Selective Encapsulation of the Polyphenols on Silk Fibroin Nanoparticles: Optimization Approaches.

The present study proposes a method for designing small bioactive nanoparticles using silk fibroin as a carrier to deliver hydrophobic polyphenols. Quercetin and trans-resveratrol, widely distributed in vegetables and plants, are used here as model compounds with hydrophobic properties. Silk fibroin nanoparticles were prepared by desolvation method and using various concentrations of ethanol solutions. The optimization of the nanoparticle formation was achieved by applying Central Composite Design (CCD) and the response surface methodology (RSM). The effects of silk fibroin and ethanol solution concentrations together with the pH on the selective encapsulation of phenolic compounds from a mixture were reported. The obtained results showed that nanoparticles with an average particle size of 40 to 105 nm can be prepared. The optimized system for the selective encapsulation of the polyphenols on the silk fibroin substrate was determined to be 60% ethanol solution and 1 mg/mL silk fibroin concentration at neutral pH. The selective encapsulation of the polyphenols was achieved, with the best results being obtained in the case of resveratrol and quercetin and encapsulation of gallic and vanillic acids being rather poor. Thin-layer chromatography confirmed the selective encapsulation and the loaded silk fibroin nanoparticles exhibited antioxidant activity.

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.

Development of Vaginal Carriers Based on Chitosan-Grafted-PNIPAAm for Progesterone Administration.

Chitosan-based hydrogels possess numerous advantages, such as biocompatibility and non-toxicity, and it is considered a proper material to be used in biomedical and pharmaceutical applications. Vaginal administration of progesterone represents a viable alternative for maintaining pregnancy and reducing the risk of miscarriage and in supporting the corpus luteum during fertilization cycles. This study aimed to develop new formulations for vaginal administration of progesterone (PGT). A previously synthesized responsive chitosan-grafted-poly (N-isopropylacrylamide) (CS-g-PNIPAAm) was formulated in various compositions with polyvinyl alcohol (PVA) as external crosslinking agent to obtain pH- and temperature-dependent hydrogels; the hydrogels had the capacity to withstand shear forces encountered in the vagina due to its mechanism of swelling once in contact with vaginal fluids. Three different hydrogels based on grafted chitosan were analyzed via Fourier-transform infrared spectroscopy (FTIR), swelling tests, in vitro drug release, and bioadhesion properties by TA.XTplus texture analysis. A higher amount of PVA decreased the swelling and the bioadhesion capacities of the hydrogel. All hydrogels showed sensitivity to temperature and pH in terms of swelling and in vitro delivery characteristics. By loading progesterone, the studied hydrogels seemed to possess even higher sensitivity than drug-free matrices. The release profile of the active substance and the bioadhesion characteristics recommended the CS-g-PNIPAAm/PVA 80/20 +PGT (P1) hydrogel as a proper constituent for the vaginal formulation for progesterone administration.

Synthesis and Application of Reactive Acrylic Latexes: Effect of Particle Morphology.

The aim of the study is the synthesis and characterization of epoxy functional reactive polyacrylic latexes, e.g., poly (BA-co-MMA-co-AN-co-GMA) with core/shell and non-structured (random) particle morphologies. Additionally, their performance as binders and coating ability in leather finishing were studied. The epoxy functional polymers were synthesized via the seeded emulsion polymerization technique and the obtained latexes were characterized by means of particle size, zeta potential, FTIR, TEM, DSC, DMTA, and TGA. The results showed that the particle size and zeta potential values were very similar for both latexes, except core/shell latex had slightly higher particle size. DSC, TEM, and DMTA studies verified the successful synthesis of core/shell latex morphology. The copolymer films were elastic in nature and had low Tg values (-13 and -20 °C). The performance results showed some different behavior for core/shell and random copolymer coatings. The abrasion resistance of the leather finish with random copolymer as binder exhibited slightly better values, especially in wet conditions. On the other hand, the leathers finished with core/shell binder showed better performance in flexing endurance and the water spotting test.

Synthesis of Bioactive Materials by In Situ One-Step Direct Loading of Syzygium aromaticum Essential Oil into Chitosan-Based Hydrogels.

Hydrogel conjugates based on chitosan and an essential oil were synthetized by an ultrasound-assisted emulsification approach. Rheology studies revealed a gel-type structure with pronounced compactness and flexibility while SEM showed the formation of a two-level ordered network with highly interconnected pores. The swelling studies indicated a pH-dependent behavior with a significant overshooting effect. The synergistic effects of the components in clove essential oil led to a strong antioxidant character and an enhanced antimicrobial activity of the conjugate hydrogels. The bioactivity was maintained for 6 months, despite a slight decrease in the antimicrobial effect. Hydrogel conjugates were found to be very stable even after two months immersed in acidic solutions that would otherwise dissolve the chitosan matrix. Ultrasound emulsification was proved as an efficient one-step loading method of hydrophobic clove essential oil into hydrophilic chitosan matrix. It was found that clove oil and its components have a double role. Besides providing bioactivity, they also behave as gelation-inducing agents, acting as an alternative to the classical chemical cross-linkers to ensure the good physical and chemical stabilization of chitosan.

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.

Chitosan-Graft-Poly(N-Isopropylacrylamide)/PVA Cryogels as Carriers for Mucosal Delivery of Voriconazole.

The objective of this study was to prepare and characterize physically crosslinked gel formulations of chitosan (CS)-graft-poly(N-isopropyl acrylamide) (PNIPAAm) and polyvinyl alcohol (PVA) for smart delivery of an antifungal drug, Voriconazole, for mucosal applications. For this purpose, cryogels of CS-g-PNIPAAm/PVA and CS/PVA were tested by means of texture profile analysis and rheology to determine optimal matrix properties for topical application. The ratio of 75/25 v/v % CS-g-PNIPAAm/PVA was selected to be used for formulation since it gave low compressibility and hardness (1.2 and 0.6 N) as well as high adhesion properties and non-Newtonian flow behavior. The cryogels and formulations were further characterized by means of FTIR spectroscopy, swelling behavior, texture analysis, scanning electron microscopy (SEM), thermal (differential scanning calorimetry (DSC) and TGA), and rheological behavior. The drug loading capacity and in vitro release profile of the drug, storage stability, and cytotoxicity tests were also performed for the gel formulation. The FTIR, DSC, and TGA results verified the successful formation of cryogels. Swelling studies revealed a pH-dependent swelling ability with a maximum swelling degree of 1200% in acid and 990% in phosphate buffer (pH 7.4). Thermal studies showed that CS-g-PNIPAAm/PVA 75/25 had higher thermal stability proving the structural complexity of the polymer. The loading capacity of Voriconazole was found to be 70% (w/w). The in vitro release profiles of Voriconazole showed Fickian release behavior for CS-g-PNIPAAm/PVA 75/25 gel with an approximate delivery of 38% within 8 h, slower than matrices containing unmodified chitosan. The storage stability test exhibited that the gel formulation was still stable even after aging for two months. Moreover, the cell culture assays revealed a non-toxic character of the polymeric matrix. Overall results showed that the CS-g-PNIPAAm/PVA 75/25 hydrogel has the potential to be used as a smart polymeric vehicle for topical applications.

New Alginate/PNIPAAm Matrices for Drug Delivery.

This paper deals with a comparative study on the interpolymeric complexes of alginate poly(N-isopropyl acryl amide (PNIPAAm) and corresponding graft copolymers with various compositions in respect to their toxicity, biocompatibility and in vitro and in vivo release of theophylline (THP). Loading of the various matrices with theophylline and characterization of loaded matrices was studied by near infrared spectroscopy⁻chemical imaging (NIR⁻CI) analysis, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). It was appreciated that THP loading is higher than 40% and the drug is relatively homogeneous distributed within all matrices because of some specific interactions between components of the system. All samples have been found to be non-toxic and biocompatible. It was established that graft copolymers having a good stability show a better drug carrier ability, a higher THP loading, a prolonged release (longer release duration for graft copolymers of 235.4⁻302.3 min than that for IPC 72/28 of 77.6 min, which means approximately four times slower release from the graft copolymer-based matrices than from the interpolymeric complex) and a good bioavailability. The highest values for THP loading (45%), prolonged release (302.3 min) and bioavailability (175%) were obtained for graft copolymer AgA-g-PNIPAAm 68. The drug release mechanism varies with composition and architecture of the matrix.

Preparation and in vitro evaluation of melatonin-loaded HA/PVA gel formulations.

Melatonin-loaded hyaluronic acid (HA) and poly(vinyl alcohol) (PVA) gels were prepared by using freeze-thaw technique and an emulsion method followed by freeze-thaw technique to produce a new synergistic system for topical application. Freeze-thaw hydrogels and emulgels were characterized by means of Fourier transform infrared spectroscopy, rheology and swelling tests. The porous structure of the hydrogels was shown by scanning electron microscopy observations and thermal properties were tested by differential scanning calorimetry measurements. Bioadhesion and in vitro release characterization of formulations were performed by texture profile analysis and dialysis bag method, respectively. The pore size of both formulations was ranging from 900 nm to 30 µm. Melatonin showed a good compatibility with the polymeric matrices as the pores were smaller for the drug-loaded systems. In vitro release studies showed that the release was improved by emulgel formulations. After 24 h, the release percentage was found to be 13.240% ± 1.094 and 15.192% ± 2.270 for hydrogel and emulgel, respectively. Emulgels had better bioadhesion properties than simple freeze-thaw samples. As a conclusion, regarding the in vitro characterization studies HA and PVA hydrogel and emulgel formulations and their lyophilized forms could be promising systems for topical application of melatonin.

Toxicity, Biocompatibility, pH-Responsiveness and Methotrexate Release from PVA/Hyaluronic Acid Cryogels for Psoriasis Therapy.

Poly(vinyl alcohol)/hyaluronic acid cryogels loaded with methotrexate were studied. The physical⁻chemical characterization of cryogels was performed by FT-IR spectroscopy, scanning electron microscopy, differential scanning calorimetry and dynamic mechanical thermal analysis. Acute toxicity and haematological parameters were determined by "in vivo" tests. The biocompatibility tests proved that the obtained cryogels showed significantly decreased toxicity and are biocompatible. The pH-responsiveness of the swelling behaviour and of the methotrexate release from the poly(vinyl alcohol)/hyaluronic acid (PVA/HA) cryogels were studied in a pH interval of 2⁻7.4. A significant change in properties was found at pH 5.5 specific for treatment of affected skin in psoriasis disease.