In vitro inflammation and toxicity assessment of pre- and post-incinerated organomodified nanoclays to macrophages using high-throughput screening approaches.

BACKGROUND: Organomodified nanoclays (ONC), two-dimensional montmorillonite with organic coatings, are increasingly used to improve nanocomposite properties. However, little is known about pulmonary health risks along the nanoclay life cycle even with increased evidence of airborne particulate exposures in occupational environments. Recently, oropharyngeal aspiration exposure to pre- and post-incinerated ONC in mice caused low grade, persistent lung inflammation with a pro-fibrotic signaling response with unknown mode(s) of action. We hypothesized that the organic coating presence and incineration status of nanoclays determine the inflammatory cytokine secretary profile and cytotoxic response of macrophages. To test this hypothesis differentiated human macrophages (THP-1) were acutely exposed (0-20 µg/cm2) to pristine, uncoated nanoclay (CloisNa), an ONC (Clois30B), their incinerated byproducts (I-CloisNa and I-Clois30B), and crystalline silica (CS) followed by cytotoxicity and inflammatory endpoints. Macrophages were co-exposed to lipopolysaccharide (LPS) or LPS-free medium to assess the role of priming the NF-κB pathway in macrophage response to nanoclay treatment. Data were compared to inflammatory responses in male C57Bl/6J mice following 30 and 300 µg/mouse aspiration exposure to the same particles. RESULTS: In LPS-free media, CloisNa exposure caused mitochondrial depolarization while Clois30B exposure caused reduced macrophage viability, greater cytotoxicity, and significant damage-associated molecular patterns (IL-1α and ATP) release compared to CloisNa and unexposed controls. LPS priming with low CloisNa doses caused elevated cathepsin B/Caspage-1/IL-1ß release while higher doses resulted in apoptosis. Clois30B exposure caused dose-dependent THP-1 cell pyroptosis evidenced by Cathepsin B and IL-1ß release and Gasdermin D cleavage. Incineration ablated the cytotoxic and inflammatory effects of Clois30B while I-CloisNa still retained some mild inflammatory potential. Comparative analyses suggested that in vitro macrophage cell viability, inflammasome endpoints, and pro-inflammatory cytokine profiles significantly correlated to mouse bronchioalveolar lavage inflammation metrics including inflammatory cell recruitment. CONCLUSIONS: Presence of organic coating and incineration status influenced inflammatory and cytotoxic responses following exposure to human macrophages. Clois30B, with a quaternary ammonium tallow coating, induced a robust cell membrane damage and pyroptosis effect which was eliminated after incineration. Conversely, incinerated nanoclay exposure primarily caused elevated inflammatory cytokine release from THP-1 cells. Collectively, pre-incinerated nanoclay displayed interaction with macrophage membrane components (molecular initiating event), increased pro-inflammatory mediators, and increased inflammatory cell recruitment (two key events) in the lung fibrosis adverse outcome pathway.

Effect of incisal preparation design on the fracture strength of monolithic zirconia-reinforced lithium silicate laminate veneers.

PURPOSE: This study aimed to assess the fracture resistance of monolithic zirconia-reinforced lithium silicate laminate veneers (LVs) fabricated on various incisal preparation designs. MATERIALS AND METHODS: Sixty maxillary central incisors with various preparation designs were 3D-printed, 15 each, including preparation for: (1) LV with feathered-edge design; (2) LV with butt-joint design; (3) LV with palatal chamfer; and (4) full-coverage crown. Restorations were then designed and manufactured from zirconia-reinforced lithium silicate (ZLS) following the contour of a pre-operation scan. Restorations were bonded to the assigned preparation using resin cement and following the manufacturer's instructions. Specimens were then subjected to 10,000 thermocycles at 5 to 55°C with a dwell time of 30 s. The fracture strength of specimens was then assessed using a universal testing machine at a crosshead speed of 1.0 mm/min. One-way ANOVA and Bonferroni correction multiple comparisons were used to assess the fracture strength differences between the test groups (α = 0.001). Descriptive fractographic analysis of specimens was carried out with scanning electron microscopy images. RESULTS: Complete coverage crown and LV with palatal chamfer design had the highest fracture resistance values (781.4 ± 151.4 and 618.2 ± 112.6 N, respectively). Single crown and LV with palatal chamfer had no significant difference in fracture strength (p > 05). LV with feathered-edge and butt-joint designs provided significantly (p < 05) lower fracture resistance than complete coverage crown and LV with palatal chamfer design. CONCLUSION: The fracture resistance of chairside milled ZLS veneers was significantly influenced by the incisal preparation designs tested. Within the limitation of this study, when excessive occlusal forces are expected, LV with palatal chamfer display is the most conservative method of fabricating an indirect restoration.

Synthesis and Densification of Mo/Mg Co-Doped Apatite-type Lanthanum Silicate Electrolytes with Enhanced Ionic Conductivity.

Apatite-type lanthanum silicate (LSO) electrolyte is one of the most promising candidates for developing intermediate-temperature solid oxide electrolysis cells and solid oxide full cells (IT-SOECs and SOFCs) due to its stability and low activation energy. However, the LSO electrolyte still suffers from unsatisfied ionic conductivity and low relative density. Herein, a new co-doped method is reported to prepare highly purified polycrystalline powders of Mg-Mo co-doped LSO (Mg/Mo-LSO) electrolytes with high excellent densification properties and improved ionic conductivity. Introducing the Mo6+ and Mg2+ ions into the LSO structure can increase the number of interstitial oxide ions and improve the degree of densification at lower sintering temperatures, more importantly, expand the migration channel of oxide ions to enhance the ionic conductivity. As a result, the relative density of the fabricated Mo/Mg-LSO electrolytes pellets could achieve more than 98 % of the theoretical density after sintering at 1500 °C for 4 h with a grain size of about 1-3 µm and the EIS results showed the ionic conductivity increased from 0.782 mS ⋅ cm-1 for the pristine LSO to 33.94 mS ⋅ cm-1 for the doped sample La9.5 Si5.45 Mg0.3 Mo0.25 O26+δ at 800 °C. In addition, the effect of different Mo6+ doping contents was investigated systematically, in which La9.5 Si5.45 Mg0.3 Mo0.25 O26+δ possessed the highest ionic conductivity and relative density. The proposed Mo/Mg co-doped method in this work is one step forward in developing apatite-structured electrolytes offering excellent potential to address the common issues associated with the fabrication of dense, highly conductive, and thermochemically stable electrolytes for solid oxide electrolysers and fuel cells.

Bridging the Gap between Zeolites and Dense Silica Polymorphs: Formation of All-Silica Zeolite with High Framework Density from Natural Layered Silicate Magadiite.

A silica zeolite (RWZ-1) with a very high framework density (FD) was synthesized from highly crystalline natural layered silicate magadiite, bridging the gap between the two research areas of zeolites and dense silica polymorphs. Magadiite was topotactically converted into a 3D framework through two-step heat treatment. The resulting structure had a 1D micropore system of channel-like cavities with an FD of 22.1 Si atoms/1000 Å3 . This value is higher than those of all other silica zeolites reported so far, approaching those of silica polymorphs (tridymite (22.6) and α-quartz (26.5)). RWZ-1 is a slight negative thermal expansion material with thermal properties approaching those of dense silica polymorphs. It contributes to the creation of a new field on microporous high-density silica/silicates. Synergistic interactions are expected between the micropores with molecular sieving properties and the dense layer-like building units with different topologies which provide thermal and mechanical stabilities.

Enhancing Aqueous Carbonation of Calcium Silicate through Acid and Base Pretreatments with Implications for Efficient Carbon Mineralization.

Carbon dioxide (CO2) mineralization based on aqueous carbonation of alkaline earth silicate minerals is a promising route toward large-scale carbon removal. Traditional aqueous carbonation methods largely adopt acidification-based approaches, e.g., using concentrated/pressurized CO2 or acidic media, to accelerate mineral dissolution and carbonation. In this study, we designed and tested three distinctive routes to evaluate the effect of pretreatments under different pH conditions on aqueous carbonation, using amorphous calcium silicate (CS) as an example system. Pretreating CS with high concentrations (100 mM) of HCl (Route I) or NaOH (Route II and III) enhanced their carbonation degrees. However, NaOH pretreatment overall yielded higher carbonation degrees than the HCl pretreatment, with the highest carbonation degree achieved through Route III, where an extra step is taken after the NaOH pretreatment to remove the solution containing dissolved silica prior to carbonation. The HCl and NaOH pretreatments formed different intermediate silica products on the CS surface. Silica precipitated from the HCl pretreatment had a minimal effect on the carbonation degree. The high Ca/Si ratio intermediate phases formed from the NaOH, on the other hand, can be readily carbonated. In contrast to commonly utilized acidification-based approaches, basification offers a more promising route to accelerate aqueous carbonation as it can mitigate the need for costly pH swing and high-concentration/pressurized CO2. The key to aqueous carbonation under basic conditions, as suggested by this study, is the control of aqueous silica species that have a suppressing effect on carbonation. Overall, this study highlights the critical needs for investigations of aqueous mineral carbonation in a broader pH region.

Histology, prevalence, and environmental sources for pulmonary silicates depositions in domestic and wild animals.

The source and significance of pulmonary silicate crystals in animals and people are poorly understood. To estimate the prevalence and characterize the pulmonary crystalline material in animals from St. Kitts, tissue samples from dogs, horses, cattle, sheep, goats, pigs, chickens, mongooses, and monkeys were examined by light microscopy, scanning electron microscopy with energy-dispersive x-ray analysis (SEM/EDXA), and x-ray diffraction. Crystalline material was seen in 201 of 259 (77.6%) lung samples as perivascular and interstitial accumulations of heterogeneous crystalline particulate material, free or within macrophages (silicate-laden macrophages [SLMs]), mostly lacking evidence of chronic inflammation or fibrosis. The crystalline material was birefringent, basophilic on acid-fast, and composed of silicas on SEM/EDXA. Mongooses (100%) and monkeys (98%) had the highest prevalence of SLM, followed by cattle and chickens. Lesions were graded on a 3-point scale based on the histologic location and extent of silicates and SLM and were significantly more severe in mongooses (median = 3) than in monkeys (median = 2), dogs (median = 2), and chickens (median = 1). On EDXA, the crystalline material from lungs, air, and topsoil was composed of silicon, oxygen, aluminum, and iron, with a particulate matter size between 2.5 and 10 µm. We hypothesize Saharan dust, volcanic ash, topsoil, and rock quarry dust are potential sources of siliceous dust inhalation and SLM accumulations lacking chronic inflammation (silicosis); dust generation may be potentiated by road vehicle or wind suspension. Future investigations are warranted on the role of silicate inhalation and respiratory comorbidities in people, with monkeys, mongooses, or chickens serving as possible sentinels for exposure.

Orthodontic resins loaded with niobium silicate particles: Impact of filler concentration on the physicochemical and biological properties.

OBJECTIVES: White spot lesions (WSL) are prevalent in patients using orthodontic appliances. The presence of ion-releasing compounds in the tooth-appliance interface may limit enamel demineralization to control WSL incidence. Thus, this study aims to evaluate the mineral formation on SiNb-containing experimental orthodontic resins and the influence of these fillers on the physicochemical and biological properties of developed materials. MATERIALS AND METHODS: The SiNb particles were synthesized via the sol-gel route and characterized by their molecular structure and morphology. Photopolymerizable orthodontic resins were produced with a 75 wt% Bis-GMA/25 wt% TEGDMA and 10 wt%, 20 wt%, or 30 wt% addition of SiNb. A control group was formulated without SiNb. These resins were tested for their degree of conversion, softening in solvent, cytotoxicity in fibroblasts, flexural strength, shear bond strength (SBS), and mineral deposition. RESULTS: The addition of 10 wt% of SiNb did not impair the conversion of monomers, cytotoxicity, and flexural strength. All groups with SiNb addition presented similar softening in solvent. The presence of these particles did not affect the bond strength between metallic brackets and enamel, with SBS values ranging from 16.41 to 18.66 MPa. The mineral deposition was observed for all groups. CONCLUSION: The use of niobium silicate as filler particles in resins may be a strategy for the adhesion of orthodontic appliances. The 10 wt% SiNb concentration resulted in a material with suitable physicochemical and biological properties while maintaining the bond strength to tooth enamel and promoting mineral deposition.

In situ X-ray diffraction of silicate liquids and glasses under dynamic and static compression to megabar pressures.

Properties of liquid silicates under high-pressure and high-temperature conditions are critical for modeling the dynamics and solidification mechanisms of the magma ocean in the early Earth, as well as for constraining entrainment of melts in the mantle and in the present-day core-mantle boundary. Here we present in situ structural measurements by X-ray diffraction of selected amorphous silicates compressed statically in diamond anvil cells (up to 157 GPa at room temperature) or dynamically by laser-generated shock compression (up to 130 GPa and 6,000 K along the MgSiO3 glass Hugoniot). The X-ray diffraction patterns of silicate glasses and liquids reveal similar characteristics over a wide pressure and temperature range. Beyond the increase in Si coordination observed at 20 GPa, we find no evidence for major structural changes occurring in the silicate melts studied up to pressures and temperatures exceeding Earth's core mantle boundary conditions. This result is supported by molecular dynamics calculations. Our findings reinforce the widely used assumption that the silicate glasses studies are appropriate structural analogs for understanding the atomic arrangement of silicate liquids at these high pressures.

Disentangling the Orientations of Spectrally Overlapping Transition Dipoles in Dense Dye Layers.

The transition dipole orientations of dye assemblies in heterostructures have a crucial impact on the efficiency of novel optoelectronic devices such as organic thin-film transistors and light-emitting diodes. These devices are frequently based on heterojunctions and tandem structures featuring multiple optical transitions. Precise knowledge of preferred orientations, spatial order, and spatial variations is highly relevant. We present a fast and universal large-area screening method to determine the transition dipole orientations in dye assemblies with diffraction-limited spatial resolution. Moreover, our hyperspectral imaging approach disentangles the orientations of different chromophores. As a demonstration, we apply our technique to dye monolayers with two optical transitions sandwiched between two ultrathin silicate nanosheets. A comprehensive model for dipole orientation distributions in monolayers reveals a long-range orientational order and a strong correlation between the two transitions.

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.

Chabazite Synthesis and Its Exchange with Ti, Zn, Cu, Ag and Au for Efficient Photocatalytic Degradation of Methylene Blue Dye.

A chabazite-type zeolite was prepared by the hydrothermal method. Before ion exchange, the chabazite was activated with ammonium chloride (NH4Cl). The ion exchange process was carried out at a controlled temperature and constant stirring to obtain ion-exchanged chabazites of Ti4+ chabazite (TiCHA), Zn2+ chabazite (ZnCHA), Cu2+ chabazite (CuCHA), Ag+ chabazite (AgCHA) and Au3+ chabazite (AuCHA). Modified chabazite samples were characterized by X-ray diffraction (XRD), scanning electron microscope equipped with energy-dispersive spectroscopy (SEM-EDS), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), N2 adsorption methods and UV-visible diffuse reflectance spectroscopy (DRS). XRD results revealed that the chabazite structure did not undergo any modification during the exchange treatments. The photocatalytic activity of chabazite samples was evaluated by the degradation of methylene blue (MB) in the presence of H2O2 under ultraviolet (UV) light illumination. The photodegradation results showed a higher degradation efficiency of modified chabazites, compared to the synthesized chabazite. CuCHA showed an efficiency of 98.92% in MB degradation, with a constant of k = 0.0266 min-1 following a first-order kinetic mechanism. Then, it was demonstrated that the modified chabazites could be used for the photodegradation of dyes.

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.

Some Novel Results Involving Prototypical Computation of Zagreb Polynomials and Indices for SiO4 Embedded in a Chain of Silicates.

A topological index as a graph parameter was obtained mathematically from the graph's topological structure. These indices are useful for measuring the various chemical characteristics of chemical compounds in the chemical graph theory. The number of atoms that surround an atom in the molecular structure of a chemical compound determines its valency. A significant number of valency-based molecular invariants have been proposed, which connect various physicochemical aspects of chemical compounds, such as vapour pressure, stability, elastic energy, and numerous others. Molecules are linked with numerical values in a molecular network, and topological indices are a term for these values. In theoretical chemistry, topological indices are frequently used to simulate the physicochemical characteristics of chemical molecules. Zagreb indices are commonly employed by mathematicians to determine the strain energy, melting point, boiling temperature, distortion, and stability of a chemical compound. The purpose of this study is to look at valency-based molecular invariants for SiO4 embedded in a silicate chain under various conditions. To obtain the outcomes, the approach of atom-bond partitioning according to atom valences was applied by using the application of spectral graph theory, and we obtained different tables of atom-bond partitions of SiO4. We obtained exact values of valency-based molecular invariants, notably the first Zagreb, the second Zagreb, the hyper-Zagreb, the modified Zagreb, the enhanced Zagreb, and the redefined Zagreb (first, second, and third). We also provide a graphical depiction of the results that explains the reliance of topological indices on the specified polynomial structure parameters.

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.

Synthesis and Characterization of Hypercoordinated Silicon Anions: Catching Intermediates of Lewis Base Catalysis.

Anionic hypercoordinated silicates with weak donors were proposed as key intermediates in numerous silicon-based reactions. However, their short-lived nature rendered even spectroscopic observations highly challenging. Here, we characterize hypercoordinated silicon anions, including the first bromido-, iodido-, formato-, acetato-, triflato- and sulfato-silicates. This is enabled by a new, donor-free polymeric form of Lewis superacidic bis(perchlorocatecholato)silane 1. Spectroscopic, structural, and computational insights allow a reassessment of Gutmann's empirical rules for the role of silicon hypercoordination in synthesis and catalysis. The electronic perturbations of 1 exerted on the bound anions indicate pronounced substrate activation.

Phenyl Silicates with Substituted Catecholate Ligands: Synthesis, Structural Studies and Reactivity.

While the generation of aryl radicals by photoredox catalysis under reductive conditions is well documented, it has remained challenging under an oxidative pathway. Because of the easy photo-oxidation of alkyl bis-catecholato silicates, a general study of phenyl silicates bearing substituted catecholate ligands has been achieved. The newly synthesized phenyl silicates have been fully characterized, and their reactivity has been explored. It was found that, thanks to the substitution of the catecholate moiety, notably with the 4-cyanocatecholato ligand, the phenyl radical could be generated and trapped. Computational studies provided a rationale for these findings.

Rb[Li5 Si2 O7 ] - A Latecomer in the Family of Alkali Lithosilicates Hiding a Green-Emitting Lithosilicate.

In order to expand the field of alkali lithosilicates, a new representative of the substance class with a previously unknown structure type was found based on solid-state synthesis. The novel compound with the sum formula Rb[Li5 Si2 O7 ] crystallizes in the orthorhombic space group Pbcm (no. 57) with a=7.6269(3), b=9.5415(4), and c=9.4095(3) Šby means of single-crystal X-ray diffraction. The structure consists of a highly condensed lithosilicate framework, built up of corner- and edge-linked [LiO4 ]-tetrahedra and [Si2 O7 ]-units, and the rubidium ions aligned in channels. Suitable crystals of the material were obtained using sealed tantalum ampoules as reaction tube at a temperature of 750 °C. The new compound was further characterized via powder diffraction, Rietveld analysis, and EDX measurements. At first glance, Eu2+ -doped Rb[Li5 Si2 O7 ] reveals an intense green luminescence. In-depth crystal analysis shows that a core-shell formation is present even for apparently high quality single-crystals. As a minority phase, the known green phosphor RbLi[Li3 SiO4 ]2 :Eu2+ is the origin of the luminescence, representing a tiny core inside of the particles surrounded by a large matrix of transparent Rb[Li5 Si2 O7 ] dominating the single-crystal diffraction pattern.

Photocatalytic Giese-Type Reaction with Alkylsilicates Bearing C,O-Bidentate Ligands.

Herein, a photocatalytic Giese-type reaction with alkylsilicates bearing C,O-bidentate ligands as stable alkyl radical precursors has been reported. The alkylsilicates were prepared in one step from organometallic reagents. Not only primary, secondary, and tertiary alkyl radicals, but also elusive methyl radicals, could be generated by using the present reaction system. The generated radicals were trapped by electron-deficient olefins bearing various functional groups to give the desired alkyl adducts. The silicon byproduct can be recovered after the photoreaction. The radical generation process was investigated by theoretical calculations, which provided an insight into the facile generation of methyl radicals from methylsilicate bearing C,O-bidentate ligands.