Characterization and In Vitro Evaluation of Porous Polymer-Blended Scaffolds Functionalized with Tricalcium Phosphate.

Bone tissue is one of the most transplanted tissues. The ageing population and bone diseases are the main causes of the growing need for novel treatments offered by bone tissue engineering. Three-dimensional (3D) scaffolds, as artificial structures that fulfil certain characteristics, can be used as a temporary matrix for bone regeneration. In this study, we aimed to fabricate 3D porous polymer scaffolds functionalized with tricalcium phosphate (TCP) particles for applications in bone tissue regeneration. Different combinations of poly(lactic acid) (PLA), poly(ethylene glycol) (PEG with molecular weight of 600 or 2000 Da) and poly(ε-caprolactone) (PCL) with TCP were blended by a gel-casting method combined with rapid heating. Porous composite scaffolds with pore sizes from 100 to 1500 µm were obtained. ATR-FTIR, DSC, and wettability tests were performed to study scaffold composition, thermal properties, and hydrophilicity, respectively. The samples were observed with the use of optical and scanning electron microscopes. The addition of PCL to PLA increased the hydrophobicity of the composite scaffolds and reduced their susceptibility to degradation, whereas the addition of PEG increased the hydrophilicity and degradation rates but concomitantly resulted in enhanced creation of rounded mineral deposits. The scaffolds were not cytotoxic according to an indirect test in L929 fibroblasts, and they supported adhesion and growth of MG-63 cells when cultured in direct contact.

Bio-Based Polymers for Environmentally Friendly Phase Change Materials.

Phase change materials (PCMs) have received increasing attention in recent years as they enable the storage of thermal energy in the form of sensible and latent heat, and they are used in advanced technical solutions for the conservation of sustainable and waste energy. Importantly, most of the currently applied PCMs are produced from non-renewable sources and their carbon footprint is associated with some environmental impact. However, novel PCMs can also be designed and fabricated using green materials without or with a slight impact on the environment. In this work, the current state of knowledge on the bio-based polymers in PCM applications is described. Bio-based polymers can be applied as phase-change materials, as well as for PCMs encapsulation and shape stabilization, such as cellulose and its derivatives, chitosan, lignin, gelatin, and starch. Vast attention has been paid to evaluation of properties of the final PCMs and their application potential in various sectors. Novel strategies for improving their thermal energy storage characteristics, as well as to impart multifunctional features, have been presented. It is also discussed how bio-based polymers can extend in future the potential of new environmentally-safe PCMs in various industrial fields.

The Potential of Sheep or Camel Milk Constituents to Contribute to Novel Dressings for Diabetic Wounds.

Impaired wound healing is a complication of diabetes, which constitutes a serious problem in clinical practice. Currently, there is a high demand on the market for local treatment options for difficult-to-heal wounds caused by diabetes. The development of dressings that accelerate wound healing has recently been the subject of much research. Sheep and camel milk is gaining importance due to the content of many bioactive substances with health-promoting effects, such as insulin, LF, proline, or CLA. Sheep and camel milk proteins are a promising source of insulin, antidiabetic, and antihypertensive peptides. Numerous studies show that local administration of insulin has a significant impact on the healing of diabetic wounds. Sheep and camel milk, due to the highest LF content among ruminants, reduces autoimmune inflammatory processes and protects against bacterial and viral infections in the wound environment. Sheep's milk has the highest content of proline and CLA, and their addition to a hydrogel dressing can help in the development of an effective dressing material. The production of hydrogel dressings containing sheep and camel milk, which are naturally rich in the bioactive substances presented in this review, may be a promising step in the market of specialized dressings for difficult-to-heal diabetic wounds.

Novel Polyurethane-Based Systems Modified with Starch and Phase Change Materials for Bone Tissue Regeneration.

Novel polyurethane-based materials have been synthesized by a two-step process using poly(ε-caprolactone) diol (PCL) and 1,3-propanediol/starch (PDO/ST) systems as chain extenders/cross-linkers and 1,6-hexamethylane diisocyante (HDI) as a potential material for bone tissue replacement or bone cements. A poly(ethylene glycol)/starch (PEG/ST) system has been applied as a form-stable phase change material (PCM) to decrease the maximum setting temperature, while hydroxyapatite (HAp) has been used as a bioactive nanofiller. FTIR and SEM-EDX analyses were performed to investigate the structure, surface morphology, and thermal properties of the obtained polyurethanes. FTIR spectroscopy confirmed the chemical structure of the synthesized polyurethanes. SEM-EDX analysis confirmed the incorporation of starch/hydroxyapatite into the polyurethane matrix. Modification with PCMs based on PEG or PEG/starch systems allowed for a decrease in the maximum setting temperature of PUs from 6 to 7.6 °C, depending on the type of PCM used. Thus, the obtained polyurethanes show a good energy storage effect and a good application potential for the synthesis of multifunctional bioactive materials for future use as bone cements.

The Effect of Chitosan on Physicochemical Properties of Whey Protein Isolate Scaffolds for Tissue Engineering Applications.

New scaffolds, based on whey protein isolate (WPI) and chitosan (CS), have been proposed and investigated as possible materials for use in osteochondral tissue repair. Two types of WPI-based hydrogels modified by CS were prepared: CS powder was incorporated into WPI in either dissolved or suspended powder form. The optimal chemical composition of the resulting WPI/CS hydrogels was chosen based on the morphology, structural properties, chemical stability, swelling ratio, wettability, mechanical properties, bioactivity, and cytotoxicity evaluation. The hydrogels with CS incorporated in powder form exhibited superior mechanical properties and higher porosity, whereas those with CS incorporated after dissolution showed enhanced wettability, which decreased with increasing CS content. The introduction of CS powder into the WPI matrix promoted apatite formation, as confirmed by energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) analyses. In vitro cytotoxicity results confirmed the cytocompatibility of CS powder modified WPI hydrogels, suggesting their suitability as cell scaffolds. These findings demonstrate the promising potential of WPI/CS scaffolds for osteochondral tissue repair.

Fire Retardant Phase Change Materials-Recent Developments and Future Perspectives.

The accumulation of thermal energy in the form of latent heat of phase transition using phase change materials (PCMs) is one of the most attractive and studied research areas with huge application potential in both passive and active technical systems. The largest and most important group of PCMs for low-temperature applications are organic PCMs, mainly paraffins, fatty acids, fatty alcohols, and polymers. One of the major disadvantages of organic PCMs is their flammability. In many applications such as building, battery thermal management, and protective insulations, the crucial task is to reduce the fire risk of flammable PCMs. In the last decade, numerous research works have been performed to reduce the flammability of organic PCMs, without losing their thermal performance. In this review, the main groups of flame retardants, PCMs flame retardation methods as well as examples of flame-retarded PCMs and their application areas were described.

Polymer Nanocomposites: Preparation, Characterisation and Applications.

Polymer nanocomposites are an interesting and rapidly growing class of novel materials with enhanced properties, and these enhancements can be observed even at low nanofiller loading [...].

Preparation, Characterization, and Bioactivity Evaluation of Polyoxymethylene Copolymer/Nanohydroxyapatite-g-Poly(ε-caprolactone) Composites.

In this work, nanohydroxyapatite (HAp) was functionalized with poly(ε-caprolactone) (PCL), using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent, and then incorporated into the polyoxymethylene copolymer (POM) matrix using the extrusion technique. The obtained POM/HAp-g-PCL composites were investigated using FTIR, DSC, TOPEM DSC, and TG methods. Mechanical properties were studied using destructive and non-destructive ultrasonic methods, wettability, and POM crystallization kinetics in the presence of HAp-g-PCL. Moreover, preliminary bioactivity evaluation of the POM/HAp-g-PCL composites was performed using the Kokubo method. It was found that the introduction of HAp-g-PCL to the POM matrix has a limited effect on the phase transitions of POM as well as on its degree of crystallinity. Importantly, HAp grafted with PCL caused a significant increase in the thermal stability of the POM, from 292 °C for pristine POM to 333 °C for POM modified with 2.5% HAp-g-PCL. If unmodified HAp was used, a distinct decrease in the thermal stability of the POM was observed. Crystallization kinetic studies confirmed that HAp-g-PCL, in small amounts, can act as a nucleating agent for the POM crystallization process. Moreover, incorporation of HAp-g-PCL, although slightly decreasing the mechanical properties of POM composites, improved the crucial parameter in biomedical applications, namely the in vitro bioactivity.

Fly Ash as an Eco-Friendly Filler for Rigid Polyurethane Foams Modification.

There is currently a growing demand for more effective thermal insulation materials with the best performance properties. This research paper presents the investigation results on the influence of two types of filler on the structure and properties of rigid polyurethane foam composites. Fly ash as a product of coal combustion in power plants and microspheres of 5, 10, 15, and 20 wt.%, were used as rigid polyurethane foams modifiers. The results of thermal analysis, mechanical properties testing, and cellular structure investigation performed for polyurethane composites show that the addition of fly ash, up to 10 wt.%, significantly improved the majority of the tested parameters. The use of up to 20 wt.% of microspheres improves the mechanical and thermal properties and thermal stability of rigid polyurethane foams.

Recent Developments in Polyurethane-Based Materials for Bone Tissue Engineering.

To meet the needs of clinical medicine, bone tissue engineering is developing dynamically. Scaffolds for bone healing might be used as solid, preformed scaffolding materials, or through the injection of a solidifiable precursor into the defective tissue. There are miscellaneous biomaterials used to stimulate bone repair including ceramics, metals, naturally derived polymers, synthetic polymers, and other biocompatible substances. Combining ceramics and metals or polymers holds promise for future cures as the materials complement each other. Further research must explain the limitations of the size of the defects of each scaffold, and additionally, check the possibility of regeneration after implantation and resistance to disease. Before tissue engineering, a lot of bone defects were treated with autogenous bone grafts. Biodegradable polymers are widely applied as porous scaffolds in bone tissue engineering. The most valuable features of biodegradable polyurethanes are good biocompatibility, bioactivity, bioconductivity, and injectability. They may also be used as temporary extracellular matrix (ECM) in bone tissue healing and regeneration. Herein, the current state concerning polyurethanes in bone tissue engineering are discussed and introduced, as well as future trends.

Surface and Structural Properties of Medical Acrylonitrile Butadiene Styrene Modified with Silver Nanoparticles.

Acrylonitrile butadiene styrene/silver nanoparticles (ABS/AgNPs) composites were manufactured through the plastic processing method. Three different matrices were used to obtain polymer and composite samples containing 0.5 wt % and 1.0 wt % of silver nanoparticles, respectively. The aim of this study was to examine physicochemical properties and stability of the materials in the in vitro conditions for two years. The results showed that composites made from amorphous matrices had comparable mechanical properties after incorporation of AgNPs. The values of Young modulus and tensile strength increased after the first and second year of investigation. Silver nanoparticles did not alter the surface parameters-e.g., roughness and contact angle also retained stable values after the in vitro incubation in water solution. The scanning electron observation revealed homogeneous distribution of silver modifier in all the matrices. The 24-month incubation of materials proved the stability of the composites microstructure. The DSC analysis revealed that addition of AgNPs may decrease glass transition temperature of the composite materials which was also reduced after 12 and 24 months of incubation. The attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopic studies did not indicate significant changes in the ABS matrices either upon their modification with AgNPs or after the long-term testing. The conducted studies proved that all the composites are stable and may be used for a long-term working period.

Distinct Influence of Saturated Fatty Acids on Malignant and Nonmalignant Human Lung Epithelial Cells.

The impact of saturated fatty acids (FA) on viability and properties of malignant and nonmalignant cells has not been studied in detail so far. The present study was aimed at evaluation of the influence of saturated FA (10:0-18:0) on malignant (A459) and nonmalignant (BEAS-2B) human lung epithelial cells. FA strongly affected A549 cells, but not BEAS-2B cells. Viability of A549 cells incubated with 14:0-18:0 was decreased by 53-91% as compared to untreated cells. Cell membrane stiffness in those cells as measured by atomic force microscopy was also reduced. Median value of apparent Young's modulus of untreated A549 cell membrane was 16.9 kPa and it decreased to 8.9 kPa for cells incubated with 14:0. Viability and mechanical properties of BEAS-2B cells were not altered by presence of FA. Those surprising discrepancies can be related to the differences in FA uptake rate. A549 cells were found to incorporate higher amount of FA and this corresponded to decrease in cell membrane stiffness and reduced cell viability. The performed studies showed that saturated FA have distinct influence on various types of cells, which may be exploited in development of the advanced lipid drug delivery systems.

Fluidized bed combustion fly ash as filler in composite polyurethane materials.

Fly ash (FA) is a waste material having great potential as modifier of mechanical and thermal properties in polyurethane (PUR) technology. There are very few reporting the use of fluidized bed combustion (FBC) FA in the production of PUR foams. In this work, authors have used the as received FBC FA as an additive to PUR rigid foams. The composite materials containing 5, 10, 15, and 20 wt% of FA were obtained by hand mixing and casting method. Microscopic observations of both unmodified and composite foams showed a well formed, cellular structure of the rigid foam. The cell structure was uniform; most of the cells were closed, which was an important parameter influencing thermal insulation properties of PUR materials. FA was uniformly distributed within PUR matrix and placed between cells. When the content of FA in composite foams increased, cells' dimensions decreased, which suggested that FA particles acted as nucleation sites during the foam formation process. The absorption bands presented in IR spectrum of PUR foam confirmed the presence of urethane bonds in the unmodified foam material. The IR spectrum of as-received FA reconfirmed the crystalline phases recognized by XRD analysis, which were anhydrite, quartz, lime, calcite and aluminosilicate. No additional bands were observed which suggested that no chemical bonding between PUR matrix and FA particles occurred in the composite foam. The incorporation of FA into the PUR matrix, up to 10 wt%, improved the mechanical performance of the composite materials, when compared to unmodified PUR foam. Such a tendency suggested the occurrence of interfacial interactions between polymer matrix and FA particles, as well as the uniform distribution of the filler within PUR material. For all the materials analyzed, the addition of FA to PUR foam reduced both carbon content and the gross calorific value. The addition of FA improved the thermal stability of the PUR foam material (barrier effect of the FA prevented the release of gases from the foam structure).

Study of chemical, physico-mechanical and biological properties of 4,4'-methylenebis(cyclohexyl isocyanate)-based polyurethane films.

Polyurethane films were obtained in the solvent-free cycloaliphatic polyaddition process of 4,4'-methylenebis(cyclohexyl isocyanate), poly(ε-caprolactone) diol or poly(oxytetramethylene) glycol and 1,4-butanediol. Chemical structures of the polymers were confirmed by FTIR, NMR and GPC methods. Their surface, thermal and mechanical properties have been evaluated. Results of biological studies with polyurethane films as potential biomaterials for medical applications revealed their mild cytotoxicity against normal human fibroblasts (BJ) and immortalized keratinocytes (HaCaT). STATEMENT OF SIGNIFICANCE: The research is relevant for the potential uses of polyurethane films made from commercial raw materials as general medical supplies.

Multifunctional polymer coatings for titanium implants.

The aim of this work was to modify the surface of the titanium implants by application of multifunctional polymer coatings based on polyurethane and its composites with graphene and ß-TCP. Graphene was used as an antibacterial agent, TCP as a bioactive component, and polymer coating as a corrosion protection of metal. As a result, materials with different surface characteristic, from hydrophilic to hydrophobic, varying in bioactivity and biocompatibility, were obtained. Wettability of the materials was tested by the sessile drop method; surface roughness was assessed on the basis of Ra parameter, measured by contact profilometry. The surface characteristic was complemented by microhardness testing. Also, in vitro immersion tests in fluids and cell tests were performed. Obtained results suggest that it is possible to fabricate, on the surface of titanium implants, multifunctional composite coatings based on polyurethane, with optimal composition for bone surgery and dentistry applications. The study further showed that the chemical structure (composition) of the polymer and the graphene content are crucial in terms of biocompatibility of the final material, while addition of tricalcium phosphate affects its bioactivity.

Composites prepared from the waterborne polyurethane cationomers-modified graphene. Part I. Synthesis, structure, and physicochemical properties.

In the reaction of 4,4'-methylenebis(phenyl isocyanate), polycaprolactone diol, and N-methyldiethanolamine, they were synthesized aqueous dispersions of polyurethane cationomers, from which films were prepared after adding 0-2 wt% graphene. In order to obtain nanocomposites, graphene was previously noncovalent functionalized in tetrahydrofurane in the field of ultrasound. The chemical structure and the morphology of obtained nanocomposites were analyzed by IR spectroscopy, atomic force microscopy (AFM), and differential scanning calorimetry (DSC) microcalorimetry methods. It was found that the presence of graphene results in increased thermal and mechanical strength of received polymer films and contributes to the increase in hydrophobicity of generally hydrophilic coatings prepared from waterborne polyurethane cationomers. Based on received results, possible interactions between graphene and phase structure of polyurethane cationomers were discussed. Relating to the so far described applications of graphene for the modification of polyurethanes, the novelty of this work is the concept of incorporation of graphene particles to polyurethane cationomer chains exclusively through a simple noncovalent functionalization and to investigate the effect of graphene on the properties obtained in this way of thin polyurethane film.

Comparison of phase structures and surface free energy values for the coatings synthesised from linear polyurethanes and from waterborne polyurethane cationomers.

WAXS, DSC and AFM methods were employed to compare phase structures of the coatings obtained from waterborne polyurethane cationomers which had been synthesised in the reaction of some diisocyanates (MDI, IPDI, TDI and HDI) with polyoxyethylene glycols (M = 600 and 2,000) and butane1,4-diol or N-methyl- or N-butyldiethanolamine and 2,2,3,3-tetrafluoro-1,4-butanediol. The structures were also analysed of the coatings derived from linear polyurethanes which had been synthesised on the basis of similar raw materials. Better rigidity was found for generally amorphous cationomer coats. Changes were discussed in the surface free energy (SFE) values and in their components, as calculated independently with the use of the van Oss-Good and Owens-Wendt methods. Polyurethane coats turned out more hydrophobic as compared to cationomer ones. In both coat types, fluorine incorporated into cationomers contributed to lower SFE values: from 50 down to about 30 mJ/m(2).