Highly selective palladium-benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions.

The Pd-benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji-Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed.

Determination of hidden hazelnut oil proteins in extra virgin olive oil by cold acetone precipitation followed by in-solution tryptic digestion and MALDI-TOF-MS analysis.

Adulteration of extra-virgin olive oil (EVOO) with hazelnut oil (HO) is an illegal practice that could have severe health consequences for consumers due to the possible exposure to hidden hazelnut allergens. Here, matrix-assisted laser-desorption/ionization (MALDI) mass spectrometry (MS) was used as a rapid and sensitive technique for the detection of a low concentration of hazelnut proteins in oil samples. Different protocols were tested for protein extraction, and the most efficient (cold acetone) was applied to HO and EVOO adulterated with HO. The subsequent in-solution tryptic digestion of protein extracts and MALDI-MS analysis, using α-cyano-4-chlorocinnamic acid as matrix, allowed the detection of stable hazelnut peptide markers (i.e., the m/z ions 1002.52, 1356.71, 1394.70, 1440.81, 1453.85, 1555.76, 1629.83, 1363.73, and 1528.67) attributable to the main hazelnut proteins Cor a 9, Cor a 11, and Cor a 1. Thus, the approach might allow the direct detection of specific hazelnut allergens in EVOO at low concentration without time-consuming pretreatments.

Detection of sheep and goat milk adulterations by direct MALDI-TOF MS analysis of milk tryptic digests.

In dairy field, one of the most common frauds is the adulteration of higher value types of milk (sheep's and goat's) with milk of lower value (cow's milk). This illegal practice has an economic advantage for milk producers and poses a threat for consumers' health because of the presence of hidden allergens as, for example, cow milk proteins, in particular, α(s1)-casein and ß-lactoglobulin. The urgent need of sensitive techniques to detect this kind of fraud brought to the development of chromatographic, immunoenzymatic, electrophoretic and mass spectrometric assays. In the current work, we present a fast, reproducible and sensitive method based on the direct matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) MS analysis of milk tryptic digests for the detection of milk adulteration by evaluating specie-specific markers in the peptide profiles. Several pure raw and commercial milk samples and binary mixtures containing cows' and goats', cows' and sheep's and goats' and sheep's milk (concentrations of each milk varied from 0% to 100%) were prepared, and tryptic digests were analyzed by MALDI-TOF MS. The use of the new MALDI matrix α-cyano-4-chlorocinnamic acid allowed to detect cow and goat milk peptide markers up to 5% level of adulteration. Finally, from preliminary data, it seems that the strategy could be successfully applied also to detect similar adulterations in cheese samples.

Determination of delorazepam in urine by solid-phase microextraction coupled to high performance liquid chromatography.

An SPME-HPLC-UV method for the determination of delorazepam, a representative benzodiazepine, in spiked human urine samples was developed for the first time. The performances of two commercially available fibers, a carbowax/templated resin (Carbowax/TPR-100) and a polydimethylsiloxane/divinylbenzene (PDMS/DVB), were compared, indicating the latter as the most suitable for urine samples analysis. All the aspects influencing adsorption (extraction time, pH, temperature, salt addition) and desorption (desorption and injection time, desorption solvent mixture composition) of the analyte on the fiber have been investigated. In particular, short extraction times were necessary to reach the equilibrium and very short desorption times were employed. The procedure required simple sample pre-treatment and was able to detect 5 ng/ml in spiked urine, regardless of the complexity of the matrix.