Uranium analysis in urine by inductively coupled plasma dynamic reaction cell mass spectrometry

Urine uranium concentrations are the best biological indicator for identifying exposure to depleted uranium (DU). Internal exposure to DU causes an increased amount of urine uranium and a decreased ratio of ²³⁵U/²³⁸U in urine samples, resulting in measurements that vary between 0.00725 and 0.002 (i.e., natural and depleted uraniums ²³⁵U/²³⁸U ratios, respectively). A method based on inductively coupled plasma dynamic reaction cell mass spectrometry (ICP-DRC-MS) was utilized to identify DU in urine by measuring the quantity of total U and the ²³⁵U/²³⁸U ratio. The quantitative analysis was achieved using ²³³U as an internal standard. The analysis was performed both with and without the reaction gas oxygen. The reaction gas converted ionized ²³⁵U⁺ and ²³⁸U⁺ into ²³⁵UO₂⁺ (m/z=267) and ²³⁸UO₂⁺ (m/z=270). This conversion was determined to be over 90% efficient. A polyatomic interference at m/z 234.8 was successfully removed from the ²³⁵U signal under either DRC operating conditions (with or without oxygen as a reaction gas). The method was validated with 15 urine samples of known uranium compositions. The method detection limit for quantification was determined to be 0.1 pg U mL^–1 urine and an average coefficient of variation (CV) of 1–2% within the sample measurements. The method detection limit for determining ²³⁵U/²³⁸U ratio was 3.0 pg U mL^–1 urine. An additional 21 patient samples were analyzed with no information about medical history. The measured ²³⁵U/²³⁸U ratio within the urine samples correctly identified the presence or absence of internal DU exposure in all 21 patients.The opinions and assertions expressed herein are those of the authors and are not to be construed as official or as representing the views of the Armed Forces Institute of Pathology, the Department of the Army, or the Department of Defense     

A new thermoelectric material: CsBi4Te6

The highly anisotropic material CsBi(4)Te(6) was prepared by the reaction of Cs/Bi(2)Te(3) around 600 degrees C. The compound crystallizes in the monoclinic space group C2/m with a = 51.9205(8) A, b = 4.4025(1) A, c = 14.5118(3) A, beta = 101.480(1) degrees, V = 3250.75(11) A(3), and Z = 8. The final R values are R(1) = 0.0585 and wR(2) = 0.1127 for all data. The compound has a 2-D structure composed of NaCl-type [Bi(4)Te(6)] anionic layers and Cs(+) ions residing between the layers. The [Bi(4)Te(6)] layers are interconnected by Bi-Bi bonds at a distance of 3.2383(10) A. This material is a narrow gap semiconductor. Optimization studies on the thermoelectric properties with a variety of doping agents show that the electrical properties of CsBi(4)Te(6) can be tuned to yield an optimized thermoelectric material which is promising for low-temperature applications. SbI(3) doping resulted in p-type behavior and a maximum power factor of 51.5 microW/cm.K(2) at 184 K and the corresponding ZT of 0.82 at 225 K. The highest power factor of 59.8 microW/cm.K(2) at 151 K was obtained from 0.06% Sb-doped material. We report here the synthesis, physicochemical properties, doping characteristics, charge-transport properties, and thermal conductivity. Also presented are studies on n-type CsBi(4)Te(6) and comparisons to those of p-type.     

The combinatorial game Nofil played on Steiner triple systems

We introduce an impartial combinatorial game on Steiner triple systems called Next One to Fill Is the Loser (Nofil ). Players move alternately, choosing points of the triple system. If a player is forced to fill a block on their turn, they lose. By computing nim-values, we determine optimal strategies for Nofil on all Steiner triple systems up to order 15 and a sampling for orders 19, 21 and 25. The game Nofil can be thought of in terms of play on a corresponding hypergraph which will become a graph during play. At that point Nofil is equivalent to playing the game Node Kayles on the graph. We prove necessary conditions and sufficient conditions for a graph to reached playing Nofil. We conclude that the complexity of determining the outcome of the game Nofil on Steiner triple systems is PSPACE-complete for randomized reductions.     

Separation and implantation of relativistic86Kr-fragments at the FrS; half-life measurement by ion-β time-correlations

Neutron-rich Co and Fe isotopes produced by⁸⁶Kr projectile fragmentation at 500 MeV/u were separated and identified using the fragment separator (FrS) in a bunched energy mode.⁶⁶Co and⁶⁵Fe ions were selectively implanted in a double PIN-diode array where the-decay signals were measured. The half-lives were deduced from time correlations between implantation and-decay signals. The remeasurement of the⁶⁶Co half-life confirms the isotope identification. The value of the⁶⁵Fe half-life was found to be 0.45±0.15 s.     

Multistep adsorption of anionic dyes on silica/chitosan hybrid. 1. Comparative kinetic data from liquid- and solid-phase models

In this work, a hybrid silica/chitosan was synthesized and characterized by nitrogen elemental analysis and thermal analysis (TG, DTG, DTA, and DSC) and BET surface area. The hybrid was used in adsorption studies of two anionic dyes from aqueous solutions. A rise of temperature accelerates mass transfer of dyes into the hybrid. However, the maximum adsorption capacities reach similar values from 25 to 55 degrees C. The kinetic data were first evaluated in relation to the decrease of the time-related residual concentration of the dyes in solution, where the second-order model has presented the best fitting. The solid-phase interaction of dye data presents a rough fitting to the traditional first-order Lagergren kinetic model. However, a modified Avrami kinetic equation was successfully fitted to the kinetic quantities, where from five to seven kinetic regions were found. A pore-diffusion model has also demonstrated that the diffusion is the rate-controlling interaction mechanism. However, the experimental-calculated comparative values are the best way to evaluate a specific aqueous- or solid-phase kinetic model.     

New Factorial Designs to Evaluate Chemisorption of Divalent Metals on Aminated Silicas

Adsorption processes of Cu(II), Co(II), and Hg(II) on two aminated silica gel surfaces with immobilized ethylenediamine and diethylenediamine groups were studied by a new 2(3) full factorial design. Two metal quantity levels, temperatures of 25 and 50 degrees C, and silica amounts of 100 and 200 mg were employed. Our study indicates that higher factorial design levels increase adsorption for all metals evaluated, with the exception of the mass parameter. Adsorption is also significantly affected by important antagonistic and synergistic effects involving all factors. Both functionalized silica gel surfaces present higher interactions and good perspectives in preconcentration studies for mercury. The factorial design results are also discussed in terms of some solvation properties for each of the metals studied. Copyright 2001 Academic Press.     

Suppression of non-specific adsorption using sheath flow

The use of a confining sheath fluid within a microfluidic channel in order prevent non-specific adsorption of analytes to the walls of microchannels is demonstrated. A sheath-flow channel fabricated using laser cutting of Mylar films is developed. Numerical simulations of convective and diffusive mass transport within the channel are presented. The device is characterized experimentally using epifluorescence microscopy. It is demonstrated that the device is capable of preventing the adsorption of Rhodamine B to the walls of the channel for a period that would allow for adsorption-free T-sensor measurements to be made within the core of the flow channel. Generalized scaling rules based on the diffusion coefficient, sheath thickness and affinity of the potential adsorbant for the surface material are discussed. The controlled adsorption of the protein bovine serum albumin (BSA) to a gold surface is also demonstrated using SPR microscopy.     

Micellar electrokinetic capillary chromatography and data alignment analysis: a new tool in urine profiling

The complex nature of biofluids demands efficient, sensitive and high-resolution analytical methodologies to examine how the 'metabolic fingerprint' changes during disease. This paper describes how sulphated beta-cyclodextrin-modified micellar electrokinetic capillary chromatography (SbetaCD-MECC) has been combined with data alignment analysis and may prove a useful new tool in urine profiling, allowing for separation of over 80 urinary analytes in under 25 min. The optimised and validated SbetaCD-MECC methodology combined with data alignment analysis provides rapid identification of 'mismatches' between urine profiles which are not easily detected with the naked eye as well as a 'similarity score' which indicates the total sum of differences between one profile and another. The combination of SbetaCD-MECC with data alignment software should prove a useful alternative tool in metabonomic studies for rapid comparison of urine profiles.     

Recent advances in micellar electrokinetic chromatography

This review contains nearly 200 reference citations, and covers advances in electrokinetic capillary chromatography based on micelles, including stabilized micelle complexes, polymeric and mixed micelles from 2003-2004. Detection strategies, analyte determinations, and applications in micellar electrokinetic capillary chromatography (MEKC) are discussed. Information regarding methods of analyte concentration, analyte specific analyses, and nonstandard micelles has been summarized in tabular form to provide a means of rapid access to information pertinent to the reader.