New Approaches to Oxirane Containing Natural Products: Stereoselective Total Synthesis of the Antitumor Agents Gummiferol and Depudecin

La comunicación presenta la síntesis total de productos naturales con actividad antitumoral caracterizados estructuralmente por la presencia de anillos de oxirano. Para ello se empleó una nueva metodología de epoxidación asimétrica basada en una nueva clase de iluros de azufre quirales. Mediante esta metodología se realizaron las síntesis de los productos naturales Gummiferol y DepudecinaUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Predator avoidance in extremophile fish

Extreme habitats are often characterized by reduced predation pressures, thus representing refuges for the inhabiting species. The present study was designed to investigate predator avoidance of extremophile populations of Poecilia mexicana and P. sulphuraria that either live in hydrogen sulfide-rich (sulfidic) springs or cave habitats, both of which are known to have impoverished piscine predator regimes. Focal fishes that inhabited sulfidic springs showed slightly weaker avoidance reactions when presented with several naturally occurring predatory cichlids, but strongest differences to populations from non-sulfidic habitats were found in a decreased shoaling tendency with non-predatory swordtail (Xiphophorus hellerii) females. When comparing avoidance reactions between P. mexicana from a sulfidic cave (Cueva del Azufre) and the adjacent sulfidic surface creek (El Azufre), we found only slight differences in predator avoidance, but surface fish reacted much more strongly to the non-predatory cichlid Vieja bifasciata. Our third experiment was designed to disentangle learned from innate effects of predator recognition. We compared laboratory-reared (i.e., predator-naïve) and wild-caught (i.e., predator-experienced) individuals of P. mexicana from a non-sulfidic river and found no differences in their reaction towards the presented predators. Overall, our results indicate (1) that predator avoidance is still functional in extremophile Poecilia spp. and (2) that predator recognition and avoidance reactions have a strong genetic basis

Shared and unique patterns of embryo development in extremophile poeciliids

Background: Closely related lineages of livebearing fishes have independently adapted to two extreme environmental factors: toxic hydrogen sulphide (H2S) and perpetual darkness. Previous work has demonstrated in adult specimens that fish from these extreme habitats convergently evolved drastically increased head and offspring size, while cave fish are further characterized by reduced pigmentation and eye size. Here, we traced the development of these (and other) divergent traits in embryos of Poecilia mexicana from benign surface habitats (“surface mollies”) and a sulphidic cave (“cave mollies”), as well as in embryos of the sister taxon, Poecilia sulphuraria from a sulphidic surface spring (“sulphur mollies”). We asked at which points during development changes in the timing of the involved processes (i.e., heterochrony) would be detectible. Methods and Results: Data were extracted from digital photographs taken of representative embryos for each stage of development and each type of molly. Embryo mass decreased in convergent fashion, but we found patterns of embryonic fat content and ovum/embryo diameter to be divergent among all three types of mollies. The intensity of yellow colouration of the yolk (a proxy for carotenoid content) was significantly lower in cave mollies throughout development. Moreover, while relative head size decreased through development in surface mollies, it increased in both types of extremophile mollies, and eye growth was arrested in mid-stage embryos of cave mollies but not in surface or sulphur mollies. Conclusion: Our results clearly demonstrate that even among sister taxa convergence in phenotypic traits is not always achieved by the same processes during embryo development. Furthermore, teleost development is crucially dependent on sufficient carotenoid stores in the yolk, and so we discuss how the apparent ability of cave mollies to overcome this carotenoid-dependency may represent another potential mechanism explaining the lack of gene flow between surface and cave mollies

Balance histórico de nitrógeno, fósforo y azufre de la región pampeana

Se realizó un balance de superfice de nitrógeno (N), fósforo (P) y azufre (S) para la Región Pampena desde 1870 a 2010, período en que se produjo la expansión agrícola en la región. Para N se computaron como entradas el aporte atmósferico, la fijación simbiótica y la fertilización. Las salidas fueron la exportación en grano y productos animales. Para P y S el balance incluyó como entradas el aporte atmosférico y la fertilización y como salidas las mismas que para N. El balance se calculó en forma anual y acumulada y también se calculó la relación salida/entrada anual. Las bases de datos fueron censos nacionales y estadísticas oficiales para estimar las salidas y se hicieron estimaciones de aporte atmosférico, fijación simbiótica y consumo de fertilizantes. La entrada de N fue de 202 Mt, siendo el aporte atmósférico (36%) y la fijación simbiótica (58%) los componentes principales. La salida fue de 76 Mt, con la exportación en grano como principal factor (83%); resultando en un balance positivo de 126 Mt. Este flujo equivale a un cuarto del stock de N de los suelos hasta 1 m. Otros estudios mostraron que no se produjeron cambios en los stock de N pampeano entre 1960-80 y 2007-2008, período durante el cual el balance de N fue de +52 Mt. En consecuencia, se estimaron pérdidas gaseosas o por lixiviación durante este lapso de 26 kg ha-1 año-1. Para fósforo la entrada fue 4,2 Mt, con mayor peso del componente fertilizantes (67%) y la salida de 12,2 Mt, generado sobre todo por la cosecha de granos (76%), determinando un balance negativo de -8,0 Mt. La entrada de azufre fue de 3,9 Mt, principalmente generada por la atmósfera (81%) y la salida de 5,6 Mt, debido sobre todo a la exportación en grano (82%), con un balance negativo de -1,7 Mt. Estos resultados indican pérdida de P y S desde las reservas de los suelos. La relación salida/entrada de N pasó de 0,2 a 0,7 en el lapso estudiado, mientras que para P y S ha sido mayor a 1 desde hace décadas.A surface balance for nitrogen (N), phosphorus (P), and sulfur (S) was performed for the Argentine Pampas during the 1870- 2010 time interval, comprising the agricultural expansion period in the region. Nitrogen inputs accounted in the balance were atmospheric deposition, symbiotic fixation, and fertilization. Outputs included were grain harvest and livestock products. P and S balances included atmospheric deposition and fertilization as inputs and the same outputs than in the case of N balance. Annual and cumulative balances were calculated and also an annual output/input ratio. National information and official statistics were used to determine the nutrient outputs whereas atmospheric deposition, symbiotic fixation, and fertilizer inputs were estimated. Cumulative N input was of 202 Mt, atmospheric deposition (36%) and symbiotic fixation (58%) represented the main components. The output was of 76 Mt, with grain harvest as main factor (83%), thus resulting in a positive N balance of 126 Mt. This nutrient flow is equivalent to one quart of the soil N stock to 1 m depth. As previous studies showed that soil N stock did not changed between 1960-1980 and 2007-2008, period during which a positive N balance of 52 Mt was calculated, this resulted in a loss of 26 kg ha-1 yr-1 due to gas emissions and leaching in recent decades. Phosphorus input was 4.2 Mt, mainly explained by fertilization (67%), and the output was 12.2 Mt, generated mainly by grain harvest (76%), which determined a negative balance of -8.0 Mt. Sulfur input was 3.9 Mt, mainly determined by atmospheric deposition (81%) and the output was 5.6 Mt, mainly due to grain harvest (82%) resulting also in a negative balance of -1.7 Mt. These results indicate P and S losses from soil stocks. The N output/input ratio varied from 0.2 to 0.7 along the study period, while the P and S ratios have been higher than 1 since decades.Fil: Alvarez, Roberto. Universidad de Buenos Aires. Facultad de Agronomía; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario; ArgentinaFil: Steinbach, Haydee S.. Universidad de Buenos Aires. Facultad de Agronomía; ArgentinaFil: de Paepe, Josefina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario; Argentina. Universidad de Buenos Aires. Facultad de Agronomía; Argentin

A new and morphologically distinct population of cavernicolous Poecilia mexicana (Poeciliidae: Teleostei)

The cave molly, Poecilia mexicana, from the Cueva del Azufre, a sulfur cave in Tabasco, Mexico, ranks among the best-studied cave fishes worldwide, despite being known from a single population only. Here we describe a newly discovered second population of cave-dwelling P. mexicana from a nearby, but mostly non-sulfidic cave (Luna Azufre). Despite apparent similarities between the two populations (such as reduced eye diameter and reduced pigmentation), a geometric morphometric analysis revealed pronounced morphological differentiation between the two cave form

Validación de los métodos espectrofotométricos para la determinación de SOx y NOx en muestras de aire

Este documento describe la manera y el procedimiento utilizados a la hora de ser validados los métodos para análisis de dióxido de azufre y óxidos de nitrógeno en muestras de aire; estos métodos son: El método espectrofotométrico de tetracloruromercurato/pararrosanilina para análisis de dióxido de azufre y El método colorimétrico para análisis de dióxido de nitrógeno en la atmosfera. Estos compuestos presentes en el aire son monitoreados por medio de un equipo recolector de gases en este caso un TRIGAS marca ENERGI, el cual por medio de una bomba de succión absorbe el aire; este es pasado a una solución absorbente que por medio de burbujeo se mezcla y así poder capturar el gas a analizar en este caso SOX (solución absorbente TCM) y NOX (solución absorbente NEDA). Posteriormente son analizados en el laboratorio por el método de tetracloruromercurato/pararrosanilina para análisis de dióxido de azufre y El método colorimétrico para análisis de dióxido de nitrógeno en la atmosfera. El laboratorio de análisis de Aguas y Alimentos de la UTP; en busca de calidad y de certificación; implemento la validación de estos métodos; basándose en el protocolo para la vigilancia y seguimiento del modulo aire del sistema de información ambiental, del IDEAM. Es posible ahora con los procedimientos de cada método desarrollados identificar dióxido de azufre a 570.8 nm y dióxido de nitrógeno; más específicamente dióxido de nitrógeno a 541nm. En muestras de aire burbujeado

Proceso y catalizadores para la oxidación selectiva de compuestos de azufre presentes en gasolina, queroseno y diésel

Referencia OEPM: P200102754.-- Fecha de solicitud: 30/11/2001.-- Titulares: Universidad Politécnica de Valencia (UPV), Consejo Superior de Investigaciones Científicas (CSIC).La presente invención tiene por objeto un proceso para la oxidación de compuestos de azufre presentes en las fracciones gasolina, queroseno y diésel, caracterizado porque comprende realizar una oxidación de dichos compuestos de azufre utilizando peróxidos o hidroperóxidos como agentes oxidantes, y un catalizador o mezclas de catalizadores, los cuales están basados en tamices moleculares microporosos que contienen canales con anillos de 12 o más miembros y conteniendo en su composición Ti conjuntamente en posiciones de red y no reticulares. Estos catalizadores pueden también contener Si unido a C.Peer reviewe

A primer on sulfur for the planetary geologist

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described

Betunes modificados con azufre: aditivos estabilizadores

En el presente trabajo se estudia la influencia de aditivos encaminados a conseguir la estabilidad de dichos betunes modificados. Mediante medidas de viscosidad y penetración se ha comprobado que la presencia combinada de diciclopentadieno + aminas, favorece la interacción del azufre con el betún por formación de polisulfuros. Asimismo, se ha analizado la influencia de inhibidores de radicales libre

Inner ear morphology in the Atlantic molly Poecilia mexicana

Fishes show an amazing diversity in hearing abilities, inner ear structures, and otolith morphology. Inner ear morphology, however, has not yet been investigated in detail in any member of the diverse order Cyprinodontiformes. We, therefore, studied the inner ear of the cyprinodontiform freshwater fish Poecilia mexicana by analyzing the position of otoliths in situ, investigating the 3D structure of sensory epithelia, and examining the orientation patterns of ciliary bundles of the sensory hair cells, while combining μ-CT analyses, scanning electron microscopy, and immunocytochemical methods. P. mexicana occurs in different ecotypes, enabling us to study the intra-specific variability (on a qualitative basis) of fish from regular surface streams, and the Cueva del Azufre, a sulfidic cave in southern Mexico. The inner ear of Poecilia mexicana displays a combination of several remarkable features. The utricle is connected rostrally instead of dorso-rostrally to the saccule, and the macula sacculi, therefore, is very close to the utricle. Moreover, the macula sacculi possesses dorsal and ventral bulges. The two studied ecotypes of P. mexicana showed variation mainly in the shape and curvature of the macula lagenae, in the curvature of the macula sacculi, and in the thickness of the otolithic membrane. Our study for the first time provides detailed insights into the auditory periphery of a cyprinodontiform inner ear and thus serves a basis--especially with regard to the application of 3D techniques--for further research on structure-function relationships of inner ears within the species-rich order Cyprinodontiformes. We suggest that other poeciliid taxa, or even other non-poeciliid cyprinodontiforms, may display similar inner ear morphologies as described here