Correlation between C and O chemical shifts and torsional strain in spiroacetals

The relationship between the ¹³C and ¹⁷O NMR chemical shifts and the dihedral energies (non-bonding interactions) of 1,4-dioxaspiro[4.4]nonane, 1,4-dioxa- and 6,10-dioxaspiro[4.5]decane, 1,4-dioxa- and 6,11-dioxaspiro[4.6]undecane, 1,5-dioxaspiro[5.5]undecane, 1,5-dioxa and 7,12-dioxaspiro[5.6]dodecane and 1,6-dioxaspiro[6.6]tridecane were analyzed. These data showed correlation of the non-bonding interactions with the chemical shift of the spiranic carbon, as well as a linear relationship between ¹³C and ¹⁷O.     

Coelectroosmotic capillary electrophoresis of phenolic acids and derivatized amino acids using N,N-dimethylacrylamide-ethylpyrrolidine methacrylate physically coated capillaries

Two different families of compounds, i.e., phenolic and amino acids have been separated by capillary electrophoresis using a physically adsorbed polymer as capillary coating. The polymer used was N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EpyM) and it provided an stable coating by only flushing the capillary with a DMA-EpyM aqueous solution for 2 min between runs. The usefulness of this procedure has been demonstrated through the fast analysis of different families of solutes. Two different detection systems, diode-array detector and laser-induced fluorescence, have been used to determine phenolic acids and derivatized amino acids with fluorescein isothiocyanate, respectively. The main factors affecting reversal of electroosmotic flow (EOF) such as pH, type and concentration of buffer, and concentration and influence of organic solvents, as well as all the instrumental conditions were studied and optimized for both families of compounds.     

Rapid method for the determination of non-steroidal anti-inflammatory drugs in animal tissue by liquid chromatography-mass spectrometry with ion-trap detector

A rapid and new liquid chromatography-mass spectrometry with ion-trap detection method for the determination of meloxicam (MLX), flunixin meglumine (FLU), carprofen (CPF), and tolfenamic acid (TOLF) in animal tissue is described. MRLs between 10 and 500 microg kg(-1) in muscle and between 65 and 1000 microg kg(-1) in liver, from different animal species have been established in the EU for these compounds. After chemical hydrolysis, an organic extraction from homogenised tissue was performed. Final extract was injected in a liquid chromatograph with an ion-trap mass spectrometer with electrospray interface. Four identification points (one precursor and two product ions) and a minimum of one ion ratio was monitored for each compound. For quantitative purposes flunixin-D3 (FLU-D3) was used as internal standard. The method was validated using fortified blank muscle and liver from different animal species according to the 2002/657/EC European decision criteria. The decision limits (CCalpha) and detection capabilities (CCbeta) were determined and their values were at concentrations near the MRL for each substance.     

Production of artifact methylmercury during the analysis of certified reference sediments: use of ionic exchange in the sample treatment step to minimise the problem

Production of artifact methylmercury (MeHg⁺) during the analysis of two certified reference sediments, CRM-580 and IAEA-405, was investigated. Leaching of the analyte from the solid sample was achieved by ultrasound assisted acidic extraction. The aqueous leachate was either ethylated (NaBEt₄) or phenylated (NaBPh₄) using acetic/acetate or citric/citrate to buffer the solution. Preconcentration of the volatile compounds was carried out by extraction with an organic solvent (n-hexane) or solid phase microextraction (SPME). MeHg⁺ was finally separated and detected by gas chromatography with atomic emission or mass spectrometry detection (GC-MIP-AED or GC-MS). In all the cases the concentrations obtained for MeHg⁺ in the CRM-580 were significantly higher than the certified value. For the IAEA-405, however, the MeHg⁺ concentration found was always statistically indistinguishable from the certified value. Experiments were also conducted with synthetic samples, such as aqueous mixtures of MeHg⁺ and inorganic mercury (Hg²⁺) or silica-gel spiked with both compounds. The methylation rates found (defined as the percentage of Hg²⁺ present in the sample which methylates to give artifact MeHg⁺) ranged from not observable (in certain synthetic aqueous mixtures) to 0.57% (analysis of CRM-580 under certain conditions). As the amount of Hg²⁺ available in the sample seems to be the main factor controlling the magnitude of the artifact, several experiments were conducted using an ionic exchange resin (Dowex M-41) in order to minimise the concentration of this chemical in the reaction medium. First, a hydrochloric leachate of the sample was passed through a microcolumn packed with the exchanger. Second, the resin was mixed with the sample prior to extraction with HCl. In both cases, the predominant Hg²⁺ species, HgCl₄²⁻, was adsorbed on the resin, whereas MeHg⁺, mainly as MeHgCl, remained in solution. Following the second option, a new method to analyse MeHg⁺ in conflictive matrices like certain sediments was proposed. This approach produced better results for the CRM-580, but a MeHg⁺ concentration slightly, but statistically significant, higher than the reference value was still obtained.