Identification of Stochastic Multicompartmental Models in Tracer Kinetics Experiments

Two efficient algorithms are described for the estimation of dynamic parameters in a tracer kinetic experiment, when a stochastic multicompartmental model is utilized. The first approach is based on the sensitivity method, where the error between the model output and the system output is minimized. Sensitivity functions are calculated and model outputs are simulated by the algorithm at each iteration in order to estimate the optimal values of the model parameters. The concept of a whitening filter is used in the second method to convert the colored output error into a white sequence: the algorithm minimizes the estimated variance of the filtered sequence. Tests performed using simulated as well as real data confirm the effectiveness of both the techniques.     

Enrichment of H(2)(17)O from tap water, characterization of the enriched water, and properties of several (17)O-labeled compounds

A low-abundance form of water, H(2)(17)O, was enriched from 0.04% to ～90% by slow evaporation and fractional distillation of tap water. The density and refractive index for H(2)(17)O are reported. Gas chromatography-mass spectrometry (GC-MS) of (16)O- and (17)O-1-hexanols and their trimethyl silyl ethers and of (16)O- and (17)O-hexamethyl disiloxanes was used to determine the percentage of (17)O enrichment in the H(2)(17)O. Furthermore, the chemical shifts of labeled and nonlabeled water dissolved in CDCl(3) differed sufficiently that we could verify the enrichment of H(2)(17)O. (17)O hexanol was synthesized by the reaction of iodohexane with Na(17)OH. (17)O-Labeled trimethylsilanol and (17)O-labeled hexamethyldisiloxane were prepared by the reaction of H(2)(17)O with bis(trimethylsilyl)trifluoroacetamide (BSTFA). To generate standards for (17)O NMR, H(2)(17)O(2), and (17)O camphor were prepared. H(2)(17)O was electrolyzed to form (17)O-labeled hydrogen peroxide which was quantified using two colorimetric assays. (17)O-Labeled camphor was prepared by exchanging the ketone oxygen of camphor using H(2)(17)O. The (17)O-labeled compounds were characterized using (17)O, (1)H, and (13)C NMR and GC-MS. While we were characterizing the labeled camphor, we also detected an unexpected oxygen exchange reaction of primary alcohols, catalyzed by electrophilic ketones such as camphor. The reaction is a displacement of the alcohol OH group by water. This is an example of the usefulness of (17)O NMR in the study of a reaction mechanism that has not been noticed previously.     

Structural properties of amorphous hydrogenated silicon usingab initio molecular dynamics simulations

We have studied structural properties of amorphous hydrogenated silicon usingab initio molecular dynamics simulations. A sample was generated by simulated annealing using periodic boundary conditions with a supercell containing 64 silicon and 8 hydrogen atoms. The radial pair distribution functions for Si-Si, Si-H and H-H have been studied at 300 K and are found to be in good agreement with experimental data. Our results show that hydrogen saturates the dangling bonds and reduces bond strain. We also report existence of Si-H-Si bridge sites which are likely to play an important role in understanding the light induced metastability in this material.     

Studies of cryotreatment on the performance of integral diaphragm pressure transducers for space application

The integral diaphragm pressure transducers machined out of precipitation hardened martensite stainless steel (APX4) are widely used for propellant pressure measurements in space applications. These transducers are expected to exhibit dimensional stability and linearity for their entire useful life. These vital factors are very critical for the reliable performance and dependability of the pressure transducers. However, these transducers invariably develop internal stresses during various stages of machining. These stresses have an adverse effect on the performance of the transducers causing deviation from linearity. In order to eliminate these possibilities, it was planned to cryotreat the machined transducers to improve both the long-term linearity and dimensional stability. To study these effects, an experimental cryotreatment unit was designed and developed based on the concept of indirect cooling using the concept of cold nitrogen gas forced closed loop convection currents. The system has the capability of cryotreating large number of samples for varied rates of cooling, soaking and warm-up. After obtaining the initial levels of residual stress and retained austenite using X-ray diffraction techniques, the pressure transducers were cryotreated at 98 K for 36 h. Immediately after cryotreatment, the transducers were tempered at 510 °C for 3 h in vacuum furnace. Results after cryo treatment clearly indicated significant reduction in residual stress levels and conversion of retained austenite to martensite. These changes have brought in improvements in long term zero drift and dimensional stability. The cryotreated pressure transducers have been incorporated for actual space applications.     

Pervaporation of chlorinated hydrocarbon-acetone mixtures through poly(ethylene-co-vinyl acetate) membranes

Crosslinked and uncrosslinked ethylene-vinyl acetate copolymer membranes were prepared. The permeation characteristics in the pervaporation process were examined using carbon tetrachloride-acetone mixtures. Modified membranes exhibit carbon tetrachloride permselectivity, but unmodified membranes did not display the permselectivity of crosslinked polymer. Furthermore, membranes modified with dicumyl peroxide (DCP) showed a higher flux and selectivity than those of benzoyl peroxide (BP) modified ones. The effects of feed concentration, molecular size, and polarity of the permeating species on pervaporation were analyzed. The influence of crosslinking density of the membranes on pervaporation was also analyzed. The maximum separation and flux were found to be associated with an optimum amount of crosslinking agent in the membrane. A mixture of chloroform and acetone having a composition near the azeotropic region was also separated by the pervaporation technique. © 1996 John Wiley & Sons, Inc.     

A quantitative analysis of low density polyethylene and linear low density polyethylene blends by differential scanning calorimetery and fourier transform infrared spectroscopy methods

Blends of low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are widely used for blown film applications. An accurate and rapid test scheme to identify the type and composition of α-olefin in LDPE/LLDPE blends has been developed that utilizes differential scanning calorimetery (DSC) and Fourier transform infrared (FTIR) spectroscopy techniques. The melting point of LDPE varies with density and usually is in the range of 106°C to 112°C for film grade resins. The DSC thermogram of LLDPE is characterized by a broad range of melting peaks with a lower melting peak around 106°C to 110°C and a higher one in the range of 120°C to 124°C. In a blend with LDPE, the ratio of the two endothermic peak heights changes. At a given weight percent of LDPE, this ratio depends on the type of LLDPE (i.e., the comonomer used). Separate calibrations for butene-1, hexene-1, and octene-1 LLDPEs have been developed to quantify the blend composition from DSC thermograms where the α-olefin type is successfully identified by FTIR over the entire blend composition range. The calibration curves are applicable to narrow melt index (MI) and density range conventional film grade LDPE and LLDPE resins and are not intended to be used for the metallocene type LLDPEs.     

Hydrogen-transfer catalytic activity of minerals common to coal

The hydrogenation/dehydrogenation catalytic activity of minerals commonly present in coal was investigated. The extent of reaction undergone by the model hydrogen-transfer system tetralin/1,2-dihydronaphthalene/naphthalene at 400 °C in the presence of these minerals was used to measure the catalytic activity. For the four most active minerals, the order of catalytic activity per gram of mineral, for a given range of particle size, is limonites > pyrites > diaspore > magnetites. The pure chemical analog of the limonites, Fe₂O₃, was found to have catalytic activity similar to that of the limonites. Heating the minerals at 400 °C before running the reaction was found to decrease these catalytic activities, despite the surface-area increases resulting from the annealing process. The catalytic activity per unit area of mineral was determined and used as an index of the catalytic activity of the reactive sites for these heterogeneous systems. The order of decreasing site catalytic activity for the more active minerals is pyrites > magnetites > diaspore > limonites. The observed mineral/ chemical compound catalytic activities indicate that the more reactive mineral hydrogenation/ dehydrogenation catalytic sites are composed of iron compounds.     

Molecular Cross-Talk between Gravity- and Light-Sensing Mechanisms in Euglena gracilis

Euglena gracilis is a photosynthetic flagellate. To acquire a suitable position in its surrounding aquatic environment, it exploits light and gravity primarily as environmental cues. Several physiological studies have indicated a fine-tuned relationship between gravity sensing (gravitaxis) and light sensing in E. gracilis. However, the underlying molecular mechanism is largely unknown. The photoreceptor photoactivated adenylyl cyclase (PAC) has been studied for over a decade. Nevertheless, no direct/indirect interaction partner (upstream/downstream) has been reported for PAC. It has been shown that a specific protein, kinase A (PKA), showed to be involved in phototaxis and gravitaxis. The current study reports the localization of the specific PKA and its relationship with PAC.