Reduction of uranyl nitrate ions in a continuous flow electrochemical reactor

In a contemporary salt-free flowsheet of nuclear fuel reprocessing, uranous ions are used as a reducing agent to accomplish the separation of uranium and plutonium from each other which is normally produced electrochemically. In the present study, continuous mode electrochemical reduction of uranyl ions in nitric acid medium and in the presence of hydrazine nitrate was carried out in a divided cell at three different feed flow rates and cathodic current densities for the purpose of optimizing the process conditions for better conversion efficiency. A correlation function is described as a mathematical model in which, mass transfer parameter is expressed as a function of current density and flow rate. From the multivariable nonlinear regression of the experimental data, rate parameter was determined. The electro reduction of uranyl ions was not influenced by the initial acidity. The maximum conversion rate of 87 % was obtained for the electro-reduction of 100 g/l U(VI) in 3 M nitric acid with feed flow rate as 0.3 l/h and current density as 15 mA/cm². The results for the reduction of 100 g/l uranyl ions indicate that an optimum flow rate of about 0.5 l/h and 15 mA/cm² as cathodic current density may suffice for the conversion with efficiency better than 60 %. The calculated steady state concentrations for U(IV) were found to be in good agreement with the experimental results.     

NOTE The Johnson Graphs Satisfy a Distance Extension Property

G has property if whenever F and H are connected graphs with and |H|=|F|+1, and and are isometric embeddings, then there is an isometric embedding such that . It is easy to construct an infinite graph with for all k, and holds in almost all finite graphs. Prior to this work, it was not known whether there exist any finite graphs with . We show that the Johnson graphs J(n,3) satisfy whenever , and that J(6,3) is the smallest graph satisfying . We also construct finite graphs satisfying and local versions of the extension axioms studied in connection with the Rado universal graph. Received June 9, 1998     

Effect of film ageing on the surface properties of lactoglobulin and lactoglobulin+sucrose stearate monolayers

The change in β-lactoglobulin and β-lactoglobulin+sucrose stearate spread monolayers over time (ageing effect) at room temperature was studied. Measurements of the surface pressure π-mean area per molecule A isotherms of the monolayers were used to probe any time dependent changes. The increase of the protein film area with time was attributed to protein unfolding. At certain ratios of surfactant to protein, a higher film area increase was observed. This correlated well with the excess film areas of 45 h aged films. The excess film areas for newly spread films of the same composition seemed to follow the opposite trend indicating that the protein–surfactant interactions change as the conformational changes of the protein molecules progress.     

Self-induced redox cycling coupled luminescence on nanopore recessed disk-multiscale bipolar electrodes

We present a new configuration for coupling fluorescence microscopy and voltammetry using self-induced redox cycling for ultrasensitive electrochemical measurements. An array of nanopores, each supporting a recessed disk electrode separated by 100 nm in depth from a planar multiscale bipolar top electrode, was fabricated using multilayer deposition, nanosphere lithography, and reactive-ion etching. Self-induced redox cycling was induced on the disk electrode producing ∼30× current amplification, which was independently confirmed by measuring induced electrogenerated chemiluminescence from Ru(bpy)₃ ^2/3+/tri-n-propylamine on the floating bipolar electrode. In this design, redox cycling occurs between the recessed disk and the top planar portion of a macroscopic thin film bipolar electrode in each nanopore. Electron transfer also occurs on a remote (mm-distance) portion of the planar bipolar electrode to maintain electroneutrality. This couples the electrochemical reactions of the target redox pair in the nanopore array with a reporter, such as a potential-switchable fluorescent indicator, in the cell at the distal end of the bipolar electrode. Oxidation or reduction of reversible analytes on the disk electrodes were accompanied by reduction or oxidation, respectively, on the nanopore portion of the bipolar electrode and then monitored by the accompanying oxidation of dihydroresorufin or reduction of resorufin at the remote end of the bipolar electrode, respectively. In both cases, changes in fluorescence intensity were triggered by the reaction of the target couple on the disk electrode, while recovery was largely governed by diffusion of the fluorescent indicator. Reduction of 1 nM of Ru(NH₃)₆ ³⁺ on the nanoelectrode array was detected by monitoring the fluorescence intensity of resorufin, demonstrating high sensitivity fluorescence-mediated electrochemical sensing coupled to self-induced redox cycling.     

Development of an X-ray computed tomography (CT) system with sparse sources: application to three-phase pipe flow visualization

This paper describes the application of a two-beam X-ray computed tomography (CT) system to multiphase (gas–oil–water) flow measurement. Two high-voltage (160 keV) X-ray sources are used to penetrate a 4-in. (101.6 mm ID) pipeline. A rotating filter wheel mechanism is employed to alternately “harden” and “soften” the X-ray spectra to provide discrimination between the three phases. Because this system offers only two projections, conventional back-projection algorithms are ineffective and thus a new reconstruction technique has been developed. A matrix equation is formed, to which additional “smoothing equations” are added to compensate for the lack of projection data. The tomographic result is obtained by computing an inverse matrix. This is a one-off computation and the inverse is stored for repeated use; reconstructed images from synthesized data demonstrate the effectiveness of this technique. Three-phase tomographic images of a horizontal slug flow are presented, which clearly show the mixing of oil and water layers within the slug body. The relevance of this work to the offshore oil and gas industry is summarized.     

Quantum octonions

This paper constructs a quantum deformation of the complex Cayley dgebra. The method uses the representation theory of U _q(sl(2)), the quantized enveloping algebra of the simple complex Lie algebra s/(2). The paper begins by constructing a quantum deforma-tion of the complex quaternion algebra, since this simpler case illustrates all of the necessary steps. As intermediate results, deformations are constructed of sl(2) and the 7-dimensional simple Malcev algebra.     

Simultaneous Determination of Testosterone and Testosterone Enanthate in Equine Plasma by UHPLC-MS-MS

Testosterone and testosterone enanthate are performance-enhancing substances that are banned in racehorses competing in the State of Pennsylvania (PA). A tolerance concentration of 2,000 pg mL^?1 plasma has been established for testosterone in intact colts and stallions at the time they are competing in PA. Testosterone enanthate is a precursor of testosterone and can be used to boost plasma testosterone concentration above natural, age and seasonally variable plasma concentration. To control abuse, a verifiable method for rapid determination of both substances in equine plasma was needed. For this reason, an ultra high performance liquid chromatography-tandem mass spectrometry method for high-throughput analysis of both analytes in equine plasma was developed. Analytes were recovered from plasma by liquid–liquid extraction using mixture of methyl tert-butyl ether and ethyl acetate (50:50, v/v), separated on a C₁₈ sub-2 μm column and detected on a triple quadrupole mass spectrometer using positive electrospray ionization mode with selected reaction monitoring scan. SRM ion transitions of m/z 289 → m/z 97, m/z 289 → m/z 109, m/z 289 → m/z 79 were used for testosterone identification while m/z 401 → m/z 253, m/z 401 → m/z 271, m/z 401 → m/z 97 were employed for testosterone enanthate. Retention time and product ion intensity ratio were used as confirmation criteria to ascertain the presence of both analytes in equine plasma. The limits of detection, quantification and confirmation were 50 pg 0.5 mL^?1, 100 pg 0.5 mL^?1 and 250 pg 0.5 mL^?1, respectively for both analytes. The method was validated for recovery efficiency, sensitivity, matrix effect, linearity, precision and accuracy. This method is routinely used in the PA program for androgenic anabolic steroids doping control in racehorses and in the on-going testosterone enanthate pharmacokinetics study. The method is defensible, fast, selective, specific and reproducibly reliable.     

The impact of sampling time on peak capacity and analysis speed in on-line comprehensive two-dimensional liquid chromatography

Comprehensive two-dimensional liquid chromatography (2DLC) offers a number of practical advantages over optimized one-dimensional LC in peak capacity and thus in resolving power. The traditional “product rule” for overall peak capacity for a 2DLC system significantly overestimates peak capacity because it neglects under-sampling of the first dimension separation. Here we expand on previous work by more closely examining the effects of the first dimension peak capacity and gradient time, and the second dimension cycle times on the overall peak capacity of the 2DLC system. We also examine the effects of re-equilibration time on under-sampling as measured by the under-sampling factor and the influence of molecular type (peptide vs. small molecule) on peak capacity. We show that in fast 2D separations (less than 1 h), the second dimension is more important than the first dimension in determining overall peak capacity and conclude that extreme measures to enhance the first dimension peak capacity are usually unwarranted. We also examine the influence of sample types (small molecules vs. peptides) on second dimension peak capacity and peak capacity production rates, and how the sample type influences optimum second dimension gradient and re-equilibration times.