their ratio, and processing parameters led to high performance antimicrobial/antioxidant/biocompatible/environmentally degradable materials. The polyethylene glycol (PEG)-plasticized PLA/chitosan/powdered rosemary extract biocomposites of various compositions were characterized in respect to their mechanical and rheological properties, structure by spectroscopy, antioxidant and antimicrobial activities, and in vitro and in vivo biocompatibility. Scanning electron microscopy images evidence the morphology features added by rosemary powder presence in polymeric materials. Incorporation of additives improved elongation at break, antibacterial and antioxidant activity and also biocompatibility. Migration of bioactive components into D1 simulant is slower for PEG-plasticized PLA containing 6 wt % chitosan and 0.5 wt % rosemary extract (PLA/PEG/6CS/0.5 R) biocomposite and it occurred by a diffusion-controlled mechanism. The biocomposites show high hydrophilicity and good in vitro and in vivo biocompatibility. No hematological, biochemical and immunological modifications are induced by subcutaneous implantation of biocomposites. All characteristics of the PEG-plasticized PLA-based biocomposites recommend them as valuable materials for biomedical implants, and as well as for the design of innovative drug delivery systems. Also, the developed biocomposites could be a potential nature-derived active packaging with controlled release of antimicrobial/antioxidant compounds.

Chitosan-Based Bionanocomposite Films Prepared by Emulsion Technique for Food Preservation.

Biopolymer nanocomposite films were prepared by casting film-forming emulsions based on chitosan/Tween 80/rosehip seed oil and dispersed montmorillonite nanoclay C30B. The effect of composition on structural, morphological characteristics and, mechanical, barrier, antimicrobial and antioxidant properties was studied. The presence of rosehip seed oil in chitosan films led to the formation of flexible films with improved mechanical, gas and water vapour barrier properties and antioxidant activity. The in vitro antibacterial tests against Escherichia coli, Salmonella typhymurium, and Bacillus cereus showed that the chitosan/rosehip seed oil/montmorillonite nanoclay composites effectively inhibited all the three microorganisms.

Evaluation of the Rosemary Extract Effect on the Properties of Polylactic Acid-Based Materials.

New multifunctional materials containing additives derived from natural resources as powdered rosemary ethanolic extract were obtained by melt mixing and processed in good conditions without degradation and loss of additives. Incorporation of powdered rosemary ethanolic extract (R) into poly(lactic acid) (PLA) improved elongation at break, rheological properties, antibacterial and antioxidant activities, in addition to the biocompatibility. The good accordance between results of the chemiluminescence method and radical scavenging activity determination by chemical method evidenced the increased thermoxidative stability of the PLA biocomposites with respect to neat PLA, with R acting as an antioxidant. PLA/R biocomposites also showed low permeability to gases and migration rates of the bioactive compounds and could be considered as high-performance materials for food packaging. In vitro biocompatibility based on the determination of surface properties demonstrated a good hydrophilicity, better spreading and division of fibroblasts, and increased platelet cohesion. The implantation of PLA/R pellets, was proven to possess a good in vivo biocompatibility, and resulted in similar changes in blood parameters and biochemical responses with the control group, suggesting that these PLA-based materials demonstrate very desirable properties as potential biomaterials, useful in human medicine for tissue engineering, wound management, orthopedic devices, scaffolds, drug delivery systems, etc. Therefore, PLA/R-based materials show promising properties for applications both in food packaging and as bioactive biomaterials.

Biodegradation of poly(lactic acid) and some of its based systems with Trichoderma viride.

The purpose of this study was to assess the biodegradation of poly(lactic acid) (PLA) and some plasticized PLA based systems by Trichoderma viride fungus, in liquid medium and controlled laboratory conditions. The studied systems were achieved using PLA, hydrolyzed collagen (HC) as biological macromolecules and other additives by melt processing procedure. PLA and the systems' biodegradability was examined by the weight losses of the samples (after 7 and 21 days of exposure) and FTIR-ATR, GPC, SEM analyses (after 21 fungus inoculation days). The thermogravimetry (TG-DTG) study showed that the thermostability of the samples decreased after biodegradation and was influenced by the chemical structure of the systems' components.