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Molecular dynamics implementation in MSINDO: study of silicon clusters.

Born-Oppenheimer molecular dynamics is implemented in the semiempirical self-consistent field molecular orbital method MSINDO. The method is employed for the investigation of the structure and dynamics of silicon clusters of various sizes. The reliability of the present parameterization for silicon compounds is demonstrated by a comparison of the results of simulated annealing and of density functional calculations of Si(n) clusters (n = 5-7). The melting behavior of the Si(7) cluster is investigated and the MSINDO results are compared to previous high-level calculations. The efficiency of the present approach for the treatment of large systems is demonstrated by an extensive simulated annealing study of the Si(45) and Si(60) clusters. New Si(45) and Si(60) structures are found and evaluated. The relative stability of various energy minimum structures is compared with density functional calculations and available literature data.

Journal Article↗

Experimental retinal tolerance to very low viscosity silicone oil (100 cs) as a vitreous substitute compared to higher viscosity silicone oil (5000 cs).

We evaluated the toxicity of very low viscosity (100 centistokes) and higher viscosity silicone oil (5000 centistokes) in rabbit eyes as a short-to-long-term postoperative vitreous substitute (6 weeks to 5 months). Emulsification of 100-cs and 5000-cs silicone oil did not occur in eyes which were followed for as long as 5 months. No toxic effects to retinal cells were detected by light or electron microscopy. Because no toxic effects were seen with 100-cs silicone oil, it can be used in an outpatient setting as a short-term postoperative tamponading agent. Electroretinographic responses of silicone-injected eyes were normal.

Animals↗

Balkan endemic nephropathy: still a mysterious disease.

Balkan endemic nephropathy (BEN) is an acquired, environmental, polytopical disease of the entire urinary tract, with long latency. Tubulointerstitial chronic nephritis, urotheliomas of all localities, and renal cell carcinoma occur with a significantly higher frequency in the affected population. These represent only clinical manifestations of one unique nosological entity. BEN occurs in focuses. Within them, it agglomerates in households, without any evidence of hereditary background. Patients with various clinical manifestations of the disease can be simultaneously found within one single household. BEN appears equally among members of different ethnic groups. Its aetiology is not clear enough. There is no evidence of a causal relationship with silicon compounds, heavy metals and viruses. Much attention has been recently focused on research of the aetiological role of mycotoxins, mainly ochratoxin A. Toxic and carcinogenic agents of natural origin are commonly accepted as the major cause of BEN.

Balkan Nephropathy↗

Biosilicification: the role of the organic matrix in structure control.

Silicon (although never in the elemental form) is present in all living organisms and is required for the production of structural materials in single-celled organisms through to higher plants and animals. Hydrated amorphous silica is a mineral of infinite functionality and yet it is formed into structures with microscopic and macroscopic form. Research into the mechanisms controlling the process have highlighted proteins and proteoglycans as possible control molecules. Such molecules are suggested to play a critical role in the catalysis of silica polycondensation reactions and in structure direction. This article reviews information on silica form and function, silica condensation chemistry, the role of macromolecules in structure control and in vitro studies of silica formation using biomolecules extracted from biological silicas. An understanding of the mechanisms by which biological organisms regulate mineral formation will assist in our understanding of the essentiality of silicon to life processes and in the generation of new materials with specific form and function for industrial application in the 21st century.

Animals↗

Tracers of sewage sludge in the marine environment: a review.

A review of the available and potential tracers of the movement and distribution of sewage sludge ('sludge') in and on marine sediments is presented. A brief review of 'active' sludge tracers is followed by a more extensive review of 'passive' sludge tracers. These can be broken down into five categories: Natural organic components of sludge--organic carbon, faecal steroids, carbohydrate/TOC ratio, tomato seeds. Synthetic organic compounds--silicones, chlorinated hydrocarbons, non-ionic surfactants and their degradation products, linear alkylbenzenes. Stable isotopes of carbon, nitrogen, hydrogen and sulphur. Inorganic substances and their properties--minerals, paint pigments, trace elements, magnetic properties. Biological/Microbiological--faecal bacteria, Clostridium welchii spores, amoebae, viruses, nitrogen-fixing enterobacteriaceae. A wide variety of sludge tracers are available with the choice of suitable tracers in an individual situation governed by the available equipment and expertise, cost considerations, ease of sampling requirements and determination, and the nature of other pollutant inputs in the vicinity of the input of interest. Ideally, the sludge tracers chosen should be unique to the input of interest, but this will rarely be achievable in practice. In areas of gross sludge contamination, a marine geophysical survey technique can be used to delineate the area affected and this provides a rapid cost-effective method for large areas.

Amoeba↗

Removal of phenol from aqueous solution by adsorption onto OTMAC-modified attapulgite.

The potential of octodecyl trimethyl ammonium chloride (OTMAC)-modified attapulgite (AT) for phenol adsorption from aqueous solutions was studied. The comparison of natural AT and modified AT showed that it is possible to utilize the sonication-modified OTMAC-AT in the treatment of phenol-contaminated wastewaters. Batch sorption studies were carried out to evaluate the effect of contact time, shaking frequency, temperature and the amount of AT. The results showed that in a lab-scale reactor, at room temperature, with an amount of the modified AT added (2.5 g), and a shaking frequency of 140 rev/min, the adsorption rate of phenol could be 60.4% for a duration of 60 min. The sorption kinetics were described by a pseudo-second-order model, and the values of k and q(e) were 1.367 mg/ig min and 0.7901 ig/mg, respectively. The analysis of equilibrium data showed that the Freundlich isotherms were found to be applicable for the adsorption equilibrium data. K and 1/n were estimated to be 14.53 and 0.8438, respectively.

Adsorption↗

Modification of clay barriers with a cationic surfactant to improve the retention of pesticides in soils.

In this work, the efficiency of reactive clay barriers in the immobilisation of organic pesticides in a sandy soil was studied. Reactive barriers were prepared by modification of montmorillonite, kaolinite and palygorskite clay minerals, and of a clayey soil with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA). Percolation curves of the pesticides linuron, atrazine and metalaxyl of different hydrophobic character, were obtained in columns packed with a natural sandy soil with these barriers intercalated under saturated flow conditions. The cumulative curves in the unmodified soil indicated a leaching of pesticides greater than 85% of the total amount of compound added. After barrier intercalation, the breakthrough curves (BTC) indicated a dramatic decrease in the amounts of linuron leached in all columns and a significant modification of the leaching kinetics of atrazine and metalaxyl. Retardation factors, R, of the pesticides in the columns were significantly correlated with the organic matter content (OM) derived from the ODTMA of the organo clay/soil barriers (r2>or=0.78). Significant correlations were also found between these R factors and the pore volume values corresponding to the maximum peaks of the BTCs (r2=0.83; p<0.01) or the total volumes leached (r2=0.44; p<0.05) for the pesticides atrazine and metalaxyl. The results obtained point to the interest in the use of reactive clay barriers for almost complete immobilisation of hydrophobic pesticides or for decreasing the leaching of moderately hydrophobic pesticides coming from point-like sources of pollution. These barriers would avoid the generation of elevated concentrations of these compounds in the soils due to their rapid washing.

Aluminum Silicates↗

Adsorption studies of a water soluble dye, Reactive Red MF-3B, using sonication-surfactant-modified attapulgite clay.

The removal of water-soluble Reactive Red MF-3B from aqueous media by sonication-surfactant-modified attapulgite clay was studied in a batch system. The surfactant used was octodecyl trimethyl ammonium chloride (OTMAC). Adsorbent characterizations were investigated using X-ray diffraction, infrared spectroscopy, and surface area analysis. The effects of pH, contact time, initial solute concentration, adsorbent dose, and temperature on the adsorption of Reactive Red MF-3B onto modified clay were investigated. On the basis of kinetic studies, specific rate constants involved in the processes were calculated and second-order adsorption kinetics was observed in the case. Film diffusion was found to be the rate-limiting step. Reactive Red MF-3B adsorption was found to increase with increase temperature. The Reactive Red MF-3B equilibrium adsorption data were fitted to Freundlich and Langmuir isotherm models, the former being found to provide the better fit of the experimental data. Thermodynamic parameters were calculated. From the results it can be concluded that the surfactant-modified clay could be a good adsorbent for treating Reactive Red MF-3B-contaminated waters.

Adsorption↗

A Fourier transform infrared spectroscopic study of Mg-rich, Mg-poor and acid leached palygorskites.

The FTIR spectra of pure magnesium-rich (Mg-rich) and magnesium-poor (Mg-poor) palygorskites, before and after short-term (<7 h) and long-term (360 h) acid leaching are presented here. Comparison of decomposition spectra of Mg-rich and Mg-poor palygorskites clearly shows that the absorption peaks related to pairs of octahedral cation differ depending on the octahedral site occupancy. Short-term acid leaching of palygorskites results in significant changes to FTIR absorption bands near 1200 and 790 cm-1. As the acid attack progresses, the band at 1200 cm-1 shifts to lower wavenumbers, whilst the band at 790 cm-1, which here is assigned to SiU-O-SiD symmetrical stretching vibration, shifts to higher wavelengths. Longer-term leaching of palygorskites results in the disappearance of 900-1200 cm-1 absorption bands, showing that the palygorskite has largely decomposed to amorphous silica. Assignments of several other bands have been made as follows: several vibrations relate to OH, i.e. 847 cm-1, hygroscopic water (1635 cm-1), Si-O vibrations 1100, 611-621, 470-481 cm-1, etc. appear in the FTIR spectra of 360 h acid leached palygorskite. Three bands near 1100, 611-621 and 470-481 cm-1 relate to Si-O vibration of an ideal hexagonal (Si2O5)n sheet.

Acids↗

Octamethylcyclotetrasiloxane exhibits estrogenic activity in mice via ERalpha.

Octamethylcyclotetrasiloxane (D4) is a low molecular weight cyclic silicone used in the synthesis of larger silicone polymers and in the formulation of a variety of personal care products. The effects of oral D4 exposure in mice on serum estradiol levels, uterine wet weight, and uterine peroxidase activity were investigated. Additionally, in vitro estrogen receptor binding activity was evaluated. Serum estradiol levels decreased in a dose-dependent manner after exposure to 100 mg/kg to 1000 mg/kg D4. Studies with adrenalectomized animals demonstrated that the decreased serum estradiol levels were not due to elevated serum corticosterone levels. Uterine wet weights in ovariectomized mice were significantly increased in a dose-dependent manner by exposure to 250-1000 mg of D4/kg, but not by exposure to other silicone compounds tested (hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, and octaphenylcyclotetrasiloxane). Uterine peroxidase activity, a marker for estrogenic activity, was also significantly increased in D4-exposed mice, but not in mice exposed to the other siloxanes. Pretreating mice with the estrogen receptor antagonist ICI 182,780 completely blocked the D4-induced increase in uterine weight, and ovariectomized estrogen receptor-alpha knockout mice showed no increases in uterine weights when orally exposed to D4 or estradiol. In an in vitro estrogen receptor binding assay, D4 showed significant competition with (3)H-estradiol for binding to estrogen receptor-alpha, but not estrogen receptor-beta. The data presented here indicate that D4 has weak estrogenic activity, and that these effects are mediated through estrogen receptor-alpha.

Adjuvants, Immunologic↗

Indentation modulus and hardness of whisker-reinforced heat-cured dental resin composites.

OBJECTIVES: Recent studies showed that ceramic whisker reinforcement imparted a two-fold increase in the strength of dental composites. The aim of this study was to investigate the indentation response and measure the elastic modulus, hardness, and brittleness of whisker-reinforced heat-cured resin composites as a function of filler level, heat-cure temperature, and heat-cure duration. METHODS: Silica particles were fused onto silicon nitride whiskers to facilitate silanization and to roughen the whiskers for improved retention in matrix. Whisker filler mass fractions of 0, 20, 40, 60, 70, 74 and 79% were tested. Heat-cure temperature ranged from 100 to 180 degrees C, and duration from 10 min to 24 h. A nano-indentation system enabled the measurement of elastic modulus. Fracture toughness was measured and composite brittleness index was calculated. An inlay/onlay composite and a prosthetic composite were tested as controls. RESULTS: Whisker filler level and heat-cure duration had significant effects on composite properties, while heat-cure temperature had non-significant effects. The whisker composite with 79% filler level had a modulus in GPa (mean (SD); n = 6) of 26.9 (1.0), significantly higher than 15.1 (0.2) of an inlay/onlay control, and 16.1 (0.3) of a prosthetic control (Tukey's multiple comparison test; family confidence coefficient = 0.95). The fracture toughness in MPa.m1/2 was 2.22 (0.26) for the whisker composite, higher than 0.95 (0.11) for inlay/onlay control, and (1.13 +/- 0.19) for prosthetic control. The brittleness index was (0.49 +/- 0.07) for whisker composite, lower than (1.02 +/- 0.12) for inlay/onlay control and (0.63 +/- 0.13) for prosthetic control. SIGNIFICANCE: Whisker filler level had a profound influence, heat-cure duration had significant effects, while temperature did not have significant effects, on the properties of whisker composite. The whisker composite had significantly higher elastic modulus and fracture toughness, and lower brittleness than the inlay/onlay and prosthetic controls.

Analysis of Variance↗

Dental resin composites containing ceramic whiskers and precured glass ionomer particles.

OBJECTIVES: Glass ionomer, resin-modified glass ionomer, and compomer materials are susceptible to brittle fracture and are inadequate for use in large stress-bearing posterior restorations. The aim of this study was to use ceramic single crystal whiskers to reinforce composites formulated with precured glass ionomer, and to examine the effects of whisker-to-precured glass ionomer mass ratio on mechanical properties, fluoride release, and polishability of the composites. METHODS: Silica particles were fused onto silicon nitride whiskers to facilitate silanization and to improve whisker retention in the matrix. Hardened glass ionomer was ground into a fine powder, mixed with whiskers, and used as fillers for a dental resin. Four control materials were also tested: a glass ionomer, a resin-modified glass ionomer, a compomer, and a hybrid composite. A three-point flexural test was used to measure flexural strength, modulus, and work-of-fracture. A fluoride ion-selective electrode was used to measure fluoride release. Composite surfaces polished simulating clinical procedures were examined by SEM and profilometry. RESULTS: At whisker/(whisker + precured glass ionomer) mass fractions of 1.0 and 0.91, the whisker composite had a flexural strength in MPa (mean (SD); n = 6) of (196 (10)) and (150 (16)), respectively, compared to (15 (7)) for glass ionomer, (39 (8)) for resin-modified glass ionomer, (89 (18)) for compomer, and (120 (16)) for hybrid composite. The whisker composite had a cumulative fluoride release of nearly 20% of that of the glass ionomer after 90 days. The whisker composites had surface roughness comparable to the hybrid resin composite. SIGNIFICANCE: Composites filled with precured glass ionomer particles and whiskers exhibit moderate fluoride release with improved mechanical properties; the whisker-to-glass ionomer ratio is a key microstructural parameter that controls fluoride release and mechanical properties.

Acrylic Resins↗

Analysis of the response of planar polarization interferometer to molecular layer formation: fibrinogen adsorption on silicon nitride surface.

The most sensitive optical method of interferometry was exploited for determination of changes in the refractive index following the adsorption of biological molecules onto the solid surface. Instead of having two waveguiding arms (the main and the reference) in traditional Mach-Zhender interferometer, two ortogonal TM and TE modes propagating through the SiO(2)-Si(3)N(4)-SiO(2) waveguide structure were employed in planar polarization interferometer (PPI). Multiperiodic PPI response was, therefore, formed due to the phase shift between TM and TE modes. A matrix simulation procedure was developed in order to investigate the influence of both the refractive index and molecular layer thickness on the PPI response. Nonspecifical binding of fibrinogen to silicon nitride surface was studied as a model object for PPI testing. The results obtained are in good agreement with the known information about fibrinogen adsorption on the different surfaces. An attempt to introduce the concept of 'surface molecular concentration and molecular polariziability' instead of 'molecular layer thickness and refractivity' was undertaken.

Adsorption↗

Photoluminescence from (Si/SiO2)n superlattices and their use as emitters in [SiO2/Si]n SiO2 [Si/SiO2]m microcavities.

Si/SiO2 superlattices are recently under investigation to add optical functionality to silicon based microelectronics. In such superlattices quantum-confinement should drive Si to become a good light emitter. Emission properties can be further improved and controlled by placing the emitter in optical microcavities. In this paper emission properties of (Si/SiO2), superlattices grown by Low Pressure Chemical Vapour Deposition will be compared with the ones obtained by other growth techniques and the origin of the emission will be discussed. Emission properties can be further improved and controlled by placing the emitter in optical microcavities. Optical properties of microcavities produced with standard complementary metal-oxide-semiconductor techniques containing Si/SiO2 superlattices as light emitter will be reviewed and a comparison between properties estimated from calculations and experiments will be given.

Biophysical Phenomena↗

A modular approach to the synthesis of new reagents useful in the chemical synthesis of modified DNA probes: derivatives of 3-(tert-butyldimethylsiloxy)glutaric anhydride as versatile building blocks in the synthesis of new phosphoramidites and modified solid supports.

We present a flexible and cost-efficient synthetic strategy for the preparation of a new family of phosphoramidite and solid-support reagents that can introduce a broad range of modifications into DNA probes. The key intermediate material 3 is synthesized using the inexpensive and commercially available 3-(tert-butyldimethylsiloxy)glutaric anhydride 1 and can be used as common starting material for the preparation of new labeling reagents.

Anhydrides↗

Surface charge heterogeneities measured by atomic force microscopy.

Unfavorable aggregation and deposition of colloidal particles in natural and engineered systems is still a subject of debate. Complicating factors such as surface roughness, secondary minimum aggregation, and the nature of discrete surface charge and surface potential make it difficult to attribute a specific cause to these phenomena. The presence of surface charge heterogeneity and its influence on interaction forces, which are responsible for aggregation and deposition, are studied in this work through the application of atomic force microscopy (AFM). Force-volume-mode AFM was used to map interaction forces on a surface and relate them to surface charge heterogeneities. The experimental system consisted of a silica plate and a standard silicon nitride AFM tip. Copper ions were used for sorption on the silica surface in order to modify the surface charge and cause charge reversal. Different concentrations of copper ions were selected to identify conditions of partial coverage of the silica surface. The pH and ionic strength of the solutions were varied, and the extension of the surface charge modification and its influence on the resulting interaction forces were monitored via AFM force measurements. Depending on the pH and ionic strength, the interaction force was found to change at certain regions on the surface from attraction to either weak or strong repulsion. Force imaging allowed the visual localization of zones of strong repulsive interaction that diminished in size with increasing ionic strength. X-ray photoelectron spectroscopy analysis was used to confirm the presence of copper on the surface. Local charge differences on a surface result in local differences in surface forces, not only in magnitude but also in direction. This behavior may explain the aggregation, deposition, and transport of colloidal particles under unfavorable chemical conditions.

Colloids↗