Simultaneous Evaluation of Intact Glucosinolates and Phenolic Compounds by UPLC-DAD-MS/MS in Brassica oleracea L. var. botrytis

A method for the simultaneous determination of intact glucosinolates and main phenolic compounds (flavonoids and sinapic acid derivatives) in Brassica oleracea L. var. botrytis was proposed. A simplified sample extraction procedure and a UPLC separation were carried out to reduce the total time of analysis. Brassica oleracea samples were added with internal standards (glucotropaeolin and rutin), and extracted with boiling methanol. Crude extracts were evaporated under nitrogen, redissolved in mobile phase and analyzed by UPLC with double detection (ESI--MRM for glucosinolates and flavonoids, and DAD for main sinapic acid derivatives). The proposed method allowed a satisfactory quantification of main native sinapic acid derivatives, flavonoids and glucosinolates with a reduced time of analysis.

Natural Products from Antarctic Colonial Ascidians of the Genera Aplidium and Synoicum: Variability and Defensive Role

Ascidians have developed multiple defensive strategies mostly related to physical, nutritional or chemical properties of the tunic. One of such is chemical defense based on secondary metabolites. We analyzed a series of colonial Antarctic ascidians from deep-water collections belonging to the genera Aplidium and Synoicum to evaluate the incidence of organic deterrents and their variability. The ether fractions from 15 samples including specimens of the species A. falklandicum, A. fuegiense, A. meridianum, A. millari and S. adareanum were subjected to feeding assays towards two relevant sympatric predators: the starfish Odontaster validus, and the amphipod Cheirimedon femoratus. All samples revealed repellency. Nonetheless, some colonies concentrated defensive chemicals in internal body-regions rather than in the tunic. Four ascidian-derived meroterpenoids, rossinones B and the three derivatives 2,3-epoxy-rossinone B, 3-epi-rossinone B, 5,6-epoxy-rossinone B, and the indole alkaloids meridianins AG, along with other minoritary meridianin compounds were isolated from several samples. Some purified metabolites were tested in feeding assays exhibiting potent unpalatabilities, thus revealing their role in predation avoidance. Ascidian extracts and purified compound-fractions were further assessed in antibacterial tests against a marine Antarctic bacterium. Only the meridianins showed inhibition activity, demonstrating a multifunctional defensive role. According to their occurrence in nature and within our colonial specimens, the possible origin of both types of metabolites is discussed.

Natural Products from Antarctic Colonial Ascidians of the Genera Aplidium and Synoicum: Variability and Defensive Role

Ascidians have developed multiple defensive strategies mostly related to physical, nutritional or chemical properties of the tunic. One of such is chemical defense based on secondary metabolites. We analyzed a series of colonial Antarctic ascidians from deep-water collections belonging to the genera Aplidium and Synoicum to evaluate the incidence of organic deterrents and their variability. The ether fractions from 15 samples including specimens of the species A. falklandicum, A. fuegiense, A. meridianum, A. millari and S. adareanum were subjected to feeding assays towards two relevant sympatric predators: the starfish Odontaster validus, and the amphipod Cheirimedon femoratus. All samples revealed repellency. Nonetheless, some colonies concentrated defensive chemicals in internal body-regions rather than in the tunic. Four ascidian-derived meroterpenoids, rossinones B and the three derivatives 2,3-epoxy-rossinone B, 3-epi-rossinone B, 5,6-epoxy-rossinone B, and the indole alkaloids meridianins AG, along with other minoritary meridianin compounds were isolated from several samples. Some purified metabolites were tested in feeding assays exhibiting potent unpalatabilities, thus revealing their role in predation avoidance. Ascidian extracts and purified compound-fractions were further assessed in antibacterial tests against a marine Antarctic bacterium. Only the meridianins showed inhibition activity, demonstrating a multifunctional defensive role. According to their occurrence in nature and within our colonial specimens, the possible origin of both types of metabolites is discussed.

Natural Products from Antarctic Colonial Ascidians of the Genera Aplidium and Synoicum: Variability and Defensive Role

Ascidians have developed multiple defensive strategies mostly related to physical, nutritional or chemical properties of the tunic. One of such is chemical defense based on secondary metabolites. We analyzed a series of colonial Antarctic ascidians from deep-water collections belonging to the genera Aplidium and Synoicum to evaluate the incidence of organic deterrents and their variability. The ether fractions from 15 samples including specimens of the species A. falklandicum, A. fuegiense, A. meridianum, A. millari and S. adareanum were subjected to feeding assays towards two relevant sympatric predators: the starfish Odontaster validus, and the amphipod Cheirimedon femoratus. All samples revealed repellency. Nonetheless, some colonies concentrated defensive chemicals in internal body-regions rather than in the tunic. Four ascidian-derived meroterpenoids, rossinones B and the three derivatives 2,3-epoxy-rossinone B, 3-epi-rossinone B, 5,6-epoxy-rossinone B, and the indole alkaloids meridianins A-G, along with other minoritary meridianin compounds were isolated from several samples. Some purified metabolites were tested in feeding assays exhibiting potent unpalatabilities, thus revealing their role in predation avoidance. Ascidian extracts and purified compound-fractions were further assessed in antibacterial tests against a marine Antarctic bacterium. Only the meridianins showed inhibition activity, demonstrating a multifunctional defensive role. According to their occurrence in nature and within our colonial specimens, the possible origin of both types of metabolites is discussed.

Lamellarin D bioconjugates I: synthesis and cellular internalization of PEG-derivatives

Herein is reported the design and synthesis of poly(ethylene glycol) derivatives of Lamellarin D with the aim of modulating their physicochemical properties, and improving the biological activity. Mono-, di- and tri-PEG conjugates with improved solubility were obtained in 18-57% overall yields from the corresponding partially protected phenolic derivatives of Lamellarin D. Conjugates 1-9 were tested in a panel of three human tumor cell lines (MDA-MB-231 breast, A-549 lung and HT-29 colon) to evaluate their cytotoxicity. Several compounds exhibited enhanced cellular internalization, and more than 85% of the derivatives showed a lower GI50 than Lam-D. Furthermore, cell cycle arrest at G2 phase, and apoptotic cell-death pathways were determined for Lamellarin D and these derivatives.

Lamellarin D bioconjugates II: synthesis and cellular internalization of dendrimer and nuclear location signal derivatives

The design and synthesis of Lamellarin D conjugates with a nuclear localization signal peptide and a poly(ethylene glycol)-based dendrimer are described. Conjugates 1-4 were obtained in 8-84% overall yields from the corresponding protected Lamellarin D. Conjugates 1 and 4 are 1.4 to 3.3-fold more cytotoxic than the parent compound against three human tumor cell lines(MDA-MB-231 breast, A-549 lung, and HT-29 colon). Besides, conjugates 3, 4 showed a decrease in activity potency in BJ skin fibroblasts, a normal cell culture. Cellular internalization was analyzed and nuclear distribution pattern was observed for 4, which contains a nuclear localization signalling sequence.

Lamellarin D bioconjugates I: synthesis and cellular internalization of PEG-derivatives

Herein is reported the design and synthesis of poly(ethylene glycol) derivatives of Lamellarin D with the aim of modulating their physicochemical properties, and improving the biological activity. Mono-, di- and tri-PEG conjugates with improved solubility were obtained in 18-57% overall yields from the corresponding partially protected phenolic derivatives of Lamellarin D. Conjugates 1-9 were tested in a panel of three human tumor cell lines (MDA-MB-231 breast, A-549 lung and HT-29 colon) to evaluate their cytotoxicity. Several compounds exhibited enhanced cellular internalization, and more than 85% of the derivatives showed a lower GI50 than Lam-D. Furthermore, cell cycle arrest at G2 phase, and apoptotic cell-death pathways were determined for Lamellarin D and these derivatives.

A note on the application of integrals involving cyclic products kernels

A l'estadística de processos estocàstics i camps aleatoris, una funció de moments o un cumulant d'un estimador de la funció de correlació o de la densitat espectral sovint pot contenir una integral amb un producte cíclic de nuclis. En aquest treball es defineix i s'investiga aquesta classe d'integrals i es demostra la desigualtat de Young-Hölder que permet estudiar el comportament asimptòtic de les esmentades integrals en la situació quan els nuclis depenen d'un pàràmetre. Es considera una aplicació al problema d'estimació de la funció de resposta en un sistema de Volterra.

Distortion of wreath products in some finitely presented groups

"Vegeu el resum a l'inici del document del fitxer adjunt."

Between specialization and globalization. The marketing of agrarian products and its environmental impacts seen from a historical perspective: the province of Barcelona in the mid-nineteenth century

Ecological economics has five good reasons to consider that economic globalisation, spurred by commercial and financial fluxes, to be one of the main driving forces responsible for causing environmental degradation to our planet. The first, is the energy consumption and the socio-environmental impacts which long-distance haulage entails. The second, is the ever-increasing flow of goods to far-away destinations which renders their recycling practically impossible. This is particularly significant, because it prevents the metabolic lock of the nutrients present in food and other agrarian products from taking place. The third, is that the high degree of specialization attained in agriculture, forestry, cattle, mining and industry in each region, generates deleterious effects not only on the eco-landscape structure of the uses of the soil, but on the capability to provide habitat and environmental functions to maintain biodiversity as well

Effect of high pressure processing on the microbiology of skin-vacuum packaged sliced meat products: cooked pork ham, dry cured pork ham and marinated beef loin

High hydrostatic pressure is being increasingly investigated in food processing. It causes microbial inactivation and therefore extends the shelf life and enhances the safety of food products. Yeasts, molds, and vegetative cells of bacteria can be inactivated by pressures in the range of 200 to 700 MPa. Microorganisms are more or less sensitive to pressure depending on several factors such as type, strain and the phase or state of the cells. In general, Gram-positive organisms are usually more resistant than Gram-negative. High pressure processing modifies the permeability of the cell membrane, the ion exchange and causes changes in morphology and biochemical reactions, protein denaturations and inhibition of genetic mechanisms. High pressure has been used successfully to extend the shelf life of high-acid foods such as refrigerated fruit juices, jellies and jams. There is now an increasing interest in the use of this technology to extend the shelf life of low-acid foods such as different types of meat products.

Bioequivalence of meat products treated with high pressure processing

The effects of high pressure on the composition of food products have not been evaluated extensively. Since, it is necessary to take in consideration the possible effects in basis to the changes induced in the bio molecules by the application of high pressures. The main effect on protein is the denaturation, because the covalent bonds are not affected; however hydrogen bonding, hydrophobic and intermolecular interactions are modified or destroyed. 1 High pressure can modify the activity of some enzymes. If this is done the proteolysis and lipolysis could be more or less intense and the content of free amino acids and fatty acids will be different. This could be related to the bioavailability of these compounds. Low pressures (100 MPa) have been shown to activate some enzymes (monomeric enzymes). Higher pressures induce loss of the enzyme activity. However some enzymes are very stable (ex. Lipase ~ 600 - 1000 MPa). Lipoxygenase is less stable, and there is little information about the effects on antioxidant enzymes. Other important issue is the influence of high pressure on oxidation susceptibility. This could modify the composition of lipids if the degree of the oxidation would have been higher or lower than in the traditional product. Pressure produces the damage of cell membranes favouring the contact between substrates and enzymes, exposure to oxidation of membrane fatty acids and loos of the efficiency of vitamin E. These effects can also affect to protein oxidation. In this study different compounds were analysed to establish the differences between non-treated and high-pressure treated products.

Determinació de diferents compostos bioactius en ingredients naturals per a l'elaboració de bombons funcionals amb beneficis cardiovasculars

Durant les darreres dècades, i degut, principalment, a un canvi en els hàbits alimentaris, hi ha hagut un augment a nivell mundial de malalties cròniques (l’obesitat, malalties cardiovasculars, etc.). En els països mediterranis hi ha menys incidència d’aquestes malalties i sembla ser que això es deu a l’anomenada dieta mediterrània. La dieta mediterrània es caracteritza per una combinació d’oli d’oliva com a grassa principal, verdures, hortalisses i fruites en abundància, lleguminoses, fruits secs, formatges i iogurt, peix, pa, pasta, cereals i els seus derivats i un consum moderat de vi i carns. Aquest model alimentari, ric en tocoferols, fitosterols i fitoestanols que ajuden a reduir el contingut de colesterol en sang, fa que en les poblacions mediterrànies hi hagi menys incidència de malalties cardiovasculars. Aquests compostos inhibeixen el deteriorament oxidatiu dels olis, actuen com agent antipolimerització per olis de fregir. Tenen capacitat de reduir els nivells de colesterol, evitant la incidència de malalties cardiovasculars. Els fitoesterols y fitoestanols es poden trobar en forma lliure o esterificada amb àcids grassos, àcids fenòlics i glucosa. Els objectius d’ aquest treball han estat, primer en el desenvolupament de mètodes d'anàlisi ràpids, fiables i robusts dels tocoferols, fitoesterols i fitoestanols i la seva aplicació en fruits sec, oli de segó, oli de pinyol de raïm i productes que els continguin. El primer mètode va estar basat en la cromatografía líquida (HPLC-DAD) amb extracció en fase sòlida (SPE) com tècnica alternativa a la saponificació para la determinació de fitoesterols lliures. Aquest mètode va estar aplicada a mostres de bombons que contenia fitoesterols. El segon mètode va estar basat en la cromatografia de gasos (GCFID) amb aponificació i SPE per quantificar fitoesterols i fitoestanols lliures, esterificats i totals. En els documents annexos es descriuen a profunditat els mètodes desenvolupats.

On the intersection of free subgroups in free products of groups

"Vegeu el resum a l'inici del document del fitxer adjunt."

Aplicació de la termoquimiolisi - cromatografia de gasos - espectrometria de masses a l'estudi de la matèria orgànica del sòl

Estudi realitzat a partir d’una estada a la Université de Poitiers, França, entre 2007 i 2009. El treball s'ha centrat en dues activitats bàsiques. El treball realitzat s’ha centrat en dues activitats bàsiques. D’una banda, la posada a punt d'un protocol de fraccionament de la matèria orgànica del sòl, per extraccions successives amb solvents alcalins després d'una seqüència de pretractaments al sòl: cap pretractament, atac amb àcid (per destruir els carbonats), atac amb ditionit (per reduir els òxids de Fe i Al i facilitar l'extracció de la matèria orgànica associada a aquests compostos). El protocol dóna una visió de conjunt de la situació de la matèria orgànica del sòl, combinant aspectes físics (protecció, precipitació, oclusió per carbonats) i químics (grau d'humificació). D’altra banda, l'aprenentatge de la tècnica de termoquimiolisi-cromatografia de gasos-espectrometria de masses. Aquest era l'objectiu de l'estada a Poitiers, al qual hem donat prioritat. Ens hem centrat en l'estudi de fraccions físiques (densimètriques) obtingudes en estudis anteriors sobre sòls forestals. Les fraccions considerades són: fracció lleugera (FL), tres fraccions ocluïdes (OC1, OC2 i OC3) i fracció densa (FD). L’aplicació de la termoquimiolisi permet de caracteritzar diversos grups de substàncies, de les quals ens hem centrat en alguns indicadors bioquímics: àcids grasos, alcohols, diàcids, productes fenòlics i altres productes aromàtics, derivats de carbohidrats. L’estudi de conjunt d’aquests productes indica que és a les fraccions ocluïdes (que solen ser minoritàries a tots els horitzons) on la matèria orgànica d’origen microbià és dominant, mentre que a les fraccions lleugera (FL) i densa (FD) la matèria orgànica d’origen vegetal sembla dominant. Es preveu aplicar aquesta tècnica a l’estudi de les fraccions obtingudes a la primera part del treball, actualment congelades i a l’espera de ser processades.