Multiresidue method for simultaneous determination of ten quinolone antibacterial residues in multimatrix/multispecies animal tissues by liquid chromatography with fluorescence detection: single laboratory validation study

Quinolone antibacterials are veterinary drugs authorized for use in food animal production. The analysis of residual amounts of drugs in food from animal origin is important for quality control of products for consumers. For this purpose, Maximum Residue Limits (MRLs) have been set up by a European Union Council Regulation on Veterinary Drug Residues (No. 90/2377/EEC and subsequent), and 8 quinolones received MRLs at concentration levels depending on both the matrix and the animal species of interest. A method was developed for screening and confirming 10 quinolone residues (ciprofloxacin, danofloxacin, difloxacin, enrofloxacin, flumequine, marbofloxacin, nalidixic acid, norfloxacin, oxolinic acid, sarafloxacin) in a wide variety of matrixes of different animal species. It involves extraction of the residues from the biological tissues/fluids by acidic aqueous solution, centrifugation and filtration prior to injection on a C18 narrow-bore column, and detection through a 3-step-mode fluorescence detector. The method was validated during a 2-week study for a set of 8 species-matrixes (i.e., bovine raw milk, bovine muscle, porcine muscle, porcine kidney, porcine liver, fish flesh and skin, poultry muscle, whole egg). Residues were quantified down to 15 microg/kg with limits of detection and quantitation ranging from 4 to 11 and 13 to 36 microg/kg, respectively, which are sufficient compared to the wide range of MRLs set for these substances (from 30 microg/kg for danofloxacin in milk to 1900 microg/kg for difloxacin in poultry liver). The limit of performance of the method in terms of CCalpha and CCbeta, the critical concentrations stated in the Decision No. 2002/657/EC and the ISO Standard No. 11843, has been calculated for the authorized (MRL) substances but only estimated in the case of the nonauthorized (non-MRL) substances.     

Close-packed C(70)(3-) phases - synthesis, structure, and electronic properties

The high symmetry and resulting electronic degeneracy of the C(60)(3)(-) anion is viewed as the key molecular feature in the high superconducting transition temperatures of fulleride and oxidized fullerene systems. The experimental evaluation of this hypothesis requires the synthesis of face-centered cubic (fcc) trivalent fulleride anion salts derived from higher fullerenes such as C(70), which have thus far proved elusive with only stable A(1)C(70), A(4)C(70), and A(6)C(70) phases known. In this paper, we report the synthesis of fcc A(3)C(70) phases stabilized by size-matching the tetrahedral site with the sodium cation. The structures are strongly dependent on the cooling protocol due to the existence of metastable partially or completely orientationally disordered phases. EPR data indicate that the phases are metallic but not superconducting. The densities of states at the Fermi level appear too low to give superconductivity at above 5 K, consistent with recent observations that four electrons per C(70) anion are required for superconductivity. Size-matching on both the octahedral and tetrahedral sites is required for A(3)C(70) stability - K(2)CsC(70) is only stable at elevated temperature and Na(2)C(70) is unstable, the composition corresponding to C(70) and a sodium-rich trigonal phase.     

Preparation of Chiral Amino Esters by Asymmetric Phase‐Transfer Catalyzed Alkylations of Schiff Bases in a Ball Mill

The asymmetric alkylation of Schiff bases under basic conditions in a ball mill was performed. The starting Schiff bases of glycine were prepared beforehand by milling protected glycine hydrochloride and benzophenone imine, in the absence of solvent. The Schiff base was then reacted with a halogenated derivative in a ball mill in the presence of KOH. By adding a chiral ammonium salt derived from cinchonidine, the reaction proceeded asymmetrically under phase‐transfer catalysis conditions, giving excellent yields and enantiomeric excesses up to 75 %. Because an equimolar amount of starting material was used, purification was greatly simplified.     

Optimal acoustic fields in compact thermoacoustic refrigerators

Thermoacoustic refrigerators have been developed during the last 15 years, employing quasi-standing resonant acoustic waves inside fluid-filled cavities to transfer heat along a stack region. Because higher efficiency can be reached when a significant travelling wave component exists in the resonator, specific resonant thermoacoustic devices have been designed allowing to adjust more or less the ratio of travelling and standing wave components. However, the acoustic pressure field and the particle velocity field do not appear to be the optimal ones, for the thermal quantities of interest. Thus, it is the aim of the paper to present a new kind of thermoacoustic standing wave-like device which allows to control easily and independently the pressure field and the particle velocity field, after investigating the optimal acoustic field, in the stack region, for the main parameters of interest, i.e. the temperature gradient, the thermoacoustic heat flow and the coefficient of performance.     

Solvent-free synthesis of nitrones in a ball-mill

Various C-aryl and C-alkyl-nitrones were synthesized within 0.5–2 h via condensation of an equimolar amount of aldehydes and N-substituted-hydroxylamines under solvent-free conditions in a ball-mill apparatus. Reactions can be performed without the need of excluding air and moisture and yields the expected products with no need for further purification. The study has been complemented by Differential Scanning Calorimetry (DSC) and solid-state ¹³C MAS nuclear magnetic resonance experiments. We have also studied the temperature profile during the reaction. A comparative study with the corresponding solvent-free microwave activated reaction showed the superiority of the ball-milling method; 31 examples are described, including the synthesis of the anti-aging agent C-phenyl-N-tert-butyl nitrone (PBN) and one of its analogues C-2-pyridyl-N-tert-butylnitrone (2-PyBN).     

Short‐term dynamics of isotopic composition of leaf‐respired CO2 upon darkening: measurements and implications

Recent advances in understanding the metabolic origin and the temporal dynamics in δ¹³C of dark‐respired CO₂ (δ¹³C_res) have led to an increasing awareness of the importance of plant isotopic fractionation in respiratory processes. Pronounced dynamics in δ¹³C_res have been observed in a number of species and three main hypotheses have been proposed: first, diurnal changes in δ¹³C of respiratory substrates; second, post‐photosynthetic discrimination in respiratory pathways; and third, dynamic decarboxylation of enriched carbon pools during the post‐illumination respiration period. Since different functional groups exhibit distinct diurnal patterns in δ¹³C_res (ranging from 0 to 10‰ diurnal increase), we explored these hypotheses for different ecotypes and environmental (i.e. growth light) conditions. Mass balance calculations revealed that the effect of respiratory substrates on diurnal changes in δ¹³C_res was negligible in all investigated species. Further, rapid post‐illumination changes in δ¹³C_res (30 min), which increased from 2.6‰ to 5‰ over the course of the day, were examined by positional ¹³C‐labelling to quantify changes in pyruvate dehydrogenase (PDH) and Krebs cycle (KC) activity. We investigated the origin of these dynamics with Rayleigh mass balance calculations based on theoretical assumptions on fractionation processes. Neither the estimated changes of PDH and KC, nor decarboxylation of a malate pool entirely explained the observed pattern in δ¹³C_res. However, a Rayleigh fractionation of ¹²C‐discriminating enzymes and/or a rapid decline in the decarboxylation rate of an enriched substrate pool may explain the post‐illumination peak in δ¹³C_res. These results are highly relevant since δ¹³C_res is used in large‐scale carbon cycle studies. Copyright © 2009 John Wiley & Sons, Ltd.     

Ligand influence in the selective gold-mediated synthesis of allenes

The use of [(IPr)AuOH] permits the generation of gold(i)-amine complexes by a silver-free protocol. These in situ or well-defined complexes are used in a straightforward synthetic route to substituted allenes from propargylic acetates. The catalytic activity can be modulated as a function of the nature of the ligand bound to the gold-NHC moiety.     

Chemistry of cobalt(II) confined in the pores of ordered silica monoliths: from the formation of the monolith to the CoFe Prussian blue analogue nanocomposite

Recently we conceived of an original strategy that allows the precipitation of Prussian blue analogues (PBAs) in the ordered pores of silica monoliths to lead to photomagnetic CoFe PBA-silica nanocomposites. To determine the critical parameters and fully control the synthesis of the photoactive CoFe PBA in the pores of the silica matrix, X-ray absorption spectroscopy was performed at the cobalt K-edge. This study showed that cobalt cation chemistry is the keystone of the entire process. The local environment and the electronic structure of the cobalt cation undergo several modifications during the formation process: first the incorporation of the cation as an octahedral complex into the ordered block copolymer phase, then the deprotonation by thermohydrolysis to give a fourfold-coordinated deprotonated lowly condensed species and finally the formation of the 3D coordination network of CoFe PBA in acidic conditions through a rapid reprotonation followed by nucleophilic substitution accompanied by the electronic transfer, thus leading to the photomagnetic Co(III)(LS)-Fe(II)(LS) (LS=low spin) pairs.     

Measuring Causal Invariance Formally

Invariance is one of several dimensions of causal relationships within the interventionist account. The more invariant a relationship between two variables, the more the relationship should be considered paradigmatically causal. In this paper, I propose two formal measures to estimate invariance, illustrated by a simple example. I then discuss the notion of invariance for causal relationships between non-nominal (i.e., ordinal and quantitative) variables, for which Information theory, and hence the formalism proposed here, is not well suited. Finally, I propose how invariance could be qualified for such variables.     

An active noise reduction earplug using a piezoelectric laterally radiating loudspeaker

This paper describes the electroacoustic behaviour of a new piezoelectric Active Noise Reduction (ANR) earplug device. The sensor is a microphone having suitable characteristics chosen from among commercially available electret microphones. The actuator is a cylindrical piezoelectric ceramic loaded with a thin fluid film. An analytic model of laterally radiating loudspeaker, based on fundamental equations of acoustics, which takes into account the effect of viscosity and heat conduction is adapted to describe the acoustic radiation of the actuator. Theoretical and experimental frequency responses in a small cavity and an example of the ANR that can be obtained with the earplug are presented.