High-aluminum-affinity silica is a nanoparticle that seeds secondary aluminosilicate formation.

Despite the importance and abundance of aluminosilicates throughout our natural surroundings, their formation at neutral pH is, surprisingly, a matter of considerable debate. From our experiments in dilute aluminum and silica containing solutions (pH ~ 7) we previously identified a silica polymer with an extraordinarily high affinity for aluminium ions (high-aluminum-affinity silica polymer, HSP). Here, further characterization shows that HSP is a colloid of approximately 2.4 nm in diameter with a mean specific surface area of about 1,000 m(2) g(-1) and it competes effectively with transferrin for Al(III) binding. Aluminum binding to HSP strongly inhibited its decomposition whilst the reaction rate constant for the formation of the β-silicomolybdic acid complex indicated a diameter between 3.6 and 4.1 nm for these aluminum-containing nanoparticles. Similarly, high resolution microscopic analysis of the air dried aluminum-containing silica colloid solution revealed 3.9 ± 1.3 nm sized crystalline Al-rich silica nanoparticles (ASP) with an estimated Al:Si ratio of between 2 and 3 which is close to the range of secondary aluminosilicates such as imogolite. Thus the high-aluminum-affinity silica polymer is a nanoparticle that seeds early aluminosilicate formation through highly competitive binding of Al(III) ions. In niche environments, especially in vivo, this may serve as an alternative mechanism to polyhydroxy Al(III) species binding monomeric silica to form early phase, non-toxic aluminosilicates

Silicon balance in human volunteers; a pilot study to establish the variance in silicon excretion versus intake.

BACKGROUND: Accumulating evidence suggests a role for silicon in optimal connective tissue health. Further proof of its importance/essentiality may be provided by studies involving imposed depletion followed by 29Si challenge to estimate metabolic balance. Prior to conducting these expensive studies, we first established the variance of estimating normal Si excretion versus intake using a single oral dose of typical dietary Si, orthosilicic acid. METHODS: Healthy volunteers were recruited from Loei Rajabhat University, separated into two matched groups (three males and three females/group) and maintained on a standardized diet for the three study days. One group ingested 500 ml water containing orthosilicic acid (28.9 mg Si) and the other group received 500 ml water alone, all on a fasted stomach. Blood samples and total urine and faeces were collected over the 48 h post-dose period and 24 h before-hand (baseline) and analysed for silicon by inductively coupled plasma optical emission spectrometry. RESULTS: Serum Si analysis confirmed the ready absorption of silicon from the orthosilicic acid solution. Mean total urinary and faecal Si excretions over the 24 h post-dose period accounted for 57 ± 9.5% and 39 ± 9.4% of the ingested dose, respectively. Thus in total 96.3 ± 5.8% of the ingested dose was recovered in faecal plus urinary excretions over the 24 h post-dose period. CONCLUSIONS: We report that in healthy subjects (presumably in Si balance), the ingestion of a soluble dose of dietary Si results in the same quantity (within analytical error) being excreted within 24 h. It is currently not known if this all originated from the dose solution or if there was some exchange with the body Si pool but, given the low variance in these silicon balance data, isotopic studies are now merited

Kinetics of Surfactant Adsorption at Fluid-Fluid Interfaces: Surfactant Mixtures

The adsorption at the interface between an aqueous solution of several surface-active agents and another fluid (air or oil) phase is addressed theoretically. We derive the kinetic equations from a variation of the interfacial free energy, solve them numerically and provide an analytic solution for the simple case of a linear adsorption isotherm. Calculating asymptotic solutions analytically, we find the characteristic time scales of the adsorption process and observe the behavior of the system at various temporal stages. In particular, we relate the kinetic behavior of the mixture to the properties of its individual constituents and find good agreement with experiments. In the case of kinetically limited adsorption, the mixture kinetics is found to be considerably different from that of the single-surfactant solutions because of strong coupling between the species.Comment: 19 pages, 7 figures, to be published in Langmui

The silicon supplement 'Monomethylsilanetriol' is safe and increases the body pool of silicon in healthy Pre-menopausal women.

BACKGROUND: Monomethylsilanetriol (MMST) has been used for decades as an oral silicon supplement for bone and connective tissue health, although there are no formal data on its in vivo utilisation or safety following sustained dosing. METHODS: To investigate whether MMST contributes to the body pool of silicon and, secondly, to establish its safety following 4 weeks' supplementation in humans, twenty-two healthy pre-menopausal women (22-38 years) were recruited and supplemented with MMST at the maximum daily recommended dose (10.5 mg Si/day) for 4 weeks in a double-blind, randomised, placebo-controlled, cross-over design (i.e. 8 weeks in total). Fasting serum and urine samples were collected at baseline and at the end of the 4-week supplementation/placebo periods for analysis of total silicon by inductively coupled plasma optical emission spectrometry, MMST by proton nuclear magnetic resonance spectroscopy and full serum biochemistry. Participants also reported on, by questionnaire, their health, well-being and quality of life at 0, 4 and 8 weeks. RESULTS: Overall, 4-weeks supplementation with MMST significantly increased total fasting Si concentrations in serum and urine (P ≤ 0.003; paired t-test). MMST was semi-quantifiable in serum and quantifiable in urine, but only accounted for ca. 50% and 10%, respectively, of the increased total-Si concentration. There were no reported adverse effects (i.e. changes to health and well-being) or serum biochemical changes with MMST versus placebo. CONCLUSIONS: Our data indicate that oral MMST is safe, is absorbed and undergoes sufficient metabolism in vivo to raise fasting serum silicon levels, consistent with other well absorbed forms of dietary silicon (e.g. orthosilicic acid). It thus appears to be a suitable silicon supplement

Silicon and boron differ in their localization and loading in bone.

Silicon and boron share many similarities, both chemically and biochemically, including having similar effects on bone, although their mechanisms of action are not known. Here we compared the loading of silicon and boron into bone, their localization and how they are influenced by age (growth & development), to obtain further clues as to the biological effects of these elements and, especially, to see if they behave the same or not. Bone samples were obtained from two different studies where female Sprague Dawley rats had been maintained on a normal maintenance diet for up to 43 weeks. Total bone elemental levels were determined by ICP-OES following microwave assisted acid digestion. Silicon and boron levels in the decalcified bones (i.e. the collagen fraction) were also investigated. Silicon and boron showed marked differences in loading and in their localization in bone. Highest silicon and lowest boron concentrations were found in the under-mineralized bone of younger rats and lowest silicon and highest boron concentrations were found in the fully mineralized bone of the adult rat. Overall, however total bone silicon content increased with age, as did boron content, the latter mirroring the increase in calcium (mineral) content of bone. However, whereas silicon showed equal distribution in the collagen and mineral fractions of bone, boron was exclusively localized in the mineral fraction. These findings confirm the reported association between silicon and collagen, especially at the early stages of bone mineralization, and show that boron is associated with the bone mineral but not connective tissues. These data suggest that silicon and boron have different biological roles and that one is unlikely, therefore, to substitute for the other, or at least boron would not substitute for Si in the connective tissues. Finally, we noted that silicon levels in the mineral fraction varied greatly between the two studies, suggesting that one or more nutritional factor(s) may influence the loading of Si into the mineral fraction of bone. This and the nature of the interaction between Si and collagen deserve further attention.We thank the Medical Research Council (grant number MC_US_A090_0008/Unit Programme number U1059) and the charitable foundation of the Institute of Brewing and Distilling and for their support

Adsorption of Amorphous Silica Nanoparticles onto Hydroxyapatite Surfaces Differentially Alters Surfaces Properties and Adhesion of Human Osteoblast Cells.

Silicon (Si) is suggested to be an important/essential nutrient for bone and connective tissue health. Silicon-substituted hydroxyapatite (Si-HA) has silicate ions incorporated into its lattice structure and was developed to improve attachment to bone and increase new bone formation. Here we investigated the direct adsorption of silicate species onto an HA coated surface as a cost effective method of incorporating silicon on to HA surfaces for improved implant osseointegration, and determined changes in surface characteristics and osteoblast cell adhesion. Plasma-sprayed HA-coated stainless steel discs were incubated in silica dispersions of different concentrations (0-42 mM Si), at neutral pH for 12 h. Adsorbed Si was confirmed by XPS analysis and quantified by ICP-OES analysis following release from the HA surface. Changes in surface characteristics were determined by AFM and measurement of surface wettability. Osteoblast cell adhesion was determined by vinculin plaque staining. Maximum Si adsorption to the HA coated disc occurred after incubation in the 6 mM silica dispersion and decreased progressively with higher silica concentrations, while no adsorption was observed with dispersions below 6 mM Si. Comparison of the Si dispersions that produced the highest and lowest Si adsorption to the HA surface, by TEM-based analysis, revealed an abundance of small amorphous nanosilica species (NSP) of ~1.5 nm in diameter in the 6 mM Si dispersion, with much fewer and larger NSP in the 42 mM Si dispersions. 29Si-NMR confirmed that the NSPs in the 6 mM silica dispersion were polymeric and similar in composition to the larger NSPs in the 42 mM Si dispersion, suggesting that the latter were aggregates of the former. Amorphous NSP adsorbed from the 6 mM dispersion on to a HA-coated disc surface increased the surface's water contact angle by 53°, whereas that adsorbed from the 42 mM dispersion decreased the contact angle by 18°, indicating increased and decreased hydrophobicity, respectively. AFM showed an increase in surface roughness of the 6 mM Si treated surface, which correlated well with an increase in number of vinculin plaques. These findings suggest that NSP of the right size (relative to charge) adsorb readily to the HA surface, changing the surface characteristics and, thus, improving osteoblast cell adhesion. This treatment provides a simple way to modify plasma-coated HA surfaces that may enable improved osseointegration of bone implants.The authors acknowledge the National Institute of Health Research (NIHR) and the Medical Research Council, grant number MC_US_A090_0008/Unit Programme number U1059, www. mrc.ac.uk, to RJ; Engineering and Physical Sciences Research Council (UK), grant number EP/ F019823/1 (https://www.epsrc.ac.uk) to PK, DJM; Engineering and Physical Sciences Research Council (UK), grant number EP/K023853/1 (https://www.epsrc.ac.uk) "Leeds EPSRC Nanoscience and Nanotechnology Research Equipment Facility (LENNF)" to APB and PK. Orthopaedic Research UK Grant "Drug Delivery of Silicon from the Furlong HA-C Hip" (www.oruk.org) to PK, RAB. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.This is the final version of the article. It first appeared from PLOS via http://dx.doi.org/10.1371/journal.pone.014478

Dietary Silicon Deficiency Does Not Exacerbate Diet-Induced Fatty Lesions in Female ApoE Knockout Mice.

BACKGROUND: Dietary silicon has been positively linked with vascular health and protection against atherosclerotic plaque formation, but the mechanism of action is unclear. OBJECTIVES: We investigated the effect of dietary silicon on 1) serum and aorta silicon concentrations, 2) the development of aortic lesions and serum lipid concentrations, and 3) the structural and biomechanic properties of the aorta. METHODS: Two studies, of the same design, were conducted to address the above objectives. Female mice, lacking the apolipoprotein E (apoE) gene, and therefore susceptible to atherosclerosis, were separated into 3 groups of 10-15 mice, each exposed to a high-fat diet (21% wt milk fat and 1.5% wt cholesterol) but with differing concentrations of dietary silicon, namely: silicon-deprived (-Si; <3-μg silicon/g feed), silicon-replete in feed (+Si-feed; 100-μg silicon/g feed), and silicon-replete in drinking water (+Si-water; 115-μg silicon/mL) for 15-19 wk. Silicon supplementation was in the form of sodium metasilicate (feed) or monomethylsilanetriol (drinking water). RESULTS: The serum silicon concentration in the -Si group was significantly lower than in the +Si-feed (by up to 78%; P < 0.003) and the +Si-water (by up to 84%; P < 0.006) groups. The aorta silicon concentration was also lower in the -Si group than in the +Si-feed group (by 65%; P = 0.025), but not compared with the +Si-water group. There were no differences in serum and aorta silicon concentrations between the silicon-replete groups. Body weights, tissue wet weights at necropsy, and structural, biomechanic, and morphologic properties of the aorta were not affected by dietary silicon; nor were the development of fatty lesions and serum lipid concentrations. CONCLUSIONS: These findings suggest that dietary silicon has no effect on atherosclerosis development and vascular health in the apoE mouse model of diet-induced atherosclerosis, contrary to the reported findings in the cholesterol-fed rabbit model

Dietary Silicon Deficiency Does Not Exacerbate Diet-Induced Fatty Lesions in Female ApoE Knockout Mice.

BACKGROUND: Dietary silicon has been positively linked with vascular health and protection against atherosclerotic plaque formation, but the mechanism of action is unclear. OBJECTIVES: We investigated the effect of dietary silicon on 1) serum and aorta silicon concentrations, 2) the development of aortic lesions and serum lipid concentrations, and 3) the structural and biomechanic properties of the aorta. METHODS: Two studies, of the same design, were conducted to address the above objectives. Female mice, lacking the apolipoprotein E (apoE) gene, and therefore susceptible to atherosclerosis, were separated into 3 groups of 10-15 mice, each exposed to a high-fat diet (21% wt milk fat and 1.5% wt cholesterol) but with differing concentrations of dietary silicon, namely: silicon-deprived (-Si; <3-μg silicon/g feed), silicon-replete in feed (+Si-feed; 100-μg silicon/g feed), and silicon-replete in drinking water (+Si-water; 115-μg silicon/mL) for 15-19 wk. Silicon supplementation was in the form of sodium metasilicate (feed) or monomethylsilanetriol (drinking water). RESULTS: The serum silicon concentration in the -Si group was significantly lower than in the +Si-feed (by up to 78%; P < 0.003) and the +Si-water (by up to 84%; P < 0.006) groups. The aorta silicon concentration was also lower in the -Si group than in the +Si-feed group (by 65%; P = 0.025), but not compared with the +Si-water group. There were no differences in serum and aorta silicon concentrations between the silicon-replete groups. Body weights, tissue wet weights at necropsy, and structural, biomechanic, and morphologic properties of the aorta were not affected by dietary silicon; nor were the development of fatty lesions and serum lipid concentrations. CONCLUSIONS: These findings suggest that dietary silicon has no effect on atherosclerosis development and vascular health in the apoE mouse model of diet-induced atherosclerosis, contrary to the reported findings in the cholesterol-fed rabbit model

Urinary Excretion of Silicon in Men, Non-pregnant Women, and Pregnant Women: a Cross-sectional Study

Abstract: Silicon is a trace element found mainly in plant-based food and proposed to be beneficial for bone health. Urinary excretion of Si has been shown to be a surrogate measure of its uptake in the gastrointestinal tract. The objective of this study was to describe and compare the levels of urinary Si excretion, and consequently Si uptake, in Swedish men, non-pregnant women, and pregnant women. No formal assessment of dietary Si intake was carried out in this study. This cross-sectional study included 89 men, 42 non-pregnant women, and 60 pregnant women. The subjects collected urine over a 24-h period and the samples were assayed for total Si using inductively coupled plasma optical emission spectrometry. The excretion levels of creatinine were used to validate the completeness of the urine sample collections. The mean 24-h urinary excretions of Si were 7.8 mg for the cohort of young men, 7.6 mg for the cohort of non-pregnant women, and 12.4 mg for the cohort of pregnant women. Creatinine excretion was similar between pregnant and non-pregnant women (10.4 vs. 10.8 mmol/day) and significantly higher in men (15.4 mmol/day). The pregnant women excreted significantly higher levels of Si than the young men and non-pregnant women, respectively (p < 0.05). The higher urinary excretion of Si by pregnant women compared with men and non-pregnant women is a novel finding possibly caused by temporary physiological changes during pregnancy such as increased gastrointestinal uptake of Si, altered bone metabolism, and increased renal excretion of Si