3D Printed Poly(𝜀-caprolactone)/Hydroxyapatite Scaffolds for Bone Tissue Engineering: A Comparative Study on a Composite Preparation by Melt Blending or Solvent Casting Techniques and the Influence of Bioceramic Content on Scaffold Properties.

Bone tissue engineering has been developed in the past decades, with the engineering of bone substitutes on the vanguard of this regenerative approach. Polycaprolactone-based scaffolds are fairly applied for bone regeneration, and several composites have been incorporated so as to improve the scaffolds' mechanical properties and tissue in-growth. In this study, hydroxyapatite is incorporated on polycaprolactone-based scaffolds at two different proportions, 80:20 and 60:40. Scaffolds are produced with two different blending methods, solvent casting and melt blending. The prepared composites are 3D printed through an extrusion-based technique and further investigated with regard to their chemical, thermal, morphological, and mechanical characteristics. In vitro cytocompatibility and osteogenic differentiation was also assessed with human dental pulp stem/stromal cells. The results show the melt-blending-derived scaffolds to present more promising mechanical properties, along with the incorporation of hydroxyapatite. The latter is also related to an increase in osteogenic activity and promotion. Overall, this study suggests polycaprolactone/hydroxyapatite scaffolds to be promising candidates for bone tissue engineering, particularly when produced by the MB method.

Optimization of Extraction Conditions for Gracilaria gracilis Extracts and Their Antioxidative Stability as Part of Microfiber Food Coating Additives.

Incorporation of antioxidant agents in edible films and packages often relies in the usage of essential oils and other concentrated hydrophobic liquids, with reliable increases in antimicrobial and antioxidant activities of the overall composite, but with less desirable synthetic sources and extraction methods. Hydroethanolic extracts of commercially-available red macroalgae Gracilaria gracilis were evaluated for their antioxidant potential and phenolic content, as part of the selection of algal biomass for the enrichment of thermoplastic film coatings. The extracts were obtained through use of solid-liquid extractions, over which yield, DPPH radical reduction capacity, total phenolic content, and FRAP activity assays were measured. Solid-to-liquid ratio, extraction time, and ethanol percentages were selected as independent variables, and response surface methodology (RSM) was then used to estimate the effect of each extraction condition on the tested bioactivities. These extracts were electrospun into polypropylene films and the antioxidant activity of these coatings was measured. Similar bioactivities were measured for both 100% ethanolic and aqueous extracts, revealing high viability in the application of both for antioxidant coating purposes, though activity losses as a result of the electrospinning process were above 60% in all cases.

Bioplastics: Innovation for Green Transition.

Bioplastics are one of the possible alternative solutions to the polymers of petrochemical origins. Bioplastics have several advantages over traditional plastics in terms of low carbon footprint, energy efficiency, biodegradability and versatility. Although they have numerous benefits and are revolutionizing many application fields, they also have several weaknesses, such as brittleness, high-water absorption, low crystallization ability and low thermal degradation temperature. These drawbacks can be a limiting factor that prevents their use in many applications. Nonetheless, reinforcements and plasticizers can be added to bioplastic production as a way to overcome such limitations. Bioplastics materials are not yet studied in depth, but it is with great optimism that their industrial use and market scenarios are increasing; such growth can be a positive driver for more research in this field. National and international investments in the bioplastics industry can also promote the green transition. International projects, such as EcoPlast and Animpol, aim to study and develop new polymeric materials made from alternative sources. One of their biggest problems is their waste management; there is no separation process yet to recycle the nonbiodegradable bioplastics, and they are considered contaminants when mixed with other polymers. Some materials use additives, and their impact on the microplastics they leave after breaking apart is subject to debate. For this reason, it is important to consider their life cycle analysis and assess their environmental viability. These are materials that can possibly be processed in various ways, including conventional processes used for petrochemical ones. Those include injection moulding and extrusion, as well as digital manufacturing. This and the possibility to use these materials in several applications is one of their greatest strengths. All these aspects will be discussed in this review.

Evaluation of the Potential of Metakaolin, Electric Arc Furnace Slag, and Biomass Fly Ash for Geopolymer Cement Compositions.

The widespread use of geopolymer cement (GPC) has been hindered by a lack of scientific knowledge that still exists regarding its synthesis process. Key points, such as the release of aluminosilicate species from the raw materials and its link to the properties of GPC, have still not been completely studied. As a result, most of the GPC formulations covered in the literature are based on precursors' elemental analysis using XRF (X-ray Fluorescence), or other equivalent analysis methods, and consider that the total aluminosilicate content of the precursors is available for participating in the geopolymerization process, which seems very unlikely. In this study, the amounts of aluminate and silicate species released from metakaolin (MK), electric arc furnace slag (EAFS), and biomass fly ash (BFA) in alkaline dissolution tests were determined by simple spectrophotometric methods. It was found that MK yields the highest aluminosilicate dissolution amount, about 2.1 mmol of silicate + aluminate per gram of MK, while EAFS and BFA yield about 0.53 and 0.32 mmol/g precursor, respectively. These results were used to estimate the total amounts of dissolved aluminosilicates in a series of GPC mortars prepared from these raw materials, which were thereafter subjected to mechanical tests. It was shown that the mortars' compressive strength (which ranged from 1 to 63 MPa) is linearly correlated with their estimated total amount of dissolved aluminosilicates, with the best linear fit yielding a coefficient of determination above 0.99. It was concluded that by using the results of the dissolution tests, the estimation of compressive strength is greatly improved when compared to using the elemental analysis obtained by XRF, which yields a coefficient of determination of 0.88 and a larger dispersion of data points. The results reveal the usefulness of this simple method for evaluating the potential of inorganic industrial waste streams as precursors for GPC.

Recycling Ophthalmic Lens Wastewater in a Circular Economy Context: A Case Study with Microalgae Integration.

Water pollution poses a global threat to ecosystems and human health and is driven by the presence of various contaminants in wastewater, including nano- and microplastics. Despite the magnitude of this problem, the majority of global wastewater is released untreated into water bodies. To combat this issue, a multi-strategy approach is needed. This study explores a circular economy-based solution for treating emerging pollutants, particularly wastewater from ophthalmic spectacle lens production. Our approach integrates solid waste materials into polymeric and cement matrices while also utilising wastewater for microalgae cultivation. This innovative strategy focuses on biomass generation and economic valorisation. By adopting a circular economy model, we aim to transform environmental pollutants from wastewater into valuable organic products. A key component of our approach is the utilisation of microalgae, specifically Nannochloropsis sp., known for its high lipid content and resilience. This microalgae species serves as a promising biobased feedstock, supporting the production of innovative biobased products, such as biopolymers, for ophthalmic lens manufacturing. Our interdisciplinary approach combines microalgae technology, analytical chemistry, cement production, and polymer processing to develop a sustainable circular economy model that not only addresses environmental concerns, but also offers economic benefits. This study underscores the potential of harnessing high-value products from waste streams and underscores the importance of circular economy principles in tackling pollution and resource challenges.

Advanced Face Mask Filters Based on PCL Electrospun Meshes Dopped with Antimicrobial MgO and CuO Nanoparticles.

The pandemic situation caused by coronavirus clearly demonstrated the need for alternatives able to protect the respiratory tract and inactivate the infectious agents. Based on this, antibacterial face-mask filters of polycaprolactone (PCL) dopped with magnesium oxide (MgO) and copper oxide (CuO) nanoparticles (NPs) were produced using an electrospinning technique. A morphological analysis of electrospun meshes evaluated the success of nanoparticles' incorporation as well as the average fibers' diameters (481 ± 272 nm). The performance of electrospun nanofibers was also assessed in terms of tensile strength (0.88 ± 0.25 MPa), water vapor permeability (11,178.66 ± 35.78 g·m-2·day-1), stability under wet conditions and antibacterial activity according to the standard guidelines. The filters showed structural stability up to 2 h of washing and improved antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) for optimized concentrations of MgO and CuO NPs. Overall, electrospun meshes with antibacterial activity were successfully developed for advanced filtering applications.

Green Copolymers and Nanocomposites from Myrcene and Limonene Using Algerian Nano-Clay as Nano-Reinforcing Filler.

In this work, we report a new facile method for the preparation of myrcene-limonene copolymers and nanocomposites using a Lewis acid as a catalyst (AlCl3) and organo-modified clay as a nano-reinforcing filler. The copolymer (myr-co-lim) was prepared by cationic copolymerization using AlCl3 as a catalyst. The structure of the obtained copolymer is studied and confirmed by Fourier Transform Infrared spectroscopy, Nuclear Magnetic Resonance spectroscopy, and Differential Scanning Calorimetry. By improving the dispersion of the matrix polymer in sheets of the organoclay, Maghnite-CTA+ (Mag-CTA+), an Algerian natural organophilic clay, was used to preparenanocomposites of linear copolymer (myr-co-lim). In order to identify and assess their structural, morphological, and thermal properties, the effect of the organoclay, used in varyingamounts (1, 4, 7, and 10% by weight), and the preparation process were investigated. The Mag-CTA+ is an organophylic montmorillonite silicate clay prepared through a direct exchange process in which they were used as green nano-reinforcing filler. The X-ray diffraction of the resulting nanocomposites revealed a considerable alteration in the interlayer spacing of Mag-CTA+. As a result, interlayer expansion and myr-co-lim exfoliation between layers of Mag-CTA+ were observed. Thermogravimetric analysis provided information on the synthesized nanocomposites' thermal properties. Fourier transform infrared spectroscopy and scanning electronic microscopy, respectively, were used to determine the structure and morphology of the produced nanocomposites (myr-co-lim/Mag). The intercalation of myr-co-lim in the Mag-CTA+ sheets has been supported by the results, and the optimum amount of organoclay needed to create a nanocomposite with high thermal stability is 10% by weight. Finally, a new method for the preparation of copolymer and nanocomposites from myrcene and limonene in a short reaction time was developed.

Evaluating the Injection Moulding of Plastic Parts Using In Situ Time-Resolved Small-Angle X-ray Scattering Techniques.

In this study, we describe the design and fabrication of an industrial injection moulding system that can be mounted and used on the NCD-SWEET small-angle X-ray scattering beamline at ALBA. We show how highly useful time-resolved data can be obtained using this system. We are able to evaluate the fraction of the material in the mould cavity and identify the first material to solidify and how this varies with the injection temperature. The design follows current industrial practice and provides opportunities to collect time-resolved data at several points within the mould cavity so that we can build up a 4D perspective of the morphology and its temporal development. The quantitative data obtained will prove invaluable for the optimisation of the next generation of injection moulding techniques. This preliminary work used results from the injection moulding of a general-purpose isotactic polypropylene.

Changing the Paradigm-Controlling Polymer Morphology during 3D Printing Defines Properties.

Direct digital manufacturing consists of a set of techniques that enable products to be fabricated directly from their digital definition, without the use of complex tooling or moulds. This manufacturing approach streamlines prototyping and small-scale production, as well as the mass customization of parts with complex designs immediately fixed before fabrication. With broad applicability, there are clearly opportunities in the field of medical devices for its use. However, many of the developments of direct digital manufacturing focus on simply specifying the shape or the form of the product, and this limited scope throws away many of the particular advantages of direct digital manufacturing. This work is focused on remedying this situation so that the digital specification of the fabricated product includes the properties as well as the form of the product. We use in situ time-resolving small-angle X-ray scattering measurements performed at the ALBA Synchrotron Light Source in Barcelona to evaluate the control that can be exerted on the morphology of a semi-crystalline polymer during extruder-based 3D printing. We use this as a methodology for printing the patterns of the morphology of the polymer to realise the patterns of properties of the polymeric material, specifically the modulus of the polymer. We give an example of products produced in this manner that contain spatial variation in their properties.

Fabrication of Poly(ε-caprolactone) Scaffolds Reinforced with Cellulose Nanofibers, with and without the Addition of Hydroxyapatite Nanoparticles.

Biomaterial properties and controlled architecture of scaffolds are essential features to provide an adequate biological and mechanical support for tissue regeneration, mimicking the ingrowth tissues. In this study, a bioextrusion system was used to produce 3D biodegradable scaffolds with controlled architecture, comprising three types of constructs: (i) poly(ε-caprolactone) (PCL) matrix as reference; (ii) PCL-based matrix reinforced with cellulose nanofibers (CNF); and (iii) PCL-based matrix reinforced with CNF and hydroxyapatite nanoparticles (HANP). The effect of the addition and/or combination of CNF and HANP into the polymeric matrix of PCL was investigated, with the effects of the biomaterial composition on the constructs (morphological, thermal, and mechanical performances) being analysed. Scaffolds were produced using a single lay-down pattern of 0/90°, with the same processing parameters among all constructs being assured. The performed morphological analyses showed a satisfactory distribution of CNF within the polymer matrix and high reliability was obtained among the produced scaffolds. Significant effects on surface wettability and thermal properties were observed, among scaffolds. Regarding the mechanical properties, higher scaffold stiffness in the reinforced scaffolds was obtained. Results from the cytotoxicity assay suggest that all the composite scaffolds presented good biocompatibility. The results of this first study on cellulose and hydroxyapatite reinforced constructs with controlled architecture clearly demonstrate the potential of these 3D composite constructs for cell cultivation with enhanced mechanical properties.