A note on the "split oil drop" technique.
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High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NCG 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.
An oscillator pore is identified that generates intermittent, large amplitude, ionic current in the plasma membrane. The pore is thought to be composed of 10-12 units of subunit c of ATP synthase. Pore opening and closing is a co-operative process, dependent on the release, or binding, of as many as six calcium ions. This mechanism suggests a more general method of co-operative threshold detection of chemical agents via protein modification, the output being directly amplified in a circuit. Here the authors describe steps in the development of a sensor of chemical agents. The subunit c pore in a lipid bilayer spans a nanometer-scale hole in a silicon nitride barrier. Either side of the barrier are electrolyte solutions and current through the pore is amplified by circuitry. The techniques of laser ablation, electron beam lithography and ion beam milling are used to make successively smaller holes to carry the lipid patch. Holes of diameter as small as 20 nm are engineered in a silicon nitride barrier and protein activity in lipid membranes spanning holes as small as 30 nm in diameter is measured. The signal-to-noise ratio of the ionic current is improved by various measures that reduce the effective capacitance of the barrier. Some limits to scale reduction are discussed.
A sensitive and accurate method for detection and quantitation of deuterated fatty acids in the presence of large amounts of unlabeled fatty acids is described using mass fragmentography in combination with the preparation of tertiarybutyldimethylsilyl esters (t-BDMS). The method has been applied to determination of deuterated stearic, oleic, elaidic and linoleic acids in human plasma lipoproteins following duodenal perfusion with a micellar mixture of acids. Over a concentration range of 10-1000 ng/ml, the average coefficient of variation for the linoleate was 3% and for the oleate (elaidate) ester was 2%.
A sensitive high-performance liquid chromatographic assay was developed using chloride attachment negative chemical ionization mass spectrometry for detection of glyceryl esters and ceramides, and positive chemical ionization mass spectrometry for detection of free cholesterol and cholesteryl esters in minimal quantities of plasma. The novel technique was validated by high temperature gas-liquid chromatography with flame ionization detection. Sample preparation was achieved by phospholipase C digestion of whole plasma, total lipid extraction and derivatization of any free carboxyl and hydroxyl groups by trimethyl- or tert-butyldimethyl-chlorosilane. The lipids were separated by reverse phase HPLC with 20-90% propionitrile in acetonitrile containing 1% dichloromethane, which served as the reagent and the source of chloride. Negative chemical ionization with chloride attachment is estimated to provide about 100 times higher response for the triacylglycerols and the trimethylsilyl or tert-butyldimethylsilyl ethers of diacylglycerols, and about 500 times higher response for the trimethylsilyl or tert-butyldimethylsilyl ethers of ceramides than positive chemical ionization mass spectrometry. Determination of the full negative chemical ionization mass spectra showed that each glycerolipid and ceramide species yielded a single ionic species corresponding to the chloride-attachment product of the parent ion. The cholesteryl esters and ethers failed to attach chloride and remained undetected by negative chemical ionization. However, the cholesteryl esters and ethers gave a high response for the steroid nucleus in positive chemical ionization mass spectrometry. Chloride attachment negative chemical ionization mass spectrometry is suitable for the unequivocal identification of plasma glycerolipids and ceramides in high-performance liquid chromatography and for the quantitation of molecular species in any unresolved peaks following appropriate calibration of the instrument response.
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BACKGROUND: The favorable properties of silicon nitride (Si3N4) ceramic, such as high stability and biocompatibility suggest its biomedical use as an implant material. The aim of this study was to test its suitability for osteosynthesis. MATERIALS AND METHODS: A Si3N4 prototype minifixation system was manufactured and implanted for osteosynthesis of artificial frontal bone defects in three minipigs. After 3 months, histological sections, CT and MRI scans were obtained. Finite element modeling (FEM) was used to simulate stresses and strains on Si3N4 miniplates and screws to calculate survival probabilities. RESULTS: Si3N4 miniplates and screws showed satisfactory intraoperative workability. There was no implant loss, displacement or fracture. Bone healing was complete in all animals and formation of new bone was observed in direct contact to the implants. CONCLUSIONS: Si3N4 ceramic showed a good biocompatibility outcome both in vitro and in vivo. This ceramic may serve as biomaterial for osteosynthesis, e.g. of the midface including reconstruction of the floor of the orbit and the skull base. Advantages compared to titanium are no risk of implantation to bone with mucosal attachment, no need for explantation, no interference with radiological imaging.
Gate oxynitride structures of TFT-LCDs were investigated by SIMS, and successful solutions are demonstrated to overcome difficulties arising due to the charging effects of the multilayer systems, the matrix effect of the method, and the small pattern sizes of the samples. Because of the excellent reproducibility achieved by applying exponential relative sensitivity functions for quantitative analysis, minor differences in the barrier gate-oxynitride composition deposited on molybdenum capped aluminium-neodymium metallisation electrodes were determined between the centre and the edge of the TFT-LCD substrates. No differences were found for molybdenum-tungsten metallisations. Furthermore, at the edge of the glass substrates, aluminium, neodymium, and molybdenum SIMS depth profiles show an exponential trend. With TEM micrographs an inhomogeneous thickness of the molybdenum capping is revealed as the source of this effect, which influences the electrical behaviour of the device. The production process was improved after these results and the aging behaviour of TFT-LCDs was investigated in order to explain the change in control voltage occurring during the lifetime of the displays. SIMS and TEM show an enrichment of neodymium at the interface to the molybdenum layer, confirming good diffusion protection of the molybdenum barrier during accelerated aging. The reason for the shift of the control voltage was finally located by semi-quantitative depth profiling of the sodium diffusion originating from the glass substrate. Molybdenum-tungsten was a much better buffer for the highly-mobile charge carriers than aluminium-neodymium. Best results were achieved with PVD silicon oxynitride as diffusion barrier and gate insulator deposited on aluminium-neodymium metallisation layers.
Two potash-lime-silica model glasses with compositions similar to those of medieval stained glass were exposed at 26 test sites all over Europe and in North America for 3-6 years. The objectives of this large-scale field exposure programme were: (a) a qualitative analysis of the weathering products formed on the surface of the samples in the (environmental) scanning electron microscope in combination with energy dispersive X-ray microanalysis (ESEM/EDX or SEM/EDX, respectively); (b) a statistical evaluation of the weathering phenomena by applying a multiple linear regression (MLR) analysis to find correlations between the degree of weathering, which was measured in terms of surface coverage with reaction products, and environmental parameters such as the concentration (c) of the acidifying gases SO(2), NO(2) and O(3), the temperature (T) and the relative humidity (RH); and (c) the calculation of a time-dependence function of the weathering process of these glasses. Mainly sulfates of calcium and potassium such as gypsum (CaSO(4).2 H(2)O), arcanite (K(2)SO(4)) and syngenite (CaSO(4).K(2)SO(4).H(2)O) could be identified in the SEM and ESEM. Carbonates, nitrates and many particles deposited on the glass surface were found as well. MLR calculations exhibit significant dependencies of the degree of weathering on T, RH, c(NO(x)), c(SO(2)) and c(O(3)). Applying a time-dependence function of the general form y= a. t(b) (t=time) results in a value of approximately 0.42 for the exponent b, which comes close to values expected from various studies in the literature.
A method has been developed for the chromatographic determination of methanethiol (MT) and ethanethiol (ET) as contaminants in amino acid parenteral nutrition (PN) solutions. The clean-up of the samples before chromatographic analysis was investigated by solid-phase extraction (SPE) on pre-columns filled with polyethylene powder (PE), aluminium oxide (AlOx), silica (SiOx), or polyurethane foam (PUF) as adsorbents. The thiols were more efficiently separated from the matrices by SPE on PUF pre-columns. Simultaneous derivatization and elution with DTNB (5,5'-dithiobis(2-nitrobenzoic acid)) enabled further discrimination between MT and ET by reversed-phase HPLC with spectrophotometric detection. The retention times for the derivatized MT and ET species were 12.5 and 23.0 min, respectively. Recoveries from spiked PN samples were calculated to be approximately 90%, and the MT and ET content of commercial PN solutions was determined using the methodology described. Detection limits of 15 and 10 microg L(-1) were calculated for MT and ET, respectively.
An inductively coupled plasma-high resolution isotope dilution mass spectrometric (ICP-HRIDMS) method in combination with a microwave-assisted decomposition technique has been developed for the determination of traces of silicon in biological and clinical samples. A 30Si-enriched spike solution was used for the isotope dilution step. Decomposition of the samples was achieved by use either of HNO3 or a mixture of HNO3 and HF. By application of both methods of digestion to the same sample it was possible to differentiate between a poorly soluble silicate fraction and an HNO3-soluble silicon species. Traces of silicon were determined in different reference materials, which are not certified for this element, and in other biological and clinical samples. A concentration range of 1-600 microgram g(-1) was covered by the different samples. For homogeneous samples relative standard deviations of 2-4% were obtained. The detection limit was strongly affected by the blank. In this connection purification of water, used in the analytical procedure, was especially critical. The blank contribution of the ICP-MS instrument could be minimized by applying a nebulizer and a spray chamber made of PFA, a sapphire injection tube, and a silicon nitride torch. Under these conditions detection limits of 0.15 microgram g(-1) and 0.2 microgram g(-1) were obtained for the HNO3 and HNO3-HF digestion methods, respectively, when a sample weight of 0.5 g was used. With regard to expected silicon content this enables determination in almost all biological and clinical samples. The ICP-HRIDMS results were compared with those recently obtained in an interlaboratory study. This isotope-dilution method is an potential option for certification of silicon in reference materials, a method for which is still required.
Laboratory biobarriers were evaluated for their ability to remove selenite from flowing groundwater. Microbial activity in aquifers is usually limited by substrate availability, and biobarriers stimulate microbial activity by providing a substrate; for these studies soybean oil was used. Water containing 10 mg L(-1) selenite-Se was pumped through the biobarriers for 74 days and the amount present in the effluent monitored. The amounts remained high for the first 2 weeks of the study but then declined. From day 28 until the end of the study the amount of selenite-Se in the column effluents averaged 0.20 +/- 0.04 mg L(-1), a decrease of approximately 98%. At the end of the study about half of the selenite-Se applied to the columns was recovered as immobilized selenium trapped by the biobarrier. This study suggests that biobarriers containing vegetable oil might be used as a process for removing selenite from contaminated groundwater.
UNLABELLED: Nephrocalcinosis and/or urinary calculi are rare in infants. Furosemide treatment during the neonatal period, vitamin D intoxication, hereditary diseases such as hyperoxaluria or distal tubular acidosis are among the most common aetiologies. We report the case of a 6-month-old boy with an extra-hepatic biliary duct atresia treated by the Kasai procedure and a gastro-oesophageal reflux treated with a silicate containing milk thickener (Gelopectose, 5.5% colloidal silicate) since the neonatal period. He did not present any other endogenous risk factor for urinary stone formation (normal urinary calcium/creatinine ratio; normal urinary magnesium excretion). The nephrolithiasis was discovered as the boy presented painful episodes of macroscopic haematuria. Ultrasound examination revealed bilateral nephrocalcinosis and multiple bilateral calculi without infection or urinary obstruction. Infrared spectroscopy revealed silicate as the major component suggesting silicate absorption to be responsible for the described symptoms. After replacement of the silicate-containing agent by a silicate-free milk thickener, the lesions were completely reversible as confirmed by repeated renal ultrasound examinations over a 2-month period. CONCLUSION: Silicate-containing milk thickeners can be responsible for urinary calculi and/or nephrocalcinosis.
Syagrus coronata is an economically important palm tree grown as an ornament, for the oil extracted from its seeds, and the wax from its leaves which has several applications in industry. Silicon biocomposites were analyzed in leaves of S. coronata. Silica bodies were found as extracellular silica masses between the hypodermal-layer cell walls and in granules present in the vacuoles of palisade cells. Scanning electron microscopy of the hypodermal layer of cells showed a collection of spherical bodies embedded in enveloping cavities that outlined the general structure of the bodies. Globular subunits with sharp edges formed the spherical bodies that ranged from 6 to 10 microm in diameter (average, 7.8 microm). X-ray microanalysis detected only silicon and oxygen homogeneously distributed throughout the bodies. Vacuoles of palisade cells contained a large number of granules ranging from 20 nm to 1.2 microm in size (average, 300 nm). Transmission electron microscopy associated with electron spectroscopic imaging and electron energy loss spectroscopy were used to determine the elemental composition of the granules. Vacuolar granules were amorphous and composed of silicon and oxygen, suggesting they consist of amorphous silica biominerals. No nitrogen, indicative of organic matter, was detected in the granules.
A field investigation was conducted at all water treatment plants throughout 11 states and Federal Territory in Peninsular Malaysia. The sampling points in this study include treatment plant operation, service reservoir outlet and auxiliary outlet point at the water pipelines. Analysis was performed by solid phase micro-extraction technique with a 100 microm polydimethylsiloxane fibre using gas chromatography with mass spectrometry detection to analyse 54 volatile organic compounds (VOCs) of different chemical families in drinking water. The concentration of VOCs ranged from undetectable to 230.2 microg/l. Among all of the VOCs species, chloroform has the highest concentration and was detected in all drinking water samples. Average concentrations of total trihalomethanes (THMs) were almost similar among all states which were in the range of 28.4--33.0 microg/l. Apart from THMs, other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichloro - benzene. Principal component analysis (PCA) with the aid of varimax rotation, and parallel factor analysis (PARAFAC) method were used to statistically verify the correlation between VOCs and the source of pollution. The multivariate analysis pointed out that the maintenance of auxiliary pipelines in the distribution systems is vital as it can become significant point source pollution to Malaysian drinking water.
Alumina and Ti6Al4V alloys are widely used for orthopedics and dental applications due to their good mechanical properties and biocompatibility. Unfortunately they can not provide a satisfactory osteointegration when implanted. In fact, both alumina and Ti6Al4V are not bioactive and thus they can only guarantee a morphological fixation with the surrounding tissues without a suitable chemical anchorage. Aiming to impart bioactive properties to these materials a coating can be proposed. At this purpose, a bioactive glass belonging to the SiO2-CaO-K2O system was selected and prepared. This glass, named SCK, possess a thermal expansion coefficient matching with the alumina (8.5x 10(- 6)/ degrees C) and Ti6Al4V (9 x 10(- 6)/ degrees C) ones and thus is a good candidate to produce coatings on both of them. Simple and low-cost enameling and glazing techniques were used to realize the coatings. Structural, morphological and compositional characterizations of the coatings were carried out by means of X-ray diffraction, optical and scanning microscopy and compositional analyses. The in vitro properties of the coatings were investigated by soaking them in a simulated body fluid (SBF) in order to study the precipitation, on their surfaces, of a biologically active layer of hydroxylapatite (HAp).
Ab initio density functional plane-wave calculations are performed on silicon-substituted hydroxyapatite (SiHA). Formation energies are obtained for the substitution of a phosphorus atom by a silicon atom in each of the six phosphate groups of the unit cell in turn. It is found that the co-removal of a hydroxyl group to maintain charge neutrality is energetically favourable and the calculated unit cell volumes for the single silicon substitutions agree extremely well with experimental observation. The substitution of a second silicon atom in the unit cell is found to be almost as energetically favourable as the first (and on one site more favourable) and there can be an attractive interaction between the two Si substituents when they are closely separated. However, experimental observation suggests that for this concentration of silicon a phase transformation to a different structure occurs which, because of the imposed boundary conditions, could not be accessed in the calculations. The density of states of the SiHA indicates that new states are introduced deep into the valence band and the band gap decreases by 1.6 eV compared to phase-pure HA. No new states are introduced into the band gap indicating that the Si incorporation does not make the material inherently electrically active. Furthermore a population analysis shows that the Si impurity has only a small effect on the neighbouring ionic charge.
Highly bioactive scaffolds for tissue engineering were synthesized using a glass belonging to the SiO2-CaO-K2O (SCK) system. The glass SCK was prepared by a traditional melting-quenching route and its bioactivity was assessed by in vitro tests in a simulated body fluid (SBF). The glass was ground and sieved to obtain powders of specific size that were subsequently mixed with polyethylene particles of two different dimensions. The powders were then uniaxially pressed to obtain a crack free green compact that was thermally treated to remove the organic component and to sinter the inorganic phase. The obtained biomaterial was characterised by means of X-ray Diffraction, SEM equipped with EDS, mercury intrusion porosimetry, density measurements, image analysis, mechanical tests and in vitro evaluations. A glass-ceramic macroporous scaffold with a homogenously distributed and highly interconnected porosity was obtained. The amount and size of the introduced porosity could be tailored using various amounts of polyethylene powders of different size.