Confirmation of phenylbutazone residues in bovine kidney by liquid chromatography/mass spectrometry

A confirmatory method is described for phenylbutazone (PB) residues in bovine kidney tissue. Ground kidney tissue is diluted with water, and the mixture is made basic with 25% ammonium hydroxide in water; the lipids are extracted with ethyl and petroleum ethers. The ether layer is discarded, and the tissue is acidified with 6N HCl. PB residues are extracted with tetrahydrofuranhexane (1 + 4). The extract is passed through a silica solid-phase extraction column, and the eluate is evaporated to dryness. The residue is dissolved in acidified acetonitrile-water-acetic acid (50 + 49.4 + 0.6). A single quadrupole mass spectrometer coupled to a liquid chromatograph with an electrospray interface is used to confirm the identity of the PB residues in the kidney extract. Negative-ion detection with selected-ion monitoring of 4 ions is used. Sets of control and fortified-control kidney tissues (at 50, 100, and 200 ppb PB) and several kidney tissue field samples were analyzed for method validation. The method was tested further during the course of a survey to determine the incidence of PB residues in bovine kidney samples obtained from slaughterhouses across the country. In addition, the method was tested for use with an ion-trap mass spectrometer coupled to a liquid chromatograph, which allowed confirmation of PB at lower levels (5-10 ppb) in kidney tissue.     

Natural time analysis of critical phenomena: The case of acoustic emissions in triaxially deformed Etna basalt

Acoustic emissions exhibit complex correlations between space, time, and magnitude. As such, they present a unique example for a complex time series. We apply the recently introduced method of natural time analysis, which enables the detection of long-range temporal correlations even in the presence of heavy tails and find that the acoustic emissions exhibits features similar to that of other equilibrium or non-equilibrium critical systems such as worldwide seismicity as presented in the Centennial earthquake catalogue which includes global seismicity events with magnitude _Mw>7.0$M_w>7.0$. These results support the universal behaviour of the fracturing processes from the laboratory to the global scale.     

On the non-extensive nature of the isothermal depolarization relaxation currents in cement mortars

The study of isothermal depolarization current relaxation during the cement hardening process follows a generalized exponential function, which explicitly introduces hierarchically constrained dynamics and macroscopic interactions. The interactions are associated to the non-extensive entropy parameter q, which varies during hardening evolution. Combining ideas of Levy and Tsallis statistics we argue that a Levy walk type mechanism can organize the geometry of the cement mortar heterogeneous system. The estimation of non-extensive q parameter safe concludes that cement's hardening is a subextensive process.     

Identification and quantification of glutathione adducts of clozapine using ultra-high-performance liquid chromatography with orthogonal acceleration time-of-flight mass spectrometry and inductively coupled plasma mass spectrometry

The application of sulphur-specific detection via ultra-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (UPLC/ICPMS) to detect and quantify the glutathione (GSH)-adducts produced via the in vitro formation of reactive metabolites is demonstrated. The adducts were formed in human liver microsomes supplemented with unlabelled GSH for clozapine. The calculation of adduct concentration was performed via comparison of the peak areas to calibration curves constructed from omeprazole, a sulphur-containing compound over the range of 0.156 to 15.62 μM of sulphur with a detection limit of 1.02 ng of sulphur on-column. Identification of the adducts was performed using conventional UPLC/time-of-flight (TOF)-MS with the calculation of clozapine intrinsic clearance carried out by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). The use of ICPMS in this way appears to offer a novel, rapid and sensitive means of determining the quantity of GSH conjugates with the combined adducts producing 0.9 μM of reactive metabolite out of a total of 3.5 μM of metabolites. The GSH adduct therefore represents 26% of this total produced as a result of the metabolism of drug to reactive species.     

Interlaboratory comparison of methods for the determination of incurred tilmicosin residues in bovine liver

The objective of this study was to compare 2 methods for the determination of tilmicosin residues in bovine liver samples. Three laboratories participated in the comparison of the 2 methods. The first method was described in a New Animal Drug Application (NADA 140-929), and the second was a modification of that method in which hexane was substituted for carbon tetrachloride in one cleanup step. Each of the 3 laboratories analyzed subsamples of 10 bovine livers containing incurred tilmicosin. Residues ranged from 2.3 to 81 ppm tilmicosin in the 10 liver samples with an 11.8% relative standard deviation obtained by using both methods. In addition, fortified-control liver tissue samples were analyzed concurrently with tissues containing incurred residues by using the modified method in one of the laboratories. The fortification levels ranged from 0.3 to 112 ppm, with recoveries ranging from 76 to 92%. The results from the 3 laboratories were comparable, indicating that the modified method was not only as effective as the original NADA method, but also more desirable because of the change to a less hazardous solvent.     

Combination of molecular rods and half-discs: transition from lamellar to columnar order in multichain mononuclear ortho-palladated metallomesogens

Novel ortho-palladated phenylpyrimidine-1,3-diketonato organyls with successively increasing numbers of alkyl chains were synthesized and investigated by polarizing optical microscopy and X-ray diffraction. A discontinuous transition from a lamellar to a columnar organization is observed, dependent on the number of chains: molecules with four or five chains from smectic phases (SmA, SmC), the related compound with six chains in the molecule is nonmesomorphic, whereas molecules with seven or eight chains form hexagonal columnar mesophases.     

A [24-MC-6] zinc metallacoronate with a nonsteroidal antiinflammatory drug as the constructing ligand

The interaction of ZnCl(2) with 2-dipyridylketonoxime (=Hpko) and flufenamic acid (=Hfluf) in a basic methanolic solution leads to the formation of a hexanuclear 24-membered metallacoronate, [Zn(6)(OH)(2)(pko)(4)(fluf)(6)] (1), with a [Zn-O-C-O] repeat unit and a nonsteroidal antiinflammatory drug as the constructing ligand. Compound 1 retains its structure in a dimethyl sulfoxide solution, as shown by (1)H NMR spectroscopy and molar conductance.     

Is plate tectonics a case of non-extensive thermodynamics?

Bird (2003) [5] proposed that the distribution of areas of the tectonic plates follows a power law and that this distribution fitted well with the concepts of a few major plates and a hierarchical self-similar organization of blocks at the boundary scale, a fractal plate distribution and a self-organized system. Here we apply the concepts of non-extensive statistical mechanics (NESM) to plate tectonics. The application of NESM is appropriate to systems such as tectonic plates where non-linearity, long-range interactions, memory effects and scaling are important. We calculate the probability density function for the areas of the tectonic plates. Our results show that three classes (small, intermediate and large) of tectonic plates can be distinguished, which is consistent with the observations of Bird. Furthermore, taking into account that for the intermediate class of tectonic plates the cumulative frequency distribution behaves as a power law with exponent 1/3, we estimate a thermodynamic q parameter of q=1.75, which supports the conclusion that the plate tectonics system is a sub-extensive one.