Elucidating the formation of Al-NBO bonds, Al-O-Al linkages and clusters in alkaline-earth aluminosilicate glasses based on molecular dynamics simulations.

Exploring the reasons for the initiation of Al-O-Al bond formation in alkali-earth alumino silicate glasses is a key topic in the glass-science community. Evidence for the formation of Al-O-Al and Al-NBO bonds in the glass composition 38.7CaO-9.7MgO-12.9Al2O3-38.7SiO2 (CMAS, mol%) has been provided based on Molecular Dynamics (MD) simulations. Analyses in the short-range order confirm that silicon and the majority of aluminium cations form regular tetrahedra. Well-separated homonuclear (Si-O-Si) and heteronuclear (Si-O-Al) cluster regions have been identified. In addition, a channel region (C-Region), separated from the network region, enriched with both NBO and non-framework modifier cations, has also been identified. These findings are in support of the previously proposed extended modified random network (EMRN) model for aluminosilicate glasses. A detailed analysis of the structural distributions revealed that a majority of Al, 51.6%, is found in Si-O-Al links. Although the formation of Al-O-Al and Al-NBO bonds is energetically less favourable, a significant amount of Al is found in Al-O-Al links (33.5%), violating Lowenstein's rule, and the remainder is bonded with non-bridging oxygen (NBO) in the form of Al-NBO (Al-O-(Ca, Mg)). The conditions necessary for the formation of less favourable bonds are attributed to the presence of a high amount of modifier cations in current CMAS glass and their preferable coordination.

Structure and thermal relaxation of network units and crystallization of lithium silicate based glasses doped with oxides of Al and B.

The current study reports on the relaxation behaviour of lithium silicate based glasses as probed by NMR spectroscopy. A total of four glass compositions were studied with the parent composition being 28Li2O-72SiO2, and added dopants of Al and B. All the compositions showed significant differences in the NMR spectra of both annealed and non-annealed glasses demonstrating the structural relaxation behaviour. We extended our binary statistical mechanical model to these complex compositions to study the relaxation behaviour. By the combined use of the extended statistical mechanical model and broken ergodicity, we shed light on the mechanism of structural relaxation as understood by NMR spectroscopy. We studied the crystallization behaviour of the glasses and reported on the variations of the residual glass composition changes in the crystallization fraction.

Statistics of silicate units in binary glasses.

In this paper, we derive a new model to determine the distribution of silicate units in binary glasses (or liquids). The model is based on statistical mechanics and assumes grand canonical ensemble of silicate units which exchange energy and network modifiers from the reservoir. This model complements experimental techniques, which measure short range order in glasses such as nuclear magnetic resonance (NMR) spectroscopy. The model has potential in calculating the amounts of liquid-liquid phase segregation and crystal nucleation, and it can be easily extended to more complicated compositions. The structural relaxation of the glass as probed by NMR spectroscopy is also reported, where the model could find its usefulness.

Insights on the properties of levofloxacin-adsorbed Sr- and Mg-doped calcium phosphate powders.

Several types of biodegradable materials have been investigated for the treatment of osteomyelitis. Calcium phosphate (CaP) ceramics are among the most performing materials due to their resemblance to human hard tissues in terms of mineralogical composition, and proven ability to adsorb and deliver a number of drugs. This research work was intended to study the suitability of modified CaP powders loaded with a fluoroquinolone as drug delivery systems for osteomyelitis treatment. Levofloxacin (LEV) was chosen due to the well-recognized anti-staphylococcal activity and adequate penetration into osteoarticular tissues. Substituted CaP powders (5 mol% Sr(2+) or 5 mol% Mg(2+)) were synthesised through aqueous precipitation. The obtained powders were characterised by X-ray diffraction, SEM and FTIR analysis. The X-ray diffraction patterns confirmed the presence of HA and ß-tricalcium phosphates (ß-TCP) phases in doped compositions, especially in the case of Mg-doped system. The fixation of LEV at the surface of the particles occurred only by physisorption. Both the in vitro microbiological susceptibility, against Staphylococcus spp, and biocompatibility of LEV-loaded CaP powders have not been compromised.

Fostering hydroxyapatite bioactivity and mechanical strength by Si-doping and reinforcing with multiwall carbon nanotubes.

The aim of the present study was to prepare resorbable hydroxyapatite (HA) based bone graft materials reinforced with carbon nanotubes as a way to cope with the inability of pure HA to resorb and its intrinsic brittleness and poor strength that restrict its clinical applications under load-bearing conditions. With this purpose, a Si-doped HA nanopowder (n-Si0.8HA) was prepared by chemical synthesis and used as composite matrix reinforced with different amounts of functionalized multiwall carbon nanotubes (MWCNTs). The effect of the added amounts of MWCNTs on the mechanical properties of nanocomposites and their in vitro biomineralization was assessed by bending strength measurements, immersing tests in simulated body fluid solution (SBF), scanning electron microscopy (SEM), and inductively coupled plasma atomic emission spectroscopy analysis (ICP-AES). The bioactivity and bending strength were enhanced, reaching maximum balanced values for an optimum addition of 3 wt.% f-MWCNTs. These results might contribute to broaden the potential applications of HA-based bone grafts.

In Vitro Evaluation of Biphasic Calcium Phosphate Scaffolds Derived from Cuttlefish Bone Coated with Poly(ester urea) for Bone Tissue Regeneration.

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.

Multi-Parametric Exploration of a Selection of Piezoceramic Materials for Bone Graft Substitute 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.

Surfactant-assisted hydrothermal synthesis of hydroxyapatite nanopowders.

Rod-like hydroxyapatite nanoparticles (n-HAp) with a highly ordered nanostructure were prepared by hydrothermal synthesis from calcium chloride, and phosphoric acid, as calcium and phosphorus sources, respectively. Various surfactant families such as cationic (CTAB), anionic (SDS) and nonionic (Triton X-100) were used as regulators of the nucleation and crystal growth. The synthesized nanopowders were characterized using X-ray diffraction (XRD), Fourier transform infrared spectrograph (FTIR) and transmission electron microscopy (TEM). The rod-like morphology was obtained regardless of the surfactant used during the hydrothermal treatment, but the aspect ratio of the crystals was found to be surfactant dependent. The mechanism of crystal growth as well-oriented nanostructure is discussed.

Fabrication and biological evaluation of three-dimensional (3D) Mg substituted bi-phasic calcium phosphate porous scaffolds for hard tissue engineering.

This work reports on the fabrication of three-dimensional (3D) magnesium substituted bi-phasic calcium phosphate (Mg-BCP) scaffolds by gel-casting, their structural and physico-chemical characterization, and on the assessment of their in vitro and in vivo performances. The crystalline phase assemblage, chemical functional groups and porous morphology features of the scaffolds were evaluated by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) and field emission scanning electron microscopy (FE-SEM), respectively. The sintered scaffolds revealed an interconnected porosity with pore sizes ranging from 4.3 to 7.28 µm. The scaffolds exhibited good biomineralization activity upon immersion in simulated body fluid (SBF), while an in vitro study using MG-63 cell line cultures confirmed their improved biocompatibility, cell proliferation and bioactivity. Bone grafting of 3D scaffolds was performed in non-load bearing bone defects surgically created in tibia of rabbits, used as animal model. Histological and radiological observations indicated the successful restoration of bone defects. The overall results confirmed the suitability of the scaffolds to be further tested as synthetic bone grafts in bone regeneration surgeries and in bone tissue engineering applications.

New and Efficient Bioactive Glass Compositions for Controlling Endodontic Pathogens.

Endodontic treatment aims to conserve teeth through removing infected tissue, disinfecting, and filling/sealing the root canal. One of the most important treatment steps is the removal of microorganisms to avoid reinfection and consequent tooth loss. Due to increased resistance to intracanal medications, new alternative procedures are needed. Thus, an intracanal medication is suggested using three bioactive glass (BG) compositions (BG1, BG2, and BG3) produced by the sol-gel method, with different molar contents of bactericidal oxides. The BGs were morphologically and physically characterized. Their ability to inhibit the growth of two oral pathogens responsible for the failure of endodontic treatments (E. faecalis and C. albicans) was also studied. The results suggest that BG2 and BG3 can inhibit the growth of E. faecalis after 48 h of incubation, and all BG samples have a significant effect on C. albicans survival.

Robocasting of 3D printed and sintered ceria scaffold structures with hierarchical porosity for solar thermochemical fuel production from the splitting of CO2.

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.

Antimicrobial Activity of a 3D-Printed Polymethylmethacrylate Dental Resin Enhanced with Graphene.

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.

Sr and Mg Doped Bi-Phasic Calcium Phosphate Macroporous Bone Graft Substitutes Fabricated by Robocasting: A Structural and Cytocompatibility Assessment.

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 ß-tricalcium phosphate (ß-TCP)/hydroxyapatite mass concentration ratio of ~1.8. Remarkably, Mg and Sr were found to be predominantly incorporated in the ß-TCP lattice. These findings could be important for the future development of BCP-based bone graft substitutes since the higher dissolution rate of ß-TCP enables an easier release of the therapeutic ions. This may pave the road toward medical devices with more predictable in vivo performance.

Sol-Gel Synthesis and Characterization of a Quaternary Bioglass for Bone Regeneration and Tissue Engineering.

Sol-gel synthesis using inorganic and/or organic precursors that undergo hydrolysis and condensation at room temperature is a very attractive and less energetic method for preparing bioactive glass (BG) compositions, as an alternative to the melt-quenching process. When properly conducted, sol-gel synthesis might result in amorphous structures, with all of the components intimately mixed at the atomic scale. Moreover, developing new and better performing materials for bone tissue engineering is a growing concern, as the aging of the world's population leads to lower bone density and osteoporosis. This work describes the sol-gel synthesis of a novel quaternary silicate-based BG with the composition 60 SiO2-34 CaO-4 MgO-2 P2O5 (mol%), which was prepared using acidified distilled water as a single solvent. By controlling the kinetics of the hydrolysis and condensation steps, an amorphous glass structure could be obtained. The XRD results of samples calcined within the temperature range of 600-900 °C demonstrated that the amorphous nature was maintained until 800 °C, followed by partial crystallization at 900 °C. The specific surface area-an important factor in osteoconduction-was also evaluated over different temperatures, ranging from 160.6 ± 0.8 m2/g at 600 °C to 2.2 ± 0.1 m2/g at 900 °C, accompanied by consistent changes in average pore size and pore size distribution. The immersion of the BG particles in simulated body fluid (SBF) led to the formation of an extensive apatite layer on its surface. These overall results indicate that the proposed material is very promising for biomedical applications in bone regeneration and tissue engineering.

Fabrication of three dimensional bioactive Sr2+ substituted apatite scaffolds by gel-casting technique for hard tissue regeneration.

This study aimed to fabricate three-dimensional (3D) bioactive Sr2+ -substituted apatite (Sr-HAP) scaffolds prepared by gel-casting with polymer sponge infiltration technique. 3D Sr-HAP scaffolds were prepared as engineering constructs with interconnected porous structure with a pore size of 200-600 µm ranging from a 10 × 10 × 6 mm size was designed. The characterization of X-ray diffraction, field emission scanning electron microscopy, and energy dispersion spectroscopy was utilized in order to evaluate the crystalline phase, structure, and morphology in the interconnected porous of the synthesized Sr-HAP scaffold. The bioactive and biocompatible of the resultant Sr-HAP scaffolds were analyzed by using simulated body fluid solution. Furthermore, the cytotoxicity and proliferation of MG-63 cell lines on the scaffolds were examined in 24 h culture. Furthermore, in vivo experiments demonstrated that the tibia bone defect with 4 mm diameter in rabbits was successfully healed by Sr-HAP porous scaffold after 45 days implantation. The histological images indicated the improved cell proliferation and new bone formation occurred in the porous scaffold treated group. The results indicated that the fabricated Sr-HAP scaffold is a promising capacity to infuse bone regeneration and promote in vivo tissue repair.

3D Printing of Macro Porous Sol-Gel Derived Bioactive Glass Scaffolds and Assessment of Biological Response.

3D printing emerged as a potential game-changer in the field of biomedical engineering. Robocasting in particular has shown excellent capability to produce custom-sized porous scaffolds from pastes with suitable viscoelastic properties. The materials and respective processing methods developed so far still need further improvements in order to obtain completely satisfactory scaffolds capable of providing both the biological and mechanical properties required for successful and comprehensive bone tissue regeneration. This work reports on the sol-gel synthesis of an alkali-free bioactive glass and on its characterization and processing ability towards the fabrication of porous scaffolds by robocasting. A two-fold increase in milling efficiency was achieved by suitably adjusting the milling procedures. The heat treatment temperature exerted a profound effect on the surface area of mesoporous powders. Robocasting inks containing 35 vol.% solids were prepared, and their flow properties were characterized by rheological tests. A script capable of preparing customizable CAD scaffold geometries was developed. The printing process was adjusted to increase the technique's resolution. The mechanical properties of the scaffolds were assessed through compressive strength tests. The biomineralization ability and the biological performance were assessed by immersing the samples in simulated body fluid (SBF) and through MTT assays, respectively. The overall results demonstrated that scaffolds with macro porous features suitable for bone ingrowth (pore sizes of ~340 µm after sintering, and a porosity fraction of ~70%) in non-load-bearing applications could be successfully fabricated by 3D printing from the bioactive glass inks. Moreover, the scaffolds exhibited good biomineralization activity and good biocompatibility with human keratinocytes, suggesting they are safe and thus suited for the intended biomedical applications.

Highly Porous Composite Scaffolds Endowed with Antibacterial Activity for Multifunctional Grafts in Bone Repair.

The present study deals with the development of multifunctional biphasic calcium phosphate (BCP) scaffolds coated with biopolymers-poly(ε-caprolactone) (PCL) or poly(ester urea) (PEU)-loaded with an antibiotic drug, Rifampicin (RFP). The amounts of RFP incorporated into the PCL and PEU-coated scaffolds were 0.55 ± 0.04 and 0.45 ± 0.02 wt%, respectively. The in vitro drug release profiles in phosphate buffered saline over 6 days were characterized by a burst release within the first 8h, followed by a sustained release. The Korsmeyer-Peppas model showed that RFP release was controlled by polymer-specific non-Fickian diffusion. A faster burst release (67.33 ± 1.48%) was observed for the PCL-coated samples, in comparison to that measured (47.23 ± 0.31%) for the PEU-coated samples. The growth inhibitory activity against Escherichia coli and Staphylococcus aureus was evaluated. Although the RFP-loaded scaffolds were effective in reducing bacterial growth for both strains, their effectiveness depends on the particular bacterial strain, as well as on the type of polymer coating, since it rules the drug release behavior. The low antibacterial activity demonstrated by the BCP-PEU-RFP scaffold against E. coli could be a consequence of the lower amount of RFP that is released from this scaffold, when compared with BCP-PCL-RFP. In vitro studies showed excellent cytocompatibility, adherence, and proliferation of human mesenchymal stem cells on the BCP-PEU-RFP scaffold surface. The fabricated highly porous scaffolds that could act as an antibiotic delivery system have great potential for applications in bone regeneration and tissue engineering, while preventing bacterial infections.

Intercrystalline distal-effect on the afterglow phenomenon in photoluminescent SrAl2O4:CeIII, Ln nanotube growth.

We report a new method for the synthesis of photoluminescent SrAl(2)O(4):Ce(3+), Dy(3+), Eu(2+) nanotubes, PL-SNT:Ce(III), Ln, using solid-state reaction and post-annealing approach. This new optical nanotubular structure was characterized by HRTEM, SEM, AFM, EDX, steady-state and time-resolved PL spectroscopy. A series of f-f and f-d-transitions with light emission in structured bands peaking at 488 nm arising from the polymorphism of the host lattice was correlated with an intercrystalline distal-effect on the afterglow phenomenon.

Direct Ink Writing Glass: A Preliminary Step for Optical Application.

In this paper, we present a preliminary study and conceptual idea concerning 3D printing water-sensitive glass, using a borosilicate glass with high alkali and alkaline oxide contents as an example in direct ink writing. The investigated material was prepared in the form of a glass frit, which was further ground in order to obtain a fine powder of desired particle size distribution. In a following step, inks were prepared by mixing the fine glass powder with Pluoronic F-127 hydrogel. The acquired pastes were rheologically characterized and printed using a Robocasting device. Differential scanning calorimetry (DSC) experiments were performed for base materials and the obtained green bodies. After sintering, scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses were carried out in order to examine microstructure and the eventual presence of crystalline phase inclusions. The results confirmed that the as obtained inks exhibit stable rheological properties despite the propensity of glass to undergo hydrolysis and could be adjusted to desirable values for 3D printing. No additional phase was observed, supporting the suitability of the designed technology for the production of water sensitive glass inks. SEM micrographs of the sintered samples revealed the presence of closed porosity, which may be the main reason of light scattering.

Cuttlefish Bone-Derived Biphasic Calcium Phosphate Scaffolds Coated with Sol-Gel Derived Bioactive Glass.

The combination of calcium phosphates with bioactive glasses (BG) has received an increased interest in the field of bone tissue engineering. In the present work, biphasic calcium phosphates (BCP) obtained by hydrothermal transformation of cuttlefish bone (CB) were coated with a Sr-, Mg- and Zn-doped sol-gel derived BG. The scaffolds were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. The initial CB structure was maintained after hydrothermal transformation (HT) and the scaffold functionalization did not jeopardize the internal structure. The results of the in-vitro bioactivity after immersing the BG coated scaffolds in simulated body fluid (SBF) for 15 days showed the formation of apatite on the surface of the scaffolds. Overall, the functionalized CB derived BCP scaffolds revealed promising properties, but further assessment of the in-vitro biological properties is needed before being considered for their use in bone tissue engineering applications.