Recycling of Industrial Waste as Soil Binding Additives-Effects on Soil Mechanical and Hydraulic Properties during Its Stabilisation before Road Construction.

To improve the in situ soil stabilization, different chemical additives are used (ion exchange compounds, additives based on H2SO4 or vinyl polymers, and organic additives using lignosulfonates). One interesting alternative is the production of additives from various waste materials. The extensive testing of waste-based blends with soil was performed; the mechanical (unconfined compressive strength (UCS)) and hydraulic (capillary rise, water absorption, and frost resistance (FR)) soil properties were measured. The optimization process led to obtaining additive compositions ensuring high strength and sealing properties: by-pass ash from the ceramics industry, waste H2SO4, pyrolytic waxes/oils from waste mixed plastics, waste tires and HDPE, and emulsion from chewing gum waste. For sandy soil, the following additives were the most promising: emulsion from pyrolytic wax (EPW) from waste PE foil (WPEF) with the addition of waste H2SO4, pyrolytic-oil emulsion from waste tires, EPW from waste mixed plastics with the addition of "by-pass" waste ash and NaOH, EPW from WPEF with the addition of NaOH, and EPW from WPEF reaching up to 93% FR, a 79.6% 7-day UCS increase, and a 27.6% of 28-day UCS increase. For clay: EPW from WPEF with the addition of NaOH, EPW from WPEF with the addition of waste H2SO4, and solely EPW from WPEF reaching up to 7.5% FR, an 80.7% 7-day UCS increase, and a 119.1% 28-day UCS increase.

Thermosensitive composite based on agarose and chitosan saturated with carbon dioxide. Preliminary study of requirements for production of new CSAG bioink.

This study introduces a method for producing printable, thermosensitive bioink formulated from agarose (AG) and carbon dioxide-saturated chitosan (CS) hydrogels. The research identified medium molecular weight chitosan as optimal for bioink production, with a preferred chitosan hydrogel content of 40-60 %. Rheological analysis reveals the bioink's pseudoplastic behavior and a sol-gel phase transition between 27.0 and 31.5 °C. The MMW chitosan-based bioink showed also the most stable extrusion characteristic. The choice of chitosan for the production of bioink was also based on the assessment of the antimicrobial activity of the polymer as a function of its molecular weight and the degree of deacetylation, noting significant cell reduction rates for E. coli and S. aureus of 1.72 and 0.54 for optimal bioink composition, respectively. Cytotoxicity assessments via MTT and LDH tests confirm the bioink's safety for L929, HaCaT, and 46BR.1 N cell lines. Additionally, XTT proliferation assay proved the stimulating effect of the bioink on the proliferation of 46BR.1 N fibroblasts, comparable to that observed with Fetal Bovine Serum (FBS). FTIR spectroscopy confirms the bioink as a physical polymer blend. In conclusion, the CS/AG bioink demonstrates the promising potential for advanced spatial cell cultures in tissue engineering applications including skin regeneration.

Cytocompatibility, antibacterial, and corrosion properties of chitosan/polymethacrylates and chitosan/poly(4-vinylpyridine) smart coatings, electrophoretically deposited on nanosilver-decorated titania nanotubes.

The development of novel implants subjected to surface modification to achieve high osteointegration properties at simultaneous antimicrobial activity is a highly current problem. This study involved different surface treatments of titanium surface, mainly by electrochemical oxidation to produce a nanotubular oxide layer (TNTs), a subsequent electrochemical reduction of silver nitrate and decoration of a nanotubular surface with silver nanoparticles (AgNPs), and finally electrophoretic deposition (EPD) of a composite of chitosan (CS) and either polymethacrylate-based copolymer Eudragit E 100 (EE100) or poly(4-vinylpyridine) (P4VP) coating. The effects of each stage of this multi-step modification were examined in terms of morphology, roughness, wettability, corrosion resistance, coating-substrate adhesion, antibacterial properties, and osteoblast cell adhesion and proliferation. The results showed that the titanium surface formed nanotubes (inner diameter of 97 ± 12 nm, length of 342 ± 36 nm) subsequently covered with silver nanoparticles (with a diameter of 88 ± 8 nm). Further, the silver-decorated nanotubes were tightly coated with biopolymer films. Most of the applied modifications increased both the roughness and the surface contact angle of the samples. The deposition of biopolymer coatings resulted in reduced burst release of silver. The coated samples revealed potent antimicrobial activity against both Gram-positive and Gram-negative bacteria. Total elimination (99.9%) of E. coli was recorded for a sample with CS/P4VP coating. Cytotoxicity results using hFOB 1.19, a human osteoblast cell line, showed that after 3 days the tested modifications did not affect the cellular growth according to the titanium control. The proposed innovative multilayer antibacterial coatings can be successful for titanium implants as effective postoperative anti-inflammation protection.

An influence of molecular weight, deacetylation degree of chitosan xerogels on their antimicrobial activity and cytotoxicity. Comparison of chitosan materials obtained using lactic acid and CO2 saturation.

This paper presents a comparison of the antimicrobial activity and cytotoxicity against L929 cells of chitosan xerogels prepared by dissolving the polymer in a solution of lactic acid (LA) or carbonic acid (CO2) and then freeze-drying. There was no simple relationship between the antimicrobial activity and cytotoxicity of the samples obtained using both techniques (LA and CO2). Chitosan materials obtained by the LA method in a 1:1 dilution were characterized by the highest cytotoxicity against L929 cells (∼20%). For the same diluted samples prepared using the CO2 saturation method, the viability of L929 cells was approximately 2.5 times greater. Some of the tested chitosan materials obtained by the innovative method were characterized by significantly lower antimicrobial activity, for example, reduction of E. coli bacteria for MMW-LA and MMW-CO2 samples by 6.00 and 0.75 logarithmic order, respectively. This clearly indicates that in many applications, the presence of the acid necessary to dissolve chitosan is responsible for the antimicrobial activity of the polymer solution and its products.

Osteoblast and bacterial cell response on RGD peptide-functionalized chitosan coatings electrophoretically deposited from different suspensions on Ti13Nb13Zr alloy.

Metallic materials for long-term load-bearing implants still do not provide high antimicrobial activity while maintaining strong compatibility with bone cells. This study aimed to modify the surface of Ti13Nb13Zr alloy by electrophoretic deposition of a chitosan coating with a covalently attached Arg-Gly-Asp (RGD) peptide. The suspensions for coating deposition were prepared in two different ways either using hydroxyacetic acid or a carbon dioxide saturation process. The coatings were deposited using a voltage of 10 V for 1 min. The prepared coatings were examined using SEM, EDS, FTIR, and XPS techniques. In addition, the wettability of these surfaces, corrosion resistance, adhesion of the coatings to the metallic substrate, and their antimicrobial activity (E. coli, S. aureus) and cytocompatibility properties using the MTT and LDH assays were studied. The coatings produced tightly covered the metallic substrate. Spectroscopic studies confirmed that the peptide did not detach from the chitosan chain during electrophoretic deposition. All tested samples showed high corrosion resistance (corrosion current density measured in nA/cm2 ). The deposited coatings contributed to a significant increase in the antimicrobial activity of the samples against Gram-positive and Gram-negative bacteria (reduction in bacterial counts from 99% to, for CS-RGD-Acid and the S. aureus strain, total killing capacity). MTT and LDH results showed high compatibility with bone cells of the modified surfaces compared to the bare substrate (survival rates above 75% under indirect contact conditions and above 100% under direct contact conditions). However, the adhesion of the coatings was considered weak.

Microemulsion Delivery Systems with Low Surfactant Concentrations: Optimization of Structure and Properties by Glycol Cosurfactants.

Extensive use of microemulsions as delivery systems raises interest in the safe ingredients that can form such systems. Here, we assessed the use of two glycols, i.e., propylene glycol and pentylene glycol, and their mixtures to manipulate the properties and structure of microemulsions. Obtained systems with glycols were extensively characterized in terms of capacity to incorporate water phase, droplet size, polydispersity, structure type, and rheological and thermal properties. The results of these studies indicate that the composition, structure, and viscosity of the microemulsions can be changed by appropriate quantification of glycols. It has been shown that the type of glycol used and its amount may favor or worsen the formation of microemulsions with the selected oils. In addition, a properly selected composition of oils and glycols resulted in the formation of microemulsions with a reduced content of surfactants and consequently improved the safety of using microemulsions as delivery systems.

A Novel Method of Endotoxins Removal from Chitosan Hydrogel as a Potential Bioink Component Obtained by CO2 Saturation.

The article presents a new approach in the purification of chitosan (CS) hydrogel in order to remove a significant amount of endotoxins without changing its molecular weight and viscosity. Two variants of the method used to purify CS hydrogels from endotoxins were investigated using the PyroGene rFC Enzymatic Cascade assay kit. The effect of the CS purification method was assessed in terms of changes in the dynamic viscosity of its hydrogels, the molecular weight of the polymer, microbiological purity after refrigerated storage and cytotoxicity against L929 cells based on the ISO 10993-5:2009(E) standard. The proposed purification method 1 (M1) allows for the removal of significant amounts of endotoxins: 87.9-97.6% in relation to their initial concentration in the CS hydrogel without affecting the solution viscosity. Moreover, the final solutions were sterile and microbiologically stable during storage. The M1 purification method did not change the morphology of the L929 cells.

A novel method of creating thermoplastic chitosan blends to produce cell scaffolds by FDM additive manufacturing.

Due to its remarkable and promising biological and structural properties, chitosan has been widely studied in several potential applications in the biomedical sector. Attempts are being made to use this polymer and its properties in thermoplastics dedicated to 3D printing in FDM technology. However, chitosan can be processed only from acid solution, which limits its applications. The paper presents a new path for the production of filaments based on unstable chitosan hydrogel obtained by carbon dioxide saturation, as well as synthetic polymers such as polyvinyl alcohol and polycaprolactone. The results confirm that the absence of acid allows formation of thermally stable and printable filaments containing from 5% to 15% of chitosan, capable of reducing S. aureus and E. coli bacteria by 0.41-1.43 in logarithmic scale (56-94%) and 0.28-0.94 in logarithmic scale (36-89%), respectively.

Morphology, Thermo-Mechanical Properties and Biodegradibility of PCL/PLA Blends Reactively Compatibilized by Different Organic Peroxides.

Reactive blending is a promising approach for the sustainable development of bio-based polymer blends and composites, which currently is gaining more and more attention. In this paper, biodegradable blends based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared via reactive blending performed in an internal mixer. The PCL and PLA content varied in a ratio of 70/30 and 55/45. Reactive modification of PCL/PLA via liquid organic peroxides (OP) including 0.5 wt.% of tert-butyl cumyl peroxide (BU), 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane (HX), and tert-butyl peroxybenzoate (PB) is reported. The materials were characterized by rotational rheometer, atomic force microscopy (AFM), thermogravimetry (TGA), differential scanning calorimetry (DSC), tensile tests and biodegradability tests. It was found that the application of peroxides improves the miscibility between PCL and PLA resulted in enhanced mechanical properties and more uniform morphology. Moreover, it was observed that the biodegradation rate of PCL/PLA blends reactively compatibilized was lower comparing to unmodified samples and strongly dependent on the blend ratio and peroxide structure. The presented results confirmed that reactive blending supported by organic peroxide is a promising approach for tailoring novel biodegradable polymeric systems with controllable biodegradation rates.

Influence of Rhamnolipids and Ionic Cross-Linking Conditions on the Mechanical Properties of Alginate Hydrogels as a Model Bacterial Biofilm.

The literature indicates the existence of a relationship between rhamnolipids and bacterial biofilm, as well as the ability of selected bacteria to produce rhamnolipids and alginate. However, the influence of biosurfactant molecules on the mechanical properties of biofilms are still not fully understood. The aim of this research is to determine the effect of rhamnolipids concentration, CaCl2 concentration, and ionic cross-linking time on the mechanical properties of alginate hydrogels using a Box-Behnken design. The mechanical properties of cross-linked alginate hydrogels were characterized using a universal testing machine. It was assumed that the addition of rhamnolipids mainly affects the compression load, and the value of this parameter is lower for hydrogels produced with biosurfactant concentration below CMC than for hydrogels obtained in pure water. In contrast, the addition of rhamnolipids in an amount exceeding CMC causes an increase in compression load. In bacterial biofilms, the presence of rhamnolipid molecules does not exceed the CMC value, which may confirm the influence of this biosurfactant on the formation of the biofilm structure. Moreover, rhamnolipids interact with the hydrophobic part of the alginate copolymer chains, and then the hydrophilic groups of adsorbed biosurfactant molecules create additional calcium ion trapping sites.

Tin Oxide Encapsulated into Pyrolyzed Chitosan as a Negative Electrode for Lithium Ion Batteries.

Tin oxide is one of the most promising electrode materials as a negative electrode for lithium-ion batteries due to its higher theoretical specific capacity than graphite. However, it suffers lack of stability due to volume changes and low electrical conductivity while cycling. To overcome these issues, a new composite consisting of SnO2 and carbonaceous matrix was fabricated. Naturally abundant and renewable chitosan was chosen as a carbon source. The electrode material exhibiting 467 mAh g-1 at the current density of 18 mA g-1 and a capacity fade of only 2% after 70 cycles is a potential candidate for graphite replacement. Such good electrochemical performance is due to strong interaction between amine groups from chitosan and surface hydroxyl groups of SnO2 at the preparation stage. However, the charge storage is mainly contributed by a diffusion-controlled process showing that the best results might be obtained for low current rates.

The Synergistic Microbiological Effects of Industrial Produced Packaging Polyethylene Films Incorporated with Zinc Nanoparticles.

Zinc compounds in polyolefin films regulate the transmission of UV-VIS radiation, affect mechanical properties and antimicrobial activity. According to hypothesis, the use of zinc- containing masterbatches in polyethylene films (PE) with different chemical nature-hydrophilic zinc oxide (ZO) and hydrophobic zinc stearate (ZS)-can cause a synergistic effect, especially due to their antimicrobial properties. PE films obtained on an industrial scale containing zinc oxide and zinc stearate masterbatches were evaluated for antimicrobial activity against E. coli and S. aureus strains. The morphology of the samples (SEM), composition (EDX), UV barrier and transparency, mechanical properties and global migration level were also determined. SEM micrographs confirmed the good dispersion of zinc additives in the PE matrix. The use of both masterbatches in one material caused a synergistic effect of antimicrobial activity against both bacterial strains. The ZO masterbatch reduced the transparency of films, increased their UV-barrier ability and improved tensile strength, while the ZS masterbatch did not significantly change the tested parameters. The global migration limit was not exceeded for any of the samples. The use of ZO and ZS masterbatch mixtures enables the design of packaging with high microbiological protection with a controlled transmission for UV and VIS radiation.

Obtaining and Characterization of the PLA/Chitosan Foams with Antimicrobial Properties Achieved by the Emulsification Combined with the Dissolution of Chitosan by CO2 Saturation.

A new method of obtaining functional foam material has been proposed. The materials were created by mixing the poly lactic acid (PLA) solution in chloroform, chitosan (CS) dissolved in water saturated with CO2 and polyethylene glycol (PEG), and freeze-dried for removal of the solvents. The composite foams were characterized for their structural (SEM, FT-IR, density, porosity), thermal (DSC), functional (hardness, elasticity, swelling capacity, solubility), and biological (antimicrobial and cytotoxic) properties. Chitosan in the composites was a component for obtaining their foamed form with 7.4 to 22.7 times lower density compared to the neat PLA and high porosity also confirmed by the SEM. The foams had a hardness in the range of 70-440 kPa. The FT-IR analysis confirmed no new chemical bonds between the sponge ingredients. Other results showed low sorption capacity (2.5-7.2 g/g) and solubility of materials (less than 0.2%). The obtained foams had the lower Tg value and improved ability of crystallization compared to neat PLA. The addition of chitosan provides the bacteriostatic and bactericidal properties against Escherichia coli and Staphylococcus aureus. Biocompatibility studies have shown that the materials obtained are not cytotoxic to the L929 cell line.

The Production Possibility of the Antimicrobial Filaments by Co-Extrusion of the PLA Pellet with Chitosan Powder for FDM 3D Printing Technology.

The last decades have witnessed a major advancement and development in three-dimensional (3D) printing technology. In the future, the trend's utilization of 3D printing is expected to play an important role in the biomedical field. This work presents co-extrusion of the polylactic acid (PLA), its derivatives (sPLA), and chitosan with the aim of achieving filaments for printing 3D objects, such as biomedical tools or implants. The physicochemical and antimicrobial properties were evaluated using SEM, FT-IR, DSC, instrumental mechanical test, and based on the ASTM E2149 standard, respectively. The addition of chitosan in the PLA and sPLA filaments increased their porosity and decreased density. The FT-IR analysis showed that PLA and chitosan only formed a physical mixture after extrusion. The addition of chitosan caused deterioration of the mechanical properties of filaments, especially elongation at break and Young's modulus. The addition of chitosan to the filaments improved their ability to crystallize and provide their antimicrobial properties against Escherichia coli and Staphylococcus aureus.

The Drop-in-Drop Encapsulation in Chitosan and Sodium Alginate as a Method of Prolonging the Quality of Linseed Oil.

Nowadays, the encapsulation of sensitive products by various techniques has become popular as a promising preservation method. In particular, this applies to oils with a high content of unsaturated fatty acids and a high susceptibility to deterioration. This work presents the possibility of using a chitosan and sodium alginate in the form of a hydrogel membrane to protect food ingredients such as linseed oil, which is stored in an aquatic environment. The obtained results showed the high efficiency of the coaxial method encapsulation, which did not affect the quality of the oil measured after encapsulation. The greatest protective effect was observed in the linseed oil⁻chitosan membrane system, in which the primary and secondary oxidation products content were 88% and 32% lower than in the control sample, respectively. The smallest changes of the fatty acid profile, conjugated dienes, and trienes were observed in the chitosan capsules with linseed oil compared to the control sample.

Investigation of an elutable N-propylphosphonic acid chitosan derivative composition with a chitosan matrix prepared from carbonic acid solution.

Porous chitosan composites using CO2 dissolution procedure and including water soluble N-propylphosphonic chitosan derivative (p-CHI) were obtained and characterized. In contrast to the control material, composites containing modified chitosan distinguished by a rapid moisture absorption and good adhesion to the skin. The FTIR analysis confirmed the presence of propylphosphonic group in the structure of the polymer. The porosity of the materials was in the range 55-77% and decreased with increasong amount of modified chitosan in materials. Solubility of composites was dependent on the content of p-CHI in scaffolds (40%, 25% and 15%) and reached values 11%, 9% and 6,5%, respectively. The values of other parameters like swelling degree (30g/g) good antioxidant and antimicrobial properties (almost 100% reduction of S.aureus, E.coli and C. albicans growth) and low in vitro cytotoxicity against fibroblasts were highly advantageous for possible biomedical applications of the composites.