Sol-Gel Technologies to Obtain Advanced Bioceramics for Dental Therapeutics.

The aim of this work is to review the application of bioceramic materials in the context of current regenerative dentistry therapies, focusing on the latest advances in the synthesis of advanced materials using the sol-gel methodology. Chemical synthesis, processing and therapeutic possibilities are discussed in a structured way, according to the three main types of ceramic materials used in regenerative dentistry: bioactive glasses and glass ceramics, calcium phosphates and calcium silicates. The morphology and chemical composition of these bioceramics play a crucial role in their biological properties and effectiveness in dental therapeutics. The goal is to understand their chemical, surface, mechanical and biological properties better and develop strategies to control their pore structure, shape, size and compositions. Over the past decades, bioceramic materials have provided excellent results in a wide variety of clinical applications related to hard tissue repair and regeneration. Characteristics, such as their similarity to the chemical composition of the mineral phase of bones and teeth, as well as the possibilities offered by the advances in nanotechnology, are driving the development of new biomimetic materials that are required in regenerative dentistry. The sol-gel technique is a method for producing synthetic bioceramics with high purity and homogeneity at the molecular scale and to control the surfaces, interfaces and porosity at the nanometric scale. The intrinsic nanoporosity of materials produced by the sol-gel technique correlates with the high specific surface area, reactivity and bioactivity of advanced bioceramics.

Ab initio calculations of CO2 adsorption on ß-C2S(100) and M3-C3S(001) surfaces: An exploration of early CO2 sequestration pathways.

Investigating CO2 sequestration in cement-based materials is significant for achieving carbon neutrality in the cement and concrete industries. The early CO2 sequestration pathways on cement-based materials are fundamental for CO2 sequestration, which is not clear. Towards this, the adsorption behavior of CO2 on ß-C2S(100) and M3-C3S(001) was investigated at the atomic level using density functional theory calculations, which were then compared with water adsorption results. The molecular adsorption configurations of CO2 on both ß-C2S(100) and M3-C3S(001) were tilted from their initial configurations due to the influence of surface Ca and O atoms. The CO2 adsorption energy on M3-C3S(001) and ß-C2S(100) were -0.458 eV and -0.426 eV, respectively, indicating adsorption on M3-C3S(001) was more energetically favorable. After CO2 adsorption, electrons were transferred from the surface to the CO2 molecule. Furthermore, the Ca-O bond orders of ß-C2S(100) and M3-C3S(001) after CO2 adsorption were maximally decreased by 2.79% and 6.99%, respectively. A more significant adsorption influence on surfaces was found for H2O, with more negative adsorption energy, more evident electron transfer, and a greater decrease in bond order. The CO2 adsorption on ß-C2S(100) and M3-C3S(001) were still spontaneous at 298 K and 1 atm. This study provides important theoretical insights into early CO2 sequestration at the atomic level, which has practical implications for the design of efficient CO2 sequestration technologies.

Present status and future directions: Hydraulic materials for endodontic use.

BACKGROUND: Hydraulic materials are used in Endodontics due to their hydration characteristics namely the formation of calcium hydroxide when mixing with water and also because of their hydraulic properties. These materials are presented in various consistencies and delivery methods. They are composed primarily of tricalcium and dicalcium silicate, and also include a radiopacifier, additives and an aqueous or a non-aqueous vehicle. Only materials whose primary reaction is with water can be classified as hydraulic. OBJECTIVES: Review of the classification of hydraulic materials by Camilleri and the literature pertaining to specific uses of hydraulic cements in endodontics namely intra-coronal, intra-radicular and extra-radicular. Review of the literature on the material properties linked to specific uses providing the current status of these materials after which future trends and gaps in knowledge could be identified. METHODS: The literature was reviewed using PUBMED, and for each clinical use, the in vitro properties such as physical, chemical, biological and antimicrobial characteristics and clinical data were extracted and evaluated. RESULTS: A large number of publications were retrieved for each clinical use and these were grouped depending on the property type being investigated. CONCLUSIONS: The hydraulic cements have made a difference in clinical outcomes. The main shortcoming is the poor testing methodologies employed which provide very limited information and also inhibits adequate clinical translation. Furthermore, the clinical protocols need to be updated to enable the materials to be employed effectively.

Chemical-Physical Properties and Bioactivity of New Premixed Calcium Silicate-Bioceramic Root Canal Sealers.

The aim of the study was to analyze the chemical−physical properties and bioactivity (apatite-forming ability) of three recently introduced premixed bioceramic root canal sealers containing varied amounts of different calcium silicates (CaSi): a dicalcium and tricalcium silicate (1−10% and 20−30%)-containing sealer with zirconium dioxide and tricalcium aluminate (CERASEAL); a tricalcium silicate (5−15%)-containing sealer with zirconium dioxide, dimethyl sulfoxide and lithium carbonate (AH PLUS BIOCERAMIC) and a dicalcium and tricalcium silicate (10% and 25%)-containing sealer with calcium aluminate, tricalcium aluminate and tantalite (NEOSEALER FLO). An epoxy resin-based sealer (AH PLUS) was used as control. The initial and final setting times, radiopacity, flowability, film thickness, open pore volume, water absorption, solubility, calcium release and alkalizing activity were tested. The nucleation of calcium phosphates and/or apatite after 28 days aging in Hanks balanced salt solution (HBSS) was evaluated by ESEM-EDX, vibrational IR and micro-Raman spectroscopy. The analyses showed for NeoSealer Flo and AH Plus the longest final setting times (1344 ± 60 and 1300 ± 60 min, respectively), while shorter times for AH Plus Bioceramic and Ceraseal (660 ± 60 and 720 ± 60 min, respectively). Radiopacity, flowability and film thickness complied with ISO 6876/12 for all tested materials. A significantly higher open pore volume was observed for NeoSealer Flo, AH Plus Bioceramic and Ceraseal when compared to AH Plus (p < 0.05), significantly higher values were observed for NeoSealer Flo and AH Plus Bioceramic (p < 0.05). Ceraseal and AH Plus revealed the lowest solubility. All CaSi-containing sealers released calcium and alkalized the soaking water. After 28 days immersion in HBSS, ESEM-EDX analyses revealed the formation of a mineral layer that covered the surface of all bioceramic sealers, with a lower detection of radiopacifiers (Zirconium for Ceraseal and AH Plus Bioceramic, Tantalum for NeoSealer Flo) and an increase in calcium, phosphorous and carbon. The calcium phosphate (CaP) layer was more evident on NeoSealer Flo and AH Plus Bioceramic. IR and micro-Raman revealed the formation of calcium carbonate on the surface of all set materials. A thin layer of a CaP phase was detected only on AH Plus Bioceramic and NeoSealer Flo. Ceraseal did not show CaP deposit despite its highest calcium release among all the tested CaSi-containing sealers. In conclusion, CaSi-containing sealers met the required chemical and physical standards and released biologically relevant ions. Slight/limited apatite nucleation was observed in relation to the high carbonation processes.

The Influence of the Matrix on the Apatite-Forming Ability of Calcium Containing Polydimethylsiloxane-Based Cements for Endodontics.

This study aimed to characterize the chemical properties and bioactivity of an endodontic sealer (GuttaFlow Bioseal) based on polydimethylsiloxane (PDMS) and containing a calcium bioglass as a doping agent. Commercial PDMS-based cement free from calcium bioglass (GuttaFlow 2 and RoekoSeal) were characterized for comparison as well as GuttaFlow 2 doped with dicalcium phosphate dihydrate, hydroxyapatite, or a tricalcium silicate-based cement. IR and Raman analyses were performed on fresh materials as well as after aging tests in Hank's Balanced Salt Solution (28 d, 37 °C). Under these conditions, the strengthening of the 970 cm−1 Raman band and the appearance of the IR components at 1455−1414, 1015, 868, and 600−559 cm−1 revealed the deposition of B-type carbonated apatite. The Raman I970/I638 and IR A1010/A1258 ratios (markers of apatite-forming ability) showed that bioactivity decreased along with the series: GuttaFlow Bioseal > GuttaFlow 2 > RoekoSeal. The PDMS matrix played a relevant role in bioactivity; in GuttaFlow 2, the crosslinking degree was favorable for Ca2+ adsorption/complexation and the formation of a thin calcium phosphate layer. In the less crosslinked RoekoSeal, such processes did not occur. The doped cements showed bioactivity higher than GuttaFlow 2, suggesting that the particles of the mineralizing agents are spontaneously exposed on the cement surface, although the hydrophobicity of the PDMS matrix slowed down apatite deposition. Relevant properties in the endodontic practice (i.e., setting time, radiopacity, apatite-forming ability) were related to material composition and the crosslinking degree.

Biocompatibility Study of a New Dental Cement Based on Hydroxyapatite and Calcium Silicates: Focus on Liver, Kidney, and Spleen Tissue Effects.

The effects of a new material based on hydroxyapatite and calcium silicates, named ALBO-MPCA, were investigated on the liver, kidney and spleen. The material was administrated orally for 120 days in an in vivo model in Wistar rats, and untreated animals served as a control. Hematological and biochemical blood parameters were analyzed. Qualitative histological analysis of tissues, change in mitotic activity of cells, and histological characteristics was conducted, as well as quantitative stereological analysis of parenchymal cells, blood sinusoids, and connective tissues. Additionally, the protein expressions of Ki67 and CD68 markers were evaluated. Histological analysis revealed no pathological changes after the tested period. It showed the preservation of the architecture of blood sinusoids and epithelial cells and the presence of mitosis. Additionally, the significantly increased number of the Ki67 in the presence of ALBO-MPCA confirmed the proliferative effect of the material noticed by stereological analysis, while immunoreactive CD68 positive cells did not differ between groups. The study showed non-toxicity of the tested material based on the effects on the hematological, biochemical, and observed histological parameters; in addition, it showed evidence of its biocompatibility. These results could be the basis for further steps toward the application of tested materials in endodontics.

Influence of resveratrol application with pulp-capping materials on the genetic expression levels of stem cells.

AIM: To evaluate in a laboratory setting the response of human mesenchymal stem cells (MSCs) to pulp-capping materials with and without resveratrol (RSV). METHODOLOGY: Five materials, Calcimol LC, Life, TheraCal LC, ProRoot MTA and Biodentine, were prepared according to the manufacturers' instructions. Human MSCs were then exposed to these materials, with and without RSV, for 24 h (n = 8). Cell viability was evaluated using the MTT assay, and total cell death was quantified by annexin V-FITC staining with flow cytometry. The expression levels of the IL-8, IL-10, HBD-2 and BCL-2 genes were investigated using real-time polymerase chain reaction (RT-PCR). Data obtained from MTT test were analysed using one-way anova, and Tukey's multiple-comparison test. The paired Student t test was employed to compare the effects of materials on gene expression (significance level of 5%). RESULTS: The group cell viabilities were Calcimol LC 53%, Life 43%, TheraCal LC 78%, ProRoot MTA 75% and Biodentine 78%. Calcimol LC and Life exhibited significant differences compared with the control groups (P < 0.05). The percentages of necrotic/late apoptotic cells associated with Calcimol LC and TheraCal LC were greater than in the other materials. However, when RSV was added to wells containing materials, cell viability increased to Calcimol LC 63%, Life 52%, TheraCal LC 82%, ProRoot MTA 91% and Biodentine 96%, and the percentages of early apoptotic and late apoptotic/necrotic cells decreased. Calcimol LC + RSV and Life + RSV differed significantly from the control group (P < 0.05). The expression of IL-8 gene was high for all materials, ProRoot MTA caused significant overexpression, and the addition of RSV reduced the expression of IL-8 in the Calcimol LC, TheraCal LC and ProRoot MTA groups and led to increased expression of IL-10 in the Calcimol LC, Life and Biodentine groups. HBD-2 and BCL-2 exhibited increased expression in ProRoot MTA with RSV (P < 0.05). CONCLUSIONS: The addition of RSV exerted a protective effect on MSCs and regulated the inflammatory process by altering the expression levels of pro- and anti-inflammatory genes.

Mineral density in carious dentine after treatment with calcium silicates and polyacrylic acid-based cements.

AIM: To test the hypothesis that polyacrylic acid-based and calcium silicate materials are able to increase mineral density of artificially demineralized dentine produced by a microcosm model for caries formation. METHODOLOGY: Forty-five dentine cavities were prepared in nine sound human third molars (five in each tooth). Specimens received a bacterial inoculum and were incubated in BHI plus 5% of sucrose for 96 h to allow biofilm formation. After that, the specimens were scanned in a high energy micro-CT (baseline stack) and then, each cavity was filled with different cements: zinc polycarboxylate (Poly Zinc™, Prevest DenPro, Jammu, India), conventional glass-ionomer (Ketac Molar, 3M ESPE, Seefeld, Germany) and two calcium silicate-based materials (MTA, Angelus, Londrina, Brazil and Biodentine™, Septodont, Saint Maur des Fosses, France) whilst the central cavity was filled with utility wax (negative control). Specimens were kept for 45 days under simulated intrapulpal pressure using simulated body fluid and after, they were again scanned (treated stacks). Reconstruction of the acquired projections was accomplished using standardized parameters, and the percentage mineral density change was calculated around each cavity. Data were tested for normality using the Shapiro-Wilk test, followed by nonparametric methods. RESULTS: A microcosm artificial caries model was able to cause dentine demineralization (±90% related to sound dentine). Significant increases in dentine mineral density were achieved using MTA or Poly Zinc™ (43.56% and 41.64% remineralization), followed by Biodentine™ (36.40%) and Ketac Molar (32.54%), P < 0.05. CONCLUSION: All cements increased mineral density in demineralized dentine, but zinc polycarboxylate cement and MTA had greater bioactive potential. Micro-CT proved to be an effective method to evaluate changes in mineral density within dentine in contact with bioactive materials.

Evaluation of cytotoxicity and adaptability of a novel bioceramic root canal sealer: An in vitro and scanning electron microscope study.

Context: Cytotoxicity and adaptability are among the highly imperative tests that should be performed on a novel endodontic material to ensure its successful implementation in endodontic treatment. Aims: Assess a recently introduced bioceramic root canal sealer CeramoSeal with TotalFill BC and AH plus sealers regarding the cytotoxicity and adaptability. Materials and Methods: Five sealer discs were prepared for each sealer and their extracts were cultured in 96-well plates containing human fibroblasts for 24 h. After their incubation, MTT solution was added to each well plate using an enzyme-linked immunosorbent assay plate reader was implemented to calculate the percentage of viable cells. Thirty mandibular single-rooted premolars were prepared using the Edge Endo rotary system, teeth were divided into three groups (n = 10) based on the sealer type: Group 1 CeramoSeal, Group 2 Totalfill, and Group 3 AH plus sealer. Teeth were sectioned longitudinally and viewed under a scanning electron microscope where the region with the gaps was identified and quantified as a percentage of the root canal's overall area. Statistical Analysis: One-way ANOVA test was used for cytotoxicity, while Kruskal-Wallis and Friedman's tests were used for adaptability. Results: Ceramoseal statistically significantly showed the lowest viability, at high concentrations AH plus showed the highest cell viability, while at lower concentration Totalfill BC sealer showed the highest cell viability percentage. The gap percentages were statistically significantly higher in Ceramoseal group, there was no statistically significant difference between AH Plus and Totalfill groups. Conclusions: Ceramoseal sealer exhibited the lowest viability and highest gap percentage compared to the other sealers.

Silicon impacts collagen remodelling and mineralization by human dental pulp stem cells in 3D pulp-like matrices.

OBJECTIVES: Silicon-releasing biomaterials are widely used in the field of dentistry. However, unlike bone, very little is known about the role of silicon on dental tissue formation and repair. This study investigates the influence of silicic acid on the survival, differentiation and mineralizing ability of human dental pulp stem cells (hDPSCs) in 3D pulp-like environments METHODS: Dense type I collagen hydrogels seeded with hDPSCs were cultured over 4 weeks in the presence of silicic acid at physiological (10 µM) and supraphysiological (100 µM) concentrations. Cell viability and proliferation were studied by Alamar Blue and live/dead staining. The collagen network was investigated using second harmonic generation imaging. Mineral deposition was monitored by histology and scanning electron microscopy. Gene expression of mineralization- and matrix remodeling-associated proteins was studied by qPCR. RESULTS: Presence of silicic acid did not show any significant influence on cell survival, metabolic activity and gene expression of key mineralization-related proteins (ALP, OCN, BSP). However, it induced enhanced cell clustering and delayed expression of matrix remodeling-associated proteins (MMP13, Col I). OPN expression and mineral deposition were inhibited at 100 µM. It could be inferred that silicic acid has no direct cellular effect but rather interacts with the collagen network, leading to a modification of the cell-matrix interface. SIGNIFICANCE: Our results offer advanced insights on the possible role of silicic acid, as released by pulp capping calcium silicates biomaterials, in reparative dentine formation. More globally, these results interrogate the possible role of Si in pulp pathophysiology.

Synthesis and Characterization of Novel Hybrid Wollastonite-Metakaolin-Based Geopolymers.

Over the past few decades, researchers have focused on developing new production methods for geopolymers to improve their properties for use in multiple applications as a functional material. This study introduces a new geopolymer system based on wollastonite and metakaolin as precursors. The role of wollastonite was also explored alongside metakaolin in geopolymers. Geopolymers were synthesized by adding wollastonite to metakaolin in different ratios: 0 wt.%, 12.5 wt.%, 25 wt.%, and 50 wt.%. The alkaline activator was then mixed with the powder, wollastonite, and metakaolin to prepare the geopolymers. In addition to mechanical tests, the hardened geopolymers were characterized using XRD, TGA, and SEM techniques. The findings revealed that adding wollastonite in amounts of 0 wt.%-12.5 wt.% did not affect the strength of the geopolymers. Increasing wollastonite between 25 wt.% and 50 wt.% significantly increased the geopolymers' flexural and compressive strength from 3 MPa to 12.3 MPa and from 23 MPa to 54 MPa, respectively. The use of wollastonite as a precursor also led to fundamental changes in the microstructural structure of the geopolymer matrix: a new crystal phase, (Ca5(SiO4)2(OH)2), calciochondrodite was formed, and the Si-Al-Na crystal phase disappeared, leading to significant changes in the amorphous phase.

Ultrathin calcium silicate hydrate nanosheets with large specific surface areas: synthesis, crystallization, layered self-assembly and applications as excellent adsorbents for drug, protein, and metal ions.

A simple and low-cost solution synthesis is reported for low-crystalline 1.4 nm tobermorite-like calcium silicate hydrate (CSH) ultrathin nanosheets with a thickness of ~2.8 nm and with a large specific surface area (SSA), via a reaction-rate-controlled precipitation process. The BET SSA of the CSH ultrathin nanosheets can reach as high as 505 m(2) g(-1) . The CSH ultrathin nanosheets have little cytotoxicity and can be converted to anhydrous calcium silicate (ACS) ultrathin nanosheets with a well preserved morphology via a heat treatment process. The crystallinity of CSH ultrathin nanosheets can be improved by solvothermal treatment in water/ethanol binary solvents or a single solvent of water, producing well-crystalline 1.1 nm tobermorite-like CSH nanobelts or nanosheets. CSH ultrathin nanosheets acting as building blocks can self-assemble into layered nanostructures via three different routes. The CSH ultrathin nanosheets are investigated as promising adsorbents for protein (hemoglobin, Hb), drug (ibuprofen, IBU), and metal ions (Cr(3+) , Ni(2+) , Cu(2+) , Zn(2+) , Cd(2+) , Pb(2+) ). The highest adsorbed percentages of Hb and IBU are found to be 83% and 94%, respectively. The highest adsorption capacities of Hb and IBU are found to be as high as 878 milligram Hb per gram CSH and 2.2 gram IBU per gram CSH, respectively. The ppm level metal ions can be totally adsorbed from aqueous solution in just a few minutes. Thus, the CSH ultrathin nanosheets are a promising candidate as excellent adsorbents in the biomedical field and for waste water treatment. Several empirical laws are summarized based on the adsorption profiles of Hb and IBU using CSH ultrathin nanosheets as the adsorbent. Furthermore, the ACS ultrathin nanosheets as adsorbents for Hb protein and IBU drug are investigated.

Resistance of Pastes from Carbonated, Low-Lime Calcium Silica Cements to External Sulfate Attack.

This paper presents the results of a study on the evaluation of resistance of pastes from carbonated, low-lime calcium silica cements to external sulfate attack. The extent of chemical interaction between sulfate solutions and paste powders was assessed by quantifying the amount of species that leached out from carbonated pastes using ICP-OES and IC techniques. In addition, the loss of carbonates from the carbonated pastes exposed to sulfate solutions and the corresponding amounts of gypsum formed were also monitored by using the TGA and QXRD techniques. The changes in the structure of silica gels were evaluated using FTIR analysis. The results of this study revealed that the level of resistance of carbonated, low-lime calcium silicates to external sulfate attack was affected by the degree of crystallinity of calcium carbonate, the type of calcium silicate, and the type of cation present in the sulfate solution.

Effects of calcium silicate-based cements on odonto/osteogenic differentiation potential in mesenchymal stem cells.

The objective of this study was to evaluate the biological effects and odonto/osteogenic differentiation potential of Biodentine, NeoMTA Plus and TheraCal LC in tooth germ-derived stem cells (TGSCs). TGSCs were exposed to the material extracts. Biocompatibility was tested with MTS cell proliferation assay. Odonto/osteogenic differentiation was assessed with alkaline phosphatase (ALP) activity and mRNA gene expressions (RUNX2, DSPP and DMP-1). Scanning electronic microscopy/energy-dispersive X-ray (SEM/EDX) analysis and pH analysis were also performed for the materials. Data were evaluated using the one-way ANOVA and Tukey's tests. TGSCs remained viable after 7 days of incubation with all tested materials. Biodentine and NeoMTA Plus showed high ALP activity and increased expression of RUNX2, DSPP and DMP-1 compared to that of TheraCal LC. All materials can induce odonto/osteogenic differentiation of MSCs in various levels. Biocompatibility and odonto/osteogenic differentiation potential of Biodentine and NeoMTA Plus are similar and superior to that of TheraCal LC.

The Use of Premixed Calcium Silicate Bioceramic Sealer with Warm Carrier-Based Technique: A 2-Year Study for Patients Treated in a Master Program.

BACKGROUND: Recently several calcium silicate flowable sealers have been introduced as endodontic materials for the root canal. This clinical study tested the use of a new premixed calcium silicate bioceramic sealer in association with the Thermafil warm carrier-based technique (TF). Epoxy-resin-based sealer with the warm carrier-based technique was the control group. METHODOLOGY: Healthy consecutive patients (n = 85) requiring 94 root canal treatments were enrolled in this study and assigned to one filling group (Ceraseal-TF n = 47, AH Plus-TF n = 47) in accordance with operator training and best clinical practice. Periapical X-rays were taken preoperatively, after root canal filling and after 6, 12 and 24 months. Two evaluators blindly assessed the periapical index (PAI) and sealer extrusion in the groups (k = 0.90). Healing rate and survival rate were also evaluated. Chi-square tests was used to analyze significant differences between the groups. Multilevel analysis was performed to evaluate the factors associated with healing status. RESULTS: A total of 89 root canal treatments in 82 patients were analyzed at the end-line (24 months). The total drop-out was 3.6% (3 patients; 5 teeth). A total of 91.1% of healed teeth (PAI 1-2) was observed in Ceraseal-TF, with 88.6% in AH Plus-TF. No significant difference was observed on healing outcome and survival among the two filling groups (p > 0.05). Apical extrusion of the sealers occurred in 17 cases (19.0%). Of these, 6 occurred in Ceraseal-TF (13.3%) and 11 in AH Plus-TF (25.0%). Three Ceraseal extrusions were radiographically undetectable after 24 months. All the AH Plus extrusions did not change during the evaluation time. CONCLUSIONS: The combined use of the carrier-based technique and premixed CaSi-based bioceramic sealer showed clinical results comparable with carrier-based technique and epoxy-resin-based sealer. The radiographical disappearance of apically extruded Ceraseal is a possible event in the first 24 months.

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.

Efficacy of different calcium silicate materials as pulp-capping agents: Randomized clinical trial.

BACKGROUND/PURPOSE: Calcium hydroxide-based materials were the gold standard in vital pulp therapies for decades' despite of several shortcomings. However, calcium silicates have been discussed as an alternative to overcome these drawbacks. It was aimed to investigate the in-vivo effectiveness of different calcium silicates based materials in pulp capping in this study. MATERIALS AND METHODS: A parallel-design, randomized controlled trial with 213 patients who has deep dentin caries, vital pulps and without spontaneous pain or history of swelling was designed. 525 M teeth were randomized, blinded and allocated to one of the five groups for pulp capping treatment (n = 105). All teeth were followed up clinically and radiographically (after 1st, 6th, 12th and 36th months) by blinded investigators. The clinical and radiographic success, and the effect of the pulp exposure to the success rate analyzed with Wald chi-square and Z tests. RESULTS: Clinical and radiographic success of MTA+ (86.3%, 85.4%) and Biodentine (79.4%, 80.1%) were found the highest. Although results of Theracal LC group (72.1%, 73.6%) were better than Dycal group (69.4%, 70.2%), the difference was nonsignificant (p > 0.05). Only in light-cured groups, (TheraCal LC & LC Calcihyd) pulpal exposure size effected the success of the materials (p < 0.05). MTA+ and Biodentine resulted better scores, when compared with TheraCal LC in large pulpal exposures (p < 0.05). CONCLUSION: After 36-month follow-up, both MTA+ and Biodentine were found to be the appropriate material for direct pulp capping in permanent teeth. The filler ingredient of the Theracal-LC eases the usage of calcium silicates but decreases the success rate.

Green Hydrogels Composed of Sodium Mannuronate/Guluronate, Gelatin and Biointeractive Calcium Silicates/Dicalcium Phosphate Dihydrate Designed for Oral Bone Defects Regeneration.

Innovative green, eco-friendly, and biologically derived hydrogels for non-load bearing bone sites were conceived and produced. Natural polysaccharides (copolymers of sodium D-mannuronate and L-guluronate) with natural polypeptides (gelatin) and bioactive mineral fillers (calcium silicates CaSi and dicalcium phosphate dihydrate DCPD) were used to obtain eco-sustainable biomaterials for oral bone defects. Three PP-x:y formulations were prepared (PP-16:16, PP-33:22, and PP-31:31), where PP represents the polysaccharide/polypeptide matrix and x and y represent the weight % of CaSi and DCPD, respectively. Hydrogels were tested for their chemical-physical properties (calcium release and alkalizing activity in deionized water, porosity, solubility, water sorption, radiopacity), surface microchemistry and micromorphology, apatite nucleation in HBSS by ESEM-EDX, FT-Raman, and micro-Raman spectroscopies. The expression of vascular (CD31) and osteogenic (alkaline phosphatase ALP and osteocalcin OCN) markers by mesenchymal stem cells (MSCs) derived from human vascular walls, cultured in direct contact with hydrogels or with 10% of extracts was analysed. All mineral-filled hydrogels, in particular PP-31:31 and PP-33:22, released Calcium ions and alkalized the soaking water for three days. Calcium ion leakage was high at all the endpoints (3 h-28 d), while pH values were high at 3 h-3 d and then significantly decreased after seven days (p < 0.05). Porosity, solubility, and water sorption were higher for PP-31:31 (p < 0.05). The ESEM of fresh samples showed a compact structure with a few pores containing small mineral granules agglomerated in some areas (size 5-20 microns). PP-CTRL degraded after 1-2 weeks in HBSS. EDX spectroscopy revealed constitutional compounds and elements of the hydrogel (C, O, N, and S) and of the mineral powders (Ca, Si and P). After 28 days in HBSS, the mineral-filled hydrogels revealed a more porous structure, partially covered with a thicker mineral layer on PP-31:31. EDX analyses of the mineral coating showed Ca and P, and Raman revealed the presence of B-type carbonated apatite and calcite. MSCs cultured in contact with mineral-filled hydrogels revealed the expression of genes related to vascular (CD31) and osteogenic (mainly OCN) differentiation. Lower gene expression was found when cells were cultured with extracts added to the culture medium. The incorporation of biointeractive mineral powders in a green bio-derived algae-based matrix allowed to produce bioactive porous hydrogels able to release biologically relevant ions and create a suitable micro-environment for stem cells, resulting in interesting materials for bone regeneration and healing in oral bone defects.

Wollastonite as filler of an experimental dental adhesive.

OBJECTIVE: The aim of this study was to formulate experimental dental adhesives with wollastonite and evaluate the physical, chemical, and bioactivity properties of the resins. METHODS: Wollastonite was characterized by Fourier transform infrared spectroscopy, X-ray and laser diffraction analyses, and scanning electronic microscopy. An experimental adhesive resin was formulated, and wollastonite was used as filler at 0 (control group), 0.5, 1, or 2 wt.%. Radiopacity, degree of conversion (DC%), microhardness, softening in solvent, ultimate tensile strength (UTS), 24 h- and 1 year- microtensile bond strength (µTBS), mineral deposition, and color of the adhesives were evaluated. RESULTS: Wollastonite particles showed a needle-like shape, a mean diameter of 70 (± 30) µm, characteristic chemical peaks, and pure crystalline ß-CaSiO3 phase. There were no significant differences (p > 0.05) for radiopacity, softening in solvent, and color change. The group with 2 wt.% of wollastonite showed higher microhardness and UTS in comparison to the control group (p < 0.05). After one year, the control group showed reduced µTBS compared to the immediate value (p < 0.05). The groups with wollastonite presented stable µTBS after one year in comparison to the immediate µTBS (p > 0.05). Wollastonite induced mineral deposition on the adhesive surface over the time of storage in simulated body fluid. CONCLUSION: The addition of wollastonite improved the mechanical behavior of the adhesive without changing the analyzed chemical properties. The adhesives with this filler presented mineral deposition and acceptable clinical color. Moreover, dentin treated with wollastonite-doped adhesives showed higher bonding stability after one year of aging. CLINICAL SIGNIFICANCE: Wollastonite, a silicate-based material, provided bioactivity for the adhesives, which assists in producing therapeutic tooth-restoration interfaces. Moreover, the incorporation of this mineral improOfiller to improve the biological properties of adhesives and assist in dentin-restoration stability.

Moisture Influence on Compressive Strength of Calcium Silicate Masonry Units-Experimental Assessment and Normative Calculations.

This paper primarily assesses the scale of adverse changes to the compressive strength of different types of silicates due to the influence of moisture. The study covers three groups of silicate units of different strength classes-15, 20 and 25-obtained from three different manufacturers. It was demonstrated that in all studied groups, moisture significantly decreased the compressive strength by about 30-40%. In addition, microstructural studies were conducted to analyze the relationship between the specific porosity structure of each group of silicate bricks and their compressive strength. On the basis of SEM (Scanning Electron Microscopy) and EDS (Electron Dispersive Spectroscopy) analysis, the elemental composition of individual silicates was determined and the contact zone between the aggregate and the binder was determined, which largely influenced the obtained compressive strength of each silicates. Next, the study referred to the utility of the normative procedure used to determine the strength class of samples with different geometries and at different moisture concentrations. The results of the calculations showed the high accuracy of the normative-based assessment of strength class, regardless of the manufacturer and the moisture values during examination.