Human Heme Oxygenase Oxidation of 5- and 15-Phenylhemes

Human heme oxygenase-1 (hHO-1) catalyzes the O2- dependent oxidation of heme to biliverdin, CO, and free iron. Previous work indicated that electrophilic addition of the terminal oxygen of the ferric hydroperoxo complex to the -meso-carbon gives 5-hydroxyheme. Earlier efforts to block this reaction with a 5-methyl substituent failed, as the reaction still gave biliverdin IX . Surprisingly, a 15-methyl substituent caused exclusive cleavage at the -meso- rather than at the normal, unsubstituted -meso-carbon. No CO was formed in these reactions, but the fragment cleaved from the porphyrin eluded identification. We report here that hHO-1 cleaves 5-phenylheme to biliverdin IX and oxidizes 15- phenylheme at the -meso position to give 10-phenylbiliverdin IX . The fragment extruded in the oxidation of 5-phenylheme is benzoic acid, one oxygen of which comes from O2 and the other from water. The 2.29- and 2.11-Å crystal structures of the hHO-1 complexes with 1- and 15-phenylheme, respectively, show clear electron density for both the 5- and 15-phenyl rings in both molecules of the asymmetric unit. The overall structure of 15-phenylheme-hHO-1 is similar to that of heme-hHO-1 except for small changes in distal residues 141–150 and in the proximal Lys18 and Lys22. In the 5-phenylhemehHO-1 structure, the phenyl-substituted heme occupies the same position as heme in the heme-HO-1 complex but the 5-phenyl substituent disrupts the rigid hydrophobic wall of residues Met34, Phe214, and residues 26–42 near the -meso carbon. The results provide independent support for an electrophilic oxidation mechanism and support a role for stereochemical control of the reaction regiospecificity.Fil: Wang, Jingling. University of California; Estados UnidosFil: Niemevz, Fernando. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; ArgentinaFil: Lad, Latesh. University of California; Estados UnidosFil: Huang, Liusheng. University of California; Estados UnidosFil: Alvarez, Diego Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; ArgentinaFil: Buldain, Graciela Yolanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay; Argentina. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Química Orgánica; ArgentinaFil: Poulos, Thomas L.. University of California; Estados UnidosFil: Ortiz de Montellano, Paul R.. University of California; Estados Unido

Possible ring material around centaur (2060) Chiron

We propose that several short duration events observed in past stellar occultations by Chiron were produced by rings material. From a reanalysis of the stellar occultation data in the literature we determined two possible orientations of the pole of Chiron's rings, with ecliptic coordinates l=(352+/-10) deg, b=(37+/-10) deg or l=(144+/-10) deg, b=(24+/-10) deg . The mean radius of the rings is (324 +/- 10) km. One can use the rotational lightcurve amplitude of Chiron at different epochs to distinguish between the two solutions for the pole. Both imply lower lightcurve amplitude in 2013 than in 1988, when the rotational lightcurve was first determined. We derived Chiron's rotational lightcurve in 2013 from observations at the 1.23-m CAHA telescope and indeed its amplitude is smaller than in 1988. We also present a rotational lightcurve in 2000 from images taken at CASLEO 2.15-m telescope that is consistent with our predictions. Out of the two poles the l=(144+/-10) deg, b=(24+/-10) deg solution provides a better match to a compilation of rotational lightcurve amplitudes from the literature and those presented here. We also show that using this preferred pole, Chiron's long term brightness variations are compatible with a simple model that incorporates the changing brightness of the rings as the tilt angle with respect to the Earth changes with time. Also, the variability of the water ice band in Chiron's spectra in the literature can be explained to a large degree by an icy ring system whose tilt angle changes with time and whose composition includes water ice, analogously to the case of Chariklo. We present several possible formation scenarios for the rings from qualitative points of view and speculate on the reasons why rings might be common in centaurs. We speculate on whether the known bimodal color distribution of centaurs could be due to presence of rings and lack of them

Visible and near-infrared observations of asteroid 2012 DA14 during its closest approach of February 15, 2013

Near-Earth asteroid 2012 DA14 made its closest approach on February 15, 2013, when it passed at a distance of 27,700 km from the Earth's surface. It was the first time an asteroid of moderate size was predicted to approach that close to the Earth, becoming bright enough to permit a detailed study from ground-based telescopes. Asteroid 2012 DA14 was poorly characterized before its closest approach. We acquired data using several telescopes on four Spanish observatories: the 10.4m Gran Telescopio Canarias (GTC) and the 3.6m Telescopio Nazionale Galileo (TNG), both in the El Roque de los Muchachos Observatory (ORM, La Palma); the 2.2m CAHA telescope, in the Calar Alto Observatory (Almeria); the f/3 0.77m telescope in the La Hita Observatory (Toledo); and the f/8 1.5m telescope in the Sierra Nevada Observatory (OSN, Granada). We obtained visible and near-infrared color photometry, visible spectra and time-series photometry. Visible spectra together with color photometry of 2012 DA14 show that it can be classified as an L-type asteroid, a rare spectral type with a composition similar to that of carbonaceous chondrites. The time-series photometry provides a rotational period of 8.95 +- 0.08 hours after the closest approach, and there are indications that the object suffered a spin-up during this event. The large amplitude of the light curve suggests that the object is very elongated and irregular, with an equivalent diameter of around 18m. We obtain an absolute magnitude of H_R = 24.5 +- 0.2, corresponding to H_V = 25.0 +- 0.2. The GTC photometry also gives H_V = 25.29 +- 0.14. Both values agree with the value listed at the Minor Planet Center shortly after discovery. From the absolute photometry, together with some constraints on size and shape, we compute a geometric albedo of p_V = 0.44 +- 0.20, which is slightly above the range of albedos known for L-type asteroids (0.082 - 0.405).Comment: 7 pages, 4 figures, 1 table. Accepted in A&A (June 17 2013

Efecto de las fuentes de polen sobre el rendimiento en la extracción de aceite y perfil de ácidos grasos de las semillas de dátil (Phoenix dactylifera L.) cultivar Medjool de México

The present investigation aimed to assess the effect of pollen sources on the mass, dimension, oil content and fatty acid profile of the seeds from female palms of the Medjool date cultivar. The palms were pollinated with Deglet Noor, Khadrawy, Medjool and Zahidi cultivars. In addition, three palms were pollinated as the treatment control. The fatty acids were evaluated by gas chromatography-mass spectrometry. The surface morphology of date seed powder was examined using SEM, before and after n-hexane interaction. The seeds of the Medjool treatment had the greatest mass (1.42 g), but the lowest oil content (5.37% w/w); the control seeds showed smaller mass (1.21 g), but higher oil content (13.57% w/w). The proportion of fatty acids varied significantly among the treatments with respect to the control. The most abundant fatty acids were oleic (C18:1), lauric (C12:0), myristic (C14:0), palmitic (C16:0), linoleic (C18:2), and stearic (C18:0). Together these fatty acids presented a composition between 98.3 and 98.67% for treatments, and 99.0% for the control. The results indicate that the pollen sources from Deglet Noor, Khadrawy, Medjool and Zahidi cultivars had a significant effect on mass, dimension, oil content and fatty acid profile of the seeds of the date cultivar Medjool. The date seed oil could be used as edible oil, in food products, and in pharmaceutical and cosmetic applications.La presente investigación tuvo como objetivo evaluar el efecto de las fuentes de polen, sobre la masa, dimensión, contenido de aceite y el perfil de ácidos grasos de las semillas de dátil del cultivar Medjool. Las palmas hembras del cultivar Medjool fueron polinizadas con cultivares Deglet Noor, Khadrawy, Medjool y Zahidi. Además, tres palmas fueron polinizadas como tratamiento control. Los ácidos grasos se evaluaron por cromatografía de gases-espectrometría de masas. La morfología de la superficie del polvo de semillas de dátil se examinó utilizando un equipo SEM, antes y después de la interacción n-hexano. Las semillas del tratamiento Medjool resultaron con mayor masa (1,42 g), pero menor contenido de aceite (5,37% p/p); la semilla control, mostró una masa más pequeña (1,21 g), pero un mayor contenido de aceite (13,57% p/p). La composición de ácidos grasos varió significativamente entre los tratamientos con respecto al control. Los ácidos grasos mayoritarios fueron: oleico (C18:1), láurico (C12:0), mirístico (C14:0), palmítico (C16:0), linoleico (C18:2) and esteárico (C18:0). En total, estos ácidos grasos alcanzan una composición entre 98.3 y 98.67% para los tratamientos, y 99.0% para el control. Los resultados indican que la fuente de polen de los cultivares Deglet Noor, Khadrawy, Medjool y Zahidi tiene un efecto significativo sobre la masa, dimensión, contenido de aceite y el perfil de ácidos grasos de la semilla del cultivar de dátil Medjool. El aceite de la semilla de dátil, podría usarse como aceite comestible, productos alimenticios, aplicaciones farmacéuticas y cosméticas

Glycated haemoglobin (HbA1c ) and fasting plasma glucose relationships in sea-level and high-altitude settings.

AIM: Higher haemoglobin levels and differences in glucose metabolism have been reported among high-altitude residents, which may influence the diagnostic performance of HbA1c . This study explores the relationship between HbA1c and fasting plasma glucose (FPG) in populations living at sea level and at an altitude of > 3000 m. METHODS: Data from 3613 Peruvian adults without a known diagnosis of diabetes from sea-level and high-altitude settings were evaluated. Linear, quadratic and cubic regression models were performed adjusting for potential confounders. Receiver operating characteristic (ROC) curves were constructed and concordance between HbA1c and FPG was assessed using a Kappa index. RESULTS: At sea level and high altitude, means were 13.5 and 16.7 g/dl (P > 0.05) for haemoglobin level; 41 and 40 mmol/mol (5.9% and 5.8%; P < 0.01) for HbA1c ; and 5.8 and 5.1 mmol/l (105 and 91.3 mg/dl; P < 0.001) for FPG, respectively. The adjusted relationship between HbA1c and FPG was quadratic at sea level and linear at high altitude. Adjusted models showed that, to predict an HbA1c value of 48 mmol/mol (6.5%), the corresponding mean FPG values at sea level and high altitude were 6.6 and 14.8 mmol/l (120 and 266 mg/dl), respectively. An HbA1c cut-off of 48 mmol/mol (6.5%) had a sensitivity for high FPG of 87.3% (95% confidence interval (95% CI) 76.5 to 94.4) at sea level and 40.9% (95% CI 20.7 to 63.6) at high altitude. CONCLUSION: The relationship between HbA1c and FPG is less clear at high altitude than at sea level. Caution is warranted when using HbA1c to diagnose diabetes mellitus in this setting

Hybrid simulations of extensive air showers

We present a fast one dimensional hybrid method to efficiently simulate extensive air showers up to the highest observed energies. Based on precalculated pion showers and a bootstrap technique, our method predicts the average shower profile, the number of muons at detector level above several energy thresholds as well as the fluctuations of the electromagnetic and hadronic components of the shower. We study the main characteristics of proton-induced air showers up to ultra high energy, comparing the predictions of three different hadronic interaction models: SIBYLL 1.7, SIBYLL 2.1 and QGSJET98. The influence of the hadronic interaction models on the shower evolution, in particular the elongation rate, is discussed and the applicability of analytical approximations is investigated.66

Hallazgo de Fasciola hepatica (Trematoda: Digenea) en un carpincho (Hydrochaeris hydrochaeris) de la Provincia de Corrientes, Argentina

El propósito del trabajo fue determinar la prevalencia del trematodo asciola hepatica en carpinchos (Hydrochaeris hydrochaeris) de la Provincia de Corrientes (Argentina) y el rol que podría cumplir en la epizootiología de la fasciolosis hepática para otras especies hospedadoras del parásito. Para comprobar la presencia del trematodo se obtuvieron 18 hígados de carpinchos silvestres provenientes de distintas zonas de Corrientes. Del total de órganos examinados, solamente un caso resultó positivo a F. hepatica (5,56%), identificándose 10 ejemplares por sus caracteres morfológicos y la presencia de abundantes de huevos típicos que se recuperaron durante el examen. Este hallazgo debe considerarse como la primera comunicación del parasitismo de F. hepatica en H. hydrochaeris en el país

Quantitative magneto-optical investigation of superconductor/ferromagnet hybrid structures

We present a detailed quantitative magneto-optical imaging study of several superconductor/ferromagnet hybrid structures, including Nb deposited on top of thermomagnetically patterned NdFeB, and permalloy/niobium with erasable and tailored magnetic landscapes imprinted in the permalloy layer. The magneto-optical imaging data is complemented with and compared to scanning Hall probe microscopy measurements. Comprehensive protocols have been developed for calibrating, testing, and converting Faraday rotation data to magnetic field maps. Applied to the acquired data, they reveal the comparatively weaker magnetic response of the superconductor from the background of larger fields and field gradients generated by the magnetic layer.Comment: 21 pages, including 2 pages of supplementary materia