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6Li nuclear magnetic resonance chemical shifts, coordination number and relaxation in crystalline and glassy silicates.

Unlike 7Li magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra, 6Li MAS NMR spectra of silicates are dominated by chemical shift effects, often have a very high resolution and hence can provide significant structural information. In this study we demonstrate a good correlation between 6Li isotropic chemical shifts and oxygen coordination number, and use this result to describe the range of coordination environments for Li in silicate glasses. We also show that the second-order quadrupolar shift for 7Li can often be derived from 7Li and 6Li MAS spectra acquired at a single magnetic field. For a series of natural lepidolite samples with significant but varying contents of Mn and Fe, spin-lattice relaxation data show a power-law behavior and a three-dimensional distribution of paramagnetic centers, but homonuclear dipolar couplings can be important. The 6Li spectrum for lithium orthosilicate (which has three-, four-, five- and six-coordinated Li) is consistent with that predicted by the X-ray structure.

Crystallization↗

One- and two-dimensional 1H magic-angle spinning experiments on hydrous silicate glasses.

Applications of various one- and two-dimensional 1H magic-angle spinning nuclear magnetic resonance (MAS NMR) techniques for the elucidation of structural properties of hydrous silicate glasses are described. Advantages and limitations of one-dimensional experiments [MAS and combined rotation and multiple-puls spectroscopy (CRAMPS)] and of two-dimensional approaches (spin-exchange experiments, "MAS-CRAMPS" correlation plus extended versions) are discussed. The various 1H MAS NMR techniques are illustrated by practical examples of spectra obtained from a hydrous silicate glass of Na2O.4SiO2.0.7H2O composition.

Glass↗

Effect of silicon level on rate, quality and progression of bone healing within silicate-substituted porous hydroxyapatite scaffolds.

The osseous response to silicon (Si) level (0, 0.2, 0.4, 0.8 and 1.5 wt% Si) within 5 batches of matched porosity silicate-substituted hydroxyapatite (SA) scaffold was assessed by implantation of 4.6 mm diameter cylinders in the femoral intercondylar notch of New Zealand White rabbits for periods of 1, 3, 6 and 12 weeks. Histological evaluation and histomorphometric quantification of bone ingrowth and mineral apposition rate (MAR) demonstrated the benefits to early (<1 week) bone ingrowth and repair through incorporation of Si, at all levels, in porous hydroxyapatite (HA) lattices as compared to stoichiometric (0 wt% Si) HA. The group containing 0.8 wt% Si supported significantly more bone ingrowth than all other groups at 3 and 6 weeks (P<0.05), initially through its elevated MAR between weeks 1 and 2, which was significantly higher than that of all other Si-containing groups (P<0.05). The level of silicate substitution also influenced the morphology and stability of the repair, with elevated levels of bone resorption and apposition apparent within other Si-containing groups at timepoints >3 weeks as compared to the 0 and 0.8 wt% Si groups. At 12 weeks, the net amount of bone ingrowth continued to rise in the 0, 0.8 and 1.5 wt% groups, apparently as a result of adaptive remodelling throughout the scaffold. Ingrowth levels remained highest in the 0.8 wt% Si group, was characterised by a dense trabecular morphology in the superficial region graduating to a more open network in the deep zone. These results highlight the sensitivity of healing response to Si level and suggest that an optimal response is obtained when SA is substituted with 0.8 wt% Si through its effect on the activity of both bone forming and bone resorbing cells.

Animals↗

MIN6 cells-enclosing aminopropyl-silicate membrane templated by alginate gels differences in guluronic acid content.

Mouse insulinoma (MIN6) cells were encapsulated into aminopropyl-silicate membrane deposited on calcium alginate gel beads via the sol-gel synthesis. Two alginates with different guluronic acid (G) contents, high and intermediate, but with the same molecular weights were used. Viability of the cells in the membrane templated by the alginate with an intermediate content of guluronic acid (intermediate-G) was approximately 10% higher than those in the membrane templated by the alginate with a high content of guluronic acid immediately after encapsulation. Growth of cells in vitro was hindered in case of encapsulation in the aminopropyl-silicate membrane deposited on the high-G alginate gel. The MIN6 cells in the microcapsule made from high-G alginate needed a longer period to establish a normoglycemic in recipients than those in the microcapsule made from intermediate-G alginate despite the same number of viable cells implantation. Recipients of the microcapsule with the core made from the intermediate-G alginate maintained their blood glucose values less than 300 mg/dl for a longer period.

Alginates↗

Alginate-magnesium aluminum silicate films: effect of plasticizers on film properties, drug permeation and drug release from coated tablets.

The effect of hydrophilic plasticizers, namely glycerin and polyethylene glycol 400 (PEG400), on physicochemical properties of sodium alginate-magnesium aluminum silicate (SA-MAS) microcomposite films was characterized and application of the films for controlling drug release from tablets was evaluated as well. The plasticizers could possibly interact with SA or MAS by formation of hydrogen bonding, as revealed using FTIR spectroscopy. PXRD studies presented that glycerin or PEG400 could intercalate into the silicate layers of MAS and higher crystallinity of the films with PEG400 was obtained. This led to a different thermal behavior of the films. Glycerin gave more flexibility of the films than PEG400. Incorporation of plasticizers into the films did not affect water uptake in acid medium, but increasing an erosion of the films because of the leaching of the plasticizers. Water vapor permeability of the films decreased with increasing amount of plasticizers in the range of 10-30% (w/w). Diffusion coefficient (D) of acetaminophen (ACT) across the films in acid medium increased with addition of the plasticizers because the leaching of plasticizers could reduce tortuosity of aqueous pore channels of the films. The tablets coated with plasticized films had a quite smooth surface without defect as shown by SEM. The ACT release profiles from the coated tablets showed a zero-order release kinetic with drug diffusion mechanism across in situ insoluble composite films in acid medium, and coating film swelling and erosion mechanism in pH 6.8 phosphate buffer. Moreover, neither the release rate nor the release pattern of the ACT coated tablets was obviously changed. The findings show that glycerin or PEG400 could improve physicochemical properties of the SA-MAS films and the plasticized films could control the drug release from tablets in gastro-intestinal condition.

Acetaminophen↗

Structure analysis of intercalated layer silicates: combination of molecular simulations and experiment.

Na(+)-montmorillonite type Wyoming, cloisite Na(+) from Southern Clay Products, Inc., was intercalated (i) with octadecylammonium cations and subsequently intercalated with octadecylamine molecules, (ii) with dodecylamine molecules, and (iii) with octylamine molecules to determine the applicability of these intercalates for nanocomposite materials on the base of polymer/clay. The structures were determined on the basis of a combination of results from X-ray diffraction and molecular simulations. The calculated values of basal spacings are in good agreement with experimental basal spacings when experimental samples were prepared. The interlayer space of intercalated montmorillonite shows a monolayer or bilayer arrangement of alkyl chains in dependence on the concentration of the intercalation solution. The values of the total sublimation energy, interaction energy, and exfoliation energy were calculated for all investigated samples. Low values of exfoliation energies lead to better exfoliation of intercalated silicate layers and this material appears suitable for use as a precursor for polymer/clay nanocomposites. The values of exfoliation energy for the investigated samples show that montmorillonite intercalated with dodecylamine or octadecylamine molecules is suitable for exfoliation of silicate layers.

Models, Chemical↗

Adsorption properties of gases on mesoporous chromium silicate.

The properties of nitrogen, carbon dioxide, and nitrogen dioxide adsorption onto mesoporous chromium silicates were studied by measurements of both the adsorption isotherms and the IR spectra. The pore sizes of two types of chromium silicates, Cr-FSM-16 (Si/Cr=170 (Cr-FSM-16 [170]) and 390 (Cr-FSM-16 [390])), which contain different amount of Cr, were 2.75 nm. BET surface areas of Cr-FSM-16 were 590 m2/g and they were smaller than that onto FSM-16. The initial heat of adsorption of nitrogen onto Cr-FSM-16 was higher than that onto FSM-16. But the initial heat of adsorption of carbon dioxide onto Cr-FSM-16 was smaller than that onto FSM-16. These results indicated that Cr in Cr-FSM-16 decreased adsorption interaction with carbon dioxide. When nitrogen dioxide was adsorbed on FSM-16 and Cr-FSM-16 at 303 K under no light, an absorption band of nitrogen monoxide adsorbed was measured by IR spectroscopy. This decomposition of nitrogen dioxide by FSM-16 and Cr-FSM-16 was caused by SiOH and Cr, respectively.

Adsorption↗

A novel calcium silicate based microspheres of repaglinide: in vivo investigations.

The objective of the present investigation was to evaluate gastro-retentive performance and pharmacokinetic parameters of optimized floating microspheres (RgFMCS4) consisting of (i) calcium silicate (CS) as porous carrier; (ii) repaglinide (Rg), an oral hypoglycemic agent; and (iii) Eudragit S (ES) as polymer. The optimized formulation demonstrated favorable in-vitro-floating and drug release characteristics. The gastro-retentive behavior of this optimized formulation was compared with non-floating microspheres (RgNFM) prepared from the identical polymer. Stability test of (99m)Tc-labeled formulations were carried out using appropriate standard buffer solutions of pH 2.0, 6.8 and 7.4. The organ distribution study was performed in albino rats in order to measure labeling efficiency of the formulation with (99m)Tc. The gamma scintigraphy of the formulations was carried out in albino rabbits to monitor the transit of RgFMCS4 and RgNFM in the gastrointestinal (GI) tract. Prolonged gastric residence time (GRT) of over 6 h was achieved in all animals for calcium silicate based floating microspheres of Rg. Rg loaded optimized formulation was orally administered to albino rabbits and blood samples were used to determine pharmacokinetic parameters of Rg from floating microspheres, which were compared with pharmacokinetic parameters of the marketed tablet formulation. The relative bioavailability of Rg loaded floating microspheres was found to be increased about 3.17 times in comparison to that of the marketed tablet. The enhanced bioavailability and eliminated half-lives of Rg formulation observed in the present study are attributed to the floating nature of the designed formulations.

Animals↗

The chemical species distribution and transformation of polyaluminum silicate chloride coagulant.

The chemical species distributions of polyaluminum silicate chloride (PASC) and polyaluminum chloride (PACl) determined by Al-Ferron complexation timed spectrophotometric and 27Al-NMR methods, respectively, have been compared and analyzed. The experimental results show that the species distribution and transformation of PASC are different from those of PACl, due to the interaction of polysilicic acid and hydrolyzed aluminum species. At the same basicity (B), the contents of, Al(b), Al13 and the monomer species Almono (also determined by 27Al-NMR) in PASC are lower than those in PACl, while the contents of Al(c) and the Alother determined by 27Al-NMR in PASC are higher than those in PACl. The differences between PASC and PACl with respect to these species enlarge as the molar ratio of Al/Si in PASC decreases. Further, in PACl the ratio of Al13 to Al(b) closes to 1.0, indicating that the amount of the two fractions are similar. In PASC, however, such an agreement does not exist at the lower B values and Al/Si molar ratios. When the B value and Al/Si molar ratios increase, however, the amount of Al13 and Al(b) species tends to close. The study findings indicate that polysilicic acid can react with hydrolyzed aluminum species to form an aluminum silicate polymer composite and result in the change in species distribution of PASC.

Aluminum Hydroxide↗

Silicate core-organic refractory mantle particles as interstellar dust and as aggregated in comets and stellar disks.

The principal observational properties of silicate core-organic refractory mantle interstellar dust grains in the infrared at 3.4 microns and at 10 microns and 20 microns are discussed in terms of the cyclic evolution of particles forming in stellar atmospheres and undergoing subsequent accretion, photoprocessing and destruction (erosion). Laboratory plus space emulation of the photoprocessing of laboratory analog ices and refractories are discussed. The aggregated interstellar dust model of comets is summarized. The same properties required to explain the temperature and infrared properties of comet coma dust are shown to be needed to account for the infrared silicate and continuum emission of the beta Pictoris disk as produced by a cloud of comets orbiting the star.

Cosmic Dust↗

A spectroscopic NMR investigation of the calcium silicate hydrates present in cement and concrete.

NMR spectroscopy is applied to study microstructure of calcium silicate hydrates present in cement and concrete. It is shown that 29Si NMR gives information on the siliceous skeleton of the hydrates. 1H NMR, using CRAMPS techniques, allows to discriminate between protons linked to silicon atoms or to calcium atoms. A first investigation of reference compounds indicates that 43Ca NMR will be powerful to determine calcium atom sites in the structure.

Calcium Compounds↗

Carbon and silicate grains in the laboratory as analogues of cosmic dust.

Carbon and silicate grains are the two main components of cosmic dust. There is increasing spectroscopic evidence that their composition varies according to the cosmic environment and the experienced processing. Irradiation from ultraviolet photons and cosmic rays, as well as chemical interactions with the interstellar gas play a crucial role for grain transformation. The study of 'laboratory analogues' represents a powerful tool to better understand the nature and evolution of cosmic materials. In particular, simulations of grain processing are fundamental to outline an evolutionary pathway for interstellar particles. In the present work, we discuss the ultraviolet and infrared spectral changes induced by thermal annealing, ultraviolet irradiation, ion irradiation and hydrogen atom bombardment in carbon and silicate analogue materials. The laboratory results give the opportunity to shed light on the long-standing problems of the attribution of ultraviolet and infrared interstellar spectral features.

Astronomical Phenomena↗

Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

Cesium↗

Aqueous solubility diagrams for cementitious waste stabilization systems. 4. A carbonation model for Zn-doped calcium silicate hydrate by Gibbs energy minimization.

A thermodynamic Gibbs energy minimization (GEM) solid solution-aqueous solution (SSAS) equilibrium model was used to determine the solubility of Zn from calcium silicate hydrate (CSH) phases doped with 0, 0.1, 1, 5, and 10% Zn at a unity (Ca+Zn)/Si molar ratio. Both the stoichiometry and standard molar Gibbs energy (G(o)298) of the Zn-bearing end-member in the ideal ternary Zn-bearing calcium silicate hydrate (CZSH) solid solution were determined by a "dual-thermodynamic" (GEM-DT) estimation technique. The SSAS model reproduces a complex sequence of reactions suggested to occur in a long-term weathering scenario of cementitious waste forms at subsurface repository conditions. The GEM model of CZSH leaching at several Zn loadings and solid/water (s/w) ratios in a C02-free system showed that, upon complete dissolution of portlandite and calcium zincate phases at decreasing s/w < 0.01 mol x kg(H2O)(-1), the total dissolved concentrations Si(aq), Ca(aq), and Zn(aq) are controlled by a CZSH solid solution of changing composition, with a trough-like Znaq drop by 2-3 orders of magnitude. Carbonation was simulated in another GEM model run series by CO2 titration of the system with initial s/w approximately 0.9 mol/kg(H2O). Formation of (Ca,Zn)-CO3 nonideal solid solution was predicted already at early reaction stage in the presence of both portlandite and calcium zincate hydrate phases. Upon their disappearance, pH, Zn(aq), C(aq), and fCO2 were predicted to change due to the incongruent dissolution of two concurrent CZSH-I and CZSH-II solid solutions, until the total re-partitioning of Ca and Zn into a carbonate solid solution coexisting with amorphous silica at fCO2 > 0.1 bar. Along this solid-phase transition, dissolved Zn(aq) concentrations follow a highly nonlinear trend. The model results predict that at low to moderate Zn loading (< or = 1% per mole Si), CZSH-type compounds can efficiently immobilize Zn in the near field of a cement-stabilized waste repository.

Calcium Compounds↗

Arsenate and arsenite removal by zerovalent iron: effects of phosphate, silicate, carbonate, borate, sulfate, chromate, molybdate, and nitrate, relative to chloride.

Batch tests were performed to evaluate the effects of inorganic anion competition on the kinetics of arsenate (As(V)) and arsenite (As(III)) removal by zerovalent iron (Peerless Fe0) in aqueous solution. The oxyanions underwent either sorption-dominated reactions (phosphate, silicate, carbonate, borate, and sulfate) or reduction-dominated reactions (chromate, molybdate, and nitrate) with Peerless Fe0 in the presence of As(V) or As(III), relative to chloride. Pseudo-first-order rate equations were found to describe satisfactorily both As(V) and As(III) removal kinetics in the presence of each competing anion. Of the oxyanions tested for Peerless Fe0 in the pH range from 7 to 9, phosphate caused the greatest decrease in As removal rate (7.0 x 10(-3) to 18.5 x 10(-3) h(-1)) relative to chloride (34.9 x 10(-3) to 36.2 x 10(-3) h(-1)). Silicate, chromate, and molybdate also caused strong inhibition of As removal, followed by carbonate and nitrate, whereas borate and sulfate only caused slight inhibition to As(III) removal. Present results show that Peerless Fe0 may be an excellent permeable reactive barrier medium for a suite of mixed inorganic contaminants. The anion competing effects should be considered when designing permeable reactive barriers composed of zerovalent iron for field applications to remediate As(V) and As(III).

Adsorption↗

Silicate enhanced enzymatic dehairing: a new lime-sulfide-free process for cowhides.

A conventional dehairing process with sodium sulfide and lime is a major source of the pollution from the tanning industry. In other words, conventional dehairing processes degrade the hair to the extent that it cannot be recovered; thus, these processes become a major contributor to wastewater pollution. In this study, an attempt has been made to develop a lime and sulfide-free dehairing process using a commercial enzyme formulation with the activation of a silicate salt. A dip and pile method of application has been standardized. The amount of enzyme and sodium metasilicate has also been optimized based on complete removal of hair. Enhancement of enzyme activity by the addition of silicate has been demonstrated through activity measurements. Hair removal is found to be complete using scanning electron microscope analysis. Strength and bulk properties of the experimental leathers are comparable to that of control leathers. The process enjoys a significant reduction in chemical oxygen demand (COD) and total solids (TS) by 53 and 26%, respectively. More importantly, the application of enzyme for dehairing results in an 8% area increase in the final leather. Also, the process is proven to be techno-economically feasible.

Animals↗

Spirocyclic zwitterionic lambda5Si-silicates with two bidentate ligands derived from alpha-amino acids or alpha-hydroxycarboxylic acids: synthesis, structure, and stereodynamics.

A series of zwitterionic lambda(5)Si-silicates with a (2,2,6,6-tetramethylpiperidinio)methyl group and two identical bidentate ligands derived from glycine, (S)-alanine, (S)-phenylalanine, glycolic acid, (S)-lactic acid, (S)-3-phenyllactic acid, or (S)-mandelic acid were synthesized and structurally characterized (solution and solid-state NMR spectroscopy; single-crystal X-ray diffraction). The chiral lambda(5)Si-silicates with ligands derived from optically active alpha-amino acids or alpha-hydroxycarboxylic acids were isolated as enantiomerically and diastereomerically pure compounds that undergo a (Lambda)/(Delta)-epimerization in solution.

Amino Acids↗

Preparation and palladium-catalyzed cross-coupling of aryl triethylammonium bis(catechol) silicates with aryl triflates.

Pentavalent aryl and heteroaryl bis(catechol) silicates undergo palladium-catalyzed cross-coupling with aryl and heteroaryl triflates in the presence of a fluoride source in excellent yields. These solid, air-stable bis(catechol) silicates are prepared from a high-yielding displacement reaction between catechol and an aryl siloxane in the presence of an amine base. The cross-coupling reaction is tolerant of a wide range of electron-donating and electron-withdrawing groups. Several examples of di-ortho-substituted triflates are successfully coupled with these reagents.

Catalysis↗