Sol–Gel Synthesis of Endodontic Cements: Post-Synthesis Treatment to Improve Setting Performance and Bioactivity

The sol–gel process is a wet chemical technique that allows very fine control of the composition, microstructure, and final textural properties of materials, and has great potential for the synthesis of endodontic cements with improved properties. In this work, the influence of different sol–gel synthesis variables on the preparation of endodontic cement based on calcium silicate with Ca/Si stoichiometry equal to 3 was studied. Starting from the most optimal hydraulic composition selected, a novel second post-synthesis treatment using ethanol was essayed. The effects of the tested variables were analyzed by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen physisorption, and Gillmore needles to determine the setting time and simulated body fluid (SBF) immersion to measure the bioactive response in vitro. The results indicated that the sol–gel technique is effective in obtaining bioactive endodontic cements (BECs) with high content of the hydraulic compound tricalcium silicate (C3S) in its triclinic polymorph. The implementation of a novel post-synthesis treatment at room temperature using ethanol allows obtaining a final BEC product with a finer particle size and a higher CaCO₃ content, which results in an improved material in terms of setting time and bioactive response.     

Development of Efficient One-Pot Methods for the Synthesis of Luminescent Dyes and Sol–Gel Hybrid Materials

This paper presents a comparison of the simultaneous preparation of di-O-alkylated and ether–ester derivatives of fluorescein using different methods (conventional or microwave heating). Shortening of the reaction time and increased efficiency were observed when using a microwave reactor. Moreover, described here for the first time is the application of a fast, simple, and eco-friendly ball-assisted method to exclusively obtain ether–ester derivatives. We also demonstrate that fluorescein can be effectively functionalized by O-alkylation carried out under microwave or ball-milling conditions, saving time and energy and affording the desired products with good yields and minimal byproduct formation. All the synthesized products as well as pH-dependent (prototropic) forms trapped in the SiO₂ matrix were examined using UV–Vis and fluorescence spectroscopy.     

Hydrophobic Thin Films from Sol–Gel Processing: A Critical Review

Fabrication of hydrophobic thin films from a liquid phase is a hot topic with critical technological issues. Interest in the production of hydrophobic surfaces is growing steadily due to their wide applications in several industrial fields. Thin films from liquid phases can be deposited on different types of surfaces using a wide variety of techniques, while the design of the precursor solution offers the possibility of fine-tuning the properties of the hydrophobic coating layers. A general trend is the design of multifunctional films, which have different properties besides being hydrophobic. In the present review, we have described the synthesis through sol–gel processing of hydrophobic films enlightening the main achievements obtained in the field.     

Nanoscale Piezoelectric Properties and Phase Separation in Pure and La-Doped BiFeO3 Films Prepared by Sol–Gel Method

Pure BiFeO₃ (BFO) and doped Bi_0.9La_0.1FeO₃ (BLFO) thin films were prepared on Pt/TiO₂/SiO₂/Si substrates by a modified sol–gel technique using a separate hydrolysis procedure. The effects of final crystallization temperature and La doping on the phase structure, film morphology, and nanoscale piezoelectric properties were investigated. La doping and higher crystallization temperature lead to an increase in the grain size and preferred (102) texture of the films. Simultaneously, a decrease in the average effective piezoelectric coefficient (about 2 times in La-doped films) and an increase in the area of surface non-polar phase (up to 60%) are observed. Phase separation on the films’ surface is attributed to either a second phase or to a non-polar perovskite phase at the surface. As compared with undoped BFO, La-doping leads to an increase in the average grain size and self-polarization that is important for future piezoelectric applications. It is shown that piezoelectric activity is directly related to the films’ microstructructure, thus emphasizing the role of annealing conditions and La-doping that is frequently used to decrease the leakage current in BFO-based materials.     

Setting Up and Assessing a New Micro-Structured Waveguiding Fluorescent Architecture on Glass Entirely Elaborated by Sol–Gel Processing

Channel waveguides with diffraction gratings at their input and output for light injection and extraction, respectively, are extensively exploited for optical and photonic applications. In this paper, we report for the first time on such an architecture on glass entirely elaborated by sol–gel processing using a titanium-oxide-based photoresist that can be imprinted through a single photolithography step. This work is more particularly focused on a fluorescent architecture including channel waveguides doped with a ruthenium-complex fluorophore (tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II), Rudpp). The study demonstrates that this original sol–gel micro-structured architecture is well adapted to efficient channel waveguide/diffraction grating coupling and propagation of the fluorescence excitation and emission signals in the core of the channel waveguide. It demonstrates, in particular, a relatively large tolerance of several degrees in the angular injection fiber positioning and an important axial and vertical fiber spatial positioning tolerance of more than 100 µm at the Rudpp emission wavelength. The measurements also indicate that, in the conditions tested in this work, a Rudpp concentration of around 0.1 mM and a channel waveguide length of 2 to 5 mm offer the best trade-off in terms of excitation signal propagation and emission signal detection. This work constitutes a promising preliminary step toward the integration of our architecture into a microfluidic platform for fluorescence measurement in a liquid medium and waveguiding configuration.     

Formation of Composite Coatings on Galvanized Steel from Organosilane Solutions Using Electrophoresis and Sol–Gel Technology

New hybrid composite coatings (HCCs) on hot-dip galvanized steel (HDGS) were obtained using electrophoresis (cathodic polarization (CP)) and sol–gel technology. For this purpose, a technique for the preparation of a cationic precursor based on TiCl₄ and aminopropyltriethoxysilane was developed. Electrophoresis of the charged particles of the precursor and organosilanes promotes the production of denser sol–gel coatings with improved adhesion. Using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) methods, the formation mechanism and protective properties of HCC on galvanized steel were investigated.     

High Refractive Index Silica-Titania Films Fabricated via the Sol–Gel Method and Dip-Coating Technique—Physical and Chemical Characterization

Crack-free binary SiO_x:TiO_y composite films with the refractive index of ~1.94 at wavelength 632.8 nm were fabricated on soda-lime glass substrates, using the sol–gel method and dip-coating technique. With the use of transmission spectrophotometry and Tauc method, the energy of the optical band gap of 3.6 eV and 4.0 eV were determined for indirect and direct optical allowed transitions, respectively. Using the reflectance spectrophotometry method, optical homogeneity of SiO_x:TiO_y composite films was confirmed. The complex refractive index determined by spectroscopic ellipsometry confirmed good transmission properties of the developed SiO_x:TiO_y films in the Vis-NIR spectral range. The surface morphology of the SiO_x:TiO_y films by atomic force microscopy (AFM) and scanning electron microscopy (SEM) methods demonstrated their high smoothness, with the root mean square roughness at the level of ~0.15 nm. Fourier-transform infrared (FTIR) spectroscopy and Raman spectroscopy were used to investigate the chemical properties of the SiO_x:TiO_y material. The developed binary composite films SiO_x:TiO_y demonstrate good waveguide properties, for which optical losses of 1.1 dB/cm and 2.7 dB/cm were determined, for fundamental TM₀ and TE₀ modes, respectively.     

Antimicrobial Activity of a Novel Cu(NO3)2-Containing Sol–Gel Surface under Different Testing Conditions

In this study, assessment of the antimicrobial activity of a novel, plasma-cured 2.5% (w/v) Cu(NO₃)₂-containing sol–gel surface was performed. In contrast to state-of-the-art sol–gel coatings, the plasma curing led to a gradient in cross-linking with the highest values at the top of the coating. As a result, the coating behaved simultaneously hard, scratch-resistant, and tough, the latter due to the more flexible bulk of the coating toward the substrate. Further, the diffusion and permeation through the coating also increased toward the substrate. In our study, tests according to ISO 22196 showed antibacterial activity of the 2.5% (w/v) Cu(NO₃)₂-containing sol–gel surface against all bacterial strains tested, and we expanded the testing further using a “dry” evaluation without an aqueous contact phase, which confirmed the antimicrobial efficacy of the 2.5% (w/v) Cu(NO₃)₂-containing sol–gel surface. However, further investigation under exposure to soiling with the addition of 0.3% albumin, used to simulate organic load, led to a significant impairment in the antibacterial effect under both tested conditions. Furthermore, re-testing of the surface after disinfection with 70% ethanol led to a total loss of antibacterial activity. Our results showed that besides the mere application of an antimicrobial agent to a surface coating, it is also necessary to consider the future use of these surfaces in the experimental phase combining industry and science. Therefore, a number of tests corresponding to the utilization of the surface should be obligative on the basis of this assessment.     

Deposition of Sol–Gel ZnO:Mg Films and Investigation of Their Structural and Optical Properties

This work presents a facile sol–gel method for the deposition of ZnO and ZnO:Mg films. The films are spin coated on silicon and quartz substrates. The impact of magnesium concentrations (0, 0.5, 1, 2 and 3 wt%) and post-annealing treatments (300–600 °C) on the film’s structural, vibrational and optical properties is investigated. Undoped ZnO films crystallize in the wurtzite phase, with crystallite sizes ranging from 9.1 nm (300 °C) to 29.7 nm (600 °C). Mg doping deteriorates the film crystallization and shifting of 002 peak towards higher diffraction angles is observed, indicating the successful incorporation of Mg into the ZnO matrix. ZnO:Mg films (2 wt%) possess the smallest crystallite size, ranging from 6.2 nm (300 °C) to 25.2 nm (600 °C). The highest Mg concentration (3 wt%) results into a segregation of the MgO phase. Lattice constants, texture coefficients and Zn–O bond lengths are discussed. The diminution of the c lattice parameter is related to the replacement of Zn²⁺ by Mg²⁺ in the ZnO host lattice. The vibrational properties are studied by Fourier transform infrared (FTIR) spectroscopy. IR lines related to Mg–O bonds are found for ZnO:Mg films with dopant concentrations of 2 and 3 wt%. The optical characterization showed that the transmittance of ZnO:Mg thin films increased from 74.5% (undoped ZnO) to about 89.1% and the optical band gap energy from 3.24 to 3.56 eV. Mg doping leads to a higher refractive index compared to undoped ZnO films. The FESEM (field emission scanning electron microscopy) technique is used for observation of the surface morphology modification of ZnO:Mg films. The doped ZnO films possess a smoother grained surface structure, opposite to the wrinkle-type morphology of undoped sol–gel ZnO films. The smoother surface leads to improved transparency of ZnO:Mg films.     

Behavior of Silica Nanoparticles Synthesized from Rice Husk Ash by the Sol–Gel Method as a Photocatalytic and Antibacterial Agent

Silica nanoparticles (SiO₂ NPs) are one of the most well-studied inorganic nanoparticles for many applications. They offer the advantages of tunable size, biocompatibility, porous structure, and larger surface area. Thus, in this study, a high yield of SiO₂ NPs was produced via the chemical treatment of rice husk ash by the sol–gel method. Characteristics of the prepared SiO₂ NPs were validated using different characterization techniques. Accordingly, the phase, chemical composition, morphological, and spectroscopic properties of the prepared sample were studied. The average particle size of the SiO₂ NPs was found to be approximately 60–80 nm and the surface area was 78.52 m²/g. The prepared SiO₂ NPs were examined as photocatalysts for the degradation of methyl orange (MO) dye under UV irradiation. It was found that the intensity of the characteristic absorption band of MO decreased gradually with exposure time increasing, which means the successful photodegradation of MO by SiO₂ NPs. Moreover, the antibacterial activity of obtained SiO₂ NPs was investigated by counting the coliform bacteria in the surface water using the most probable number (MPN) index method. The results revealed that the MPN of coliform bacteria untreated and treated by SiO₂ NPs was estimated to be 170 CFU/100 mL and 10 CFU/100 mL, respectively, resulting in bacterial growth inhibition of 94.12%.     

Preparation of Hierarchical Porous Silicon Carbide Monoliths via Ambient Pressure Drying Sol–Gel Process Followed by High-Temperature Pyrolysis

Hierarchical porous silicon carbide (SiC) attracts great attention due to its superior chemical resistance, high thermal shock resistance, and excellent thermal stability. The preparation of a porous SiC monolith via a simple sol–gel method is limited by either the high cost of the raw materials or the special time-consuming drying process. Herein, we report an ambient drying sol–gel approach for the synthesis of organic–inorganic hybrid monolithic gels which can be converted into hierarchical porous SiC monoliths upon pyrolysis at 1400 °C. The as-synthesized SiC monoliths possess hierarchical pores with macropores of 4.5 µm and mesopores of 2.0 nm. The porosities, specific surface areas and compressive strengths of the hierarchical porous SiC monoliths are 71.3%, 171.5 m²/g and 7.0 ± 0.8 MPa, respectively.     

High Humidity Response of Sol–Gel-Synthesized BiFeO3 Ferroelectric Film

In this work, a BiFeO₃ film is prepared via a facile sol–gel method, and the effects of the relative humidity (RH) on the BiFeO₃ film in terms of capacitance, impedance and current–voltage (I–V) are explored. The capacitance of the BiFeO₃ film increased from 25 to 1410 pF with the increase of RH from 30% to 90%. In particular, the impedance varied by more than two orders of magnitude as RH varied between 30% and 90% at 10 Hz, indicating a good hysteresis and response time. The mechanism underlying humidity sensitivity was analyzed by complex impedance spectroscopy. The adsorption of water molecules played key roles at low and high humidity, extending the potential application of ferroelectric BiFeO₃ films in humidity-sensitive devices.     

Energy Storage Properties of Sol–Gel-Processed SrTiO3 Films

Dielectric films with a high energy storage density and a large breakdown strength are promising material candidates for pulsed power electrical and electronic applications. Perovskite-type dielectric SrTiO₃ (STO) has demonstrated interesting properties desirable for capacitive energy storage, including a high dielectric constant, a wide bandgap and a size-induced paraelectric-to-ferroelectric transition. To pave a way toward large-scale production, STO film capacitors were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by the sol–gel method in this paper, and their electrical properties including the energy storage performance were studied as a function of the annealing temperature in the postgrowth rapid thermal annealing (RTA) process. The appearance of a ferroelectric phase at a high annealing temperature of 750 °C was revealed by X-ray diffraction and electrical characterizations (ferroelectric P-E loop). However, this high dielectric constant phase came at the cost of a low breakdown strength and a large hysteresis loss, which are not desirable for the energy storage application. On the other hand, when the RTA process was performed at a low temperature of 550 °C, a poorly crystallized perovskite phase together with a substantial amount of impurity phases appeared, resulting in a low breakdown strength as well as a very low dielectric constant. It is revealed that the best energy storage performance, which corresponds to a large breakdown strength and a medium dielectric constant, is achieved in STO films annealed at 650 °C, which showed a large energy density of 55 J/cm³ and an outstanding energy efficiency of 94.7% (@ 6.5 MV/cm). These findings lay out the foundation for processing high-quality STO film capacitors via the manufacturing-friendly sol–gel method.     

Chemical and Structural Characterization of Amorphous and Crystalline Alumina Obtained by Alternative Sol–Gel Preparation Routes

Aluminum oxide is one of the most commonly used materials in the industry. It is used in the field of catalysis, refractories, and optics. Despite the fact that there are many techniques available, there is still a great challenge in obtaining a material with desired and designed properties. Nevertheless, there is a great flexibility in making customized alumina materials with desired physicochemical properties synthesized by sol–gel methods. This work consists in characterizing the physicochemical properties of sol–gel synthesized aluminum oxide using different sol–gel preparation routes. Three different sols were obtained by using organic precursors and underwent thermal treatment. The structure (Middle Infrared Spectroscopy, Diffused Reflectance Infrared Spectroscopy, X-ray Diffraction, Magic Angle Spinning Nuclear Magnetic Resonance) and microstructure (Scanning Electron Microscopy with Electron Dispersive Spectroscopy) tests of the materials were carried out. The specific surface area was determined by using the Brunauer–Emmett–Teller (BET) method. Thermal analysis was performed for all the powders, in order to analyze the specific temperature of materials transformation.     

Biphasic Calcium Phosphate Ceramics for Bone Regeneration and Tissue Engineering Applications

Biphasic calcium phosphates (BCP) have been sought after as biomaterials for the reconstruction of bone defects in maxillofacial, dental and orthopaedic applications. They have demonstrated proven biocompatibility, osteoconductivity, safety and predictability in in vitro, in vivo and clinical models. More recently, in vitro and in vivo studies have shown that BCP can be osteoinductive. In the field of tissue engineering, they represent promising scaffolds capable of carrying and modulating the behavior of stem cells. This review article will highlight the latest advancements in the use of BCP and the characteristics that create a unique microenvironment that favors bone regeneration.     

Synthesis,Structure–Property Evaluation and Biological Assessment of Supramolecular Assemblies of Bioactive Glass with Glycyrrhizic Acid and Its Monoammonium Salt

Medical nutrients obtained from plants have been used in traditional medicine since ancient times, owning to the protective and therapeutic properties of plant extracts and products. Glycyrrhizic acid is one of those that, apart from its therapeutic effect, may contribute to stronger bones, inhibiting bone resorption and improving the bone structure and biomechanical strength. In the present study, we investigated the effect of a bioactive glass (BG) addition to the structure–property relationships of supramolecular assemblies formed by glycyrrhizic acid (GA) and its monoammonium salt (MSGA). FTIR spectra of supramolecular assemblies evidenced an interaction between BG components and hydroxyl groups of MSGA and GA. Moreover, it was revealed that BG components may interact and bond to the carboxyl groups of MSGA. In order to assess their biological effects, BG, MSGA, and their supramolecular assemblies were introduced to a culture of human bone-marrow-derived mesenchymal stromal cells (BMSCs). Both the BG and MSGA had positive influence on BMSC growth, viability, and osteogenic differentiation—these positive effects were most pronounced when BG1d-BG and MSGA were introduced together into cell culture in the form of MSGA:BG assemblies. In conclusion, MSGA:BG assemblies revealed a promising potential as a candidate material intended for application in bone defect reconstruction and bone tissue engineering approaches.     

Design of Materials for Bone Tissue Scaffolds

The strong impulse recently experienced by the manufacturing technologies as well as the development of innovative biocompatible materials has allowed the fabrication of high-performing scaffolds for bone tissue engineering. The design process of materials for bone tissue scaffolds represents, nowadays, an issue of crucial importance and the object of study of many researchers throughout the world. A number of studies have been conducted, aimed at identifying the optimal material, geometry, and surface that the scaffold must possess to stimulate the formation of the largest amounts of bone in the shortest time possible. This book presents a collection of 10 research articles and 2 review papers describing numerical and experimental design techniques definitively aimed at improving the scaffold performance, shortening the healing time, and increasing the success rate of the scaffold implantation process.     

Vanadia–Zirconia and Vanadia–Hafnia Catalysts for Utilization of Volatile Organic Compound Emissions

Utilization is a sustainable and interesting alternative for the destructive treatment of volatile organic compounds due to avoided CO₂ emission. This work concentrates on the development of active and sulfur-tolerant catalysts for the utilization of contaminated methanol. Impregnated and sol–gel prepared vanadia–zirconia and vanadia–hafnia catalysts were thoroughly characterized by N₂ sorption, analytical (S)TEM, elemental analysis, XRD and Raman spectroscopy, and their performances were evaluated in formaldehyde production from methanol and methanethiol mixture. The results showed higher activity of the sol–gel prepared catalysts due to formation of mono- and polymeric vanadia species. Unfortunately, the most active vanadia sites were deactivated more easily than the metal-mixed oxide HfV₂O₇ and ZrV₂O₇ phases, as well as crystalline V₂O₅ observed in the impregnated catalysts. Metal-mixed oxide phases were formed in impregnated catalysts through formation of defects in HfO₂ and ZrO₂ structure during calcination at 600 °C, which was evidenced by Raman spectroscopy. The sol–gel prepared vanadia–zirconia and vanadia–hafnia catalysts were able to produce formaldehyde from contaminated methanol with high selectivity at temperature around 400 °C, while impregnated catalysts required 50–100 °C higher temperatures.     

Strontium Functionalization of Biomaterials for Bone Tissue Engineering Purposes: A Biological Point of View

Strontium (Sr) is a trace element taken with nutrition and found in bone in close connection to native hydroxyapatite. Sr is involved in a dual mechanism of coupling the stimulation of bone formation with the inhibition of bone resorption, as reported in the literature. Interest in studying Sr has increased in the last decades due to the development of strontium ranelate (SrRan), an orally active agent acting as an anti-osteoporosis drug. However, the use of SrRan was subjected to some limitations starting from 2014 due to its negative side effects on the cardiac safety of patients. In this scenario, an interesting perspective for the administration of Sr is the introduction of Sr ions in biomaterials for bone tissue engineering (BTE) applications. This strategy has attracted attention thanks to its positive effects on bone formation, alongside the reduction of osteoclast activity, proven by in vitro and in vivo studies. The purpose of this review is to go through the classes of biomaterials most commonly used in BTE and functionalized with Sr, i.e., calcium phosphate ceramics, bioactive glasses, metal-based materials, and polymers. The works discussed in this review were selected as representative for each type of the above-mentioned categories, and the biological evaluation in vitro and/or in vivo was the main criterion for selection. The encouraging results collected from the in vitro and in vivo biological evaluations are outlined to highlight the potential applications of materials’ functionalization with Sr as an osteopromoting dopant in BTE.     

Long-Term Effect of Honeycomb β-Tricalcium Phosphate on Zygomatic Bone Regeneration in Rats

In recent years, artificial bones with high biocompatibility have been developed for hard tissue reconstruction. However, current bone replacement methods are inadequate for large defects, causing infection, exposure, and damage. We have developed a new honeycomb β-tricalcium phosphate (TCP) material, which achieved good bone regeneration after implantation in a rat complete zygomatic bone defect. In this study, we further investigated the ability of honeycomb β- TCP for remodeling after bone regeneration as a long-term result. Bone morphogenic protein (BMP)-2-free honeycomb β-TCP (TCP group) and honeycomb β-TCP with BMP-2 (BMP group) were implanted in the zygomatic bone of rats. Micro-computed tomography was performed to track the zygomatic bone morphology, and specimens were histologically examined for osteogenesis and remodeling. In the TCP group, no bone formation was observed at 1 month, but it was observed at 6 months. Bone formation was observed in the BMP group at 1 month, and β-TCP absorption reproducing the zygomatic bone morphology was observed at 6 months. This honeycomb β-TCP with BMP-2 may provide appropriate remodeling that reproduces good bone formation in the early stage and good morphology in the long term, offering an alternative bone reconstruction material to vascularized bone grafts.