Some composite materials have been prepared, constituted by a cyclodextrin-bis-urethane-based nanosponge matrix in which a reduced graphene oxide/silver nanoparticles photocatalyst has been dispersed. Different chain extenders were employed for designing the nanosponge supports, in such a way as to decorate their hyper-cross-linked structure with diverse functionalities. Moreover, two different strategies were explored to accomplish the silver loading. The obtained systems were successfully tested as catalysts for the photodegradation of emerging pollutants such as model dyes and drugs. Enhancement of the photoactive species performance (up to nine times), due to the synergistic local concentration effect exerted by the nanosponge, could be assessed. Overall, the best performances were shown by polyamine-decorated materials, which were able to promote the degradation of some particularly resistant drugs. Some methodological issues pertaining to data collection are also addressed.
Biosourced and biodegradable polyesters like poly(butylene succinate-co-butylene adipate) (PBSA) are gaining traction as promising alternatives to oil-based thermoplastics for single-use applications. However, the mechanical and rheological properties of PBSA are affected by its thermomechanical sensitivity during its melt processing, also hindering PBSA mechanical recycling. Traditional reactive melt processing (RP) methods use chemical additives to counteract these drawbacks, compromising sustainability. This study proposes a green reactive method during melt compounding for PBSA based on a comprehensive understanding of its thermomechanical degradative behavior. Under the hypothesis that controlled degradative paths during melt processing can promote branching/recombination reactions without the addition of chemical additives, we aim to enhance PBSA rheological and mechanical performance. An in-depth investigation of the in-line rheological behavior of PBSA was conducted using an internal batch mixer, exploring parameters such as temperature, screw rotation speed, and residence time. Their influence on PBSA chain scissions, branching/recombination, and cross-linking reactions were evaluated to identify optimal conditions for effective RP. Results demonstrate that specific processing conditions, for example, twelve minutes processing time, 200 °C temperature, and 60 rpm screw rotation speed, promote the formation of the long chain branched structure in PBSA. These structural changes resulted in a notable enhancement of the reacted PBSA rheological and mechanical properties, exhibiting a 23% increase in elastic modulus, a 50% increase in yield strength, and an 80% increase in tensile strength. The RP strategy also improved PBSA mechanical recycling, thus making it a potential replacement for low-density polyethylene (LDPE). Ultimately, this study showcases how finely controlling the thermomechanical degradation during reactive melt processing can improve the material's properties, enabling reliable mechanical recycling, which can serve as a green approach for other biodegradable polymers.
During the processing and during their lifetime, polymers are subjected to several environmental stresses-thermomechanical, photo-oxidative, etc.-that can strongly modify their chemical and molecular structure and, consequently, their morphology. Reduction of the molecular weight and formation of double bonds and oxygenated groups are the main changes observed as a consequence of the degradation. As a result of these changes, the macroscopic properties are dramatically modified. These changes can have a relevant effect if the post-consumer plastic manufacts are recycled. In this work, a sample of polypropylene subjected to two different degradation histories-photo-oxidation in air and in marine water-is reprocessed two times in a mini twin-screw extruder in the same processing conditions. The effect of the thermomechanical degradation during the reprocessing is different. Indeed, the less severe degraded sample shows a higher degradation level during reprocessing because the shear stress is larger. This means that the thermomechanical degradation kinetics is larger in the less degraded samples. Nevertheless, the final properties of the recycled polymers are different because the properties of the photo-oxidized samples before reprocessing were very different.
Versatility of the anionic algal polysaccharide carrageenan has long been discussed and explored, especially for their affinity towards water molecules. While this feature is advantageous in certain applications such as water remediation, wound healing, etc., the usefulness of this biopolymer is extremely limited when it comes to applications such as food packaging. Scientists around the globe are carrying out research works on venturing diverse methods to integrate hydrophobic nature into these polysaccharides without compromising their other functionalities. Considering these foregoing studies, this review is designed to have an in-depth understanding of diverse methods and techniques adopted for tuning the hydrophobic nature of carrageenan-based bionanocomposites, both via surface alterations or by changes made to their chemical structure and attached functional groups. This review article mainly focuses on how the hydrophobicity of carrageenan bionanocomposites varies as a function of the type and refinement of carrageenan, and with the incorporation of additives including plasticisers, nanofillers, bioactive agents, etc. Incorporation of nanofillers such as polysaccharide-based nanoparticles, nanoclays, bioceramic and mineral based nanoparticles, carbon dots and nanotubes, metal oxide nanoparticles, etc., along with their synergistic effects in hybrid bionanocomposites are also dealt with in this comprehensive review article.
Inhaled corticosteroids are the mainstay in the management of lung inflammation associated to chronic lung diseases, such as asthma and chronic obstructive pulmonary disease (COPD). Nonetheless, available inhalation products are mostly short-acting formulations that require frequent administrations and do not always produce the desired anti-inflammatory effects. In this work, the production of inhalable beclomethasone dipropionate (BDP) dry powders based on polymeric particles was attempted. As starting material, the PHEA-g-RhB-g-PLA-g-PEG copolymer was chosen, obtained by grafting 0.6, 2.4 and 3.0 mol%, respectively, of rhodamine (RhB), polylactic acid (PLA) and polyethylene glycol 5000 (PEG) on alpha,beta-poly(N-2-hydroxyethyl)DL-aspartamide (PHEA). The drug was loaded into the polymeric particles (MP) as an inclusion complex (CI) with hydroxypropyl-cyclodextrin (HP-ß-Cyd) (at a stoichiometric ratio of 1:1) or as free form. The spray-drying (SD) process to produce MPs was optimized by keeping the polymer concentration (0.6 wt/vol%) constant in the liquid feed and by varying other parameters such as the drug concentration. The theoretical aerodynamic diameter (daer) values among the MPs are comparable and potentially suitable for inhalation, as confirmed also through evaluation of the experimental mass median aerodynamic diameter (MMADexp). BDP shows a controlled release profile from MPs that is significantly higher (more than tripled) than from Clenil®. In vitro tests on bronchial epithelial cells (16HBE) and adenocarcinomic human alveolar basal epithelial cells (A549) showed that all the MP samples (empty or drug-loaded) were highly biocompatible. None of the systems used induced apoptosis or necrosis. Moreover, the BDP loaded into the particles (BDP-Micro and CI-Micro) was more efficient than free BDP to counteract the effects of cigarette smoke and LPS on release of IL-6 and IL-8.
Nanofibrous membranes are often the core components used to produce devices for a controlled release and are frequently prepared by electrospinning (ES). However, ES requires high production times and costs and is not easy to scale. Recently, solution blow spinning (SBS) has been proposed as an alternative technique for the production of nanofibrous membranes. In this study, a comparison between these two techniques is proposed. Poly (lactic acid)-based nanofibrous membranes were produced by electrospinning (ES) and solution blow spinning (SBS) in order to evaluate the different effect of liquid (carvacrol, CRV) or solid (chlorhexidine, CHX) molecules addition on the morphology, structural properties, and release behavior. The outcomes revealed that both ES and SBS nanofibrous mat allowed for obtaining a controlled release up to 500 h. In detail, the lower wettability of the SBS system allowed for slowing down the CRV release kinetics, compared to the one obtained for ES membranes. On the contrary, with SBS, a faster CHX release can be obtained due to its more hydrophilic behavior. Further, the addition of graphene nanoplatelets (GNP) led to a decrease in wettability and allowed for a slowing down of the release kinetics in the whole of the systems.
Graphite , Nanofibers , Chlorhexidine , Delayed-Action Preparations , Polyesters/chemistry , Nanofibers/chemistry
3D printability of green composites is currently experiencing a boost in importance and interest, envisaging a way to valorise agricultural waste, in order to obtain affordable fillers for the preparation of biodegradable polymer-based composites with reduced cost and environmental impact, without undermining processability and mechanical performance. In this work, an innovative green composite was prepared by combining a starch-based biodegradable polymer (Mater-Bi®, MB) and a filler obtained from the lignocellulosic waste coming from Solanum lycopersicum (i.e., tomato plant) harvesting. Different processing parameters and different filler amounts were investigated, and the obtained samples were subjected to rheological, morphological, and mechanical characterizations. Regarding the adopted filler amounts, processability was found to be good, with adequate dispersion of the filler in the matrix. Mechanical performance was satisfactory, and it was found that this is significantly affected by specific process parameters such as the raster angle. The mechanical properties were compared to those predictable from the Halpin-Tsai model, finding that the prepared systems exceed the expected values.
The addition of natural scraps to biodegradable polymers has gained particular interest in recent years, allowing reducing environmental pollution related to traditional plastic. In this work, new composites were fabricated by adding 10% or 20% of Hedysarum coronarium (HC) flour to Poly (lactic acid) (PLA). The two formulations were first produced by twin screw extrusion and the obtained filaments were then employed for the fabrication of composites, either for compression molding (CM) or by fused deposition modeling (FDM), and characterized from a morphological and mechanical point of view. Through FDM it was possible to achieve dense structures with good wettability of the filler that, on the contrary, cannot be obtained by CM. The results indicate that the filler effectively acts as reinforcement, especially for FDM composites. The most remarkable enhancement was found in the flexural properties (+100% of modulus and ultimate strength), followed by tensile resistance and stiffness (+60%) and impact strength (+50%), whereas a moderate loss in tensile deformability was observed, especially at the highest loading. By adding HC to the polymeric matrix, it was possible to obtain a green, high-performance, and cost-effective composite, which could find applications for the fabrication of panels for furniture or the automotive industry.
In this work, an innovative green composite was produced by adding Hedysarum coronarium (HC) flour to a starch-based biodegradable polymer (Mater-Bi®, MB). The flour was obtained by grinding together stems, leaves and flowers and subsequently sieving it, selecting a fraction from 75 µm to 300 µm. Four formulations have been produced by compression molding (CM) and fused deposition modeling (FDM) by adding 5%, 10%, 15% and 20% of HC to MB. The influence of filler content on the processability was tested, and rheological, morphological and mechanical properties of composites were also assessed. Through CM, it was possible to obtain easily homogeneous samples with all filler amounts. Concerning FDM, 5% and 10% HC-filled composites proved also easily printable. Mechanical results showed filler effectively acted as reinforcement: Young's modulus and tensile strengths of the composites increased from 74.3 MPa to 236 MPa and from 18.6 MPa to 33.4 MPa, respectively, when 20% of HC was added to the pure matrix. FDM samples, moreover, showed higher mechanical properties if compared with CM ones due to rectilinear infill and fibers orientation. In fact, regarding the 10% HC composites, Young's modulus of the CM and FDM ones displayed a relative increment of 176% and 224%, respectively.
The photo-oxidation of polypropylene at two different temperatures and in three different environments-air, distilled water and sea water-has been followed as a function of the irradiation time. The photo-oxidation kinetic is dramatically dependent on the amount of oxygen available for the oxidation reactions and on the temperature. While the photo-oxidation is very fast in air, the degradation is much slower in the two aqueous media. The degradation in sea water is slightly slower than in distilled water. In all cases, the degradation kinetic increases remarkably with the temperature. This behavior has been attributed to the lower oxygen availability for the oxidation reactions of the polymers. The light difference of the degradation kinetic between the two aqueous media depends on the small difference of the oxygen concentration at the test temperatures of 40 and 70 °C. At the latter temperature, the difference between the degradation kinetic in distilled water and sea water is still less important because increasing the temperature decreases the solubility of the oxygen, and it tends to became very similar in both samples of water.
Growing environmental concerns are stimulating researchers to develop more and more efficient materials for environmental remediation. Among them, polymer-based hierarchical structures, attained by properly combining certain starting components and processing techniques, represent an emerging trend in materials science and technology. In this work, graphene oxide (GO) and/or carbon nanotubes (CNTs) were integrated at different loading levels into poly (vinyl fluoride-co-hexafluoropropylene) (PVDF-co-HFP) and then electrospun to construct mats capable of treating water that is contaminated by methylene blue (MB). The materials, fully characterized from a morphological, physicochemical, and mechanical point of view, were proved to serve as membranes for vacuum-assisted dead-end membrane processes, relying on the synergy of two mechanisms, namely, pore sieving and adsorption. In particular, the nanocomposites containing 2 wt % of GO and CNTs gave the best performance, showing high flux (800 L × m-2 h-1) and excellent rejection (99%) and flux recovery ratios (93.3%), along with antifouling properties (irreversible and reversible fouling below 6% and 25%, respectively), and reusability. These outstanding outcomes were ascribed to the particular microstructure employed, which endowed polymeric membranes with high roughness, wettability, and mechanical robustness, these capabilities being imparted by the peculiar self-assembled network of GO and CNTs.
Fiber-reinforced polymers (FRPs) are low-density, high-performance composite materials, which find important applications in the automotive, aerospace, and energy industry, to only cite a few. With the increasing concerns about sustainability and environment risks, the problem of the recycling of such complex composite systems has been emerging in politics, industry, and academia. The issue is exacerbated by the increased use of FRPs in the automotive industry and by the expected decommissioning of airplanes and wind turbines amounting to thousands of metric tons of composite materials. Currently, the recycling of FRPs downcycles the entire composite to some form of reinforcement material (typically for cements) or degrades the polymer matrix to recover the fibers. Following the principles of sustainability, the reuse and recycling of the whole composite-fiber and polymer-should be promoted. In this review paper, we report on recent research works that achieve the recycling of both the fiber and matrix phase of FRP composites, with the polymer being either directly recovered or converted to value-added monomers and oligomers.
Interest in the development of graphene-based materials for advanced applications is growing, because of the unique features of such nanomaterials and, above all, of their outstanding versatility, which enables several functionalization pathways that lead to materials with extremely tunable properties and architectures. This review is focused on the careful examination of relationships between synthetic approaches currently used to derivatize graphene, main properties achieved, and target applications proposed. Use of functionalized graphene nanomaterials in six engineering areas (materials with enhanced mechanical and thermal performance, energy, sensors, biomedical, water treatment, and catalysis) was critically reviewed, pointing out the latest advances and potential challenges associated with the application of such materials, with a major focus on the effect that the physicochemical features imparted by functionalization routes exert on the achievement of ultimate properties capable of satisfying or even improving the current demand in each field. Finally, current limitations in terms of basic scientific knowledge and nanotechnology were highlighted, along with the potential future directions towards the full exploitation of such fascinating nanomaterials.
Three dimensional-printability of green composites is recently growing in importance and interest, especially in the view of feasibility to valorize agricultural and marine waste to attain green fillers capable of reducing bioplastic costs, without compromising their processability and performance from an environmental and mechanical standpoint. In this work, two lignocellulosic fillers, obtained from Opuntia ficus indica and Posidonia oceanica, were added to PLA and processed by FDM. Among the 3D printed biocomposites investigated, slight differences could be found in terms of PLA molecular weight and filler aspect ratio. It was shown that it is possible to replace up to 20% of bioplastic with low cost and ecofriendly natural fillers, without significantly modifying the processability and the mechanical performance of the neat matrix; at the same time, an increase of surface hydrophilicity was found, with possible positive influence on the biodegradability of such materials after disposal.
Aim: To develop electrospun mats loaded with Thymus capitatus (L.) essential oil (ThymEO) and to study their morpho-mechanical and antimicrobial properties. Materials & methods: Poly(lactic acid) (PLA) mats containing ThymEO were prepared by electrospinning. The effect of ThymEO on the morpho-mechanical properties of fibers was assayed by scanning electron microscopy and dynamometer measurements. The antimicrobial activity of ThymEO delivered either in liquid or vapor phase was assessed through killing curves and invert Petri dishes method. The cytotoxicity was also investigated. Results: The mechanical properties were enhanced by integrating ThymEO into PLA. Both liquid and vapors of ThymEO released from mats caused reductions of microbial viable cells. Negligible cytotoxicity was demonstrated. Conclusion: PLA/ThymEO delivery systems could be suitable for treating microbial infections.
Anti-Infective Agents/chemistry , Lamiaceae/chemistry , Oils, Volatile/chemistry , Polyesters/chemistry , Anti-Infective Agents/pharmacology , Bacteria/drug effects , Bacteria/growth & development , Drug Liberation , Fungi/drug effects , Fungi/growth & development , Nanostructures/chemistry , Nanostructures/ultrastructure , Oils, Volatile/pharmacology
Immobilization of microorganisms capable of degrading specific contaminants significantly promotes bioremediation processes. In this study, innovative and ecofriendly biosorbent-biodegrading biofilms have been developed in order to remediate oil-contaminated water. This was achieved by immobilizing hydrocarbon-degrading gammaproteobacteria and actinobacteria on biodegradable oil-adsorbing carriers, based on polylactic acid and polycaprolactone electrospun membranes. High capacities for adhesion and proliferation of bacterial cells were observed by scanning electron microscopy. The bioremediation efficiency of the systems, tested on crude oil and quantified by gas chromatography, showed that immobilization increased hydrocarbon biodegradation by up to 23 % compared with free living bacteria. The resulting biosorbent biodegrading biofilms simultaneously adsorbed 100 % of spilled oil and biodegraded more than 66 % over 10 days, with limited environmental dispersion of cells. Biofilm-mediated bioremediation, using eco-friendly supports, is a low-cost, low-impact, versatile tool for bioremediation of aquatic systems.
Biofilms , Environmental Restoration and Remediation , Petroleum Pollution/analysis , Petroleum/metabolism , Water Pollution/analysis , Actinobacteria/cytology , Actinobacteria/metabolism , Adsorption , Biodegradation, Environmental , Chromatography, Gas , Gammaproteobacteria/cytology , Gammaproteobacteria/metabolism
Sore, infected wounds are a major clinical issue, and there is thus an urgent need for novel biomaterials as multifunctional constituents for dressings. A set of biocomposites was prepared by solvent casting using different concentrations of carboxymethylcellulose (CMC) and exfoliated graphene oxide (Exf-GO) as a filler. Exf-GO was first obtained by the strong oxidation and exfoliation of graphite. The structural, morphological and mechanical properties of the composites (CMCx/Exf-GO) were evaluated, and the obtained composites were homogenous, transparent and brownish in color. The results confirmed that Exf-GO may be homogeneously dispersed in CMC. It was found that the composite has an inhibitory activity against the Gram-positive Staphylococcus aureus, but not against Gram-negative Pseudomonas aeruginosa. At the same time, it does not exhibit any cytotoxic effect on normal fibroblasts.
The formulation of polymeric films endowed with the abilities of controlled release of antimicrobials and biodegradability is the latest trend of food packaging. Biodegradable polymer (Bio-Flex®)-based nanocomposites containing carvacrol as an antimicrobial agent, and a nanoclay as a filler, were processed into blown films. The presence of such hybrid loading, while not affecting the overall filmability of the neat matrix, led to enhanced mechanical properties, with relative increments up to +70% and +200% in terms of elastic modulus and elongation at break. FTIR/ATR analysis and release tests pointed out that the presence of nanoclay allowed higher carvacrol loading efficiency, reasonably hindering its volatilization during processing. Furthermore, it also mitigated the burst delivery, thereby enabling a more controlled release of the antimicrobial agent. The results of mass loss tests indicated that all the formulations showed a rather fast degradation with mass losses ranging from 37.5% to 57.5% after 876 h. The presence of clay and carvacrol accelerated the mass loss rate of Bio-Flex®, especially when added simultaneously, thus indicating an increased biodegradability. Such ternary systems could be, therefore, particularly suitable as green materials for food packaging applications, and for antimicrobial wrapping applications.
The current demand for new antimicrobial systems has stimulated research for the development of poly(lactic acid)/carvacrol (PLA/CAR)-based materials able to hinder the growth and spread of microorganisms. The eco-friendly characteristics of PLA and cytocompatibility make it very promising in the perspective of green chemistry applications as material for food and biomedical employments. The broad-spectrum biological and pharmacological properties of CAR, including antimicrobial activity, make it an interesting bioactive molecule that can be easily compounded with PLA by adopting the same techniques as those commonly used for PLA manufacturing. This review critically discusses the most common methods to incorporate CAR into a PLA matrix and their interference on the morphomechanical properties, release behavior, and antimicrobial activity of systems. The high potential of PLA/CAR materials in terms of chemical-physical and antimicrobial properties can be exploited for the future development of food packaging, coated medical devices, or drug delivery systems.
Anti-Bacterial Agents/chemistry , Cymenes/chemistry , Polyesters/chemistry , Anti-Bacterial Agents/chemical synthesis , Anti-Bacterial Agents/pharmacology , Cymenes/pharmacology , Food Packaging/instrumentation , Polyesters/pharmacology , Polymers/chemical synthesis , Polymers/pharmacology
The aim of this work is to study the relationship between the chemical-physical properties of graphene oxide (GO) and the performance of a polyamide 6 (PA6) in terms of mechanical reinforcement and resistance to UV-exposure. For this purpose, two samples of GO possessing different oxidation degrees were added (0.75 wt.%) to PA6 by way of a two-step technique and the materials achieved were carefully analysed from a morphological, chemical-physical, mechanical point of view. Photo-oxidation tests were carried out to assess the performance of this class of nanohybrids after 240 h of UV-exposure. The results reveal that both nanocomposites exhibit enhanced mechanical performance and durability of PA6. However, the most oxidized GO led to a higher increase of mechanical properties and a stronger resistance to UV-exposure. All the analyses confirm that both GO samples are well dispersed and covalently attached to PA6. However, the higher the oxidation level of GO the stronger and the more extended the chemical interphase of the nanocomposite. As regards photochemical stability, both GO samples display UV-shielding capacity but the most oxidized GO also shows radical scavenging activity by virtue of its nanocavities and defects, imparted by prolonged oxidation, which endows PA6 with an outstanding durability even after 240 h of UV-exposure.
