Nuclear magnetic resonance of brute force oriented110mAgAg

NMR on brute force oriented nuclei (NMRON/BF) has been observed for^110mAg in elemental silver. Resonances have been measured at approximately 7 T and 8 T with the resulting gradient of 4.583(5) MHzT⁻¹ which produces a value for the^110mAg moment of μ=3.589(4) nm (uncorrected). Factors pertinent to successful NMRON/BF in systems such as^110mAgAg, with a complex decay scheme and modestg-factor, are also discussed.     

Crystallization and ordering of complex oxide structures. I. “Splat-cooled” Nb2O5TiO2

“Splat-cooled” Nb₂O₅TiO₂ with a melt composition corresponding to TiNb₃₈O₉₇ has been examined by high-resolution electron microscopy and electron diffraction. Previous X-ray work showed this material to be crystalline, despite a cooling rate of about 10⁵ °C sec^?1. The present study reveals a variety of structures ranging from highly ordered block structures to severely disordered regions of uncertain structure and composition. “Double layer” structures are identified, and subtle contrast variations in their crystals are explained in terms of single jogs of overlap structures. Crystallization processes are discussed in the light of these results.     

Time domain investigation on vibrational dephasing and spectral diffusion in CO-doped solid N2

Infrared picosecond accumulated photon echo experiments have been performed for the first time, using the Orsay Free Electron Laser, on the v = 0-->v = 1 transition of CO in solid nitrogen. The vibrational dephasing time is found to be exceptionally long ( T2>/=120 ns) at low temperature. The analysis of the observed spectral diffusion leads one to assume different energy transfer mechanisms depending on the CO concentration.     

Electron spin relaxation time measurements using radiofrequency longitudinally detected ESR and application in oximetry

Longitudinally detected ESR (LODESR) involves transverse ESR irradiation with a modulated source and observing oscillations in the spin magnetization parallel to the main magnetic field. In this study, radiofrequency-LODESR was used for oximetry by measuring the relaxation times of the electron. T1e and T2e were measured by investigating LODESR signal magnitude as a function of detection frequency. We have also predicted theoretically and verified experimentally the LODESR signal phase dependence on detection frequency and relaxation times. These methods are valid even for inhomogeneous lines provided that T1e>T2e. We have also developed a new method for measuring T1e, valid for inhomogeneous spectra, for all values of T1e and T2e, based on measuring the spectral area as a function of detection frequency. We have measured T1e and T2e for lithium phthalocyanine crystals, for the nitroxide TEMPOL, and for the single line agent Triarylmethyl (TAM). Furthermore, we have collected spectra from aqueous solutions of TEMPOL and TAM at different oxygen concentrations and confirmed that T1e values are reduced with increased oxygen concentration. We have also measured the spin-lattice electronic relaxation time for degassed aqueous solutions of the same agents at different agent concentrations. T1e decreases as a function of concentration for TAM while it remains independent of free radical concentration for TEMPOL, a major advantage for oxygen mapping. This method, combined with the ability of LODESR to provide images of exogenous free radicals in vivo, presents an attractive alternative to the conventional transverse ESR linewidth based oximetry methods.     

Synthesis of the C21-C34 fragment of antascomicin B

The C21-C34 fragment of the potent FKBP12-binding macrolide antascomicin B was prepared using Ireland-Claisen and allylic diazene rearrangements to establish the C26/C27 and the C23 stereocenters, respectively. Directed hydrogenation installed the C29 β-configuration. The fragment possesses 7 of the 11 fixed stereocenters contained in the natural product.     

Rapid fusion method for determination of actinides in fecal samples

A new rapid fusion method for the determination of actinides in fecal samples has been developed at the Savannah River National Laboratory that can be used for emergency response or routine bioassay analyses. If a radiological dispersive device, improvised nuclear device or nuclear accident occur, there will be an urgent need for rapid analyses of environmental, food and bioassay matrices. If an inhalation event occurs and there is confirmed radionuclide activity present via urine analyses of individuals, fecal analyses will typically be required to determine the soluble/insoluble fraction of actinides present as a result of the event to allow a more reliable estimate of radiological dose. The new method for actinides in fecal samples uses accelerated furnace heating, a rapid sodium hydroxide fusion method, a lanthanum fluoride matrix removal step, and a column separation process with stacked TEVA, TRU and DGA resin cartridges. The rapid fusion method provides rugged digestion of any refractory particles present, essential for reliable analysis of actinides in fecal samples. Alpha spectrometry was used to determine the actinide isotopes, but this method can be adapted for assay by inductively-coupled plasma mass spectrometry for actinide isotopes with longer half-lives that have sufficient mass to allow measurement. The method showed high chemical recoveries and effective removal of interferences. The determination of actinides in fecal samples can be performed in less than 12 h in an emergency with excellent quality for emergency samples. The new method, which is much less tedious and time-consuming than other reported methods, can be used for emergency or routine fecal sample analyses. This enables more timely estimates of radiological dose to be performed that utilize soluble/insoluble actinide ratios.