Radiochronological age of a uranium metal sample from an abandoned facility

A piece of scrap uranium metal bar buried in the dirt floor of an old, abandoned metal rolling mill was analyzed using multi-collector inductively coupled plasma mass spectroscopy (MC-ICP-MS). The mill rolled uranium rods in the 1940 and 1950s. Samples of the contaminated dirt in which the bar was buried were also analyzed. The isotopic composition of uranium in the bar and dirt samples were both the same as natural uranium, though a few samples of dirt also contained recycled uranium; likely a result of contamination with other material rolled at the mill. The time elapsed since the uranium metal bar was last purified can be determined by the in-growth of the isotope ²³⁰Th from the decay of ²³⁴U, assuming that only uranium isotopes were present in the bar after purification. The age of the metal bar was determined to be 61 years at the time of this analysis and corresponds to a purification date of July 1950 ± 1.5 years.     

Eukaryotic Selenocysteine Incorporation: Mechanistic Insights

Cotranslational insertion of selenocysteine occurs in both prokaryotic and eukaryotic organisms. For the most part, what is known about this process in eukaryotes has been derived from extensive analysis of the RNA requirements for selenocysteine incorporation. Studies which have defined the selenocysteine insertion sequence (SECIS) element, identified its critical sequence and structural motifs, and established constraints on its spatial relationship with the UGA selenocysteine codon, have given mechanistic insights into this critical process.     

Generation and trapping of the 4-biphenylyloxenium ion by water and azide: comparisons with the 4-biphenylylnitrenium ion

Generation of the 4-biphenylyloxenium ion, 1a, from hydrolysis of 4-acetoxy-4-phenyl-2,5-cyclohexadienone, 2a, is demonstrated by common ion rate depression and azide trapping. The ion is less selective with a shorter lifetime (12 ns at 30 degrees C) in aqueous solution than the corresponding nitrenium ion, 6a (ca 0.3 mus at 30 degrees C). Its lifetime is considerably longer than those of structurally related carbenium ions. Unlike 6a, 1a reacts with N3-, in part, at the distal ring to generate 4'-azido-4-hydroxybiphenyl, 5. These results are rationalized by calculations at the HF/6-31G* and pBP/DN*//HF/6-31G* levels that show that 1a is planar but is less stable than 6a relative to their hydration products by ca. 12 kcal/mol. The p-tolyloxenium ion, 1b, has not been unequivocally demonstrated to be formed in H2O, but kinetic data show that it must be at least 104-fold less stable than 1a relative to their respective 4-acetoxy derivatives. It is also calculated to be ca. 19 kcal/mol less stable than the corresponding nitrenium ion, 6b, relative to their hydration products.     

Polymer micelles with crystalline cores for thermally triggered release

Interest in the use of poly(ethylene glycol)-b-polycaprolactone diblock copolymers in a targeted, magnetically triggered drug delivery system has led to this study of the phase behavior of the polycaprolactone core. Four different diblock copolymers were prepared by the ring-opening polymerization of caprolactone from the alcohol terminus of poly(ethylene glycol) monomethylether, M(n) ≈ 2000. The critical micelle concentration depended on the degree of polymerization for the polycaprolactone block and was in the range of 2.9 to 41 mg/L. Differential scanning calorimetry curves for polymer solutions with a concentration above the critical micelle concentration showed a melting endotherm in the range of 40 to 45 °C, indicating the polycaprolactone core was semicrystalline. Pyrene was entrapped in the micelle core without interfering with the ability of the polycaprolactone to crystallize. When the polymer solution was heated above the melting point of the micelle core, the pyrene was free to leave the core. Temperature-dependent measurements of the critical micelle concentration and temperature-dependent dynamic light scattering showed that the micelles remain intact at temperatures above the melting point of the polycaprolactone core.     

The dependence of nuclear magnetic resonance (NMR) image contrast on intrinsic and pulse sequence timing parameters

In Nuclear Magnetic Resonance (NMR) the image pixel value is governed by at least three major intrinsic parameters: the spin density N (H), the spin-lattice relaxation time T1, and the spin-spin relaxation time T2. The extent to which the signal is weighted toward one or several parameters is related to the history of the spin system preceding detection. On the simplifying, though not generally warranted assumption that the spin density does not vary significantly in soft tissues, relative tissue contrast can be predicted quantitatively provided the relaxation times are known. Signal intensities and contrast were computed on the basis of the Bloch equations and experimentally determined relaxation times as a function of pulse timing parameters and the data compared with those in images recorded at 0.5T field strength. Significant deviations from the equal density hypothesis were found for gray and white substance. Notably partial saturation but also spin echo and inversion-recovery images are not in full accordance with predictions made on the basis of relaxation times alone.     

Near-IR cavity ringdown spectroscopy and kinetics of the isomers and conformers of the butyl peroxy radical

Cavity ringdown spectra of butyl peroxy radicals have been obtained for their A-X electronic transition in the near-IR. The radicals were produced by two independent chemical methods, allowing unambiguous assignment of the spectra of the four butyl peroxy isomers with probable conformer assignments also possible for a number of cases. Using the analyzed spectra semiquantatively, isomer specific rate constants for butyl peroxy self-reaction were measured, as was the relative reactivity of the various sorts of H atoms in butane to Cl atom attack.