Osteoblast responsive biosilica-enriched gelatin microfibrillar microenvironments.

Engineering of scaffolds for bone regeneration is often inspired by the native extracellular matrix mimicking its composite fibrous structure. In the present study, we used low loadings of diatomite earth (DE) biosilica to improve the bone regeneration potential of gelatin electrospun fibrillar microenvironments. We explored the effect of increasing the DE content from 1 % to 3 % and 5 %, respectively, on the physico-chemical properties of the fibrous scaffolds denoted FG_DE1, FG_DE3, FG_DE5, regarding the aqueous media affinity, stability under simulated physiological conditions, morphology characteristics, and local mechanical properties at the surface. The presence of biosilica generated composite structures with lower swelling degrees and higher stiffness when compared to gelatin fibers. Increasing DE content led to higher Young modulus, while the stability of the protein matrix in PBS, at 37 °C, over 21 was significantly decreased by the presence of diatomite loadings. The best preosteoblast response was obtained for FG_DE3, with enhanced mineralization during the osteogenic differentiation when compared to the control sample without diatomite. 5 % DE in FG_DE5 proved to negatively influence cells' metabolic activity and morphology. Hence, the obtained composite microfibrillar scaffolds might find application as osteoblast-responsive materials for bone tissue engineering.

New 3D Printed Scaffolds Based on Walstromite Synthesized by Sol-Gel Method.

This study explores the potential utilization of walstromite (BaCa2Si3O9) as a foundational material for creating new bioceramics in the form of scaffolds through 3D printing technology. To achieve this objective, this study investigates the chemical-mineralogical, morphological, and structural characteristics, as well as the biological properties, of walstromite-based bioceramics. The precursor mixture for walstromite synthesis is prepared through the sol-gel method, utilizing pure reagents. The resulting dried gelatinous precipitate is analyzed through complex thermal analysis, leading to the determination of the optimal calcination temperature. Subsequently, the calcined powder is characterized via X-ray diffraction and scanning electron microscopy, indicating the presence of calcium and barium silicates, as well as monocalcium silicate. This powder is then employed in additive 3D printing, resulting in ceramic scaffolds. The specific ceramic properties of the scaffold, such as apparent density, absorption, open porosity, and compressive strength, are assessed and fall within practical use limits. X-ray diffraction analysis confirms the formation of walstromite as a single phase in the ceramic scaffold. In vitro studies involving immersion in simulated body fluid (SBF) for 7 and 14 days, as well as contact with osteoblast-like cells, reveal the scaffold's ability to form a phosphate layer on its surface and its biocompatibility. This study concludes that the walstromite-based ceramic scaffold exhibits promising characteristics for potential applications in bone regeneration and tissue engineering.

New Mesoporous Silica Materials Loaded with Polyphenols: Caffeic Acid, Ferulic Acid and p-Coumaric Acid as Dietary Supplements for Oral Administration.

In this study, two types of mesoporous silica with different pore structures and volumes were synthesized by the soft-templating method. The two types of mesoporous silica, type MCM-41 and MCM-48, were loaded with three polyphenols-caffeic acid, p-coumaric acid and trans-ferulic acid-in the same ratio of mesoporous silica:polyphenol (1:0.4 w/w). The materials obtained were characterized from a morphological and structural point of view through different analysis techniques. Through X-ray diffraction (XRD), the crystallization plane and the ordered structure of the mesoporous silica were observed. The difference between the two types of materials containing MCM-41 and MCM-48 was observed through the different morphologies of the silica particles through scanning electron microscopy (SEM) and also through the Brunauer-Emmet-Teller (BET) analysis, that the surface areas and volumes of pores was different between the two types of mesoporous silica, and, after loading with polyphenols, the values were reduced. The characteristic bands of silica and of polyphenols were easily observed by Fourier-transform infrared spectroscopy (FTIR), and, through thermogravimetric analysis (TGA), the residual mass was determined and the estimated amount of polyphenol in the materials and the efficient loading of mesoporous silica with polyphenols could be determined. The in vitro study was performed in two types of simulated biological fluids with different pH-simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The obtained materials could be used in various biomedical applications as systems with controlled release of natural polyphenols and the most suitable application could be as food supplements especially when a mixture of such materials is used or when the polyphenols are co-loaded within the mesoporous silica.

3D Printed Composite Scaffolds of GelMA and Hydroxyapatite Nanopowders Doped with Mg/Zn Ions to Evaluate the Expression of Genes and Proteins of Osteogenic Markers.

As bone diseases and defects are constantly increasing, the improvement of bone regeneration techniques is constantly evolving. The main purpose of this scientific study was to obtain and investigate biomaterials that can be used in tissue engineering. In this respect, nanocomposite inks of GelMA modified with hydroxyapatite (HA) substituted with Mg and Zn were developed. Using a 3D bioprinting technique, scaffolds with varying shapes and dimensions were obtained. The following analyses were used in order to study the nanocomposite materials and scaffolds obtained by the 3D printing technique: Fourier transform infrared spectrometry and X-ray diffraction (XRD), scanning electron microscopy (SEM), and micro-computed tomography (Micro-CT). The swelling and dissolvability of each scaffold were also studied. Biological studies, osteopontin (OPN), and osterix (OSX) gene expression evaluations were confirmed at the protein levels, using immunofluorescence coupled with confocal microscopy. These findings suggest the positive effect of magnesium and zinc on the osteogenic differentiation process. OSX fluorescent staining also confirmed the capacity of GelMA-HM5 and GelMA-HZ5 to support osteogenesis, especially of the magnesium enriched scaffold.

Mesoporous Bioactive Glass Nanoparticles in the SiO2-P2O5-CaO-MO (M=Mg, Zn) System: Synthesis and Properties.

Mesoporous bioactive glass nanoparticles (MBGNs) are widely recognized for their ability to bond to hard tissue, while the ions released from the BG structure enhance specific cellular pathways. In this study, the SiO2-P2O5-CaO-MgO-ZnO system was used to successfully synthesize MBGNs by a microemulsion-assisted sol-gel method. The MBGNs calcinated at 600 °C/3 h had a typical phosphosilicate structure together with a poorly crystalline hydroxyapatite (HAp). The addition of ZnO not only led to a higher degree of crystallinity of HAp but also induced a higher porosity of the particles. All MBGNs had a mesoporous structure with an interconnected network of slit shape pores. For each type of composition, two families of highly dispersed spherical nanoparticles could be identified. In vitro tests in simulated body fluid (SBF) proved that after only 3 days of immersion all the materials were covered with a layer of brushite whose degree of crystallinity decreases in the presence of Zn2+. The antibacterial assay revealed a strong inhibitory effect for all samples after 40 h of contact. Simultaneously, MBGNs did not increase the intracellular oxidative stress while it stimulated the cell proliferation process.

Processing of Calcium Magnesium Silicates by the Sol-Gel Route.

In this work, calcium magnesium silicate ceramics were processed through the sol-gel method in order to study the crystalline and morphological properties of the resulting materials in correlation with the compositional and thermal parameters. Tetraethyl orthosilicate and calcium/magnesium nitrates were employed as sources of cations, in ratios specific to diopside, akermanite and merwinite; they were further subjected to gelation, calcination (600 °C) and thermal treatments at different temperatures (800, 1000 and 1300 °C). The properties of the intermediate and final materials were investigated by thermal analysis, scanning electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction and Rietveld refinement. Such ceramics represent suitable candidates for tissue engineering applications that require porosity and bioactivity.

Mesoporous Silica Materials Loaded with Gallic Acid with Antimicrobial Potential.

This paper aimed to develop two types of support materials with a mesoporous structure of mobile crystalline matter (known in the literature as MCM, namely MCM-41 and MCM-48) and to load them with gallic acid. Soft templating methodology was chosen for the preparation of the mesoporous structures-the cylindrical micelles with certain structural characteristics being formed due to the hydrophilic and hydrophobic intermolecular forces which occur between the molecules of the surfactants (cetyltrimethylammonium bromide-CTAB) when a minimal micellar ionic concentration is reached. These mesoporous supports were loaded with gallic acid using three different types of MCM-gallic acid ratios (1:0.41; 1:0.82 and 1:1.21)-and their characterizations by FTIR, SEM, XRD, BET and drug release were performed. It is worth mentioning that the loading was carried out using a vacuum-assisted methodology: the mesoporous materials are firstly kept under vacuum at ~0.1 barr for 30 min followed by the addition of the polyphenol solutions. The concentration of the solutions was adapted such that the final volume covered the wet mesoporous support and-in this case-upon reaching normal atmospheric pressure, the solution was pushed inside the pores, and thus the polyphenols were mainly loaded inside the pores. Based on the SBET data, it can be seen that the specific surface area decreased considerably with the increasing ratio of gallic acid; the specific surface area decreased 3.07 and 4.25 times for MCM-41 and MCM-48, respectively. The sample with the highest polyphenol content was further evaluated from a biological point of view, alone or in association with amoxicillin administration. As expected, the MCM-41 and MCM-48 were not protective against infections-but, due to the loading of the gallic acid, a potentiated inhibition was recorded for the tested gram-negative bacterial strains. Moreover, it is important to mention that these systems can be efficient solutions for the recovery of the gut microbiota after exposure to antibiotics, for instance.

3D Printable Composite Biomaterials Based on GelMA and Hydroxyapatite Powders Doped with Cerium Ions for Bone Tissue Regeneration.

The main objective was to produce 3D printable hydrogels based on GelMA and hydroxyapatite doped with cerium ions with potential application in bone regeneration. The first part of the study regards the substitution of Ca2+ ions from hydroxyapatite structure with cerium ions (Ca10-xCex(PO4)6(OH)2, xCe = 0.1, 0.3, 0.5). The second part followed the selection of the optimal concentration of HAp doped, which will ensure GelMA-based scaffolds with good biocompatibility, viability and cell proliferation. The third part aimed to select the optimal concentrations of GelMA for the 3D printing process (20%, 30% and 35%). In vitro biological assessment presented the highest level of cell viability and proliferation potency of GelMA-HC5 composites, along with a low cytotoxic potential, highlighting the beneficial effects of cerium on cell growth, also supported by Live/Dead results. According to the 3D printing experiments, the 30% GelMA enriched with HC5 was able to generate 3D scaffolds with high structural integrity and homogeneity, showing the highest suitability for the 3D printing process. The osteogenic differentiation experiments confirmed the ability of 30% GelMA-3% HC5 scaffold to support and efficiently maintain the osteogenesis process. Based on the results, 30% GelMA-3% HC5 3D printed scaffolds could be considered as biomaterials with suitable characteristics for application in bone tissue engineering.

Synthesis and Characterization of ZnO(MgO)-CaO-SiO2-P2O5 Bioglass Obtained by Sol-Gel Method in Presence of Surfactant Agent.

Bioglass (BG) is a class of biomaterials increasingly approached in biomedical applications, such as in regeneration of hard tissues, due to the properties of bioactivity, osteoinductivity, osteoconductivity, but also the high rate of biodegradation, both in vitro and in vivo. The present paper addresses the obtaining of bioglasses from the ZnO(MgO)-CaO-SiO2-P2O5 system by the sol-gel method and the use of a surfactant to ensure a specific surface or high open porosity, starting from S53P4 bioglass (53% SiO2, 23% Na2O, 20% CaO, 4% P2O5), also known as BoneAlive®. The precursor powders were analyzed from the phase composition point of view by complex thermal analysis and X-ray diffraction, the vitreous powders were assessed from the compositional point of view by X-ray diffraction, morpho-structural by scanning electron microscopy, specific surface area and the pore size dimension by the Brunauer-Emmett-Teller (BET) analysis, dispersion by laser granulometry, and also cell biology and surface mineralization tests were performed by immersion in SBF (simulated body fluid). The system proposed in this paper ZnO(MgO)-CaO-SiO2-P2O5 was successfully obtained by sol-gel method. The results showed the higher interaction between the samples and the SBF medium for samples containing magnesium (M2) and the lowest degree of mineralization after immersion in SBF was noticed for samples containing zinc (M1). The results also prove that by incorporating different ionic species in bioglass composition-Zn2+ and Mg2+, biocompatibility and antibacterial properties will be significantly enhanced.

Synthesis of High-Performance CSA Cements as Low Carbon OPC Alternative.

Starting from natural raw materials, cements based calcium sulphoaluminate (CSA) clinkers have been successfully obtained as an eco-friendly alternative to ordinary Portland cement. CSA-based cements with ye'elimite as the main phase have been produced over the years and are widely used today. In this regard, the present paper considers the study of hydration processes for CSA pastes prepared with a water/cement ratio of 0.5 according to the EN-197 standard and their characterization by thermal analysis (DTA-TG), X-ray diffraction analysis (XRD), and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX). A mechanical strength of 60.9 MPa was the greatest achieved for mortars hardened for 28 days.

The Solidification/Stabilization of Wastewater (From a Landfill Leachate) in Specially Designed Binders Based on Coal Ash.

The aim of this study is to assess the possibility to solidify/stabilize a liquid waste from a municipal waste landfill using binders based on coal ash (fly ash and bottom ash) and specially designed cements for waste treatment (INERCEM). The leaching test proved that all cementitious systems are efficient for the solidification/stabilization of the studied wastes and can reduce the leaching potential of heavy metals present in both liquid waste and coal ash. Therefore, these wastes cease to be a source of environmental pollution. X-ray diffraction (XRD) and thermal complex analysis (DTA-TG) were used to assess the nature and amount of compounds formed in these cementitious systems during the hydration and hardening processes; ettringite, calcium silicate hydrates and CaCO3 were the main compounds formed in these systems assessed by these methods. The microstructure of hardened specimens was assessed by scanning electronic microscopy (SEM); the presence of hydrate phases, at the surface of cenospheres present in fly ash, proved the high pozzolanic reactivity of this phase.

Coatings Based on Phosphate Cements for Fire Protection of Steel Structures.

Fire events in buildings can cause losses to human life and important material damage, therefore a great deal of attention is paid nowadays to fire prevention. Buildings based on steel structures are especially affected in the event of a fire, due to the important loss of load-bearing capability when steel is heated at temperatures higher than 500 °C. Therefore, one possible method to mitigate the deleterious effect of fire is to protect steel structures from direct heating by applying protective coatings. In this paper, the ability of magnesium phosphate cement (MPC), based on dead burned magnesite and calcium magnesium phosphate cement (CMPC) coatings, to protect a steel substrate was assessed. CMPCs were obtained by mixing partially calcined dolomite with a KH2PO4 (MKP) solution, and in some cases, with a setting retarder (borax). The main mineralogical compounds assessed by X-ray diffraction and electronic microscopy (SEM-EDS) in CMPC are MgO, CaCO3, and K-struvite (KMgPO4·6H2O). The coatings based on MPC and CMPC, applied to steel plates, were tested in direct contact with a flame; the coatings of MPC and CMPC without the borax addition prevented the temperature increase of a metal substrate above 500 °C. No exfoliation of coatings (MPC and CMPC without borax addition) was noticed during the entire period of the test (45 min).

Magnetic silica particles functionalized with guanidine derivatives for microwave-assisted transesterification of waste oil.

This study aimed to develop a facile synthesis procedure for heterogeneous catalysts based on organic guanidine derivatives superbases chemically grafted on silica-coated Fe3O4 magnetic nanoparticles. Thus, the three organosilanes that were obtained by reacting the selected carbodiimides (N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), respectively 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) with 3-aminopropyltriethoxysilane (APTES) were used in a one-pot synthesis stage for the generation of a catalytic active protective shell through the simultaneous hydrolysis/condensation reaction with tetraethyl orthosilicate (TEOS). The catalysts were characterized by FTIR, TGA, SEM, BET and XRD analysis confirming the successful covalent attachment of the organic derivatives in the silica shell. The second aim was to highlight the capacity of microwaves (MW) to intensify the transesterification process and to evaluate the activity, stability, and reusability characteristics of the catalysts. Thus, in MW-assisted transesterification reactions, all catalysts displayed FAME yields of over 80% even after 5 reactions/activation cycles. Additionally, the influence of FFA content on the catalytic activity was investigated. As a result, in the case of Fe3O4@SiO2-EDG, a higher tolerance towards the FFA content can be noticed with a FAME yield of over 90% (for a 5% (weight) vs oil catalyst content) and 5% weight FFA content.

Phosphate Cements Based on Calcined Dolomite: Influence of Calcination Temperature and Silica Addition.

The aim of this study is to assess the possibility of obtaining phosphate cements based on dolomite calcined at various temperatures with/without quartz sand addition. A lower calcination temperature of dolomite (1200 °C) determines a high increase in the system temperature when calcined dolomite is mixed with KH2PO4 (MKP) solution and also a rapid expansion of the paste. The increase in calcination temperature up to 1400 °C reduces the oxides reactivity; however, for lower dosages of MKP, the expansion phenomenon is still recorded. The increase in MKP dosage increases the compressive strength due to the formation of K-struvite. The mixing of dolomite with sand, followed by thermal treatment at 1200 °C, modifies its composition and reactivity; the compressive strength of phosphate cements obtained by mixing this solid precursor with MKP increases up to 28 days of curing. We assessed the nature of hydrates formed in the phosphate systems studied by X-ray diffraction in order to explain the hardening processes and the mechanical properties of these systems. The microstructure and elemental composition of hardened cement pastes were assessed by scanning electronic microscopy with energy-dispersive spectroscopy. The phosphate cements based on calcined magnesite or dolomite were used to immobilize an industrial hazardous waste with high chromium content. The partial substitution of calcined magnesite/dolomite with this waste determines an important decrease in compressive strengths. Nevertheless, the leaching tests confirm an adequate immobilization of chromium in some of the matrices studied (for a waste dosage corresponding to 0.5 wt % Cr).

CO2 Sequestration in the Production of Portland Cement Mortars with Calcium Carbonate Additions.

The paper presents the obtention and characterization of Portland cement mortars with limestone filler and nano-calcite additions. The nano-calcite was obtained by the injection of CO2 in a nano-Ca(OH)2 suspension. The resulted nano-CaCO3 presents different morphologies, i.e., polyhedral and needle like crystals, depending on the initial Ca(OH)2 concentration of the suspension. The formation of calcium carbonate in suspensions was confirmed by X-ray diffraction (XRD), complex thermal analysis (DTA-TG), scanning electron microscopy (SEM) and transmission electron microscopy (TEM and HRTEM). This demonstrates the viability of this method to successfully sequestrate CO2 in cement-based materials. The use of this type of nano-CaCO3 in mortar formulations based on PC does not adversely modify the initial and final setting time of cements; for all studied pastes, the setting time decreases with increase of calcium carbonate content (irrespective of the particle size). Specific hydrated phases formed by Portland cement hydration were observed in all mortars, with limestone filler additions or nano-CaCO3, irrespective of curing time. The hardened mortars with calcium carbonate additions (in adequate amounts) can reach the same mechanical strengths as reference (Portland cement mortar). The addition of nano-CaCO3 in the raw mix increases the mechanical strengths, especially at shorter hardening periods (3 days).

Bisphenol A Adsorption on Silica Particles Modified with Beta-Cyclodextrins.

This study presents the synthesis of silica particles bearing two beta-cyclodextrin (BCD) (beta-cyclodextrin-BCD-OH and diamino butane monosubstituted beta-cyclodextrin-BCD-NH2). The successful synthesis of the BCD-modified silica was confirmed by FT-IR and TGA. Using contact angle measurements, BET analysis and SEM characterization, a possible formation mechanism for the generation of silica particles bearing BCD derivatives on their surface was highlighted. The obtained modified silica displayed the capacity to remove bisphenol A (BPA) from wastewater due to the presence of the BCD moieties on the surface of the silica. The kinetic analysis showed that the adsorption reached equilibrium after 180 min for both materials with qe values of 107 mg BPA/g for SiO2-BCD-OH and 112 mg BPA/g for SiO2-BCD-NH2. The process followed Ho's pseudo-second-order adsorption model sustaining the presence of adsorption sites with different activities. The fitting of the Freundlich isotherm model on the experimental results was also evaluated, confirming the BCD influence on the materials' adsorption properties.

Development of 3D Bioactive Scaffolds through 3D Printing Using Wollastonite-Gelatin Inks.

The bioactivity of scaffolds represents a key property to facilitate the bone repair after orthopedic trauma. This study reports the development of biomimetic paste-type inks based on wollastonite (CS) and fish gelatin (FG) in a mass ratio similar to natural bone, as an appealing strategy to promote the mineralization during scaffold incubation in simulated body fluid (SBF). High-resolution 3D scaffolds were fabricated through 3D printing, and the homogeneous distribution of CS in the protein matrix was revealed by scanning electron microscopy/energy-dispersive X-ray diffraction analysis (SEM/EDX) micrographs. The bioactivity of the scaffold was suggested by an outstanding mineralization capacity revealed by the apatite layers deposited on the scaffold surface after immersion in SBF. The biocompatibility was demonstrated by cell proliferation established by MTT assay and fluorescence microscopy images and confirmed by SEM micrographs illustrating cell spreading. This work highlights the potential of the bicomponent inks to fabricate 3D bioactive scaffolds and predicts the osteogenic properties for bone regeneration applications.

Influence of Dopant Nature on Biological Properties of ZnO Thin-Film Coatings on Ti Alloy Substrate.

In this paper, ZnO and Co2+/Mg2+-doped ZnO thin films on TiAlV alloy substrates were obtained. The films were deposited by spin coating of sol-gel precursor solutions and thermally treated at 600 °C for 2 h, in air and slow cooled. The doping ions concentration was 1.0 mol%. The study's aim was to obtain implantable metallic materials with improved biocompatibility and antibacterial qualities. The characteristics of the thin films were assessed from the point of view of microstructure, morphology, wetting properties, antibacterial activity and biological response in the presence of amniotic fluid stem cells (AFSC). The results proved that all deposited samples were nanostructured, suggesting a very good antibacterial effect and proving to be suitable supports for cellular adhesion and proliferation. All properties also depended on the doping ion nature.

PCL-ZnO/TiO2/HAp Electrospun Composite Fibers with Applications in Tissue Engineering.

The main objective of the tissue engineering field is to regenerate the damaged parts of the body by developing biological substitutes that maintain, restore, or improve original tissue function. In this context, by using the electrospinning technique, composite scaffolds based on polycaprolactone (PCL) and inorganic powders were successfully obtained, namely: zinc oxide (ZnO), titanium dioxide (TiO2) and hydroxyapatite (HAp). The novelty of this approach consists in the production of fibrous membranes based on a biodegradable polymer and loaded with different types of mineral powders, each of them having a particular function in the resulting composite. Subsequently, the precursor powders and the resulting composite materials were characterized by the structural and morphological point of view in order to determine their applicability in the field of bone regeneration. The biological assays demonstrated that the obtained scaffolds represent support that is accepted by the cell cultures. Through simulated body fluid immersion, the biodegradability of the composites was highlighted, with fiber fragmentation and surface degradation within the testing period.

Mineralogical and Microstructural Characteristics of Two Dental Pulp Capping Materials.

This paper aims to investigate the composition, surface, and microstructural characteristics, and bioactivity of two commercially available pulp capping materials known as TheraCal LC and BIO MTA+. The materials were prepared as cylindrical samples and assessed by X-ray diffraction (XRD) and complex thermal analysis for mineralogical characterization, and by scanning electron microscopy (SEM) coupled with energy dispersive of X-ray (EDX), Fourier-Transformed Infrared Spectroscopy (FT-IR), and atomic force microscopy (AFM) for microstructural and surface characteristics. The in vitro bioactivity was highlighted by surface mineralization throughout SEM coupled with EDX and FT-IR analysis. XRD analysis performed on both materials showed calcium silicate phases and different radiopacifying compounds. AFM measurements indicated a smoother and more homogenous surface with a lower average roughness for TheraCal LC due to the resin matrix from its composition. FT-IR analysis displayed bands for several compounds in both materials. Both materials exhibited bioactive properties showing surface mineralization after being immersed in solution similar to the human physiological environment. However, the MTA cement showed a better mineralization due to the anhydrous and hydrated phases.