Formation and emission of tetraalkylammonium salt molecular ions sputtered from a gelatin matrix

A gelatin matrix was simultaneously doped with nine equimolar, homologous, tetraalkylammonium salts ranging in mass from 210 to 700 Da. Bombardment of the sample with kiloelectronvolt ions resulted in a nonidentical distribution of relative cation intensities with a maximum at m/z 242 for samples with a total salt concentration of 0.004 g of salt/g of gelatin. A rapid increase in relative intensities with increasing mass is observed for the low mass salts and is believed to be linked to changes in the ionization efficiencies. The changes in ionization efficiencies are likely related to decreasing coulombic attractive forces between the organic cation and the counterion. Disappearance cross-sections, determined from decay curves, indicate that sputter-induced damage increases with increasing mass of the cation. Fragment-to-intact cation ratios also suggest that damage accumulates fastest in the heaviest salts. These observations indicate that desorption yields of the organic salts in a gelatin matrix decrease with increasing mass. In addition, suppression of lower mass tetraalkylammonium salt intact cation intensities was observed for salt-in-gelatin concentrations greater than 10⁻³ g/g.     

A kinetic model for predicting oxidative degradation rates in combined radiation-thermal environments

The complex degradation behavior of a poly(vinyl chloride) (PVC) cable jacketing material in combined radiation/temperature/air aging environments is experimentally separated into two dominant radiation dose-rate effect mechanisms. The first, operative at high dose rates, involves diffusion-limited oxidation, which leads to heterogeneously oxidized samples. The second, important at low dose rates, involves thermally-induced breakdown of intermediate peroxides. In the homogeneous degradation regime, a theoretical kinetic model is derived which, based on experimental evidence, assumes unimolecular termination kinetics and rate-determining, hydroperoxide-mediated branching reactions. Dependent upon the ratio of particular rate constants, the model predicts that dose-rate effects will either continue to increase or eventually disappear as the dose rate is lowered. Theoretical analysis of sequential (radiation followed by temperature exposures) aging experiments allows a time–temperature–dose rate shifting procedure to be developed. Using this procedure, higher temperature combined environment results can be shifted to a lower reference temperature, thereby extending the lower temperature results to lower (and experimentally inaccessible) dose rates. By applying this procedure to experimental PVC data, evidence in support of the theoretical model is obtained. In addition, model predictions are shown to agree with 12-year real-time aging results.     

Speckle imaging of spin fluctuations in a strongly interacting Fermi gas

Spin fluctuations and density fluctuations are studied for a two-component gas of strongly interacting fermions along the Bose-Einstein condensate-BCS crossover. This is done by in?situ imaging of dispersive speckle patterns. Compressibility and magnetic susceptibility are determined from the measured fluctuations. This new sensitive method easily resolves a tenfold suppression of spin fluctuations below shot noise due to pairing, and can be applied to novel magnetic phases in optical lattices.     

Chemiluminescence as a condition monitoring method for thermal aging and lifetime prediction of an HTPB elastomer

Chemiluminescence (CL) has been applied as a condition monitoring technique to assess aging related changes in a hydroxyl-terminated-polybutadiene based polyurethane elastomer. Initial thermal aging of this polymer was conducted between 110 and 50 °C. Two CL methods were applied to examine the degradative changes that had occurred in these aged samples: isothermal “wear-out” experiments under oxygen yielding initial CL intensity and “wear-out” time data, and temperature ramp experiments under inert conditions as a measure of previously accumulated hydroperoxides or other reactive species. The sensitivities of these CL features to prior aging exposure of the polymer were evaluated on the basis of qualifying this method as a quick screening technique for quantification of degradation levels. Both the techniques yielded data representing the aging trends in this material via correlation with mechanical property changes. Initial CL rates from the isothermal experiments are the most sensitive and suitable approach for documenting material changes during the early part of thermal aging.     

Ninhydrin as a building block for yohimbanones, β-carbolines, and oxyprotoberberines

Condensation of ninhydrin with tryptamide or tryptamine followed by Lewis acid-induced rearrangement provided yohimbanones that were readily converted to β-carbolines via oxidative ring cleavage. The analogous condensation-rearrangement with 3,4-dimethoxyphenethylamine and ninhydrin afforded an oxyprotoberberine, which was further oxygenated at the 13a position.     

Combined environment aging effects: Radiation-thermal degradation of polyvinylchloride and polyethylene

Results are presented for a case of polymer aging in which powerful synergisms are found between radiation and temperature. This effect was observed with formulations of polyvinylchloride and polyethylene and occurred in simultaneous and Sequential radiation-thermal experiments. Dose rate dependencies, which appear to be mechanistically related to the synergism, were also found. The evidence indicates that these aging effects are mediated by a thermally induced breakdown of peroxides initially formed by the radiation. Similar effects could be important to material degradation in a variety of other types of combined-stress environment. A new technique, which uses PH₃ treatment of intact polymer specimens to test for the importance of peroxide is the pathway that leads to changes in macroscopic tensile properties, is described.     

The methyl group as phosphate protecting group in nucleotide syntheses

A novel method is described for the removal of a methyl protecting group from phosphotriesters in oligonucleotides.     

Fabrication of polymer microsphere particle standards containing trace explosives using an oil/water emulsion solvent extraction piezoelectric printing process

We present a methodology for fabricating polymer microspheres using inkjet printing of a biodegradable polymer containing either high explosives or high explosive simulant. Poly(dl-lactide/glycolide) 85:15 (PLGA) microsphere production is based on an oil/water emulsion solvent extraction process. The inkjet printing process allows for precise control of the microsphere diameter and the chemical composition. The microspheres can be used as calibrants or verification standards for explosives trace detection instruments. Gas chromatography/mass spectrometry analysis demonstrated that the composition of the microspheres was consistent with predicted concentrations based on the amount of analyte incorporated into the polymer solution and the inkjet operating parameters. We have demonstrated that the microspheres can be fabricated with a mass fraction of 70% of an analyte compound.