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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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Plants undergo substantial biomineralization of silicon, which is deposited primarily in cell walls as amorphous silica. The mineral formation could be moderated by the structure and chemistry of lignin, a polyphenol polymer that is a major constituent of the secondary cell wall. However, the reactions between lignin and silica have not yet been well elucidated. Here, we investigate silica deposition onto a lignin model compound. Polyphenyl propanoid was synthesized from coniferyl alcohol by oxidative coupling with peroxidase in the presence of acidic tetramethyl orthosilicate, a silicic acid precursor. Raman, Fourier transform infrared, and X-ray photoelectron spectroscopies detected changes in lignin formation in the presence of silicic acid. Bonds between the Si-O/Si-OH residues and phenoxyl radicals and lignin functional groups formed during the first 3 h of the reaction, while silica continued to form over 3 days. Thermal gravimetric analysis indicated that lignin yields increased in the presence of silicic acid, possibly via the stabilization of phenolic radicals. This, in turn, resulted in shorter stretches of the lignin polymer. Silica deposition initiated within a lignin matrix via the formation of covalent Si-O-C bonds. The silica nucleants grew into 2-5 nm particles, as observed via scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. Additional silica precipitated into an extended gel. Collectively, our results demonstrate a reciprocal relation by which lignin polymerization catalyzes the formation of silica, and at the same time silicic acid enhances lignin polymerization and yield.

Silica polymerization, which involves the condensation reaction of silicic acid, is a fundamental process with wide-ranging implications in biological systems, material synthesis, and scale formation. The formation of a silica-based scale poses significant technological challenges to energy-efficient operations in various industrial processes, including heat exchangers and water treatment membranes. Despite the common strategy of applying functional polymers for inhibiting silica polymerization, the underlying mechanisms of inhibition remain elusive. In this study, we synthesized a series of nitrogen-containing polymers as silica inhibitors and elucidated the role of their molecular structures in stabilizing silicic acids. Polymers with both charged amine and uncharged amide groups in their backbones exhibit superior inhibition performance, retaining up to 430 ppm of reactive silica intact for 8 h under neutral pH conditions. In contrast, monomers of these amine/amide-containing polymers as well as polymers containing only amine or amide functionalities present insignificant inhibition. Molecular dynamics simulations reveal strong binding between the deprotonated silicic acid and a polymer when the amine groups in the polymer are protonated. Notably, an extended chain conformation of the polymer is crucial to prevent proximity between the interacting monomeric silica species, thereby facilitating effective silica inhibition. Furthermore, the hydrophobic nature of alkyl segments in polymer chains disrupts the hydration shell around the polymer, resulting in enhanced binding with ionized silicic acid precursors compared to monomers. Our findings provide novel mechanistic insights into the stabilization of silicic acids with functional polymers, highlighting the molecular design principles of effective inhibitors for silica polymerization.

Silica is extensively deposited by plants, however, only little is known about the molecular control over this process. Siliplant1 is the only known plant protein to precipitate biosilica. The protein contains seven repeats made of three domains. One of the domains exhibits a conserved sequence, which catalyzes silica precipitation in vitro. Here, silica was synthesized by the activity of a peptide carrying this conserved sequence. Infrared spectroscopy and thermal gravimetric analyses showed that the peptide was bound to the mineral. Scanning electron microscopy showed that silica-peptide particles of 22 ± 4 nm aggregated to spherical structures of 200-300 nm when the ratio of silicic acid to the peptide was below 183:1 molecules. When the ratio was about 183:1, similar particles aggregated into irregular structures, and silica gel formed at higher ratios. Solid-state NMR spectra indicated that the irregular aggregates were richer in Si-O-Si bonds as well as disordered peptide. Our results suggest that the peptide catalyzed the condensation of silicic acid and the formation of ∼20 nm particles, which aggregated into spheres. Excess of the peptide stabilized surface Si-OH groups that prevented spontaneous Si-O-Si bonding between aggregates. Under Si concentrations relevant to plant sap, the peptide and possibly Siliplant1, could catalyze nucleation of silica particles that aggregate into spherical aggregates., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Rivka Elbaum reports financial support was provided by Israel Science Foundation. Sabrina Diehn reports financial support was provided by Minerva Foundation. Vincent Otieno Ayieko reports financial support was provided by RH Smith Foundation., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Background: Silicon and aluminium oxides make the bulk of agricultural soils. Plants absorb dissolved silicon as silicic acid into their bodies through their roots. The silicic acid moves with transpiration to target tissues in the plant body, where it polymerizes into biogenic silica. Mostly, the mineral forms on a matrix of cell wall polymers to create a composite material. Historically, silica deposition (silicification) was supposed to occur once water evaporated from the plant surface, leaving behind an increased concentration of silicic acid within plant tissues. However, recent publications indicate that certain cell wall polymers and proteins initiate and control the extent of plant silicification., Scope: Here we review recent publications on the polymers that scaffold the formation of biogenic plant silica, and propose a paradigm shift from spontaneous polymerization of silicic acid to dedicated active metabolic processes that control both the location and the extent of the mineralization., Conclusion: Protein activity concentrates silicic acid beyond its saturation level. Polymeric structures at the cell wall stabilize the supersaturated silicic acid and allow its flow with the transpiration stream, or bind it and allow its initial condensation. Silica nucleation and further polymerization are enabled on a polymeric scaffold, which is embedded within the mineral. Deposition is terminated once free silicic acid is consumed or the chemical moieties for its binding are saturated., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Diatoms are an important group of algae that can produce intricate silicified cell walls (frustules). The complex process of silicification involves a set of enigmatic integral membrane proteins that are thought to actively transport the soluble precursor of biosilica, dissolved silicic acid. Full-length silicic acid transporters are found widely across the diatoms while homologous shorter proteins have now been identified in a range of other organisms. It has been suggested that modern silicic acid transporters arose from the union of such partial sequences. Here, we present a computational study of the silicic acid transporters and related transporter-like sequences to help understand the structure, function and evolution of this class of membrane protein. The AlphaFold software predicts that all of the protein sequences studied here share a common fold in the membrane domain which is entirely different from the predicted folds of non-homologous silicic acid transporters from plants. Substrate docking reveals how conserved polar residues could interact with silicic acid at a central solvent-accessible binding site, consistent with an alternating access mechanism of transport. The structural conservation between these proteins supports a model where modern silicon transporters evolved from smaller ancestral proteins by gene fusion., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Author(s). Published by Elsevier B.V. All rights reserved.)

Many of the world's most important food crops such as rice, barley and maize accumulate silicon (Si) to high levels, resulting in better plant growth and crop yields. The first step in Si accumulation is the uptake of silicic acid by the roots, a process mediated by the structurally uncharacterised NIP subfamily of aquaporins, also named metalloid porins. Here, we present the X-ray crystal structure of the archetypal NIP family member from Oryza sativa (OsNIP2;1). The OsNIP2;1 channel is closed in the crystal structure by the cytoplasmic loop D, which is known to regulate channel opening in classical plant aquaporins. The structure further reveals a novel, five-residue extracellular selectivity filter with a large diameter. Unbiased molecular dynamics simulations show a rapid opening of the channel and visualise how silicic acid interacts with the selectivity filter prior to transmembrane diffusion. Our results will enable detailed structure-function studies of metalloid porins, including the basis of their substrate selectivity., Competing Interests: Competing interests The authors declare no competing interests., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Molecular simulation was performed to study the interaction between PAMAM(DETA as the core) with different generations and silicic acid molecules, and discussed the inhibition effect mechanism against silica scale through gyration radius and radial distribution function et al. The results showed that adsorption interactions between silicic acid molecules and the PAMAM with -NH 2 terminated groups molecule (G1.0 and G2.0) were stronger than those and the PAMAM with -COOH terminated groups molecule (G0.5 and G1.5). The adsorption interactions were primarily divided into electrostatic interactions, vdW interactions as well as H-bond interactions, where electrostatic interaction was dominant. Molecular simulation results were consistent with our experimental results., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Mesoporous silica has attracted significant attention in the drug delivery area; however, impurities can be a source of toxicity. The current study used commercial microparticles produced at large scale in a well-controlled environment. Micrometer sized mesoporous silica particles were acquired through a commercial vendor and pore structures were characterized by SEM. The three silica particle formulations had a diameter of 15 micrometers and three different pore sizes of 10 nm, 30 nm, and 100 nm. The fourth formulation had particle size of 20-40 micrometers with 50 nm pores. Before in vivo tests, an in vitro cytotoxicity test was conducted with silicic acid, derived from the sol-gel particles, on EA.hy926 cells. Low concentration (2.5 µg/mL) of silicic acid showed no cytotoxicity; however, high concentration (25 µg/mL) was cytotoxic. In vivo intravitreal injection demonstrated that 15 um silica particles with 10 nm pore were safe in both rabbit and guinea pig eyes and the particles lasted in the vitreous for longer than two months. Formulations of with larger pores demonstrated variable localized vitreous cloudiness around the sol-gel particle depot and mild inflammatory cells in the aqueous humor. The incidence of reaction trended higher with larger pores (10 nm: 0%, 30 nm: 29%, 50 nm: 71%, 100 nm: 100%, p  < .0001, Cochran Armitage Trend Test). Sol-gel mesoporous silica particles have uniform particle sizes and well-defined pores, which is an advantage for implantation via a fine needle. Selected formulations may be used as an intraocular drug delivery system with proper loading and encapsulation.

The unmodified R5 peptide from silaffin in the diatom Cylindrotheca fusiformis rapidly precipitates silica particles from neutral aqueous solutions of orthosilicic acid. A range of post-translational modifications found in R5 contribute toward tailoring silica morphologies in a species-specific manner. We investigated the specific effect of R5 lysine side-chain trimethylation, which adds permanent positive charges, on silica particle formation. Our studies revealed that a doubly trimethylated R5K3,4me3 peptide has reduced maximum activity yet, surprisingly, generates larger silica particles. Molecular dynamics simulations of R5K3,4me3 binding by the precursor orthosilicate anion revealed that orthosilicate preferentially associates with unmodified lysine side-chain amines and the peptide N terminus. Thus, larger silica particles arise from reduced orthosilicate association with trimethylated lysine side chains and their redirection to the N terminus of the R5 peptide., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Silicon (Si) has numerous health properties. It is an element of the extracellular matrix; it is involved in collagen synthesis, bone mineralization, and immune system modulation; and it reduces metal accumulation in Alzheimer's disease and the risk of atherosclerosis. Given its poor intestinal absorption, Si is ingested in the form of orthosilicic acid (OSA) to promote its bioavailability. The aim of this work was to compare different commercial dietary supplements containing stabilized OSA to ascertain their bioaccessibility, bioavailability, and safety in a model of human intestinal epithelium. Biocompatibility with the glycocalyx was also investigated. Supplements containing collagen, maltodextrins, and choline as OSA stabilizers were analyzed. Bioaccessibility was explored by means of an in vitro digestive process. Bioavailability was investigated using a Caco2 cell line alone, or co-culturing with a HT29-MTX cell line. The safety of the compounds tested (in terms of intestinal epithelium integrity) was judged on the grounds of MTS assay, transepithelial electrical resistance, and apparent permeability. The three formulations were also tested in a Caco2 cell model of intestinal glycocalyx Si retention. The choline-formulated OSA formulation outperformed the maltodextrin-stabilized supplement, with a Si bioavailability about 14 times higher (P < .05). The choline-formulated OSA formulation increased cell permeability, with consequent intestinal epithelium disruption. The supplements' absorption and bioavailability (and harmfulness) differed considerably, depending on the OSA stabilizer involved. Of the three formulations tested, the collagen-formulated OSA represents the best Si dietary supplement., (© 2020 The Authors. The FASEB Journal published by Wiley Periodicals LLC on behalf of Federation of American Societies for Experimental Biology.)

This paper concerns simultaneous removal of fluoride and hydrated silica from groundwater (4.08 mg L -1 fluoride, 90 mg L -1 hydrated silica, 50 mg L -1 sulfate, 0.23 mg L -1 phosphate, pH 7.38 and 450 μS cm -1 conductivity) by electrocoagulation (EC), using an up-flow EC reactor, with a six-cell stack in a serpentine array, opened at the top of the cell to favor gas release. Aluminum plates were used as sacrificial electrodes. The effect of current density (4 ≤ j ≤ 7 mA cm -2 ) and mean linear flow rate (1.2 ≤ u ≤ 4.8 cm s -1 ), applied to the EC reactor, on the elimination of fluoride and hydrated silica was analyzed. The removal of fluoride followed the WHO guideline (<1.5 mg L -1 ), while the hydrated silica was abated at 7 mA cm -2 and 1.2 cm s -1 , with energy consumption of 2.48 kWh m -3 and an overall operational cost of 0.441 USD m -3 . Spectroscopic analyses of the flocs by XRD, XRF-EDS, SEM-EDS, and FTIR indicated that hydrated silica reacted with the coagulant forming aluminosilicates, and fluoride replaced a hydroxide from aluminum aggregates, while sulfates and phosphates were removed by adsorption process onto the flocs. The well-engineered EC reactor allowed the simultaneous removal of fluoride and hydrated silica., Competing Interests: Declaration of competing interest The authors declare that there is no conflict of interest regarding the publication of this paper., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Ti scaffolds combined with autologous human adipose-derived mesenchymal stem cells (hASCs) have been successfully applied for regenerative cranio-maxillofacial bone therapies. Future challenges reside in regeneration of larger bone defects and displacement of the permanent Ti structure, thus, advanced resorbable scaffolds are needed. Composites of β-Ca 3 (PO 4 ) 2 with 80 and 60 wt % of CaMg(SiO 3 ) 2 with improved mechanical properties compared to tricalcium phosphate (TCP) materials are presented. Synthetic CaMg(SiO 3 ) 2 and a precursor of Ca 3 (PO 4 ) 2 were used to fabricate the composites and a reference β-Ca 3 (PO 4 ) 2 material by uniaxial pressing and solid state sintering. Optimum sintering temperature of 1225°C was selected. Microstructural analysis and Weibull distributions of tensile strengths determined by the diametral compression of discs test are reported. Thermodynamic simulation of the dissolution process in simulated body fluid body fluid was done. The biological response with hASCs was analyzed using basic and osteogenic media. Viability and osteogenic potential-LIVE/DEAD assay; alkaline phosphatase activity and collagen type-I production-were characterized. The composites have higher tensile strength (>3×) than TCP materials, for similar reliability, and support viability and osteogenic differentiation of hASCs. Resorption of the high strength phase diopside is the slowest. The promising results reported here suggest possible uses of these bioactive β-Ca 3 (PO 4 ) 2 -CaMg(SiO 3 ) 2 ceramics together with hASCs in bone tissue engineering., (© 2019 Wiley Periodicals, Inc.)

Bone injury, especially bone damages due to the removal of bone tumors, is one of the most important issues in the field of therapeutic research in tissue engineering applications. In this context, ceramic-based composites have attracted widespread attention since they have mechanical properties close to the natural bone, hence providing similar conditions for the extracellular matrix (ECM). Thus, in this study, hardystonite and diopside (HT-Di) scaffolds containing various diopside amounts from 5 to 25 wt% were prepared by the space holder method. The results revealed that the fabricated scaffolds contain 70%-75% porosity with a pore size of 300-500 μm and a compressive strength of about 0.54 to 1.71 MPa which is perfectly in the range of the compressive strength of the sponge bone. Noticeably, great apatite formation ability was observed in the scaffold with diopside, although the scaffold without diopside showed poor bioactivity. The MTT assay depicted that the inclusion of diopside into hardystonite scaffold resulted in dramatic enhancement in the MG-63 cell viability. Moreover, the scaffold with diopside offered greater cell attachment and spreading than the scaffold without diopside. Therefore, the synergistic effects of the scaffold with 12.5 wt% of diopside, including great mechanical characteristic, excellent bioactivity, and appealing biocompatibility enable it to be an appealing choice for bone tissue engineering applications.

One of the significant challenges in bone tissue engineering is the fabrication of highly porous scaffolds with interconnected pores and appropriate mechanical properties. Artificial scaffolds which used in the field of medicine are usually made of single phase of polymer or ceramic. However, composition of these materials can produce the scaffolds with improve mechanical and biological properties.The aim of this study is to synthesize three-dimensional hardystonite-diopside (HT-Dio) porous scaffolds modified by polycaporolacton fumarate coating for low-load-bearing bone tissue engineering applications. The results showed that hardystonite scaffolds with 15 wt. % diopside and 6 w/v % polymer polycaporolacton fumarate (PCLF) had a significant bioactivity. The cell culture and cell attachment assay results revealed the well spreading of BMS cells on the surface of modified scaffolds which indicates the high biocompatibility of this scaffold. The modified scaffolds had a mean pore size, porosity, compressive strength, modules and toughness of 293.47 ± 5.51 μm, 74% ± 1.01, 3.37 ± 0.6 MPa, 151 ± 1.1 MPa and 31.3 ± 0.32 kJ/m 3 , respectively, which are in the appropriate range for spongy bone and hence can be a good candidate for bone tissue engineering applications., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this study, a simple and facile strategy was developed for the synthesis of novel hydroxyapatite (HA)/nanostructured monticellite ceramic composites by mechanical method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive x-ray spectroscopy (EDS) were used to peruse the phase structure, and morphology of soaked ceramic composites in simulated body fluid (SBF). The in vitro bioactivity of HA-based ceramic composites with nanostructured monticellite ranging from 0 to 50 wt% was evaluated via investigating the formation ability of bone-like calcium phosphates in SBF and the effect of obtained extracts from composites dissolution on osteoblast-like G-292 cell line. Moreover, In vitro cytocompatibility of the HA/monticellite ceramic composites was investigated by MTT, cell growth & adhesion and alkaline phosphatase (ALP) activity assays, and quantitative real-time PCR analysis. The results showed that HA/nanostructured monticellite ceramic composites could induce apatite formation in SBF. The cell proliferation and growth exposed to ceramic composites extracts were significantly stimulated and promoted at a certain concentration range compared to control for various time periods of cell culture. The optimized composite extract enhanced considerably gene expression of G-292 type X collagen (COLX) at different days. Also, G-292 cells were spread and adhered well on the ceramic composite disc. Furthermore, ALP activity of G-292 cells exposed to ceramic composites extracts was dramatically enhanced in comparison with pure HA extract (as control) at different concentrations for various time periods of cell culture. The results suggest that the optimized HA/nanostructured monticellite composite is promising biomaterial for clinical applications such as orthopedic and dentistry., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study focuses on the effect of Sr-, F-, and their co-doping on the structure, biodegradation, bioactivity and cytocompatibility of diopside-based scaffolds, using X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, Archimedes densitometry, inductively coupled plasma spectroscopy, pH-metry, and cell MTT assay. The structural characterization of the scaffolds confirmed the successful incorporation of the dopants into the ceramic. In addition, all the doped scaffolds presented higher apatite-forming ability levels in comparison to the undoped one, where the highest and the least impact of doping on bioactivity belonged to F- and co-doping, respectively. It was found that the biodegradation difference of the scaffolds in terms of principal ions and the chance of F-incorporation into precipitated apatite determine the bioactivity difference of the samples. Osteoblast-like MG-63 cells exhibited the highest and lowest compatibility to the Sr-doped and co-doped scaffolds, respectively. In summary, F- and Sr-doping offered the highest bioactivity and cytocompatibility, respectively, whereas co-doping presented the weakest behaviors comparatively., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Crystallite aluminosilicates are inorganic microporous materials with well-defined pore-size and pore-structures, and have important industrial applications, including gas adsorption and separation, catalysis, etc. Crystallite aluminosilicates are commonly synthesized via hydrothermal processes, where the oligomerization of silicic acids is crucial. The mechanisms for the oligomerization of poly-silicic acids in neutral aqueous solution were systematically investigated by extensive first-principles-based calculations. We showed that oligomerization of poly-silicic acid molecules proceeds through the lateral attacking and simultaneously proton transfer from the approaching molecule for the formation of a 5-coordinated Si species as the transition state, resulting in the ejection of a water molecule from the formed poly-silicic acid. The barriers for this mechanism are in general more plausible than the conventional direct attacking of poly-silicic acid with reaction barriers in the range of 150-160 kJ/mol. The formation of linear or branched poly-silicic acids by intermolecular oligomerization is only slightly more plausible than the formation of cyclic poly-silicic acids via intramolecular oligomerization according to the reaction barriers (124.2-133.0 vs. 130.6-144.9 kJ/mol). The potential contributions of oligomer structures, such as the length of the linear oligomers, ring distortions and neighboring linear branches, etc., to the oligomerization were also investigated but found negligible. According to the small differences among the reaction barriers, we proposed that kinetic selectivity of the poly-silicic acids condensation would be weak in neutral aqueous solution and the formation of zeolite-like structures would be thermodynamics driven.

In this research, novel monticellite/hydroxyapatite (HA) ceramic composites were successfully prepared by mechanical method. The ability of nanostructured monticellite-based ceramic composites to form a suitable bond to living hard tissues, and stimulate osteoblast-like cells proliferation may be different for various ratios of the reinforcement to monticellite matrix. The differences in physico-chemical characteristics, bone-like apatite formation, cytocompatibility, cell viability and in vitro osteogenic activity of nanostructured monticellite/HA ceramic composites were explored. The surface reactivity and bioactivity of the composite samples were evaluated in vitro in simulated body fluid (SBF). A comparative time- and dose-dependent MTT test showed that the ions release from nanostructured monticellite/HA composites dissolution significantly stimulated cell proliferation and growth than control at a certain concentration range. The cells viability exposed to the composite extract was higher than control and mineral material of bone (HA), illustrating that cytocompatibility was improved due to the presence of magnesium (Mg) and silicon (Si) elements in the composite structure. The comparative results of alkaline phosphatase (ALP) bioactivity assay showed that the osteogenic proliferation of osteoblast-like G292 cell was increased more by the ceramic composites extract than control. These comparative results demonstrated that nanostructured monticellite-based ceramic composites possessed good in vitro bioactivity, cytocompatibility and osteogenic properties, and may be utilized as the promising bioactive materials for bone tissue regeneration and replacement., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Tannic acid (TA) adheres to a broad variety of different materials and forms versatile surface coatings for technical and biological applications. In mild alkaline conditions, autoxidation processes occur and a firm monolayer is formed. Up to now, thicker coatings are obtained in only a cross-linked multilayer fashion. This study presents an alternative method to form continuous TA coatings using orthosilicic acid (Si aq ). Adsorption kinetics and physical properties of TA coatings in the presence of Si aq were determined using a quartz-crystal microbalance and nanoplasmonic spectroscopy. An in situ TA layer thickness of 200 nm was obtained after 24 h in solutions supplemented with 80 μM Si aq . Dry-state measurements indicated a highly hydrated layer in situ. Furthermore, chemical analysis by Fourier transform infrared spectroscopy revealed possible complexation of TA by Si aq , whereas UV-vis spectroscopy did not indicate an interaction of Si aq in the autoxidation process of TA. Investigation of additional metalloid ions showed that germanic acid was also able to initiate a continuous coating formation of TA, whereas boric acid prevented the polymerization process. In comparison to that of TA, the coating formation of pyrogallol (PG) and gallic acid (GA) was not affected by Si aq . PG formed continuous coatings also without Si aq , whereas GA formed only a monolayer in the presence of Si aq . However, Si aq induced a continuous layer formation of ellagic acid. These results indicate the specific importance of orthosilicic acid in the coating formation of polyphenolic molecules with multiple ortho-dihydroxy groups and open new possibilities to deposit TA on interfaces.

A novel adsorbent of chitosan/nanodiopside nanocomposite (CS-NDIO) was synthesized as a green composite for the removal of crystal violet (CV) and characterized by techniques like XRD, FT-IR, BET, and FESEM analysis. The influence of parameters like molar ratios of CS to NDIO, initial pH of the solution, dosage of adsorbent, initial concentration of CV and contact time was investigated and evaluated by central composite design (CCD; 5 levels and 4 factors). Also, Hybrid model of (ANN) model with genetic algorithm (GA) optimization was applied to the experimental data get through CCD. The optimized molar ratio of CS-NDIO was found: 20/80. Optimal parameter choice for maximum CV adsorption process using CCD and ANN-GA were as follows: pH = 7.50 and 7.499, adsorbent mass: 0.0077 and 0.0077 g, CV concentration: 20.000 and 20.002 mg/L, and contact time: 25.00 and 25.00 min, respectively. The evaluation adsorption equilibrium and kinetic data were fitted with the Langmuir monolayer isotherm model (q max : 104.66 mg g -1 and R 2 : 0.9937) and pseudo-second order kinetics mechanism (R 2 : 0.9978). Thermodynamic parameters (R 2 : 0.9180, ΔH°: -74.93 kJ mol -1 , ΔG°: -12.89 kJ mol -1 , and ΔS°: 0.93 kJ mol -1  K -1 ) were calculated and indicating adsorption to be an exothermic and spontaneous process., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The cell wall polymer callose catalyses the formation of silica in vitro and is heavily implicated in biological silicification in Equisetum (horsetail) and Arabidopsis (thale cress) in vivo Callose, a β-1,3-glucan, is an ideal partner for silicification, because its amorphous structure and ephemeral nature provide suitable microenvironments to support the condensation of silicic acid into silica. Herein, using scanning electron microscopy, immunohistochemistry and fluorescence, we provide further evidence of the cooperative nature of callose and silica in biological silicification in rice, an important crop plant and known silica accumulator. These new data along with recently published research enable us to propose a model to describe the intracellular events that together determine callose-driven biological silicification., (© 2018 The Authors.)

In the present work, the releasing heat, scaffold apatite formation, and magnetic behavior of a novel diopside-magnetite nanocomposite with various contents of magnetite (Fe 3 O 4 ) were evaluated. The N´eel and Brown relaxations did not have a significant effect on the specific absorption rate (SAR) of the composite samples. Indeed, magnetic saturation, M s , indicated a crucial effect on the heat release of the samples. The sample with 30wt% magnetite had the highest value of SAR, while the sample with 20wt% magnetite, in the form of scaffold, allowed the high amount of apatite formation on its surface., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Objective: Research to measure the chemical characterization of alginate rafts for good raft performance and ascertain how formulation can affect chemical parameters., Significance: A selection of alginate formulations was investigated all claiming to be proficient raft formers with significance between products established and ranked., Methods: Procedures were selected which demonstrated the chemical characterization allowing rafts to effectively impede the reflux into the esophagus or in severe cases to be refluxed preferentially into the esophagus and exert a demulcent effect, with focus of current research on methods which complement previous studies centered on physical properties. The alginate content was analyzed by a newly developed HPLC method. Methods were used to determine the neutralization profile and the acid neutralization within the raft determined along with how raft structure affects neutralization., Results: Alginate content of Gaviscon Double Action (GDA) within the raft was significantly superior (p < .0001) to all competitor products. The two products with the highest raft acid neutralization capacity were GDA and Rennie Duo, the latter product not being a raft former. Raft structure was key and GDA had the right level of porosity to allow for longer duration of neutralization., Conclusion: Alginate formulations require three chemical reactions to take place simultaneously: transformation to alginic acid, sodium carbonate reacting to form carbon dioxide, calcium releasing free calcium ions to bind with alginic acid providing strength to raft formation. GDA was significantly superior (p <.0001) to all other comparators.

The silicon transport and use inside cells are key processes for understanding how diatoms metabolize this element in the silica biogenic cycle in the ocean. A spin-probe electron paramagnetic resonance (EPR) study over time helped to investigate the interacting properties and the internalization mechanisms of silicic acid from different silicon sources into the cells. Diatom cells were grown in media containing biogenic amorphous substrates, such as diatomaceous earth and sponge spicules, and crystalline sodium metasilicate. It was found that the amorphous biogenic silicon slowed down the internalization process probably due to formation of colloidal particles at the cell surface after silicic acid condensation. Weaker interactions occurred with sponge spicules silicon source if compared to the other sources. The EPR results were explained by analyzing transcript level changes of silicon transporters (SITs) and silaffins (SILs) in synchronized Thalassiosira pseudonana cultures over time. The results indicated that the transport role of SITs is minor for silicic acid from both biogenic and crystalline substrates, and the role of SIT3 is linked to the transport of silicon inside the cells, mainly in the presence of sponge spicules. SIL3 transcripts were expressed in the presence of all silicon sources, while SIL1 transcripts only with sponge spicules. The data suggest that the transport of silicic acid from various silicon sources in diatoms is based on different physico-chemical interactions with the cell surface., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The silica forming repeat R5 of sil1 from Cylindrotheca fusiformis was the blueprint for the design of P 5 S 3 , a 50-residue peptide which can be produced in large amounts by recombinant bacterial expression. It contains 5 protein kinase A target sites and is highly cationic due to 10 lysine and 10 arginine residues. In the presence of supersaturated orthosilicic acid P 5 S 3 enhances silica-formation whereas it retards the dissolution of amorphous silica (SiO 2 ) at globally undersaturated concentrations. The secondary structure of P 5 S 3 during these 2 processes was studied by circular dichroism (CD) spectroscopy, complemented by nuclear magnetic resonance (NMR) spectroscopy of the peptide in the absence of silicate. The NMR studies of dual-labeled ( 13 C, 15 N) P 5 S 3 revealed a disordered structure at pH 2.8 and 4.5. Within the pH range of 4.5-9.5 in the absence of silicic acid, the CD data showed a disordered structure with the suggestion of some polyproline II character. Upon silicic acid polymerization and during dissolution of preformed silica, the CD spectrum of P 5 S 3 indicated partial transition into an α-helical conformation which was transient during silica-dissolution. The secondary structural changes observed for P 5 S 3 correlate with the presence of oligomeric/polymeric silicic acid, presumably due to P 5 S 3 -silica interactions. These P 5 S 3 -silica interactions appear, at least in part, ionic in nature since negatively charged dodecylsulfate caused similar perturbations to the P 5 S 3 CD spectrum as observed with silica, while uncharged ß-d-dodecyl maltoside did not affect the CD spectrum of P 5 S 3 . Thus, with an associated increase in α-helical character, P 5 S 3 influences both the condensation of silicic acid into silica and its decondensation back to silicic acid., (© 2017 Wiley Periodicals, Inc.)

Easy-to-prepare drug delivery systems, based on smart, silica gels have been synthesized, characterized, and studied as hosts in the controlled release of bisphosphonates. They exhibit variable release rates and final % release, depending on the nature of bisphosphonate (side-chain length, hydro-philicity/-phobicity, water-solubility), cations present, pH and temperature. These gels are robust, injectable, re-loadable and re-usable.

There is good evidence that certain silicon-containing materials promote would healing and their common feature is the delivery of orthosilicic acid (Si(OH) 4 ) either directly or following metabolism. In this respect, amorphous silica nanoparticles (NP), which dissolve in aqueous environments releasing up to 2mM orthosilicic acid, may be appropriate 'slow release' vehicles for bioactive silicon. Here we studied the impact of silica NP suspensions (primary particles∼10nm) in undersaturated conditions (below 2mM Si) with differing degrees of surface charge and dissolution rate on human dermal fibroblasts (CCD-25SK cells) viability, proliferation and migration in a cellular wound model. Silica was shown to be non-toxic for all forms and concentrations tested and whilst the anticipated stimulatory effect of orthosilicic acid was observed, the silica NPs also stimulated fibroblast proliferation and migration. In particular, the amine-functionalized particles promoted wound closure more rapidly than soluble orthosilicic acid alone. We suggest that this effect is related to easy cellular internalization of these particles followed by their intracellular dissolution releasing silicic acid at a faster rate than its direct uptake from the medium. Our findings indicate that amorphous silica-based NPs may favour the delivery and release of bioactive silicic acid to cells, promoting wound healing., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Diopside (DIOP) was introduced into polyetheretherketone/polyglycolicacid (PEEK/PGA) scaffolds fabricated via selective laser sintering to improve bioactivity. The DIOP surface was then modified using a silane coupling agent, 3-glycidoxypropyltrimethoxysilane (KH570), to reinforce interfacial adhesion. The results showed that the tensile properties and thermal stability of the scaffolds were significantly enhanced. It could be explained that, on the one hand, the hydrophilic group of KH570 formed an organic covalent bond with the hydroxy group on DIOP surface. On the other hand, there existed relatively high compatibility between its hydrophobic group and the biopolymer matrix. Thus, the ameliorated interface interaction led to a homogeneous state of DIOP dispersion in the matrix. More importantly, an in vitro bioactivity study demonstrated that the scaffolds with KH570-modified DIOP (KDIOP) exhibited the capability of forming a layer of apatite. In addition, cell culture experiments revealed that they had good biocompatibility compared to the scaffolds without KDIOP. It indicated that the scaffolds with KDIOP possess potential application in tissue engineering.

Magnesium is a trace element in the human body, known to have important effects on cell differentiation and the mineralisation of calcified tissues. This study aimed to synthesise highly porous Ca-Mg silicate foamed scaffolds from preceramic polymers, with analysis of their biological response. Akermanite (Ak) and wollastonite-diopside (WD) ceramic foams were obtained from the pyrolysis of a liquid silicone mixed with reactive fillers. The porous structure was obtained by controlled water release from selected fillers (magnesium hydroxide and borax) at 350°C. The homogeneous distribution of open pores, with interconnects of modal diameters of 160-180μm was obtained and maintained after firing at 1100°C. Foams, with porosity exceeding 80%, exhibited compressive strength values of 1-2MPa. In vitro studies were conducted by immersion in SBF for 21days, showing suitable dissolution rates, pH and ionic concentrations. Cytotoxicity analysis performed in accordance with ISO10993-5 and ISO10993-12 standards confirmed excellent biocompatibility of both Ak and WD foams. In addition, MC3T3-E1 cells cultured on the Mg-containing scaffolds demonstrated enhanced osteogenic differentiation and the expression of osteogenic markers including Collagen Type I, Osteopontin and Osteocalcin, in comparison to Mg-free counterparts. The results suggest that the addition of magnesium can further enhance the bioactivity and the potential for bone regeneration applications of Ca-silicate materials., Statements of Significance: Here, we show that the incorporation of Mg in Ca-silicates plays a significant role in the enhancement of the osteogenic differentiation and matrix formation of MC3T3-E1 cells, cultured on polymer-derived highly porous scaffolds. Reduced degradation rates and improved mechanical properties are also observed, compared to Mg-free counterparts, suggesting the great potential of Ca-Mg silicates as bone tissue engineering materials. Excellent biocompatibility of the new materials, in accordance to the ISO10993-5 and ISO10993-12 standard guidelines, confirms the preceramic polymer route as an efficient synthesis methodology for bone scaffolds. The use of hydrated fillers as porogens is an additional novelty feature presented in the manuscript., (Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

In the present study three akermanite (Ca 2 MgSi 2 O 7 ), diopside (CaMgSi 2 O 6 ) and baghdadite (Ca 3 ZrSi 2 O 9 ) applicable bioceramics were synthesized via a sol-gel based method. The combination of sol-gel method and the raw materials used in this study presents a new route for the synthesis of the mentioned bioceramics. By the use of thermal analysis, the mechanisms occurred during the synthesis of these bioceramics were investigated. The differences in the structural density and their relation with the degradation rate and mechanical properties of all three ceramics were studied. In vitro bioactivity and apatite formation mechanisms of the samples soaked in the simulated body fluid were considered. The results showed that baghdadite as a Zr-containing material has a more dense structure in comparison with the other ceramics, which leads to a lower degradation rate and also lower bioactivity. There were also main differences between akermanite and diopside as Mg-containing ceramics. Diopside showed a structure with lower porosity content compared to the akermanite samples which resulted in the lower degradation rate and higher compressive strength., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, diopside bioceramic was synthesized using a mechanical milling process and subsequent heat treatment. The simplicity of experiments and also the high energy available in ball milling lead to rapid synthesis of the products in comparison with other synthesis methods. Magnesium oxide (MgO), silicon dioxide (SiO 2 ) and eggshell (as the calcium source) powders were weighted in stoichiometric conditions and milled to initial activation of the surface of the powder's mixture. Then a sintering process was conducted to complete formation of diopside nanopowder and also evaluates its thermal stability. The mechanisms occurred during the synthesis of this bioceramic were carefully investigated. X-Ray diffraction analysis (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetry (TG), differential thermal analysis (DTA), and inductive coupled plasma atomic emission spectroscopy (ICP-AES) were used for gathering and analyzing data. The ability and rate of apatite formation on the sample surface were evaluated by Simulated Body Fluid (SBF) test, a method that is well recognized to characterize the in vitro bioactivity of ceramic materials. According to the results obtained, the diopside samples had a significant potential to form apatite layer on their surface during soaking in the SBF solution. Besides, the bonding strength of this bioceramic was about 350±7MPa which was almost more than three times of that reported for hydroxyapatite. An excellent fracture toughness of 4±0.3MPam 0.5 was also obtained for this ceramic which was higher than that of previously reported works., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In recent decades, bone scaffolds have received a great attention in biomedical applications due to their critical roles in bone tissue regeneration, vascularization, and healing process. One of the main challenges of using scaffolds in bone defects is the mechanical strength mismatch between the implant and surrounding host tissue which causes stress shielding or failure of the implant during the course of treatment. In this paper, space holder method was applied to synthesize diopside/forsterite composite scaffolds with different diopside content. During the sintering process, NaCl, as spacer agent, gradually evaporated from the system and produced desirable pore size in the scaffolds. The results showed that adding 10wt.% diopside to forsterite can enormously improve the bioactivity, biodegradability, and mechanical properties of the composite scaffolds. The size of crystals and pores of the obtained scaffolds were measured to be in the range 70-100nm and 100-250μm, respectively. Composite scaffolds containing 10wt.% diopside showed similar compressive strength and Young's modulus (4.36±0.3 and 308.15±7MPa, respectively) to that of bone., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Background: The aim of this study was to investigate the effectiveness of different remineralization agents by quantitative light-induced fluorescence digital BiluminatorTM (QLF-D)., Methods: Artificial caries lesions were created, and the teeth were divided according to the tested materials: (i) distilled water, (ii) acidulated phosphate fluoride (APF), (iii) Curodont Repair (CR), (iv) ammonium hexafluorosilicate (SiF) and (v) ammonium hexafluorosilicate plus cetylpyridinium chloride (SiF + CPC). After treatment procedures, each of the samples was placed in artificial saliva. After demineralization and 1 and 4 weeks of remineralization procedures, fluorescence loss and lesion areas were measured with QLF-D. Data were statistically analyzed (α = 0.05)., Results:: The fluorescence values of the demineralized enamel specimens treated with the various agents differed significantly compared with pretreatment values for both 1 and 4 weeks (p&lt;0.05). At 4 weeks, the highest fluorescence gain was calculated in the CR, APF and SiF groups compared with the control (p&lt;0.05)., Conclusions:: APF, SiF and CR groups yielded greater remineralization ability than SiF + CPC and control groups.

Objective: The daily removal of supragingival dental plaque is a key factor in the prevention of gingivitis. The aim of the study was to compare the gingival health benefits of a triclosan/copolymer/fluoride toothpaste (Colgate Total, a fluoride toothpaste containing an antiseptic) to a commercially available toothpaste containing 0.243% sodium fluoride in a silica base (Colgate Herbal, a conventional fluoride toothpaste with herbal extracts)., Method and Materials: A total of 50 patients with gingivitis and at least one sensitive tooth were included. The subjects were randomly stratified into two groups: Colgate Total toothpaste, and Colgate Herbal toothpaste. After a 4-week pre-experimental phase, baseline Plaque Index (Quigley-Hein Index) (PI), Gingival Index (GI), Gingival Bleeding Index (GBI), and Visual Analog Scale (VAS) were assessed. The PI, GI, GBI, and VAS were reexamined at weeks 4, 12, and 24 after the baseline., Results: Fifty subjects complied with the protocol and completed the study. The conventional fluoride toothpaste with herbal extracts group and the fluoride toothpaste containing an antiseptic group exhibited significant reductions in PI, GI, GBI, and VAS over time. The amount of reduction after 6 months of the treatment was higher in the Total group compared to Herbal group (1.82 vs 1.39, P = .015 for PI; 0.67 vs 0.37, P < .005 for GI; and 56.64% vs 34.26%, P < .005 for GBI). No significant difference was seen for VAS., Conclusion: Twice daily brushing with a toothpaste containing 0.3% triclosan and polyvinyl methyl ether and maleic acid copolymer provides a more effective level of plaque control and gingival health with no effect on decreasing dentin hypersensitivity compared to conventional fluoride toothpaste. Toothpastes containing triclosan/copolymer, in addition to fluoride, result in a higher reduction in plaque, gingival inflammation, and gingival bleeding when compared with fluoride toothpastes without triclosan/copolymer.

β-chitin/nanodiopside/nanohydroxyapatite (CT/nDP/nHAp) composite scaffolds were synthesized from the combination of chitin, nDP, and nHAp in different inorganic/organic weight ratios by the freeze-drying technique. The prepared nHAp, and composite scaffolds were characterized by BET, TG, FT-IR, SEM, and XRD studies. The composite scaffolds had 50-75% porosities with well-defined interconnected porous networks. Moreover, investigation of the cell attachment and viability using MTT, DMEM solution, and mouse preosteoblast cell proved the cytocompatibile nature of the composite scaffolds with improved cell adhesion. All these results mainly illustrated that this composite could be a candidate for bone tissue engineering application.

The immunomodulatory functions of monocytes are increasingly being recognized. Silicified collagen scaffolds (SCSs), produced by infiltrating collagen matrices with intrafibrillar amorphous silica, exhibit osteogenic and angiogenic potential and are promising candidates in tissue engineering. Here, we demonstrate that SCS promotes in situ bone regeneration and angiogenesis via monocyte immunomodulation. Increased numbers of TRAP-positive monocytes, nestin-positive bone marrow stromal cells (BMSCs) and CD31-positive and endomucin-positive new vessels can be identified from new bone formation regions in a murine calvarial defect model. In addition, sustained release of silicic acid by SCS stimulates differentiation of blood-derived monocytes into TRAP-positive cells, with increased expressions of SDF-1α, TGF-β1, VEGFa and PDGF-BB. These cytokines further promote homing of BMSCs and endothelial progenitor cells as well as neovascularization. Taken together, these novel findings indicate that SCSs possess the ability to enhance recruitment of progenitor cells and promote osteogenesis and angiogenesis by immunomodulation of monocytes., (Published by Elsevier Ltd.)

Diopside was synthesized from biowaste (Eggshell) by sol-gel combustion method at low calcination temperature and the influence of two different fuels (urea, l-alanine) on the phase formation temperature, physical and biological properties of the resultant diopside was studied. The synthesized materials were characterized by heating microscopy, FTIR, XRD, BET, SEM and EDAX techniques. BET analysis reveals particles were of submicron size with porosity in the nanometer range. Bone-like apatite deposition ability of diopside scaffolds was examined under static and circulation mode of SBF (Simulated Body Fluid). It was noticed that diopside has the capability to deposit HAP (hydroxyapatite) within the early stages of immersion. ICP-OES analysis indicates release of Ca, Mg, Si ions and removal of P ions from the SBF, but in different quantities from diopside scaffolds. Cytocompatability studies on human bone marrow stromal cells (hBMSCs) revealed good cellular attachment on the surface of diopside scaffolds and formation of extracellular matrix (ECM). This study suggests that the usage of eggshell biowaste as calcium source provides an effective substitute for synthetic starting materials to fabricate bioproducts for biomedical applications., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The supplementation of monosilicic acid [Si(OH)4] to the root growing medium is known to protect plants from toxic levels of iron (Fe), copper (Cu) and manganese (Mn), but also to mitigate deficiency of Fe and Mn. However, the physicochemical bases of these alleviating mechanisms are not fully understood. Here we applied low-T electron paramagnetic resonance (EPR) spectroscopy to examine the formation of complexes of Si(OH)4 with Mn(2+), Fe(3+), and Cu(2+) in water and in xylem sap of cucumber (Cucumis sativus L.) grown without or with supply of Si(OH)4. EPR, which is also useful in establishing the redox state of these metals, was combined with measurements of total concentrations of metals in xylem sap by inductive coupled plasma. Our results show that Si(OH)4 forms coordination bonds with all three metals. The strongest interactions of Si(OH)4 appear to be with Cu(2+) (1/1 stoichiometry) which might lead to Cu precipitation. In line with this in vitro findings, Si(OH)4 supply to cucumber resulted in dramatically lower concentration of this metal in the xylem sap. Further, it was demonstrated that Si(OH)4 supplementation causes pro-reductive changes that contribute to the maintenance of Fe and, in particular, Mn in the xylem sap in bioavailable 2+ form. Our results shed more light on the intertwined reactions between Si(OH)4 and transition metals in plant fluids (e.g. xylem sap).

The contamination of agricultural areas by heavy metals has a negative influence on food quality and human health. Various remediation techniques have been developed for the removal and/or immobilization of heavy metals (HM) in contaminated soils. Phytoremediation is innovative technology, which has advantages (low cost, easy monitoring, high selectivity) and limitations, including long time for procedure and negative impact of contaminants on used plants. Greenhouse investigations have shown that monosilicic acid can be used for regulation of the HM (Cd, Cr, Pb and Zn) mobility in the soil-plant system. If the concentration of monosilicic acid in soil was increased from 0 to 20 mg L(-1) of Si in soil solution, the HM bioavailability was increased by 30-150%. However, the negative influence on the barley by HM was reduced under monosilicic acid application. If the concentration of monosilicic acid was increased more than 20 mg L(-1), the HM mobility in the soil was decreased by 40-300% and heavy metal uptake by plants was reduced 2-3 times. The using of the monosilicic acid may increase the phytoremediation efficiency. However the technique adaptation will be necessary for phytoremediation on certain areas., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Motivation: A series of Eu2+ (0.0025≤ × ≤0.025) activated Sr2SiO4:xEu2+ (SSO:xEu2+) phosphors were synthesized via a sol-gel method. The phosphors were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) spectroscopy. The differences between α' and β phase of SSO in the density of states and energy band gap were investigated., Results: The energy gap of α'-SSO and β-SSO are 4.489 and 4.106 eV, respectively. While, two samples showed similar total and partial densities of states. Under the excitation by the ultra violet (UV) light (365 nm), the SSO:xEu2+ phosphor exhibited a green emission band from 400 to 700 nm, which was corresponding to the transition of 5d → 4f of Eu2+ ions. Two emission peaks at 464 and 532 nm could be obtained through Gauss fitting curves. The ratio of the blue to green emission peak decreased with the Eu2+ concentration and the peaks shifted regularly with it. The thermal quenching property was investigated and its activation energy was calculated. The results indicated that this phosphor could be a candidate of green phosphor for UV-based light-emitting diodes (LEDs).

In this work, diopside based ceramics was obtained by solid state reaction using conventional sintering (CS) and microwave sintering (MS). Moreover, different amounts of P2O5 (0.5-5.0 wt.%) have been added. It has been found that a relative density up to 95% theoretical was obtained for diopside containing 2.0 and 5.0 wt.% P2O5, sintered at 1250 °C for 2h and at 1075 °C only for 15 min using CS and MS. Excellent values of micro hardness (7.4 ± 0.1 GPa) and 3 point flexural strength (about 270 MPa) for samples containing 5 wt.% P2O5, sintered at 1075 °C for 15 min using MS were measured. Besides this, a relatively low weight loss ratio has been measured (0.01%) for diopside samples containing 5 wt.% P2O5, sintered under the same conditions, after soaking in physiological salt solution for 2 days. Additionally, the bioactivity of diopside by the possibility of formation of apatite on the surface of pure diopside and diopside containing 2 wt.% of P2O5 immersed in simulated body fluid (SBF) was also confirmed. Finally, particular nano-sized of Carbonated hydroxyapatite (CHA) crystals (rice shaped) were formed and covered the surface of these samples, soaked in SBF solution for 14 days., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Purposes: (1) To evaluate in vitro the surface roughness of a resin composite covered with three surface sealants and submitted to simulated toothbrushing for different periods; (2) Verify, through scanning electron microscopy (SEM), the presence of surface sealants after simulated toothbrushing; and (3) To evaluate whether the type of dentifrice influences the maintenance of the surface sealant. The study hypothesis was that neither variable would influence the surface roughness of the composite and the maintenance of the surface sealant., Methods: 108 specimens were prepared with the resin Amelogen Plus, and divided into six groups (n = 18) according to the type of surface sealant [Fortify (F), BisCover LV (B) and Permaseal (P)] and toothpaste [Total 12 Clean Mint (CT) and Colgate Total 12 Professional Whitening (PW)]. The samples were subjected to brushing cycles, simulating periods of 6, 12, 18, and 24 months. After each period, the surface roughness of the samples was measured. An additional group of 48 samples was prepared for SEM analysis. The results were analyzed by ANOVA with three fixed variables (sealants, time and toothpaste) and by Tukey's test (α = 0.05)., Results: BisCover had the lowest mean surface roughness (0.06 µm) compared with the sealants Fortify (0.09 µm) and Permaseal (0.08 µm), which were not statistically different. Fortify, at 12 months of brushing, had the highest mean roughness (0.13 µm). The mean roughness for the dentifrice CT was lower (0.07 µm) when compared with PW (0.08 µm) and was statistically different. Roughness increased up to 12 months of simulated brushing (0.04 µm, 0.08 µm and 0.11 µm), decreasing from the 18th month (0.08 µm) to the 24th month of brushing (0.07 µm). None of the sealants was observed (with SEM) to be completely removed from the resin at 24 months of brushing.

The aim of experiments was to assess the efficiency of choline-stabilized orthosilicic acid (ch-OSA; complex of orthosilicic acid with choline and a bioavailable source of silicon) application under increasing manganese (Mn) stress on the micronutritional composition and yielding of tomato (Solanum lycopersicum L. cvs. 'Alboney F1' and 'Emotion F1'). Plants were grown in rockwool with the application of a nutrient solution varied the Mn concentrations (in mg dm(-3)): 9.6 and 19.2 which cause strong oxidative stress of plants comparing with optimal concentration of that microelement in nutrient solution. The effect of ch-OSA application (at Si concentration of 0.3 mg dm(-3) nutrient solution) was investigated at both Mn-levels. Increasing Mn stress modified the concentration of microelements and silicon (Si) in tomato leaves. Application of ch-OSA also influenced the concentration of nutrients, but the determined changes were generally multidirectional and varied depending on Mn-level and cultivar. Under the increasing Mn stress a significant downward trend was observed for the mean concentration of Fe (in both cultivars) in fruits--but changes of Mn, Zn and Cu were varied depend on cultivar. In the case of cv. 'Alboney F1' ch-OSA application caused an increase the mean concentrations of Fe, Zn and Cu, while in the case of cv. 'Emotion F1' the reduction of mean concentrations of Zn and Cu was recorded. Ch-OSA treatment did not influence on the Mn concentrations in fruits. A beneficial role of ch-OSA was also found in photosynthesis activity. This was especially valid for lower levels of Mn. Application of ch-OSA improved significantly the marketable yield of tomato under stress by a low Mn level., (Copyright © 2015 The Authors. Published by Elsevier Masson SAS.. All rights reserved.)

Bioactive mesoporous diopside (m-DP) and poly(L-lactide) (PLLA) composite scaffolds with mesoporous/macroporous structure were prepared by the solution-casting and particulate-leaching method. The results demonstrated that the degradability and bioactivity of the mesoporous/macroporous scaffolds were significantly improved by incorporating m-DP into PLLA, and that the improvement was m-DP content-dependent. In addition, the scaffolds containing m-DP showed the ability to neutralize acidic degradation products and prevent the pH from dropping in the solution during the soaking period. Moreover, the scaffolds containing m-DP enhanced attachment, proliferation and alkaline phosphatase activity of MC3T3-E1 cells, which were also m-DP content-dependent. Furthermore, the histological and immunohistochemical analysis results showed that the scaffolds with m-DP significantly promoted new bone formation and improved the materials degraded in vivo, indicating good biocompatibility. The results suggested that the mesoporous/macroporous scaffolds of the m-DP/PLLA composite with osteogenesis had a potential for bone regeneration., (© 2015 The Author(s).)

We have used the additive manufacturing technology of selective laser sintering (SLS), together with post SLS heat treatment, to produce porous three dimensional scaffolds from the glass-ceramic apatite-wollastonite (A-W). The A-W scaffolds were custom-designed to incorporate a cylindrical central channel to increase cell penetration and medium flow to the center of the scaffolds under dynamic culture conditions during in vitro testing and subsequent in vivo implantation. The scaffolds were seeded with human bone marrow mesenchymal stromal cells (MSCs) and cultured in spinner flasks. Using confocal and scanning electron microscopy, we demonstrated that MSCs formed and maintained a confluent layer of viable cells on all surfaces of the A-W scaffolds during dynamic culture. MSC-seeded, with and without osteogenic pre-differentiation, and unseeded A-W scaffolds were implanted subcutaneously in MF1 nude mice where osteoid formation and tissue in-growth were observed following histological assessment. The results demonstrate that the in vivo biocompatibility and osteo-supportive capacity of A-W scaffolds can be enhanced by SLS-custom design, without the requirement for osteogenic pre-induction, to advance their potential as patient-specific bone replacement materials., (© 2015 Wiley Periodicals, Inc.)

Scope: Silicon (Si) is an abundant element on earth. It is found naturally in water in the form of orthosilicic acid (OSA), however this form is not stable under certain conditions such as in highly concentrated and non-neutral pH solutions, which lead to its polymerization and reduced bioavailability. This study aimed to assess the bioavailability of Si from OSA stabilized by vanillin (OSA-VC)., Methods and Results: This was a single-center, double-blind, cross-over randomized controlled trial. Fourteen healthy subjects were recruited and consumed either OSA-VC or a placebo on two separate occasions. Blood and urine samples were collected during 6 h following ingestion and analyzed to determine Si absorption and excretion. Plasma Si area under the curve (0-6 h) was significantly higher after OSA-VC ingestion compared to placebo ingestion (p = 0.0002). Significantly higher urinary Si excretion was also reported over the 6-h period after OSA-VC ingestion compared to placebo (p<0.0001). Approximately 21% of ingested Si was excreted in urine during this period., Conclusion: Although many studies have investigated the metabolism and bioavailability of Si supplemented in foods or as a food ingredient, this was the first to investigate and demonstrate the digestibility of OSA administered in a complex form with vanillin., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In low dimensional cesium silicate LDS-1 (monoclinic phase of CsHSi2O5), anomalous infrared absorption bands observed at 93, 155, 1210, and 1220 cm(-1) are assigned to the vibrational mode of protons, which contribute to the strong hydrogen bonding between terminal oxygen atoms of silicate chain (O-O distance = 2.45 Å). The integrated absorbance (oscillator strength) for those modes is drastically enhanced at low temperatures. The analysis of integrated absorbance employing two different anharmonic double-minimum potentials makes clear that proton tunneling through the potential barrier yields an energy splitting of the ground state. The absorption bands at 93 and 155 cm(-1), which correspond to the different vibrational modes of protons, are attributed to the optical transition between the splitting levels (excitation from the ground state (n = 0) to the first excited state (n = 1)). Moreover, the absorption bands at 1210 and 1220 cm(-1) are identified as the optical transition from the ground state (n = 0) to the third excited state (n = 3). Weak Coulomb interactions in between the adjacent protons generate two types of vibrational modes: symmetric mode (93 and 1210 cm(-1)) and asymmetric mode (155 and 1220 cm(-1)). The broad absorption at 100-600 cm(-1) reveals an emergence of collective mode due to the vibration of silicate chain coupled not only with the local oscillation of Cs(+) but also with the proton oscillation relevant to the second excited state (n = 2).