Application of ICP-MS radionuclide analysis to “Real World” samples of department of Energy radioactive waste

Germanium spectrometers must be operated at liquid nitrogen temperatures. Other detectors operate better when cooled. Many applications, because of hostile environments, inaccessibility, remote location, long duration, etc., are compromised, or totally precluded, by the requirement for liquid nitrogen. A Stirling cycle refrigerator based on a linear motor design, which is acoustically and vibrationally quiet, does not require secondary cooling, and operates unattended for years, is under development. System design and specifications are presented. Applications to cooled laser monitoring equipment. SQUID-based detection systems, environmental cleanup and monitoring, medical diagnostics, non-destructive testing systems, communication equipment, computer electronics, and imaging systems are discussed.     

Unique structural properties of the Mg-Al hydrotalcite solid base catalyst: an in situ study using Mg and Al K-edge XAFS during calcination and rehydration

The changes in the layered structure of Mg-Al hydrotalcite (Mg/ Al = 2) during heat treatment have been investigated by using in situ XAFS simultaneously at the Mg and Al K-edges. The development of unique in situ instrumentation allowed the coordination environments at both the Mg and Al centers to be monitored as a function of the temperature and heat treatment. The results of this study show that the hydrotalcite structure is highly flexible, and should lead to the further development of hydrotalcites as new solid basic catalysts. Moreover, the Mg and Al cations in the cation layers show different behavior as a function of temperature. The coordination of some octahedral Al ions decreases already at a temperature of 425 K, whereas the coordination about Mg does not show any modification at this temperature. However, hydrotalcite treated at 425 K, followed by cooling down to room temperature resulted in a complete reversal to the original octahedral Al coordination. It is proposed that Al-OH bond breakage occurs at 425 K, without the evolution of H2O. This bond is restored after cooling to room temperature. The actual dehydroxylation of hydrotalcite commences between 425 and 475 K, as indicated by a change in coordination of both the Mg and Al centers. This is accompanied by the evolution of H2O molecules and the changes are hence irreversible without the presence of excess water. Heat treatment at 725 K leads to the development of an MgO-like phase (octahedral Mg) and a mixed octahedral/tetrahedral Al phase. A subsequent rehydration at room temperature entirely restores the original coordination about the Al and Mg centers of hydrotalcite to a distance of 15 A, to which XAFS spectroscopy is sensitive.     

Parameter-free structure-property correlation via progressive reaction posets for substituted benzenes

Progressive reaction networks as frequently arise in chemistry are naturally identifiable as "partially ordered sets" (or posets). Here the direction of the reaction identifies the partial ordering of the set of molecular species. The possibility that different properties are similarly ordered is a further natural consideration and is here investigated for a suite of over 30 properties for (methyl and chloro) substituted benzenes. Such a posetic correlation is favorably demonstrated for these substituted benzenes, and it is illustrated how suitable properties may be simply predicted in an interpolative parameter-free (albeit not model-free) fashion through the use of the reaction poset. Some numerical model-quality indicators are identified, and the simple approach is deemed quite reasonable.     

Capillary isoelectric focusing-mass spectrometry: analysis of protein mixtures from human body fluids

Isoelectric focusing within a fused silica capillary (cIEF) has proved to be a powerful and practical method for high-resolution separation of analytes from complex biological mixtures. This technique overcomes many of the problems of isoelectric focusing within slab gel media. However current cIEF systems commonly utilize UV detection which limits the detail of analyte structural information that is obtained during analysis. The use of mass spectrometry (MS) as the detection system provides much greater structural information about the detected analytes allowing accurate relative molecular mass (M(r)) determination for proteins and polypeptides. We have constructed a cIEF-MS interface and compared the separation of standard proteins analyzed by cIEF-UV with cIEF-MS. This allowed rapid optimization of the cIEF-MS system performance. Further we have demonstrated the use of MS as a detection system provides accurate M(r) information and can provide analyte modification details. These factors increase the likelihood of absolute identification for physiological proteins within complex in vivo-derived mixtures. To demonstrate the value of cIEF-MS in such analyses we have undertaken an examination of cerebrospinal fluid (CSF), and tentatively identified a number of constituent proteins. We have also analyzed whole blood from control and diabetic patients. We show that glycated alpha- and beta- chains of hemoglobin are found in almost equal abundance in diabetic patient blood. From these results we suggest cIEF-MS is an efficient and useful tool for the separation and examination of in vivo-derived analytes within physiological fluids.     

Photoproteins as luminescent labels in binding assays

Certain marine organisms produce calcium-activated photoproteins that allow them to emit light for a variety of purposes, such as defense, feeding, breeding, etc. Even though there are many bioluminescent organisms in nature, only a few photoproteins have been isolated and characterized. The mechanism of emission of light in the blue region is the result of an internal chemical reaction. Because there is no need for excitation through external irradiation for the emission of bioluminescence, the signal produced has virtually no background. This allows for the detection of the proteins at extremely low levels, making these photoproteins attractive labels for analytical applications. In that regard, the use of certain photoproteins, namely, aequorin, obelin, and the green fluorescent protein as labels in the design and development of binding assays for biomolecules has been reviewed. In addition, a related fluorescent photoprotein, the green fluorescent protein (GFP), has been recently employed in bioanalysis. The use of GFP in binding assays is also discussed in this review.     

Simultaneous ab initio calculations of isoelectronic diatomic molecules

Large gaussian basis sets are employed in simultaneous configuration interaction calculations for the ground states of isoelectronic diatomic molecules. The resulting potential energy curves for three members respectively of four different isoelectronic molecule sequences show the applicability of the method. Comparisons with available results of standard configuration interaction calculations for selected molecules are given. Using our method we often get lower upper bounds for the electronic energy, save computer time and treat physically totally different molecules simultaneously.     

Phase coexistence overlap induced by steric interactions

Novel phase diagram calculations, in which the two phase-separated regions of polymer stabilized colloidal suspensions overlap under certain constraints of the reduction in the range of the steric interaction with increasing temperature, are presented. A phase diagram displaying liquid-vapour, liquid-solid and vapour-solid coexistence with two triple points, but no critical points is shown to exist in qualitative agreement with observations.     

Calculation of the 1J(PP) angular dependence in P2H4

Using the results obtained from an MO SCF ab initio calculation on P₂H₄ in four different conformations, the ¹J(PP) NMR coupling constants have been calculated. The ¹J(PP) values are highly dependent upon the rotational angle φ (?238.0 Hz in the eclipsed conformation, 10.9 Hz in the staggered one). The shape of the theoretical ¹J(PP) plot seems to be in good agreement with experimentally measured ¹J(PP) values.     

IN VIVO INDUCTION OF 4-THIOURIDINE-CYTIDINE ADDUCTS IN tRNA OF E. COLI B/r BY NEAR-ULTRAVIOLET RADIATION*

Abstract— Near-ultraviolet (near-UV; 320–405 nm) irradiation of Escherichia coli B/r induces the formation in vivo of ⁴Srd-Cyd adducts in transfer RNA, as evidenced by (1) fluorescence spectrum changes of tRNA extracted from irradiated cells and reduced with NaBH₄, (2) thin-layer chromatography on cellulose of hydrolysates of trichloroacetic acid-precipitable extracts of irradiated cells, and (3) comparison of these findings with adduct formation induced by near-UV irradiation of purified mixed tRNA from E. coli. The kinetics of induction of the ⁴Srd-Cyd adduct in vivo, and the near-UV fluences required, provide strong support for our earlier hypothesis that formation of these adducts is responsible for near-UV-induced growth delay in E. coli.     

Photophysical behaviour of azaphenanthrenes

Nitrogen position and internal heavy atom effects on the radiative and radiationless transitions from the lowest excited states of the isomeric azaphenanthrenes and some of their methyl, chlorine and bromine derivatives have been studied in E.P.A. solutions at 77 K. The nitrogen position affects the fluorescence and S₁-T₁ intersystem crossing rates more than the phosphorescence and T₁-S₀ intersystem crossing rates. Small differences in the behaviour of 9-azaphenanthrene are enhanced in non-hydroxylic solvents and at room temperature, and it is inferred that (n, π*) states play a more important role in the photophysical behaviour of this isomer. Halogen, substitution in all the isomers increases the phosphorescence rate, induces a smaller increase in the T₁-S₀ intersystem crossing rates and has a negligible effect on the fluorescence rate.