New method for determination of (E)-resveratrol in wine based on microextraction using packed sorbent and ultra-performance liquid chromatography

An ultra-fast and improved analytical methodology based on microextraction by packed sorbent (MEPS) combined with ultra-performance LC (UPLC) was developed and validated for determination of (E)-resveratrol in wines. Important factors affecting the performance of MEPS such as the type of sorbent material (C2, C8, C18, SIL, and M1), number of extraction cycles, and sample volume were studied. The optimal conditions of MEPS extraction were obtained using C8 sorbent and small sample volumes (50-250 μL) in one extraction cycle (extract-discard) and in a short time period (about 3 min for the entire sample preparation step). (E)-Resveratrol was eluted by 1×250 μL of the mixture containing 95% methanol and 5% water, and the separation was carried out on a high-strength silica HSS T3 analytical column (100 mm × 2.1 mm, 1.8 μm particle size) using a binary mobile phase composed of aqueous 0.1% formic acid (eluent A) and methanol (eluent B) in the gradient elution mode (10 min of total analysis). The method was fully validated in terms of linearity, detection (LOD) and quantification (LOQ) limits, extraction yield, accuracy, and inter/intra-day precision, using a Madeira wine sample (ET) spiked with (E)-resveratrol at concentration levels ranging from 5 to 60 μg/mL. Validation experiments revealed very good recovery rate of 95±5.8% RSD, good linearity with r(2) values >0.999 within the established concentration range, excellent repeatability (0.52%), and reproducibility (1.67%) values (expressed as RSD), thus demonstrating the robustness and accuracy of the MEPS(C8) /UPLC-photodiode array (PDA) method. The LOD of the method was 0.21 μg/mL, whereas the LOQ was 0.68 μg/mL. The validated methodology was applied to 30 commercial wines (24 red wines and six white wines) from different grape varieties, vintages, and regions. On the basis of the analytical validation, the MEPS(C8)/UPLC-PDA methodology shows to be an improved, sensitive, and ultra-fast approach for determination of (E)-resveratrol in wines with high resolving power within 6 min.     

Simple and sensitive determination of low-molecular-mass aromatic aldehydes in swimming pool water by LC-diode array detector

This work reports the development of a simple method for the quantitative determination of aromatic and aliphatic low-molecular-mass aldehydes (LMMAs) as disinfection by-products (DBPs) in indoor swimming pool waters after chlorination with a simplified SPE sample treatment. The method is based on the continuous in situ derivatization/preconcentration of the aldehydes with 2,4-dinitrophenylhydrazine (DNPH) on a Lichrolut EN column in the presence of β-CD. After elution, the 2,4-dinitrophenylhydrazine derivatives were separated on an RP-C(18) analytical column using gradient of ACN-water at 60-80%. The optimized sample treatment described here allowed the direct analysis of large volumes of water in order to improve the sensitivity of the method; LODs in the 60-120 ng/L range were achieved for aromatic LMMAs by using a volume of 50 mL of water, precision being 7.5% or better at a concentration level of 5 μg/L. These results indicate that the ensuing method is a useful choice for the determination of LMMAs in water samples that provides better results than reported LC alternatives in terms of the LOD (except for MS/MS detection), sample requirements for analysis and cost.     

Determination of azoles in sewage sludge from Spanish wastewater treatment plants by liquid chromatography-tandem mass spectrometry

A simple and rapid analytical method for the determination of 16 azoles in sewage sludge has been developed and validated. The method was based on ultrasound-assisted extraction followed by dispersive solid-phase extraction cleanup and liquid chromatography-electrospray tandem mass spectrometric detection. The azoles were selected by their intensive usage as biocides (tebuconazole, propiconazole, cyproconazole and thiabendazole), antimycotic pharmaceuticals (ketoconazole, econazole, fluconazole and clotrimazole) or fungicides in agriculture (difenoconazole, flusilazole, hexaconazole, prochloraz, bromuconazole, epoxiconazole and triticonazole). The recoveries of these compounds through the method were between 71.9 and 115.8%, with relative standard deviations lower than 20%. Detection limits were in the range of 0.5-5.0 ng/g. The developed method was applied to the analysis of azoles in sewage sludge samples collected from 19 Spanish wastewater treatment plants. Although azoles used as biocides or agriculture fungicides were present in a few sludge samples, the pharmaceuticals ketoconazole, econazole and clotrimazole were present in all of the analyzed sludge samples, being ketoconazole the one found at the highest level, representing the 68.6% of the total azole content found in the 19 sludge samples studied.     

Evaluation and evidence of natural gangliosides with two unsaturated bonds in the ceramide structure obtained by a combination of MALDI-MS and NMR spectroscopy

Gangliosides are membrane-associated glycosphingolipids. N-Acetyl GM3 and N-glycolyl GM3 are two tumor-associated antigens expressed in cancer tissues such as melanoma and mammalian cancer. In order to use these antigens in GM3-based vaccines for patients with early stage cancer, the synthetic version is recommended to avoid the risk of animal virus transmission from the source. However, the isolation of natural gangliosides is of comparative value for the structural characterization. The structures of N-acetyl and N-glycolyl GM3 extracted from dog and horse erythrocytes were evaluated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and nuclear magnetic resonance techniques; additionally, the natural N-acetyl ganglioside was compared to a synthetic one. In addition to the main compound with C24:0 fatty acid chain, a minor component with an additional unsaturation in the ceramide chain was detected, in both the dog and the horse gangliosides. This paper shows spectroscopic evidence of the aforementioned compounds.     

Quantum dot-based array for sensitive detection of <Emphasis Type="Italic">Escherichia coli</Emphasis>

A fluorescent quantum dot-based antibody array, used in sandwich format, has been developed to detect Escherichia coli O157:H7. Numerous parameters such as solid support, optimal concentration of immunoreagents, blocking reagents, and assay time were optimized for array construction. Quantum dot-conjugated anti-IgG was used as the detecting system. The array allows the detection of E. coli O157:H7 at concentrations below 10 CFU mL⁻¹ without sample enrichment, exhibiting an increase of three orders of magnitude in the limit of detection compared to ELISA. The interference caused by Gram (+) and Gram (−) bacteria was negligible at low concentrations of bacteria.     

Analysis of staphylococcal enterotoxin A in milk by matrix-assisted laser desorption/ionization-time of flight mass spectrometry

Staphylococcal enterotoxin A (SEA) is an exotoxin excreted mainly by Staphylococcus aureus and nowadays is the most prevalent compound in staphylococcal food poisoning worldwide. SEA is highly heat-resistant, and usual cooking times and temperatures are unlikely to completely inactivate it. A procedure for extraction of this toxin based on protein precipitation with a mixture of dichloromethane and acidified water was used before SDS-PAGE separation of soluble proteins. Finally, bands of interest were excised from the gel and in-gel enzymatic digestion was done. SEA from pasteurized milk was detected with matrix-assisted laser-desorption/ionization-time of flight (MALDI-TOF) mass spectrometry. Nineteen peptides (range 800-2400 Da) were identified as products of trypsin cleavage of the SEA standard with a score of 204 and 73% coverage of the protein sequence, whereas thirteen peptides were revealed for SEA extracted from milk with a score of 148 and 58% sequence coverage obtained. This procedure has been applied successfully for identification of SEA in milk.     

One-pot microwave-assisted substitution of a glucuronan trisaccharide

Substitution of a glucuronic acid trisaccharide was easily performed in one step under microwave irradiation, affording a product resulting from simultaneous glycosylation, esterification and a butyl ether formation.     

Extended canonical algebras and Fuchsian singularities

The authors introduce a new class of finite dimensional algebras called extended canonical, and determine the shape of their derived categories. Extended canonical algebras arise from a canonical algebra ?? by onepoint extension or coextension by an indecomposable projective module. Our main results concern the case of negative Euler characteristic of the corresponding weighted projective line ${\mathbb{X}}$ ; more specifically we establish, for a base field of arbitrary characteristic, a link to the Fuchsian singularity R of ${\mathbb{X}}$ which for the base field of complex numbers is isomorphic to an algebra of automorphic forms. By means of a recent result of Orlov we show that the triangulated category of the graded singularities of R (in the sense of Buchweitz and Orlov) admits a tilting object whose endomorphism ring is the corresponding extended canonical algebra. Of particular interest are those cases where the attached Coxeter transformation has spectral radius one. A K-theoretic analysis then shows that this happens exactly for 38 cases including Arnold??s 14 exceptional unimodal singularities. The paper is related to recent independent work by Kajiura, Saito and Takahashi.     

Quantifying Democracy of Wavelet Bases in Lorentz Spaces

We study the efficiency of the greedy algorithm for wavelet bases in Lorentz spaces in order to give the near best approximation. The result is used to give sharp inclusions for the approximation spaces in terms of discrete Lorentz sequence spaces.