339 research outputs found
Objeto virtual de aprendizaje para la concientización frente a los fenómenos naturales o antrópicos que se suscitan en el departamento de Nariño
La prevención y atención de desastres es una temática de interés general. En el caso particular del departamento de Nariño son diversas las amenazas a las cuales se encuentra expuesto cada uno de los municipios que lo conforman; por ello, es de gran importancia la implementación de nuevos elementos que contribuyan al conocimiento de los fenómenos que causan estas amenazas, para así contribuir en la gestión del riesgo en toda la comunidad, principalmente en la que se encuentra más vulnerable
Evaluation and nonsurgical management of rotator cuff calcific tendinopathy.
Rotator cuff calcific tendinopathy is a common finding that accounts for about 7% of patients with shoulder pain. There are numerous theories on the pathogenesis of rotator cuff calcific tendinopathy. The diagnosis is confirmed with radiography, MRI or ultrasound. There are numerous conservative treatment options available and most patients can be managed successfully without surgical intervention. Nonsteroidal anti-inflammatory drugs and multiple modalities are often used to manage pain and inflammation; physical therapy can help improve scapular mechanics and decrease dynamic impingement; ultrasound-guided needle aspiration and lavage techniques can provide long-term improvement in pain and function in these patients
Mass Spectrometry-Based Techniques to Elucidate the Sugar Code
Cells encode information in the sequence of biopolymers, such as nucleic acids, proteins, and glycans. Although glycans are essential to all living organisms, surprisingly little is known about the “sugar code” and the biological roles of these molecules. The reason glycobiology lags behind its counterparts dealing with nucleic acids and proteins lies in the complexity of carbohydrate structures, which renders their analysis extremely challenging. Building blocks that may differ only in the configuration of a single stereocenter, combined with the vast possibilities to connect monosaccharide units, lead to an immense variety of isomers, which poses a formidable challenge to conventional mass spectrometry. In recent years, however, a combination of innovative ion activation methods, commercialization of ion mobility–mass spectrometry, progress in gas-phase ion spectroscopy, and advances in computational chemistry have led to a revolution in mass spectrometry-based glycan analysis. The present review focuses on the above techniques that expanded the traditional glycomics toolkit and provided spectacular insight into the structure of these fascinating biomolecules. To emphasize the specific challenges associated with them, major classes of mammalian glycans are discussed in separate sections. By doing so, we aim to put the spotlight on the most important element of glycobiology: the glycans themselves
Exploring the Cosmic Evolution of Habitability with Galaxy Merger Trees
We combine inferred galaxy properties from a semi-analytic galaxy evolution
model incorporating dark matter halo merger trees with new estimates of
supernova and gamma ray burst rates as a function of metallicity from stellar
population synthesis models incorporating binary interactions. We use these to
explore the stellar mass fraction of galaxies irradiated by energetic
astrophysical transients and its evolution over cosmic time, and thus the
fraction which is potentially habitable by life like our own. We find that 18
per cent of the stellar mass in the Universe is likely to have been irradiated
within the last 260 Myr, with GRBs dominating that fraction. We do not see a
strong dependence of irradiated stellar mass fraction on stellar mass or
richness of the galaxy environment. We consider a representative merger tree as
a Local Group analogue, and find that there are galaxies at all masses which
have retained a high habitable fraction (>40 per cent) over the last 6 Gyr, but
also that there are galaxies at all masses where the merger history and
associated star formation have rendered galaxies effectively uninhabitable.
This illustrates the need to consider detailed merger trees when evaluating the
cosmic evolution of habitability.Comment: 11 page, 10 figures. MNRAS accepted 13th Dec 2017. Updated to match
accepted version, with additional discussion of metallicity effect
Remote participation during glycosylation reactions of galactose building blocks: Direct evidence from cryogenic vibrational spectroscopy
The stereoselective formation of 1,2‐cis‐glycosidic bonds is challenging. However, 1,2‐cis‐selectivity can be induced by remote participation of C4 or C6 ester groups. Reactions involving remote participation are believed to proceed via a key ionic intermediate, the glycosyl cation. Although mechanistic pathways were postulated many years ago, the structure of the reaction intermediates remained elusive owing to their short‐lived nature. Herein, we unravel the structure of glycosyl cations involved in remote participation reactions via cryogenic vibrational spectroscopy and first principles theory. Acetyl groups at C4 ensure α‐selective galactosylations by forming a covalent bond to the anomeric carbon in dioxolenium‐type ions. Unexpectedly, also benzyl ether protecting groups can engage in remote participation and promote the stereoselective formation of 1,2‐cis‐glycosidic bonds
Binary Population and Spectral Synthesis Version 2.1: construction, observational verification and new results
The Binary Population and Spectral Synthesis (BPASS) suite of binary stellar
evolution models and synthetic stellar populations provides a framework for the
physically motivated analysis of both the integrated light from distant stellar
populations and the detailed properties of those nearby. We present a new
version 2.1 data release of these models, detailing the methodology by which
BPASS incorporates binary mass transfer and its effect on stellar evolution
pathways, as well as the construction of simple stellar populations. We
demonstrate key tests of the latest BPASS model suite demonstrating its ability
to reproduce the colours and derived properties of resolved stellar
populations, including well- constrained eclipsing binaries. We consider
observational constraints on the ratio of massive star types and the
distribution of stellar remnant masses. We describe the identification of
supernova progenitors in our models, and demonstrate a good agreement to the
properties of observed progenitors. We also test our models against photometric
and spectroscopic observations of unresolved stellar populations, both in the
local and distant Universe, finding that binary models provide a
self-consistent explanation for observed galaxy properties across a broad
redshift range. Finally, we carefully describe the limitations of our models,
and areas where we expect to see significant improvement in future versions.Comment: 69 pages, 45 figures. Accepted for publication in PASA. Accompanied
by a full, documented data release at http://bpass.auckland.ac.nz and
http://warwick.ac.uk/bpas
Cryogenic infrared spectroscopy provides mechanistic insight into the fragmentation of phospholipid silver adducts
Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a fragment spectrum can often be increased by the addition of metal cations. In particular, the use of silver ions is deeply rooted in the history of lipidomics due to their propensity to coordinate both electron-rich heteroatoms and C = C bonds in aliphatic chains. Not surprisingly, coordination of silver ions was found to enable the distinction of sn-isomers in glycerolipids by inducing reproducible intensity differences in the fragment spectra, which could, however, not be rationalized. Here, we investigate the fragmentation behaviors of silver-adducted sn- and double bond glycerophospholipid isomers by probing fragment structures using cryogenic gas-phase infrared (IR) spectroscopy. Our results confirm that neutral headgroup loss from silver-adducted glycerophospholipids leads to dioxolane-type fragments generated by intramolecular cyclization. By combining high-resolution IR spectroscopy and computational modelling of silver-adducted fragments, we offer qualitative explanations for different fragmentation behaviors of glycerophospholipid isomers. Overall, the results demonstrate that gas-phase IR spectroscopy of fragment ions can significantly contribute to our understanding of lipid dissociation mechanisms and the influence of coordinating cations
The Influence of the Electron Density in Acyl Protecting Groups on the Selectivity of Galactose Formation
The stereoselective formation of 1,2-cis-glycosidic bonds is a major bottleneck in the synthesis of carbohydrates. We here investigate how the electron density in acyl protecting groups influences the stereoselectivity by fine-tuning the efficiency of remote participation. Electron-rich C4-pivaloylated galactose building blocks show an unprecedented α-selectivity. The trifluoroacetylated counterpart with electron-withdrawing groups, on the other hand, exhibits a lower selectivity. Cryogenic infrared spectroscopy in helium nanodroplets and density functional theory calculations revealed the existence of dioxolenium-type intermediates for this reaction, which suggests that remote participation of the pivaloyl protecting group is the origin of the high α-selectivity of the pivaloylated building blocks. According to these findings, an α-selective galactose building block for glycosynthesis is developed based on rational considerations and is subsequently employed in automated glycan assembly exhibiting complete stereoselectivity. Based on the obtained selectivities in the glycosylation reactions and the results from infrared spectroscopy and density functional theory, we suggest a mechanism by which these reactions could proceed
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