ABSTRACT Owing to the possibility of attaining variable oxidation states and coordination numbers, the specific structural roles of V 2 O 5 or Nb 2 O 5 in determining the local configurations of framework species in alkaline earth aluminoborosilicate glasses still need to be disclosed. This manuscript describes the structural changes induced by adding 5 mol% of V 2 O 5 or Nb 2 O 5 to a complex aluminoborosilicate glass (mol%) 10MgO–15CaO–25SrO–5Al 2 O 3 –5B 2 O 3 –40SiO 2 , aiming at elucidating the connectivity of these transition metal cations in the glass network. The resulting structural changes have been assessed by magic angle spinning‐nuclear magnetic resonance (MAS‐NMR) (for 29 Si, 27 Al, 11 B, 51 V, and 93 Nb nuclei), UV‐visible spectroscopy, scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared and Raman spectroscopy, differential thermal analysis (DTA), molecular dynamics (MD) simulations, and density functional theory (DFT) calculations. XPS analysis indicated the presence of V and Nb with a 5+ oxidation state. The NMR spectroscopy, MD simulations, and DFT calculations suggest that V exists in 4‐, 5‐, and 6‐coordination, whereas Nb exists mostly in 6‐coordination. Both V and Nb are well incorporated into the silicate network. The results do not suggest any clustering of either of the V‐ or Nb‐based units.

Synthetic bone graft substitutes, including calcium phosphates (CaP), bioactive glasses (BG), and their composites with biopolymer matrices are attracting interest for bone tissue repair and regeneration. A key challenge is accurately replicating the biological structure and functionality of natural bone and optimizing the porous structure to match trabecular bone. This has been addressed by doping CaPs with therapeutic ions and using scaffolding methods like polymeric sponge replication and different additive manufacturing techniques. Biomimetic approaches employing naturally occurring porous biominerals with pore sizes comparable to those of trabecular bone, offer promising alternatives. This work reviews the hydrothermal transformation of cuttlefish bone (CB) into CaP scaffolds, while preserving its original porous structure, producing hydroxyapatite (HA, Ca 10 (PO 4 ) 6 (OH) 2 ), tricalcium phosphate (TCP, Ca 3 (PO 4 ) 2 ), and biphasic CaPs, both undoped and therapeutic ion‐doped, constructs. Coating such biomimetic scaffolds with sol–gel‐derived BG and biopolymers produces multifunctional bone graft substitutes with enhanced mechanical and biological properties. Moreover, polymeric coatings can act as drug reservoirs, enabling controlled release of therapeutic agents. The review highlights that integrating biomimetic strategies with advanced coating solutions holds great promise for creating multifunctional scaffolds that mimic nature and improve therapeutic outcomes in bone tissue engineering.

Over the past two decades, the CICECO-hub scientists have devoted substantial efforts to advancing bioactive inorganic materials based on calcium phosphates and alkali-free bioactive glasses. A key focus has been the deliberate incorporation of therapeutic ions like Mg, Sr, Zn, Mn, or Ga to enhance osteointegration and vascularization, confer antioxidant properties, and impart antimicrobial effects, marking significant contributions to the field of biomaterials and bone tissue engineering. Such an approach is expected to circumvent the uncertainties posed by methods relying on growth factors, such as bone morphogenetic proteins, parathyroid hormone, and platelet-rich plasma, along with their associated high costs and potential adverse side effects. This comprehensive overview of CICECO-hub's significant contributions to the forefront inorganic biomaterials across all research aspects and dimensionalities (powders, granules, thin films, bulk materials, and porous structures), follows a unified approach rooted in a cohesive conceptual framework, including synthesis, characterization, and testing protocols. Tangible outcomes [injectable cements, durable implant coatings, and bone graft substitutes (scaffolds) featuring customized porous architectures for implant fixation, osteointegration, accelerated bone regeneration in critical-sized bone defects] were achieved. The manuscript showcases specific biofunctional examples of successful biomedical applications and effective translations to the market of bone grafts for advanced therapies.

Immune response to biomaterials, which is intimately related to their surface properties, can produce chronic inflammation and fibrosis, leading to implant failure. This study investigated the development of magnetic nanoparticles coated with silica and incorporating the anti-inflammatory drug naproxen, aimed at multifunctional biomedical applications. The synthesized nanoparticles were characterized using various techniques that confirmed the presence of magnetite and the formation of a silica-rich bioactive glass (BG) layer. In vitro studies demonstrated that the nanoparticles exhibited bioactive properties, forming an apatite surface layer when immersed in simulated body fluid, and biocompatibility with bone cells, with good viability and alkaline phosphatase activity. Naproxen, either free or encapsulated, reduced nitric oxide production, an inflammatory marker, while the BG coating alone did not show anti-inflammatory effects in this study. Overall, the magnetic nanoparticles coated with BG and naproxen showed promise for biomedical applications, especially anti-inflammatory activity in macrophages and in the bone field, due to their biocompatibility, bioactivity, and osteogenic potential.

Bioactive glasses (BGs) are known for their selective ability to (i) form a mechanically strong interfacial bond with hard (bone) or soft tissues (gingivae or cartilages) (i.e., silica-, silica-phosphate-, phosphate-, borate-phosphate-, or silica-phosphate-borate-based BGs); or (ii) serve as reservoirs for fast-release of therapeutic (osteogenic, angiogenic, anticarcinogenic, or antimicrobial) ions (i.e., phosphate-based BGs and mesoporous BGs). The strength of the bone bond yielded by the osteoproductive-capable BGs is generally equivalent to, or higher than the bone strength. The resorbability of phosphate-based BG is dependent on the content of network formers and cross-linkers. All BGs elicit excellent biochemical compatibility. However, their fracture toughness is typically less than and the elastic modulus is greater than those of bone, indicating that most BGs have suboptimal biomechanical compatibility when used in load-bearing applications. One promising approach to overcome this problem is the development of BGs in coating form, applied to the surface of load-bearing endosseous implants. This work critically assesses BG thin-layers fabricated by the radio-frequency magnetron sputtering method, an industry-ready large-scale physical vapour deposition technology. It is demonstrated that, despite the relative lack of attention paid to this technology, it enables the development of unique BG coatings with efficacious therapeutic capabilities. Here, we present an overview of the most relevant developments achieved thus far, along with the remarkable advantages, drawbacks to overcome, and future perspectives with the intention of highlighting the vast possibilities of this specific field of research.

Cancer is one of the deadliest diseases worldwide and has been responsible for millions of deaths. However, developing a satisfactory smart multifunctional material combining different strategies to kill cancer cells poses a challenge. This work aims at filling this gap by developing a composite material for cancer treatment through hyperthermia and drug release. With this purpose, magnetic nanoparticles were coated with a polymer matrix consisting of poly (L-co-D,L lactic acid-co-trimethylene carbonate) and a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer. High-resolution transmission electron microscopy and selected area electron diffraction confirmed magnetite to be the only iron oxide in the sample. Cytotoxicity and heat release assays on the hybrid nanoparticles were performed here for the first time. The heat induction results indicate that these new magnetic hybrid nanoparticles are capable of increasing the temperature by more than 5 °C, the minimal temperature rise required for being effectively used in hyperthermia treatments. The biocompatibility assays conducted under different concentrations, in the presence and in the absence of an external alternating current magnetic field, did not reveal any cytotoxicity. Therefore, the overall results indicate that the investigated hybrid nanoparticles have a great potential to be used as carrier systems for cancer treatment by hyperthermia.

Collaboration plays a key role in the success attained to date by networks of innovation ecosystems generated around entities known as Digital Innovation Hubs (DIHs), recently created following European Commission initiatives to boost the digitisation of the European economic fabric. This article proposes a conceptual framework that brings together, defines, structures and relates the concepts involved in the collaborative interaction processes within and between these innovation ecosystems to allow comprehensive conceptualisation. The developed framework also provides an approach that helps to tangibilise collaboration as a management process. Here the goal is to ultimately move towards not only qualitative, but also quantitative modelling to bridge the research gap in the state of the art in this respect. The data-driven business-ecosystem-skills-technology (D-BEST) model, devised to configure DIHs service portfolios in a collaborative context, provides the reference basis for the interorganisational asset transfer methodology (IOATM). This is the keystone that structures the framework and constitutes its main contribution. Through the IOATM, this conceptual framework points out collaboration quantification, and serves as a lever for its modelling to deal with collaboration accounting by: turning it into a more controllable management element; guiding practitioners' efforts to improve collaborative processes efficiency with an approach that pursues objectivity and maximises synergies.

Technologies connected to Industry 4.0 have over time provided a major boost in several domains. The Internet of Things has confirmed benefits in several areas from healthcare, aeronautics and automotive industries, to entertainment. Currently, the challenges requested to the industry have forced the hiring of professionals from various areas of knowledge. Technologies related to Industry 4.0, such as sensors and microcontrollers, have been providing support to the various processes that occur during manufacturing processes in industry. Business process model languages, such as Business Process Model and Notation, are good tools to help communication between the different stakeholders who share the same workplace, helping in the process of modeling the entire industrial business. These tools do not have, at least natively, the possibility to program microcontroller type devices. This paper aims to present an automation system in the context of a business model process for programming microcontroller devices following the Model Driven Architecture paradigm.

Hydroxyapatite-alginate composites with different biopolymer contents (0%, 10%, 25% and 50%) were prepared according to an eco-friendly process using low-cost precursors. The prepared materials were firstly subjected to characterizations by Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy and physisorption of N2 techniques. The composites were then tested as sorbents for Rhodamine B dye under different sets of experimental conditions, including initial pH, contact time, initial dye concentration and temperature. The aim was to investigate the effects of these parameters on the extent of dye removal and to understand the adsorption behaviour of the composites under various conditions. The dye adsorption equilibrium is reached after 20 min of contact for the unmodified hydroxyapatite, being attained within a few minutes for the composite samples. Moreover, the pseudo-second-order kinetics model was found to be suitable to describe the adsorption of dye onto the uncoated product, contrarily to the modified compounds for which the kinetic data could be better predicted by the pseudo-first-order model. The equilibrium data were analysed by different isotherm models, with the Freundlich model providing the best fit. The maximum adsorption capacity increased from 225.2 to 289.5 mg/g by the grafting effect, suggestion the potential use of these materials in wastewater treatment.

Globally, educational institutes are trying to adapt modernized and effective approaches and tools to their education systems to improve the quality of their performance and achievements. However, identifying, designing, and/or developing promising mechanisms and tools that can impact class activities and the development of students' outputs are critical success factors. Given that, the contribution of this work is to propose a methodology that can guide and usher educational institutes step by step through the implementation of a personalized package of training Toolkits in Smart Labs. In this study, the package of Toolkits refers to a set of needed tools, resources, and materials that, with integration into a Smart Lab can, on the one hand, empower teachers and instructors in designing and developing personalized training disciplines and module courses and, on the other hand, may support students (in different ways) in developing their skills. To demonstrate the applicability and usefulness of the proposed methodology, a model was first developed, representing the potential Toolkits for training and skill development. The model was then tested by instantiating a particular box that integrates some hardware to be able to connect sensors to actuators, with an eye toward implementing this system mainly in the health domain. In a real scenario, the box was used in an engineering program and its associated Smart Lab to develop students' skills and capabilities in the areas of the Internet of Things (IoT) and Artificial Intelligence (AI). The main outcome of this work is a methodology supported by a model able to represent Smart Lab assets in order to facilitate training programs through training Toolkits.

This work reports on a novel approach to deposit composite coatings based on biphasic calcium phosphate (BCP) incorporating graphene oxide (GO) on 316L stainless steel (316L SS) and on its protective nature against corrosion in the simulated body fluid (SBF). For this purpose, 2-dimensional GO was successfully incorporated in 1% and 3% weight ratios as mechanical strength enhancer and pore size reducer for the prepared coatings. It was observed that upon increasing the GO content, the corrosion rate was drastically decreased when compared to pristine BCP coating. The corrosion resistance polarization results are in good agreement with the test results obtained for SBF immersion study. The size of the particles has significantly decreased, as shown by transmission electron microscopy (from 190 to 27 nm). The experimental results indicate that the composite hydroxyapatite-beta-tricalcium phosphate-GO (HAp-beta-TCP-GO) coatings enhanced the corrosion resistance of the surgical grade 316L SS, turning it a better implanting option for orthopedic applications.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties—piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of ~50%), which yielded a promising compressive strength of ~20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

This study investigates the osteogenic differentiation of umbilical-cord-derived human mesenchymal stromal cells (hUC-MSCs) on biphasic calcium phosphate (BCP) scaffolds derived from cuttlefish bone doped with metal ions and coated with polymers. First, the in vitro cytocompatibility of the undoped and ion-doped (Sr2+, Mg2+ and/or Zn2+) BCP scaffolds was evaluated for 72 h using Live/Dead staining and viability assays. From these tests, the most promising composition was found to be the BCP scaffold doped with strontium (Sr2+), magnesium (Mg2+) and zinc (Zn2+) (BCP-6Sr2Mg2Zn). Then, samples from the BCP-6Sr2Mg2Zn were coated with poly(ԑ-caprolactone) (PCL) or poly(ester urea) (PEU). The results showed that hUC-MSCs can differentiate into osteoblasts, and hUC-MSCs seeded on the PEU-coated scaffolds proliferated well, adhered to the scaffold surfaces, and enhanced their differentiation capabilities without negative effects on cell proliferation under in vitro conditions. Overall, these results suggest that PEU-coated scaffolds are an alternative to PCL for use in bone regeneration, providing a suitable environment to maximally induce osteogenesis.

Evolutionary algorithms (EAs) are a family of optimization algorithms inspired by the Darwinian theory of evolution, and Genetic Algorithm (GA) is a popular technique among EAs. Similar to other EAs, common limitations of GAs have geometrical origins, like premature convergence, where the final population's convex hull might not include the global optimum. Population diversity maintenance is a central idea to tackle this problem but is often performed through methods that constantly diminish the search space's area. This work presents a self-adaptive approach, where the non-geometric crossover is strategically employed with geometric crossover to maintain diversity from a geometrical/topological perspective. To evaluate the performance of the proposed method, the experimental phase compares it against well-known diversity maintenance methods over well-known benchmarks. Experimental results clearly demonstrate the suitability of the proposed self-adaptive approach and the possibility of applying it to different types of crossover and EAs.

In this paper we studied the effect of NaBO2 addition to a phase-separated alkali-free bioactive glass with a composition of 38.49 SiO2 • 36.07 CaO • 19.24 MgO • 5.61 P2O5 • 0.59 CaF2. Microscopy reveals binodal phase separation involving two Si-containing microphases with a droplet size of ∼200 μm, driven by the thermodynamic LLPS mechanism. The local environments and spatial distribution of silicate, phosphate, and fluoride ions in this phase-separated system were studied, using 29Si, 31P, 11B, 19F, 25Mg, and 23Na nuclear magnetic resonance (NMR) and infrared spectroscopy. The silicate units are dominantly of the metasilicate (Si2) type. The phosphate units exist mostly as orthophosphate (P0) while the borate is present in the form of pyroborate (B1). Multinuclear dipolar re-coupling experiments indicate that the minority components F, P, B and Na all occur within a common phase. Thus, atomic distribution scenarios involving the separation of these components into separate phases can be excluded. The 31P spin echo decay (SED) method was used along with Monte Carlo simulations to characterize the spatial distribution of the phosphate component. Based on the analysis, the phosphate component forms clusters of sizes 1-4 nm, which are embedded in an environment more dilute in phosphate, having a random distribution. While 19F SED results indicate that the fluoride ions do not form clusters and are close to randomly distributed, dipolar recoupling of 31P suggests a local environment resembling that of fluorapatite.

The present chapter reviews the different preparation and characterization of Equisetum extracts and composites, including their biological properties and uses in the regeneration of bone defects derived from traumas and diseases, such as osteoporosis and arthritis. The results have shown that the Equisetum genus contains high amounts of silicon, potassium, zinc, sulfur, carbon, and other organic compounds with potential use as therapeutic drugs. The experimental variations in the preparation of extracts showed that the maximum yield (~20% w/w) can be obtained for the concentration of 10–50% of ethanol in ethanol/water solutions. The maximum total phenolic and antioxidant contents can be obtained at concentrations of 50–90% ethanol. The Equisetum genus-derived composite materials and extracts are promising for bone regeneration applications. In vivo studies revealed that the trabecular bone thickness increased by 11% and 46% when treating SHAM and ovariectomized (OVX) rats, respectively, with a diet containing 60 mg ⋅ kg−1 E. arvense (EA) extract. The cortical bone thickness of the EA extract group has increased by 14% compared to the OVX group. Quantitative analysis of composite EA extract and poly (lactic acid) (PLA) revealed alkaline phosphatase (ALP) activity three times higher in comparison to the polystyrene (21 days) and an increase in mineralization of adipose tissue-derived mesenchymal stem cells (AT-MSCs) after 14 and 21 days. In vivo and in vitro studies have concluded that E. arvense, E. hyemale, E. giganteum, and other Equisetum species showed antioxidants and osteoconductive and osteoinductive properties, which are vital for bone regeneration.

We report the first ever robocast (additive manufacturing/3D printing) sintered ceria scaffolds, and explore their use for the production of renewable fuels via solar thermochemical fuel production (STFP, water and carbon dioxide splitting using concentrated solar energy). CeO2 catalyst scaffolds were fabricated as 50 mm diameter discs (struts and voids ∼500 μm), sintered at 1450 °C, with specific surface area of 1.58 m2 g-1. These scaffolds have hierarchical porosity, consisting of the macroporous scaffold structure combined with nanoscale porosity within the ceria struts, with mesopores <75 Å and an average pore size of ∼4 nm, and microporosity <2 nm with a microporous surface area of 0.29 m2 g-1. The ceria grains were ≤500 nm in diameter after sintering. STFP testing was carried out via thermogravimetric analysis (TGA) with reduction between 1050-1400 °C under argon, and oxidation at 1050 °C with 50% CO2, gave rapid CO production during oxidation, with high peak CO production rates (0.436 μmol g-1 s-1, 0.586 ml g-1 min-1), for total CO yield of 78 μmol g-1 (1.747 ml g-1). 90% CO was obtained after just 10 min of oxidation, comparing well to reticulated ceria foams, this CO production rate being an order of magnitude greater than that for ceria powders when tested at similar temperatures.

The present study aimed to test, in vitro, the antimicrobial activity against Candida albicans and Streptococcus mutans and the surface roughness of a 3D-printed polymethylmethacrylate dental resin enhanced with graphene. A 3D-printed polymethylmethacrylate dental resin was reinforced with four different concentrations of graphene: 0.01, 0.1, 0.25 and 0.5 wt%. Neat resin was used as a control. The specimens were printed in a liquid crystal display printer. Disc specimens were used in antimicrobial evaluation, and bar-shaped specimens were used to measure surface roughness. The study of antimicrobial activity included the inhibition of the growth of C. albicans and S. mutans and their adhesion to the resin’s surface. Surface roughness increased with the increase in the graphene concentration. The growth inhibition of C. albicans was observed in the different concentrations of graphene after 24 h, with no recovery after 48 h. The specimens doped with graphene were capable of inactivating S. mutans after 48 h. The surface-adhesion studies showed that the density of microbial biofilms decreases in the case of specimens doped with graphene. Graphene, despite increasing the resin’s surface roughness, was effective in inhibiting the growth and the adhesion to the resin’s surface of the main inducers of prosthetic stomatitis.

Bi-phasic calcium phosphates (BCPs) are considered prominent candidate materials for the fabrication of bone graft substitutes. Currently, supplemental cation-doping is suggested as a powerful path to boost biofunctionality, however, there is still a lack of knowledge on the structural role of such substituents in BCPs, which in turn, could influence the intensity and extent of the biological effects. In this work, pure and Mg- and Sr-doped BCP scaffolds were fabricated by robocasting from hydrothermally synthesized powders, and then preliminarily tested in vitro and thoroughly investigated physically and chemically. Collectively, the osteoblast cell culture assays indicated that all types of BCP scaffolds (pure, Sr- or Sr–Mg-doped) delivered in vitro performances similar to the biological control, with emphasis on the Sr–Mg-doped ones. An important result was that double Mg–Sr doping obtained the ceramic with the highest β-tricalcium phosphate (β-TCP)/hydroxyapatite mass concentration ratio of ~1.8. Remarkably, Mg and Sr were found to be predominantly incorporated in the β-TCP lattice. These findings could be important for the future development of BCP-based bone graft substitutes since the higher dissolution rate of β-TCP enables an easier release of the therapeutic ions. This may pave the road toward medical devices with more predictable in vivo performance.