Pharmaceutical determination in surface and wastewaters using high-performance liquid chromatography-(electrospray)-mass spectrometry

A method was developed to determine 11 pharmaceutical compounds in water samples. The method uses SPE and HPLC coupled to MS (LC/MS) using ESI in both positive and negative modes. Three different sorbents were compared for the extraction of analytes from river and sewage treatment plant (STP) waters and OASIS HLB provided the best results. For the solid-phase extraction of 500 mL of river water samples, the recoveries were between 41 and 101% with the exception of acetaminophen, salicylic acid and naproxen. The LODs were between 3 and 5 ng/L for all the compounds, except naproxen which had an LOD of 15 ng/L. Acetaminophen, caffeine, carbamazepine, bezafibrate and ibuprofen were found in three of the tested river samples at ng/L levels and among them, the highest values were for caffeine and bezafibrate with 305 and 363 ng/L, respectively. For the influent and effluent water samples of the STP, volumes of 100 and 250 mL were used, respectively, to obtain acceptable recoveries. All the compounds showed recoveries between 33 and 91% for effluent samples and 33-72% for influent samples, with the exception of acetaminophen, salicylic acid and bezafibrate, which had lower recoveries. The method developed enabled pharmaceuticals in the influent and effluent sewage waters to be determined in five campaigns carried out between February 2004 and June 2005. Several pharmaceuticals were found in the influent samples: for instance, maximum concentrations of ibuprofen and caffeine were 6 and 40 microg/L, respectively.     

Enantioselective Synthesis of Lepadins A–D from a Phenylglycinol‐Derived Hydroquinolone Lactam

The marine alkaloids (?)‐lepadins A–C and (+)‐lepadin D, belonging to two diastereoisomeric series, were synthesized from an (R)‐phenylglycinol‐derived tricyclic lactam via a common cis‐decahydroquinoline intermediate. Crucial aspects of the synthesis are the stereochemical control in the assembly of the cis‐decahydroquinoline platform, in the introduction of the C2 methyl and C3 hydroxy substituents, and in the generation of the C5 stereocenter.     

A nonlinear principal component analysis to study archeometric data

Statistical techniques, when applied to data obtained by chemical investigations on ancient artworks, are usually expected to recognize groups of objects to classify the archeological finds, to attribute the provenance of items compared with earlier investigated ones, or to determine whether an archaelogical attribution is possible or not. The statistical technique most frequently used in archeometry is the principal component analysis (PCA), because of its simplicity in theory and implementation. However, the application of PCA to archeometric data showed severe limitations because of its linear feature. Indeed, PCA is inadequate to classify data whose behavior describe a curve or a curved subspace of the original data space. As a consequence of it, an amount of information is lost because the multi‐dimensional data space is compressed into a lower‐dimensional subspace including principal components. The aim of this work is then to test a novel statistical technique for archeometry. We propose a nonlinear PCA method to extract maximum chemical information by plotting data on the smallest number of principal components and to answer archeological questions. The higher accuracy and effectiveness of nonlinear PCA approach with respect to standard PCA for the analysis of archeometric data are shown through the study of Apulian red figured pottery (fifth–fourth century BC) coming from some of the most relevant archeological sites of ancient Apulia (Monte Sannace (Gioia del Colle), Egnatia (Fasano), Canosa, Altamura, Conversano, and Arpi(Foggia)). Copyright © 2016 John Wiley & Sons, Ltd.     

In situ analysis of soybeans and nuts by probe electrospray ionization mass spectrometry

The probe electrospray ionization (PESI) is an ESI‐based ionization technique that generates electrospray from the tip of a solid metal needle. In the present work, we describe the PESI mass spectra obtained by in situ measurement of soybeans and several nuts (peanuts, walnuts, cashew nuts, macadamia nuts and almonds) using different solid needles as sampling probes. It was found that PESI‐MS is a valuable approach for in situ lipid analysis of these seeds. The phospholipid and triacylglycerol PESI spectra of different nuts and soybean were compared by principal component analysis (PCA). PCA shows significant differences among the data of each family of seeds. Methanolic extracts of nuts and soybean were exposed to air and sunlight for several days. PESI mass spectra were recorded before and after the treatment. Along the aging of the oil (rancidification), the formation of oxidated species with variable number of hydroperoxide groups could be observed in the PESI spectra. The relative intensity of oxidated triacylglycerols signals increased with days of exposition. Monitoring sensitivity of PESI‐MS was high. This method provides a fast, simple and sensitive technique for the analysis (detection and characterization) of lipids in seed tissue and degree of oxidation of the oil samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Photoelectron Spectroscopy at the Graphene–Liquid Interface Reveals the Electronic Structure of an Electrodeposited Cobalt/Graphene Electrocatalyst

Electrochemically grown cobalt on graphene exhibits exceptional performance as a catalyst for the oxygen evolution reaction (OER) and provides the possibility of controlling the morphology and the chemical properties during deposition. However, the detailed atomic structure of this hybrid material is not well understood. To elucidate the Co/graphene electronic structure, we have developed a flow cell closed by a graphene membrane that provides electronic and chemical information on the active surfaces under atmospheric pressure and in the presence of liquids by means of X‐ray photoelectron spectroscopy (XPS). We found that cobalt is anchored on graphene via carbonyl‐like species, namely Co(CO)_x, promoting the reduction of Co³⁺ to Co²⁺, which is believed to be the active site of the catalyst.     

Evaluation of climatic factors on the yield and chemical composition of the essential oil of Myrocarpus frondosus

The species Myrocarpus frondosus is native to southern Brazil, and it is known as cabreúva. It is a large tree, and its wood is used as a reservoir for distilled spirits, especially Cachaça. In this pioneering work, the essential oil was extracted monthly from the leaves of M. frondosus, for a period of 1 year. The essential oil was extracted by using hydrodistillation and the determination of the chemical composition of essential oil was performed by using the chromatographic techniques GC-FID and GC–MS. Thirty-three compounds were identified in the essential oil and bicyclogermacrene was the major compound. Through multivariate analysis, it was determined that β-caryophyllene, limonene and terpinen-4-ol were directly proportional to climatic factors. The yield of the oil was directly proportional to temperature and radiation.     

Fracture mode,microstructure and temperature-dependent elastic moduli for thermoelectric composites of PbTe–PbS with SiC nanoparticle additions

Twenty-six (Pb_0.95Sn_0.05Te)_0.92(PbS)_0.08–0.055% PbI₂–SiC nanoparticle (SiC_np) composite thermoelectric specimens were either hot pressed or pulsed electric current sintered (PECS). Bloating (a thermally induced increase in porosity, P, for as-densified specimens) was observed during annealing at temperatures >603?K for hot-pressed specimens and PECS-processed specimens from wet milled powders, but in contrast seven out of seven specimens densified by PECS from dry milled powders showed no observable bloating following annealing at temperatures up to 936?K. In this study, bloating in the specimens was accessed via thermal annealing induced changes in (i) porosity measured by scanning electron microscopy on fractured specimen surfaces, (ii) specimen volume and (iii) elastic moduli. The moduli were measured by resonant ultrasound spectroscopy. SiC_np additions (1–3.5 vol.%) changed the fracture mode from intergranular to transgranular, inhibited grain growth, and limited bloating in the wet milled PECS specimens. Inhibition of bloating likely occurs due to cleaning of contamination from powder particle surfaces via PECS processing which has been reported previously in the literature.     

Gamma-type operators and the Black–Scholes semigroup

We study Gamma-type operators from the analytic and probabilistic viewpoint in the setting of weighted continuous function spaces and estimate the rate of convergence of their iterates towards their limiting semigroup, providing, in this way, a quantitative version of the classical Trotter approximation theorem. The semigroup itself has some interest, since it is generated by the Black–Scholes operator, frequently occurring in the theory of option pricing in mathematical finance.     

LocaPep: localization of epitopes on protein surfaces using peptides from phage display libraries

The use of peptides from a phage display library selected by binding to a given antibody is a widespread technique to probe epitopes of antigenic proteins. However, the identification of interaction sites mimicked by these peptides on the antigen surface is a difficult task. LocaPep is a computer program developed to localize epitopes using a new clusters algorithm that focuses on protein surface properties. The program is constructed with the aim of providing a flexible computational tool for predicting the location of epitopes on protein structures. As a first set of testing results, the localization of epitope regions in eight different antigenic proteins for which experimental data on their antibody interactions exist is correctly identified by LocaPep. These results represent a disparate sample of biologically different systems. The program is freely available at http://atenea.montes.upm.es.     

A piezoelectric immunosensor for <Emphasis Type="Italic">Leishmania chagasi</Emphasis> antibodies in canine serum

The American visceral leishmaniasis is an important cause of morbidity and mortality in Brazil for both humans and dogs. Attempts to make a diagnosis of this disease need to be improved, especially in endemic areas, and in the tracking and screening of asymptomatic dogs, which are their main host in urban areas. A quartz crystal microbalance immunosensor for the diagnosis of the canine visceral leishmaniasis using a recombinant antigen of Leishmania chagasi (rLci2B-NH6) was developed. The rLci2B-NH6 was tightly immobilized on a quartz crystal gold electrode by self-assembled monolayer based on short-chain length thiol. The strategy was the use of the antigen-histidine tail covalently linked to glutaraldehyde performing a Schift base which permits a major exposure of epitopes and a reduced steric hindrance. The immunosensor showed good results regarding sensitivity and reproducibility, being able to distinguish positive and negative canine serum for L. chagasi. Furthermore, the immunosensor can be reused through exposure to sodium dodecyl sulfate solution, which promotes the dissociation of antigen–antibody binding, restoring the sensor surface with immobilized biologically active antigens for further analysis.