Studies on the persistence of estradiol benzoate and nortestosterone decanoate in hair of cattle following treatment with growth promoters,determined by ultra-high-performance liquid chromatography–tandem mass spectrometry

Measurement of steroid esters in bovine hair samples, using sensitive liquid chromatography-tandem mass spectrometry (LC–MS/MS), provides a powerful tool for identifying animals treated illicitly with growth promoters. The successful application of such testing requires appropriate sampling of hair from treated animals. This paper describes the results of hair analysis by LC–MS/MS for two animal studies in which animals were treated with estradiol-3-benzoate and nortestosterone decanoate. The results from the first animal study indicate that animals treated with these anabolic steroids may not always be identified from analysis of hair samples; positive test results occur sporadically and only for some of the treated animals. The results from the second animal study identify conditions attaching to positive hair samples, such as, that concentrations of steroid esters in hair are related to distance of sampling from point of injection and to time post-treatment, that concentrations of steroid esters in hair are related to dose given to the animal but that this relationship may vary over time post-treatment, and that steroid esters may be measured in regrowth hair taken some weeks after treatment. Steroid esters are determined along the length of the hair, confirming that accumulation of steroid esters into hair occurs from various sources, including blood, sweat and sebum. The reported research provides some useful insights into the mechanisms governing the persistence of steroid esters in bovine hair following illicit treatment with growth promoters.     

Cyclic voltammetry of Th(IV) in the room-temperature ionic liquid [Me3NnBu][N(SO2CF3)2

A Th(IV) compound, [Th(TFSI)4(HTFSI)].2H2O [where TFSI = N(SO2CF3)2], has been synthesized and characterized using elemental analysis, thermogravimetric analysis, and vibrational spectroscopy. The analysis suggests that the TFSI anion coordinates to the metal center via the sulfonyl oxygens as well as provides evidence for the coordination of HTFSI. The voltammetric behavior of this compound has been studied in the room-temperature ionic liquid [Me3NnBu][TFSI], and results show that Th(IV) is reduced to Th(0) in this ionic liquid in a single reduction step. Analysis of cyclic voltammograms shows that an insoluble product is being formed at the electrode surface, which is attributed to the formation of ThO2 by reaction with water. The E0 value for the reduction of Th(IV) to Th(0) has been determined to be -2.20 V (vs Fc+/Fc; -1.80 V vs SHE). A comparison of this E0 value with those obtained for Th(IV) reduction in a LiCl-KCl eutectic (400 degrees C), water, and nonaqueous solvents shows that the reduction in [Me3NnBu][TFSI] is easier to accomplish than that in these other solvents.     

Raman and infrared spectra, conformational stability, ab initio calculations and assignment of fundamentals for 1-bromo-3-fluoropropane

The infrared and Raman spectrum of 1-bromo-3-fluoropropane is reported in the gas, liquid, amorphous solid and annealed polycrystalline states. Only one of the five possible conformers is stable in the crystal, designated the C conformer. The disordered phases show the presence of several other conformers of higher energy, due entirely to conformers designated B and D. Ab initio calculations were performed as rhf/4-31g*/MIDI-4*, rhf/6-31g* and mp2/6-31g* (both frozen core and full electron correlation) for all five conformers. The scaled harmonic force field obtained using the mp2 = full/6-31g* level of the theory is reported for the most stable conformer together with an assignment of fundamentals and potential energy distributions for local symmetry coordinates. Selected computational results are reported for all conformers together with scaled and unscaled wavenumbers and infrared and Raman intensities. The temperature dependent Raman spectrum is reported from room temperature to -100 degrees C. Only three of the five possible conformers can be identified in this spectrum, and there is no evidence of the other two. The energy differences between conformers in the liquid phase were found experimentally to be 132+/-27, 232+/-46 and 106+/-30 cm(-1), respectively between the D and C, B and C and D and B conformers. These differences are substantially less than the differences calculated ab initio at the highest level of the theory used, suggesting that energy differences were decreased by large dipole-dipole interactions present in the liquid but not in the gas.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Correlation Analysis of the Alternating Step Generator

The alternating step generator is a well-known keystream generator consisting of two stop/go clocked LFSRs, LFSR₁ and LFSR₂, whose clocks are controlled by another LFSR, LFSR₃, which is clocked regularly. A probabilistic analysis of this generator is conducted which shows that the posterior probabilites of individual bits of the first derivatives of the regularly clocked LFSR₁ and LFSR₂ sequences, when conditioned on a given segment of the first derivative of the keystream sequence, can be computed efficiently in a number of probabilistic models of interest. The expected values of these probabilities, for a random keystream sequence, are derived by an approximate theoretical analysis and are also verified by systematic computer experiments. It is pointed out that these posterior probabilities can be enhanced in a resynchronization scenario and thus used for a low-complexity fast correlation attack on the two LFSRs. More generally, it is argued that even without resynchronization these probabilities may be significantly different from one half for fast correlation attacks based on iterative decoding algorithms to be successful, although with incresead complexity. A related method for computing the posterior probabilities of individual bits of the LFSR₃ sequence, when conditioned on both the keystream sequence and the LFSR₁ and LFSR₂ sequences, is also developed. As these posterior probabilities are much more different from one half, they can be used for a low-complexity fast correlation attack on LFSR₃, provided that the initial states of LFSR₁ and LFSR₂ are previously reconstructed.     

New developments of conductometric measurements in analytical biochemistry

A recently described conductometric device with precise temperature regulation is used. For determination of cholinesterase activities, different substrates were studied; with regard to the enzyme activities present in serum or in whole blood, butyrylcholine was selected for the serum assay and propionylcholine for whole blood assay. Ethanol was determined by using alcohol and aldehyde dehydrogenases with measurement of the conductance changes, mainly from the appearance of acetate ions. In the kinetic method, the relationship between the rate of conductance variation and ethanol concentration was linear in the range 0–0.2 mM.     

High temperature gas chromatography: The development of new aluminum clad flexible fused silica glass capillary columns coated with thermostable nonpolar phases: Part 2

Samples, representative of certain classes of “high molecular weight” and/or less volatile substances, were analyzed by gas chromatography utilizing a new generation of aluminum clad flexible fused silica glass capillary columns containing thin films of a methyl polysioxane stationary phase capable of being operated isothermally to 400–425°C and temperature programmed to 425–440°C. The results obtained here were compared with those described in the literature discussing the latest advances in Supercritical Fluid Chromatography (SFC) in the analysis of precisely the same types of samples. In all instances, the gas chromatographic method provided superior speed of analysis, superior column efficiency, and superior resolution of the component bands. This was due to fundamental factors, favoring the diffusivity of the solutes in both the gas and liquid phases in this process at these high temperatures. Under these circumstances, it is thought that the strength of SFC mainly lies in the analysis of thermally labile samples until the advocates of this technique make more definitive strides in the handling of still higher molecular weight substances well beyond the newly expanded range of gas chromatography.     

Weak-anchoring effects on a Freedericksz transition in an annulus

This paper investigates the effect of weak anchoring on static orientation patterns in a sample of nematic liquid crystal confined to a cylindrical annular geometry, in the presence of a magnetic field. The particular arrangement considered in detail is that in which a magnetic field is applied in the azimuthal direction to a sample of liquid crystal that is initially uniformly aligned parallel to the cylindrical axis and is weakly anchored at the inner cylinder, but strongly anchored at the outer cylinder. A static solution of the non-linear continuum equations is presented which suggests a possible experiment for evaluating the surface elastic coefficient k₂₄. In addition, a linear stability analysis based on the dynamic theory yields results for critical phenomena in agreement with those derived from the non-linear solution.