Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity.

Natural deep eutectic solvents (NADES)-hydroxypropyl cellulose (HPC) self-assembled gels with potential for pharmaceutical applications are prepared. FT-IR, 1HNMR, DSC, TGA and rheology measurements revealed that hydrogen bond acceptor−hydrogen bond donor interactions, concentration of NADES and the water content influence significantly the physico-chemical characteristics of the studied gel systems. HPC-NADES gel compositions have thermal stabilities lower than HPC and higher than NADES components. Thermal transitions reveal multiple glass transitions characteristic of phase separated systems. Flow curves evidence shear thinning (pseudoplastic) behavior. The flow curve shear stress vs. shear rate were assessed by applying Bingham, Herschel−Bulkley, Vocadlo and Casson rheological models. The proposed correlations are in good agreement with experimental data. The studied gels evidence thermothickening behavior due to characteristic LCST (lower critical solution temperature) behavior of HPC in aqueous systems and a good biocompatibility with normal cells (human gingival fibroblasts). The order of antibacterial and antifungal activities (S.aureus, E.coli, P. aeruginosa and C. albicans) is as follows: citric acid >lactic acid > urea > glycerol, revealing the higher antibacterial and antifungal activities of acids.

Effect of Gamma Irradiation on the PLA-Based Blends and Biocomposites Containing Rosemary Ethanolic Extract and Chitosan.

The irradiation of polymeric materials with ionizing radiation (γ-rays, X-rays, accelerated electrons, ion beams, etc.) may lead to disproportion, hydrogen abstraction, arrangements, degradation, and/or the formation of new bonds. The purpose of this paper is to evaluate the effect of gamma irradiation on some new poly(lactic acid) (PLA)-based blends and biocomposites, which is crucial when they are used for food packaging or medical purposes. The polymeric blends and biocomposites based on PLA and rosemary ethanolic extract (R) and poly(ethylene glycol) (PEG) (20 wt%) plasticized PLA, chitosan (CS) (3-6 wt%) and R (0.5 wt%) biocomposites were subjected to gamma irradiation treatment using three low γ-doses of 10, 20, and 30 kGy. The effect of irradiation was evaluated by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), thermogravimetry (TG), chemiluminescence method (CL), migration studies, and antibacterial activity tests. It was found that in comparison with neat PLA, the gamma irradiation in the oxidative conditions of the PLA-based blends and biocomposites, causes modifications in the structure, morphology, and thermal properties of the materials depending on irradiation dose and the presence of natural additives such as rosemary and chitosan. It was established that under a gamma-irradiation treatment with dose of 10-20 kGy, the PLA materials showed minor changes in structure and properties being suitable for application in packaging and in addition after irradiation with such doses their antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Salmonella typhimurium is improved.

PLA-Based Materials Containing Bio-Plasticizers and Chitosan Modified with Rosehip Seed Oil for Ecological Packaging.

Several recipes based on PLA, bio-plasticizers, and active agents such as vitamin E and cold-pressed rosehip seed oil encapsulated into chitosan by the emulsion method named here as chitosan modified (CS-M) were elaborated by melt compounding for food packaging applications. Resulted biocomposites have been investigated from the point of view of physical-mechanical, thermal, barrier, antimicrobial, and antioxidant properties to select the formulations with the optimum features to produce food trays and films for packaging applications. The obtained results showed that the elaborated formulations exhibit tensile strength and flexibility dependent on their composition being either rigid or flexible, as well as antimicrobial and antioxidant activity, which will potentially lead to prolonged use for food packaging. The recipe with PLA matrix and 40:60 Lapol®108 as masterbarch/polyethylene glycol (MB/PEG) bio-plasticizers ratio was distinguished by an improvement of over 100 times in terms of flexibility compared with neat PLA, while the highest antioxidant activity (36.27%) was recorded for the sample containing a CS-M and MB/PEG ratio of 60:40. An enhancement of ~50% for the water vapor barrier was recorded for PLA/CS-M_100:0 material. By modulating the MB and PEG bio-plasticizers ratio, the design of new eco-friendly food packaging materials with antimicrobial/antioxidant characteristics by using the existing technologies for processing synthetic polymers (melt mixing, compounding, pressing, thermoforming) has been successfully realized.

Blends of sodium deoxycholate-based poly(ester ether)urethane ionomer and hydroxypropylcellulose with mucosal adhesiveness.

New mucoadhesive blends of sodium deoxycholate-based poly(ester ether)urethane ionomer (PU) and hydroxypropyl cellulose (HPC) are prepared. The presence of the intermolecular interactions between the polymeric components has been investigated by FTIR spectroscopy indicating their miscibility in the solid phase. DSC studies also revealed a single glass transition of the blends, which is indicative of miscibility of PU and HPC in the amorphous phase. The amount of HPC in the blends influences strongly the physicochemical and mucoadhesion/bioadhesion properties. It was found that the value of area attributed to ordered hydrogen bonding (FTIR), the onset temperature values of thermal degradation in N2 flow (TG/DTG), the values of the sorption capacity (Dynamic Vapor Sorption-DVS), the values of the apparent viscosity (rheological measurements) and mucoadhesion/bioadhesion properties increased by increasing the HPC content in the blends. Complex viscosity revealed shear thinning behavior for all the studied solutions evidencing the contributive role of polymer viscoelasticity on mucoadhesion. It was found that both G' and G" increase with an increase in angular frequency and G">G' which is characteristic for liquid-like (sol state) behavior for all blended solutions and this behavior is helpful in the adhesion with mucosa surface. Mucoadhesion of PU/HPC blends was assessed in the stomach mucosa at pH 2.6 and 37 °C. Bioadhesion test was performed at pH 7.4 and 37 °C and revealed a stronger interaction of PU/HPC blends with cellulose membrane than with stomach mucosa. The similar nature of the HPC and cellulose membrane determines additional adhesion forces and implicity high adhesion properties. The HPC component increases the hydrophilicity of the blends as DVS analysis revealed, but also leads to hydrolytic degradation. FTIR spectroscopy analysis was used to evaluate the hydrolytic stability in acid (pH 2.6) and slightly alkaline (pH 7.4) PBS media and a mechanism of degradation has been proposed.

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.

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.

Hybrid Nanostructures Containing Sulfadiazine Modified Chitosan as Antimicrobial Drug Carriers.

Chitosan (CH) nanofibrous structures containing sulfadiazine (SDZ) or sulfadiazine modified chitosan (SCH) in the form of functional nanoparticles attached to nanofibers (hybrid nanostructures) were obtained by mono-axial and coaxial electrospinning. The mono-axial design consisted of a SDZ/CH mixture solution fed through a single nozzle while the coaxial design consisted of SCH and CH solutions separately supplied to the inner and outer nozzle (or in reverse order). The CH ability to form nanofibers assured the formation of a nanofiber mesh, while SDZ and SCH, both in form of suspensions in the electrospun solution, assured the formation of active nanoparticles which remained attached to the CH nanofiber mesh after the electrospinning process. The obtained nanostructures were morphologically characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The SDZ release profiles and kinetics were analyzed. The SDZ or SCH nanoparticles loosely attached at the surface of the nanofibers, provide a burst release in the first 20 min, which is important to stop the possible initial infection in a wound, while the SDZ and SCH from the nanoparticles which are better confined (or even encapsulated) into the CH nanofibers would be slowly released with the erosion/disruption of the CH nanofiber mesh.

Sulfadiazine-Chitosan Conjugates and Their Polyelectrolyte Complexes with Hyaluronate Destined to the Management of Burn Wounds.

In the present study polyelectrolyte complexes (PECs) based on new sulfadiazine-chitosan conjugates with sodium hyaluronate have been developed with potential use in treatment of burn wounds. The PECs were chemically characterized using Fourier Transform-Infrared Spectroscopy, Scanning Electon Microscopy and Near Infrared Chemical Imaging Technique. The swelling behavior and in vitro sulfadiazine release were also investigated. The antimicrobial activity was evaluated towards three bacterial strains: Escherichia coli, Listeria monocytogenes and Salmonella thyphymurium. The developed PECs demonstrated their antimicrobial efficiency against tested bacterial strains, the PECs containing sulfadiazine-modified chitosan being more active than PECs containing unmodified chitosan.

Sulfadiazine modified CS/HA PEC destined to wound dressing.

AIM: To present the research results concerning enhanced antimicrobial and release properties of the chitosan derivative with sulfadiazine/hyaluronic acid polyelectrolyte complex (PEC) hydrogel. MATERIAL AND METHODS: The PECs have been prepared from chitosan of different molecular weight, sulfadiazine chitosan derivative and sodium hyaluronate. The complex structure was assessed by FT-IR spectroscopic method and swelling capacity was followed by weighing measurements. RESULTS: It has been establish that chitosan derivative influenced both PEC properties and swelling capacity. CONCLUSIONS: Incorporation in PEC of the sulfadiazine chitosan is a new way to combine bacteriostatic effect of chitosan with that of sulfadiazine, to control properties, antimicrobial activity in the treatment of the wound.

Chitosan/hyaluronic acid polyelectrolyte complex hydrogels in the management of burn wounds.

AIM: This paper is a short review on the state-of-the-art of the use of polyelectrolyte complexes containing polysaccharides for wound and burn healing and treatment using the chitosan/hyaluronic acid polyelectrolyte complex (PEC) hydrogel. RESULTS AND CONCLUSIONS: PEC is suitable for wound healing because a wet treatment can be realized and both components of PEC contribute by their properties to the enhanced antimicrobial activity, promote wound healing and prevent wound damage during treatment.

In vitro evaluation of ketoprofen controlled release from various formulations.

UNLABELLED: The aim of this study is to investigate the potential utility of some hydrogels, based on chitosan, chitosan modified with phthalic anhydride and 75/25 poly(N-isopropyl acrylamide)/alginate, for preparing drug release systems containing ketoprofen, as model drug. MATERIAL AND METHOD: The in vitro release profiles and swelling studies were done in ethanol medium, where the studied drug presents high solubility, at 25 degrees C (room temperature). The ketoprofen release was observed by monitoring the absorbance at max = 254 nm as a function of time. RESULTS: The experimental results indicated that the smallest amount of drug was released from chitosan matrices, appreciatively 31%. CONCLUSIONS: The composition of hydrogels had an important effect on ketoprofen release.