Validation of a liquid chromatography–tandem mass spectrometry method for the identification and quantification of 5-nitroimidazole drugs and their corresponding hydroxy metabolites in lyophilised pork meat

A liquid chromatography–electrospray ionisation tandem mass spectrometry method for the simultaneous detection and quantitation of 5-nitroimidazole veterinary drugs in lyophilised pork meat, the chosen format of a candidate certified reference material, has been developed and validated. Six analytes have been included in the scope of validation, i.e. dimetridazole (DMZ), metronidazole (MNZ), ronidazole (RNZ), hydroxymetronidazole (MNZOH), hydroxyipronidazole (IPZOH), and 2-hydroxymethyl-1-methyl-5-nitroimidazole (HMMNI). The analytes were extracted from the sample with ethyl acetate, chromatographically separated on a C₁₈ column, and finally identified and quantified by tandem mass spectrometry in the multiple reaction monitoring mode (MRM) using matrix-matched calibration and ²H₃-labelled analogues of the analytes (except for MNZOH, where [²H₃]MNZ was used). The method was validated in accordance with Commission Decision 2002/657/EC, by determining selectivity, linearity, matrix effect, apparent recovery, repeatability and intermediate precision, decision limits and detection capabilities, robustness of sample preparation method, and stability of extracts. Recovery at 1 μg/kg level was at 100% (estimates in the range of 101–107%) for all analytes, repeatabilities and intermediate precisions at this level were in the range of 4–12% and 2–9%, respectively. Linearity of calibration curves in the working range 0.5–10 μg/kg was confirmed, with r values typically >0.99. Decision limits (CCα) and detection capabilities (CCβ) according to ISO 11843-2 (calibration curve approach) were 0.29–0.44 and 0.36–0.54 μg/kg, respectively. The method reliably identifies and quantifies the selected nitroimidazoles in the reconstituted pork meat in the low and sub-μg/kg range and will be applied in an interlaboratory comparison for determining the mass fraction of the selected nitroimidazoles in the candidate reference material currently developed at IRMM.     

Hot-wire measurement in turbulent flow behind a parallel-line heat source

An interaction of the free turbulent shear flow and the steady temperature field, which develops to the homogeneity, was studied. The temperature field was generated by parallel thin heated wires. The isotropic grid turbulence is supposed. Heated wire generates large cross temperature gradients and development of the temperature field was investigated experimentally. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of Interaction between Metallothionein and CdTe Quantum Dots

Quantum dots (QDs) belong to a new class of fluorescent agent for biochemical, medicinal or other purposes. However, QDs based on cadmium or other metals can be risky for an organism. As one of the mechanism how to detoxify cadmium-based QDs expression of metallothioneins (MT) can be considered. Due to high affinity of metallothionein to cadmium(II) ions, we attempted to develop an approach for studying of possible interaction with QDs. We prepared QDs with CdTe core and studied the interaction with MT, which we isolated from livers of Cd-administered rabbits. To study the interaction, we used the mixture of both components MT (3.6 μM): CdTe QDs (0, 0.34, 0.68, 1.02, 1.36, 1.7, 2.04 and 2.47 μM). The mixtures were studied by spectrophotometry within the range from 200 to 750 nm with detected maxima at 260 and 505 nm. Same mixtures were also analysed by differential pulse voltammetry Brdicka reaction, which supported data from spectrophotometry. Subsequently, we used fast protein liquid chromatography for purification of protein–quantum dot conjugates. We obtained the different chromatograms for (1) Apo MT, (2) CdTe QDs and (3) MT–QD complex. We also collected the fractions and subsequently analysed them on the content of Cd and MT, which confirmed the formation of CdTe QDs–MT complex.     

Bambus[n]urils: a new family of macrocyclic anion receptors

A recently discovered anion receptor is jointed by three related macrocycles differing in the number of glycoluril units and type of substitution. The synthesis is carried out in nonpolar solvents compared to aqueous media used in the case of the original macrocycle. The size of macrocycle is controlled by a template. A hexameric macrocycle with benzyl substitution binds halide anions with an affinity exceeding 10(9) M(-1) while a tetrameric analog does not bind any of the investigated anions.     

Nano-structuring of PTFE surface by plasma treatment,etching, and sputtering with gold

Properties of pristine, plasma modified, and etched (by water and methanol) polytetrafluoroethylene (PTFE) were studied. Gold nanolayers sputtered on this modified PTFE have been also investigated. Contact angle, measured by goniometry, was studied as a function of plasma exposure and post-exposure aging times. Degradation of polymer chains was examined by etching of plasma modified PTFE in water or methanol. The amount of ablated and etched layer was measured by gravimetry. In the next step the pristine, plasma modified, and etched PTFE was sputtered with gold. Changes in surface morphology were observed using atomic force microscopy. Chemical structure of modified polymers was characterized by X-ray photoelectron spectroscopy (XPS). Surface chemistry of the samples was investigated by electrokinetic analysis. Sheet resistance of the gold layers was measured by two-point technique. The contact angle of the plasma modified PTFE decreases with increasing exposure time. The PTFE amount, ablated by the plasma treatment, increases with the plasma exposure time. XPS measurements proved that during the plasma treatment the PTFE macromolecular chains are degraded and oxidized and new –C–O–C–, –C=O, and –O–C=O groups are created in modified surface layer. Surface of the plasma modified PTFE is weakly soluble in methanol and intensively soluble in water. Zeta potential and XPS shown dramatic changes in PTFE surface chemistry after the plasma exposure, water etching, and gold deposition. When continuous gold layer is formed a rapid decrease of the sheet resistance of the gold layer is observed.     

Signal-to-noise ratio enhancement based on wavelet filtering in ultrasonic testing

In ultrasonic non-destructive testing of materials with a coarse-grained structure the scattering from the grains causes backscattering noise, which masks flaw echoes in the measured signal. Several filtering methods have been proposed for improving the signal-to-noise ratio. In this paper we present a comparative study of methods based on the wavelet transform. Experiments with stationary, discrete and wavelet packet de-noising are evaluated by means of signal-to-noise ratio enhancement. Measured and simulated ultrasonic signals are used to verify the proposed de-noising methods. For comparison, we use signal-to-noise ratio enhancement related to fault echo amplitudes and filtering efficiency specific for ultrasonic signals. The best results in our setup were achieved with the wavelet packet de-noising method.     

Persulfated molecular umbrellas as anti-HIV and anti-HSV agents

A series of persulfated molecular umbrellas have been synthesized from putrescine, spermidine, spermine, lysine, and cholic acid (1a, 2a, 3a, 4a, and 5a) and their anti-HIV and anti-HSV activities determined. Despite it size, the most active of these conjugates (5a) was able to cross phospholipid bilayers made from 1-palmitoyl-2-oleyol-sn-glycero-3-phosphocholine (POPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylglycerol (POPG). The unique combination of anti-viral activity, an ability to cross hydrophobic barriers, a lack of cytotoxicity, and a simple three-step synthesis from biogenic starting material suggests that 5a and related conjugates may be exploitable as a novel class of anti-viral agents for systemic and topical applications.     

A Bambusuril Macrocycle that Binds Anions in Water with High Affinity and Selectivity

Synthetic receptors that function in water are important for the qualitative and quantitative detection of anions, which may act as pollutants in the environment or play important roles in biological processes. Neutral receptors are particularly appealing because they are often more selective than positively charged receptors; however, their affinity towards anions in pure water is only in range of 1–10³ L mol^?1. The anion‐templated synthesis of a water‐soluble bambusuril derivative is shown to be an outstanding receptor for various inorganic anions in pure water, with association constants of up to 10⁷ L mol^?1. Furthermore, the macrocycle discriminates between anions with unprecedented selectivity (up to 500 000‐fold). We anticipate that the combination of remarkable affinity and selectivity of this macrocycle will enable the efficient detection and isolation of diverse anions in aqueous solutions, which is not possible with current supramolecular systems.     

Self-cleaning resins

This paper introduces a fundamentally new concept in adsorbents, whereby the sorption of an aqueous solute by a cross-linked polymer is controlled by a gel to liquid-crystalline phase transition. To demonstrate proof of principle, a bilayer forming surfactant, N,N-dioctadecyl,N,N-dimethylammonium bromide (DODAB) has been immobilized onto a cation exchange resin, Dowex 50WX2, and its thermotropic phase behavior and solute-adsorption properties have been investigated. Examination by a combination of differential scanning calorimetry and X-ray scattering has confirmed the retention of a gel to liquid-crystalline phase transition of the surfactant, occurring between 296 and 318 K. Adsorption measurements that were made for 4-chlorotetrahydropyran, 1,2-dichloroethane, and benzyl alcohol have also confirmed uptake by the resin in the liquid-crystalline phase and release in the gel phase.     

Removal of chlorinated solvents from carbonate-buffered water by zero-valent iron

The performance of a ground level reactive cell, filled with Fe⁰, designed for the treatment of water contaminated by chlorinated solvents, having a total input concentration of approximately 2 mg 1⁻¹ of the principal contaminants trichloroethene and perchloroethene, was tested at the Milovice site in the Czech Republic. A residence time of 1.62 days in the box was sufficient to reduce concentrations to a fraction less than 0.015 of the initial concentration. However, incomplete degradation of cis-1,2-DCE was observed. Reactions approximated first-order kinetics. The principal changes of concentrations of inorganic dissolved species in the reactive cell occurred for Ca²⁺, HCO ₃ ⁻ , NO ₃ ⁻ (decreased) and for Fe (initially increased, then decreased). Changes for Ca²⁺ and HCO ₃ ⁻ were caused by the precipitation of secondary carbonate mineral phases such as aragonite and siderite with the minor presence of green rust-CO₃. Concentration changes were gradual, along the complete length of the cell with a maximum at the inlet zone. The observations were attributed to minor increases of pH and slow kinetics of precipitation in the carbonate-buffered system. The average porosity loss was estimated to be approximately 2.7 % of the initial porosity per year, suggesting the long-term function of the permeable reactive barrier.