Critical review on recent developments in solventless techniques for extraction of analytes.

The most recent contributions on solventless extraction techniques have been reviewed. This paper deals with those techniques that use solid phases, such as solid-phase microextraction, liquid phases, such as single-drop microextraction and hollow-fibre liquid-phase microextraction, and subcritical fluids, such as subcritical water extraction. In all cases, the most recent publications have been critically studied. Direct extraction and derivatization processes to facilitate the extraction of analytes in different areas have been included. Hyphenated approaches, if available, are also included in this review. Comparison of techniques organized by analytes and matrices also enhances this critical overview of solventless techniques.

Efficiency of whole and skimmed powdered milk for trapping volatile compounds released from plastic containers in high-temperature applications.

Plastic food containers used for high-temperature applications are not completely inert, and potentially harmful chemicals may be transferred to foodstuffs when such containers are heated. The aim of this work was to investigate the role of food fat content on the efficiency of trapping volatile organic compounds from heated plastic packaging. Relatively simple food matrices such as powdered skimmed and whole milk were evaluated with respect to their retention of several selected migrants: toluene, 1-octene, ethylbenzene, o-, m-, and p-xylene, styrene, and 1,4-dichlorobenzene released from containers made of polypropylene (random and copolymer), polycarbonate, and styrene-acrylonitrile copolymer, which are all commonly used in high-temperature applications. The analytical method (purge and trap gas chromatography and mass spectrometry) was optimized for each matrix. The developed procedure had detection limits of 0.01 to 1.2 ng, depending on the analyte and sample matrix, and both reproducibility and repeatability (expressed as relative standard deviation) were below 15%. This method was applied to the different plastic materials. The concentrations of the volatile compounds in both matrices were well below the established specific migration limits. Temperature and fat content of powdered milk were the most influential variables in mass transfer processes. These values were compared with those obtained with either Tenax TA (alternative test medium for fatty food simulants) or Porapak Q (another widely used sorbent). Similar results were found in skimmed powdered milk and Tenax TA, but significant differences were observed for whole powdered milk.

Paving the way to nanoionics: atomic origin of barriers for ionic transport through interfaces.

The blocking of ion transport at interfaces strongly limits the performance of electrochemical nanodevices for energy applications. The barrier is believed to arise from space-charge regions generated by mobile ions by analogy to semiconductor junctions. Here we show that something different is at play by studying ion transport in a bicrystal of yttria (9% mol) stabilized zirconia (YSZ), an emblematic oxide ion conductor. Aberration-corrected scanning transmission electron microscopy (STEM) provides structure and composition at atomic resolution, with the sensitivity to directly reveal the oxygen ion profile. We find that Y segregates to the grain boundary at Zr sites, together with a depletion of oxygen that is confined to a small length scale of around 0.5 nm. Contrary to the main thesis of the space-charge model, there exists no evidence of a long-range O vacancy depletion layer. Combining ion transport measurements across a single grain boundary by nanoscale electrochemical strain microscopy (ESM), broadband dielectric spectroscopy measurements, and density functional calculations, we show that grain-boundary-induced electronic states act as acceptors, resulting in a negatively charged core. Besides the possible effect of the modified chemical bonding, this negative charge gives rise to an additional barrier for ion transport at the grain boundary.

Use of solid-phase microextraction for the analysis of bisphenol A and bisphenol A diglycidyl ether in food simulants.

A new method has been developed to simultaneously analyse bisphenol A (BPA) and bisphenol A diglycidyl ether (BADGE) in aqueous based food simulants. The method consists on direct immersion solid-phase microextraction (SPME) of the analytes from the liquid matrix and subsequent chromatographic analysis by gas chromatography-mass spectrometry. Using the proposed method, a whole analysis (including chromatographic step) can be completed in less than 40 min, with minimum sample handling. The SPME method shows good analytical performance for simultaneous BPA and BADGE analysis, except for BADGE determination in the aqueous alcohol (simulant C) solution. Detection limits ranging from 0.1 to 2.0 ng/g for BPA and from 13 to 15 ng/g from BADGE were obtained, with a linear range from the low-ng/g to several-microg/g range for BPA and from 0.1 microg/g to 40 microg/g for BADGE. A possible optimisation method has been also developed and introduced.

Determination of bisphenol-type contaminants from food packaging materials in aqueous foods by solid-phase microextraction-high-performance liquid chromatography.

A fast screening method consisting of off-line solid-phase microextraction coupled to HPLC and fluorescence detection, suitable for the analysis of several bisphenol derivatives and their degradation products in aqueous solution, has been developed. Detection limits of 0.7 ng ml(-1) for 2,2-bis[4-(glycidyloxy)phenyl]propane, 0.9 ng ml(-1) for bisphenol A bis(3-chloro-2-hydroxypropyl)ether, 1.1 ng ml(-1) for 2,2-bis(4-hydroxyphenyl)propane and 2.4 ng ml(-1) for bisphenol F diglycidyl ether have been achieved working in the linear range 10-500 ng ml(-1). The good analytical features achieved make the proposed method an interesting option for the direct determination of these compounds in aqueous canned food such as peas, tuna, olives, maize, artichokes or palm hearts. Both the optimization process and the results, including the analysis of real samples, are given and discussed.

[Prospective therapeutic trial of masking treatment in patients with tinnitus]. / Ensayo terapéutico prospectivo mediante tratamiento enmascarador en pacientes con acufenos.

We report the results of a therapeutic trial of patients with tinnitus of different characteristics that was unresponsive to other medical or surgical treatments. Treatment was based on a combination of biofeedback training designed to reduce stress and either pure masking therapy or masking therapy consisting of a hearing aid and masker. The results showed an improvement in subjective perceptions and in the audiometric parameter of pitch in a significant percentage of patients.

Reversible electric-field control of magnetization at oxide interfaces.

Electric-field control of magnetism has remained a major challenge which would greatly impact data storage technology. Although progress in this direction has been recently achieved, reversible magnetization switching by an electric field requires the assistance of a bias magnetic field. Here we take advantage of the novel electronic phenomena emerging at interfaces between correlated oxides and demonstrate reversible, voltage-driven magnetization switching without magnetic field. Sandwiching a non-superconducting cuprate between two manganese oxide layers, we find a novel form of magnetoelectric coupling arising from the orbital reconstruction at the interface between interfacial Mn spins and localized states in the CuO2 planes. This results in a ferromagnetic coupling between the manganite layers that can be controlled by a voltage. Consequently, magnetic tunnel junctions can be electrically toggled between two magnetization states, and the corresponding spin-dependent resistance states, in the absence of a magnetic field.

Design of a method for generation of gas-phase hydroxyl radicals, and use of HPLC with fluorescence detection to assess the antioxidant capacity of natural essential oils.

The use of natural antioxidants is of increasing importance in the human diet, because they are recognised as compounds essential to health which minimize or delay the aging process. Despite apparent simplicity, however, it is very difficult to measure and quantify such properties, for which a robust analytical method is required. Because oxidation usually is caused by the presence of OH* radicals, a new method involving the in-situ, vapour-phase generation of these radicals and their quantification in the presence and absence of potential antioxidant extracts has been developed. The oxidant atmosphere generated from hydrogen peroxide is carried by an air stream through an empty quartz chamber in which UV radiation promotes the formation of radicals by a photochemical reaction. The products then pass through a cartridge containing the essential oil, finally bubbling into an impinger containing an aqueous solution of salicylic acid, at pH 4.5, which reacts with the OH* radicals forming 2,5-dihydroxybenzoic acid. This solution is quantified by RP-HPLC using UV and fluorescence detectors connected in series. Detection and quantification limits for OH* radicals were approximately 0.01 pg g(-1) air. Description and optimization of the method are discussed, as also is the antioxidant performance of an extract of ginger (Zingiber officinale R.), which reduced the oxidation process by up to 92%.

Behaviour of Chimassorb 81 in the recycling process of agricultural films used as soil covers.

Two different films, low density polyethylene (LDPE) and an ethylene-vinyl acetate copolymer (EVA), used as agricultural soil covers were studied. The films were recycled five and ten times respectively, and both the tensile strength and the content of Chimassorb 81, a UV-stabilizer, were analysed in each cycle. Losses of 17.44% in tensile strength and 23.69% (Thermic film) and 13.22% (EVA) in the concentration of Chimassorb 81 were found after five recycling cycles. The extraction of Chimassorb 81 from the film is optimized. As these films can be recycled for the same application or even for use as food-contact materials, the standard migration tests with established simulants have been carried out. The results obtained are discussed.

Parts-per-trillion determination of styrene in yoghurt by purge-and-trap gas chromatography with mass spectrometry detection.

Headspace sampling methods prior to capillary gas chromatography have been widely used for the determination of volatile compounds present in very different kinds of samples. This paper describes an automated and rapid system to determine volatiles from yoghurt. Thirty-five volatile organic compounds (VOCs) were identified in polystyrene cups used for yoghurt packaging and 42 VOCs from yoghurt samples. Quantitation of styrene in several samples from the Spanish retail market was carried out.

Multicomponent recycled plastics: considerations about their use in food contact applications.

Two multicomponent post-use recycled plastics named as NPP40A3 (formulated with 85% HDPE and 15% of a PP-PS-PVC mixture) and NPP40A6 (formulated with 80% NPP40A3, 10% ABS and 10% HIPS), both of them with 3.1% of plasticizer and 0.6% of stabilizer to obtain a better final product, have been analysed. Plastics were extracted both with dichloromethane and methylbenzene, and analysed by HPLC and GC-MS to identify the maximum possible number of compounds. Major additives quantified were di(ethylhexyl)phthalate (3.262% and 2.955% respectively) and Irganox 1010 (0.473% and 0.498% respectively). Several degradation compounds have been detected. In order to check if these plastics could be used in food contact applications, global and specific migration tests have been applied. The results obtained are discussed.