Vapor generation – atomic spectrometric techniques. Expanding frontiers through specific-species preconcentration. A review

We review recent progress in preconcentration strategies associated to vapor generation techniques coupled to atomic spectrometric (VGT-AS) for specific chemical species detection. This discussion focuses on the central role of different preconcentration approaches, both before and after VG process. The former was based on the classical solid phase and liquid–liquid extraction procedures which, aided by automation and miniaturization strategies, have strengthened the role of VGT-AS in several research fields including environmental, clinical, and others. We then examine some of the new vapor trapping strategies (atom-trapping, hydride trapping, cryotrapping) that entail improvements in selectivity through interference elimination, but also they allow reaching ultra-low detection limits for a large number of chemical species generated in conventional VG systems, including complete separation of several species of the same element. This review covers more than 100 bibliographic references from 2009 up to date, found in SCOPUS database and in individual searches in specific journals. We finally conclude by giving some outlook on future directions of this field.     

Aza-Michael reaction with enone-modified vegetable oils: evidence of the keto–enolic equilibrium by NIR chemical imaging and evolving factor analysis

The existence of an enone–dienol tautomerism in enone-containing triglyceride, obtained from high oleic sunflower oil, was detected in an image set captured at 95 °C by fixed-size image window-evolving factor analysis. A ¹H NMR spectrum and a UV–Visible spectrum of the enone-containing triglyceride at 25 °C and at 95 °C were measured to corroborate the presence of the enol form. The presence of this equilibrium explains the different behaviour of the curing reaction between an enone-containing triglyceride and diaminodiphenylmethane, which was evaluated following the spectral evolution of two pixels that differ in the presence or absence of the enol form. As the enol form acts as a inert species in the reaction, it leads to different degree of advance depending on which growing zone is observed.     

Biosorption: a new rise for elemental solid phase extraction methods

Biosorption is a term that usually describes the removal of heavy metals from an aqueous solution through their passive binding to a biomass. Bacteria, yeast, algae and fungi are microorganisms that have been immobilized and employed as sorbents in biosorption processes. The binding characteristics of microorganisms are attributed to functional groups on the surface providing some features to the biosorption process like selectivity, specificity and easy release. These characteristics turn the biosorption into an ideal process to be introduced in solid phase extraction systems for analytical approaches. This review encompasses the research carried out since 2000, focused on the employment of biosorption processes as an analytical tool to improve instrumental analysis. Since aminoacids and peptides as synthetic analogues of natural metallothioneins, proteins present in the cell wall of microorganisms, have been also immobilized on solid supports (controlled pore glass, carbon nanotubes, silica gel polyurethane foam, etc.) and introduced into solid phase extraction systems; a survey attending this issue will be developed as well in this review.     

Ion-mobility spectrometry for environmental analysis

Advances and changes in practical aspects of ion-mobility spectrometry (IMS) have led to its widespread use for applications of environmental concern due to its unique characteristics, which include portability, ruggedness, relatively low acquisition costs and speed of analysis. However, limitations regarding the complexity of environmental samples and strict requirements on limits of detection have to be overcome.This article critically reviews existing environmental applications using IMS for the determination of different families of compounds. We also consider the analytical tools developed to solve the limitations regarding selectivity and sensitivity, including those approaches that have led to advances in the instrumentation of IMS and its combination with other techniques for extraction and pre-concentration of analytes, pre-separation of analytes and its coupling to other detection systems.Finally, we discuss current trends that facilitate the deployment of IMS for on-site or in-field analysis.     

In-vivo and in-vitro testing to assess the bioaccessibility and the bioavailability of arsenic, selenium and mercury species in food samples

In-vivo and in-vitro gastrointestinal (GI) extractions, also known as oral bioaccessibility and bioavailability, are important approaches to assess chemical risk to humans. We give an overview of in-vivo and in-vitro bioaccessibility and bioavailability assays for testing arsenic, selenium and mercury (As, Se and Hg) species from food samples. We critically evaluate the parameters affecting in-vivo and in-vitro processes. In addition, we consider the effect of cooking food on bioaccessibility and bioavailability, and stability and transformation, of species during in-vivo or in-vitro processes. The bioaccessibility and bioavailability of As, Se and Hg species are affected by the sample matrix, cooking food and the experimental conditions applied (gastric and intestinal pH, incubation temperature and residence time). Regarding species degradation and transformation during in-vitro procedures, good stability has been observed for most As species, except for certain arsenosugars. Important transformations during in-vitro processes have been reported for Se species [e.g., conversion of γ-glu-Se-MeSeCys to Se-MeSeCys, and organic Se species (MeSeCys, SeCys2 and SeMet) degradation to inorganic Se]. Finally, we summarize speciation and detection conditions for As, Se and Hg speciation, and quality control to assure reliable measurements.     

Anisotropic magnetoresistance and piezoresistivity in structured Fe3O4-silver particles in PDMS elastomers at room temperature

Magnetorheological elastomers, MREs, based on elastic organic matrices displaying anisotropic magnetoresistance and piezoresistivity at room temperature were prepared and characterized. These materials are dispersions of superparamagnetic magnetite forming cores of aggregated nanoparticles inside silver microparticles that are dispersed in an elastomeric polymer (poly(dimethylsiloxane), PDMS), curing the polymer in the presence of a uniform magnetic field. In this way, the elastic material becomes structured as the application of the field induces the formation of filaments of silver-covered inorganic material agglomerates (needles) aligned in the direction of the field (parallel to the field). Because the magnetic particles are covered with silver, the MREs are not only magnetic but also electrical conductors. The structuration induces elastic, magnetic, and electrical anisotropic properties. For example, with a low concentration of particles in the elastic matrix (5% w/w) it is possible to obtain resistances of a few ohms when measured parallel to the needles or several megaohms in the perpendicular direction. Magnetite nanoparticles (Fe(3)O(4) NP) were synthesized by the coprecipitation method, and then agglomerations of these NPs were covered with Ag. The average size of the obtained magnetite NPs was about 13 nm, and the magnetite-silver particles, referred to as Fe(3)O(4)@Ag, form micrometric aggregates (1.3 μm). Nanoparticles, microparticles, and the MREs were characterized by XRD, TEM, SEM, EDS, diffuse reflectance, voltammetry, VSM, and SQUID. At room temperature, the synthesized magnetite and Fe(3)O(4)@Ag particles are in a superparamagnetic state (T(B) = 205 and 179 K at 0.01 T as determined by SQUID). The elastic properties and Young's modulus of the MREs were measured as a function of the orientation using a texture analysis device. The magnetic anisotropy in the MRE composite was investigated by FMR. The electrical conductivity of the MRE (σ) increases exponentially when a pressure, P, is applied, and the magnitude of the change strongly depends on what direction P is exerted (anisotropic piezoresistivity). In addition, at a fixed pressure, σ increases exponentially in the presence of an external magnetic field (H) only when the field H is applied in the collinear direction with respect to the electrical flux, J. Excellent fits of the experimental data σ versus H and P were achieved using a model that considers the intergrain electron transport where an H-dependent barrier was considered in addition to the intrinsic intergrain resistance in a percolation process. The H-dependent barrier decreases with the applied field, which is attributed to the increasing match of spin-polarization in the silver covers between grains. The effect is anisotropic (i.e., the sensitivity of the magnetoresistive effect is dependent on the relative orientation between H and the current flow J). In the case of Fe(3)O(4)@ Ag, when H and J are parallel to the needles in the PDMS matrix, we obtain changes in σ up to 50% for fields of 400 mT and with resistances on the order of 1-10 Ω. Magnetoresistive and magnetoelastic properties make these materials very interesting for applications in flexible electronics, electronic skins, anisotropic pressure, and magnetic field sensors.     

Evaluation of single-walled carbon nanohorns as sorbent in dispersive micro solid-phase extraction

A new dispersive micro solid-phase extraction method which uses single-walled carbon nanohorns (SWNHs) as sorbent is proposed. The procedure combines the excellent sorbent properties of the nanoparticles with the efficiency of the dispersion of the material in the sample matrix. Under these conditions, the interaction with the analytes is maximized. The determination of polycyclic aromatic hydrocarbons was selected as model analytical problem. Two dispersion strategies were evaluated, being the functionalization via microwave irradiation better than the use of a surfactant. The extraction was accomplished by adding 1 mL of oxidized SWHNs (o-SWNHs) dispersion to 10 mL of water sample. After extraction, the mixture was passed through a disposable Nylon filter were the nanoparticles enriched with the PAHs were retained. The elution was carried out with 100 μL of hexane. The limits of detection achieved were between 30 and 60 ng L⁻¹ with a precision (as repeatability) better than 12.5%. The recoveries obtained for the analytes in three different water samples were acceptable in all instances. The performance of o-SWNHs was favourably compared with that provided by carboxylated single-walled carbon nanotubes and thermally treated carbon nanocones.     

A novel and rapid method for determination of natamycin in wines based on ultrahigh-performance liquid chromatography coupled to tandem mass spectrometry: validation according to the 2002/657/EC European decision

A novel, simple, and rapid reversed-phase liquid chromatography–tandem mass spectrometric methodology was developed for the analysis of natamycin in wine samples. Natamycin was protonated to form singly charged ions in an electrospray positive ion mode. Data acquisition under MS/MS was achieved by applying multiple reaction monitoring (MRM) of three fragment ion transitions (666.3 → 648.2, 666.3 → 503.3, and 666.3 → 485.2) to provide a high degree of sensitivity and specificity. Chromatographic separation was performed on a rapid resolution column using a mobile phase consisting of an acetonitrile/water mixture with a total run time of 5.0 min. After only filtration as pretreatment, the sample was injected into the chromatographic system. The proposed method was validated in terms of selectivity, trueness, precision, decision limit (CCα), and detection capability (CCβ) according to 2002/657/EC Commission decision. The values for trueness, reported as bias (%), agreed with those established by the aforementioned document. Repeatability (intraday variability) values were 12.37% at a concentration of 1.0 μg L⁻¹ and 8.99–4.19% at concentrations between 2.5 and 10 μg L⁻¹. The overall within-laboratory (interday variability) reproducibility was 15.47% at a concentration of 1.0 μg L⁻¹, which was significantly lower than the indicative value reported in the EU decision. The results indicated that the proposed approach is a sensitive, fast, reproducible, and robust methodology suitable for the analysis of natamycin levels in wine samples.     

Chemical composition, antifungal and herbicidal effects of essential oil isolated from Chersodoma Argentina (Asteraceae)

Analysis of the hydrodistilled essential oil of the aerial parts of Chersodoma argentina Cabrera by GC-MS and NMR spectroscopy revealed that over 80% consisted of monoterpene hydrocarbons such as alpha-thujene, alpha-pinene and beta-pinene. Contact and headspace volatile exposure assays of the essential oil demonstrated antifungal activity against Sclerotinia sclerotiorum, Sclerotium rolfsii and Rhizoctonia solani with the contact assay showing greater activity than the headspace assay. Herbicidal activity was shown by reduced root growth of Allium porrum, Solanum lycopersicon and Sorghum halepense in both assays.