Direct coupling of ionic liquid based single-drop microextraction and GC/MS

The use of ionic liquids as extracting media in single-drop liquid-phase microextraction (SDME) and its direct coupling to gas chromatography/mass spectrometry (GC/MS) is presented. For this purpose, a new removable interface that enables the introduction of the extracted analytes into the GC system, while preventing the ionic liquid from entering the column, has been developed. The determination of three representative pollutants in water samples has been used as a model analytical problem in order to demonstrate the feasibility of the proposed interface. The analytes (dichloromethane, p-xylene, and n-undecane) were coextracted from the aqueous sample in a 2-microL drop of 1-butyl-3-methylimidazolium hexaflourophosphate. Then, the syringe used to perform the SDME was directly introduced into the interface, which was held at 140 degrees C in order to achieve a complete volatilization of the target compounds. After the injection, the ionic liquid was retained in the interface, while a carrier gas transferred the volatilized analytes into the GC inlet. The optimization of the operational variables affecting the new interface (temperature, carrier flow rate, sample volume and injection technique) was accomplished. The analytes could be determined with detection limits in the low-nanogram per milliliter concentration range, and the relative standard deviations were between 3.3 and 4.4%.     

Characterization of an attenuated total reflection-based sensor for integrated solid-phase extraction and infrared detection

A novel attenuated total reflection (ATR) sensor, which integrates solid-phase extraction (SPE) and infrared detection, is presented. The flow cell, which enables the on-line coupling with a sequential injection system, is the core of the proposed sensor since it allows the continuous delivery of different solutions through the ATR and also the continuous spectrum acquisition. A SPE sorbent material (LiChrolut EN) was located in the sensitive element of the ATR without using any external coating substance, increasing the versatility of the system. A marked sensitivity enhancement was obtained as the analyte was concentrated before detection. The new sensor was qualitatively and quantitatively validated using the determination of caffeine in soft drinks as the model analytical problem. Linearity, precision (RSD = 4%), and sensitivity (LOD = 7 microg/mL) levels have been established. Finally, the main advantages and limitations of the new proposal are presented and compared with existing alternatives.     

Multiclass determination of sunscreen chemicals in water samples by liquid chromatography-tandem mass spectrometry

A novel analytical method based on solid-phase extraction (SPE) and liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) for the determination of UV sunscreen agents in the water environment is presented. After a thorough investigation of SPE and LC-MS/MS conditions, it permits the enrichment and determination of nine of these compounds in a single methodology, including three very polar sulfonates (e.g., 2-phenylbenzimidazole-5-sulfonic acid, PBSA) and six other less polar compounds (e.g., benzophenone-3, BP-3; octocrylene, OC,...). Other important matters of concern in the determination of UV filters at trace levels in water, i.e., adsorption on glassware and blank contamination problems, have also been discussed and minimized. This methodology affords detection limits between 7 and 46 ng L-1 and SPE recoveries in the range 63-102% from different real water matrixes, except for butylmethoxydibenzoylmethane (BM-DBM), which was not determinable in wastewater samples due to adsorption problems. The application of the method allowed reporting the levels of benzophenone-4 (BP-4) in environmental water samples for the first time, where it was identified as one of the most important in concentration among the UV filters studied, particularly in wastewater (237-1481 ng L-1).     

STD NMR study of the interactions between antibody 2G12 and synthetic oligomannosides that mimic selected branches of gp120 glycans

The human immunodeficiency virus type-1 (HIV-1) is able to shield immunogenic peptide epitopes on its envelope spike (a trimer of two glycoproteins, gp120 and gp41) by presenting numerous host-derived N-linked glycans. Nevertheless, broadly neutralizing antibodies against gp120 and gp41 have been isolated from HIV-1-infected patients and provide protection against viral challenge in animal models. Among these, the monoclonal antibody 2G12 binds to clusters of high-mannose-type glycans that are present on the surface of gp120. These types of glycans have thus been envisaged as target structures for the development of synthetic agents capable of eliciting 2G12-like antibodies. High-resolution structural studies of 2G12 and chemically defined glycan-type ligands, including crystallographic data, have been performed to gain an insight into this interaction. Further studies are still required to design a carbohydrate-based vaccine for HIV. Our previous NMR studies highlighted different recognition modes of two branched synthetic oligosaccharides, a penta- and a heptamannoside, by 2G12 in solution. In order to clarify the underlying structural reasons for such different behaviors, we have herein "dissected" the branches into the linear tri- and tetra- oligomannosides by chemical synthesis and studied their interactions with 2G12 in solution by saturation transfer difference (STD) NMR spectroscopy. The results confirm the distinct preferences of 2G12 for the studied branches and afford explanations for the observed differences. This study provides important structural information for further ligand optimizations. Possible effects of structural modifications on the solvent-exposed end of the ligands are also discussed.     

Free amino acids and biogenic amines in Alicante Monastrell wines

The simultaneous determination of 17 free amino acids and 8 biogenic amines in Alicante Monastrell wines was investigated for the first time. The quantification was carried out by using a RP-HPLC method, based on a pre-column derivatization with o-phthaldialdehyde (OPA) and fluorescence detection. From the results obtained it may be concluded that the most abundant free amino acids were Glu, Arg, Ala Asp, and Lys. None of the wine samples analysed had histamine (HIM) or Tyramine (TYM) levels above the limits considered as a possible toxic risk for healthy individuals. No measurable amounts of cadaverine (CAD) or methylamine (MEA) were found, showing no spoilage symptoms of sensory properties of the wines. Tryptamine (TRM) content was significantly higher in aged wines compared to young wines. However ethanolamine (ETA) content was lower. These data were used to make a preliminary classification of the samples using cluster analysis.     

Multivariate data analysis applied to the definition of two Catalan viticultural regions I. Cluster analysis

Summary Five multivariate data analysis methods, namely principal components analysis, non-linear mapping, hierarchical clustering, minimal spanning tree and mode analysis, were used to analyse the natural structure of red wines from Tarragona (Catalonia, Spain). Seventeen parameters were analysed for each sample to determine the multi-dimensional spectrum in which the wines are studied. In spite of the homogeneity of the wine samples which resulted from the similarity of the edaphic, varietal factors as well as the cultural conditions of the producing areas, two different clusters can be distinguished on the basis of all the methods used. The groups of wine samples obtained coincide with two viticultural zones that differ with regard to climate and geographical conditions. Therefore, a natural distinction can bei made between the wines produced in each adjacent zone, forming the basis for future differentiation according to brand name.

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Mehrfache Varianzanalyse für die Bestimmung von zwei katalanischen Weinregionen I. Cluster Analyse

Zusammenfassung Fünf Methoden von Multivarianz-Analysen (Hauptkomponenten-Analyse, Non Linear Mapping, Hierarchisches Clustering, Minimal Spanning Tree und Mode Analyse wurden angewandt, um die natürliche Struktur von 28 Rotweinen aus dem Tarragona-Bereich (Katalonien, Spanien) zu analysieren. Für jede Probe wurden 17 Parameter herangezogen, um das multidimensionale Spektrum zu bestimmen, mit dem die Weine analysiert wurden. Trotz der Homogenität der Weinmuster, die sich aus den ähnlichen, edaphologischen Sorten- und Anbau-Faktoren des Produktionsgebietes ergeben, können zwei verschiedene Cluster auf Grund der angewandten Methoden unterschieden werden. Die aus den Weingruppen erhaltenen Muster stimmen mit den gegenwärtigen Weinzonen überein, die in ihren klimatischen und geographischen Verhältnissen verschieden sind, so daß eine natürliche Unterscheidung zwischen den Weinen möglich ist, die in benachbarten Zonen produziert werden, was eine Basis für die zukünftige Unterscheidung ihrer Herkunft schafft.

     

As, Hg, and Se flue gas sampling in a coal-fired power plant and their fate during coal combustion

As, Hg, and Se are the most volatile elements in the flue gas from a coal-fired power plant. Significant amounts of these elements cause an undesired direct gaseous emission, which leads to a serious environmental health risk. The main focus of this study is to evaluate the possibility of simultaneous sampling of these volatile elements using an accurate official method for Hg (the most volatile element). A study of As, Hg, and Se emissions from a 1400 MW coal-fired power plant equipped with electrostatic precipitators (ESPs) was carried out for the combustion of a mixture of two types of coal. Simultaneous sampling of coal, bottom ash, fly ash, flue gas, and particles associated with the gas phase has been performed. Flue gas has been sampled by the Ontario Hydro Method Sampling Train, an ASTM method for Hg speciation. This sampling method was tested for As and Se sampling. As and Se determinations have been performed by HG-AAS, and Hg has been determined by CV-AAS. The results were used to examine the following: overall mass balances, relative distribution of these elements in the coal-fired power plant; As, Hg, and Se concentrations in coal and combustion residues; and predominant oxidation state for Hg in flue gas. The mass balances obtained for As, Hg, and Se were satisfactory in all cases; nevertheless, relative enrichment values in fly ash for As and Se were low; therefore, we concluded that As sampling in flue gas can be conducted by application of the Ontario Hydro Method; nevertheless Se released in the gas phase is not completely collected by this sampling train. Application of this sampling method allowed for performance of Hg speciation. The results indicated that Hg(II) was the predominant species in flue gas. It has also been proved that 24%, more than 99.8%, and 90% for As, Hg, and Se in the stack emissions, respectively, were in the gaseous phase.     

Comparison of a pair of synthetic tea-catechin-derived epimers: synthesis, antifolate activity, and tyrosinase-mediated activation in melanoma

Despite bioavailability issues, tea catechins have emerged as promising chemopreventive agents because of their efficacy in various animal models. We synthesized two catechin-derived compounds, 3-O-(3,4,5-trimethoxybenzoyl)-(-)-catechin (TMCG) and 3-O-(3,4,5-trimethoxybenzoyl)-(-)-epicatechin (TMECG), in an attempt to improve the stability and cellular absorption of tea polyphenols. The antiproliferative and pro-apoptotic activities of both compounds were analyzed with various cancer cell systems, and TMCG, which was easily synthesized in excellent yield, was more active than TMECG in both melanoma and non-melanoma cell lines. TMCG was also a better inhibitor of dihydrofolate reductase and was more efficiently oxidized by tyrosinase, potentially explaining the difference in activity between these epimers.