76 research outputs found
Rising and falling diapirs, shifting depocenters, and flap overturning in the Cretaceous Sopeira and Sant Gervàs subbasins (Ribagorça Basin, southern Pyrenees)
The halokinetic structure of inverted salt-related continental margins is frequently obliterated by compressional overprinting. The Cretaceous Sopeira and Sant Gervàs subbasins of the Ribagorça Basin (south central Pyrenees) show evidence of salt-related extensional tectonics and diapiric growth along the Iberian Margin of the Mesozoic Pyrenean rift. We present an integrated field-based tectonic-sedimentary study to reconstruct the evolution of the Ribagorça Basin system previous to, and in the early stages of, the Pyrenean orogeny. The ~4km thick Albian-Cenomanian Sopeira minibasin infill thins toward the basin borders, especially toward the eastern, N-S trending, Llastarri salt weld. The 90° tilt to the south of the Sopeira basin bottom records the growth of the buried north dipping Sopeira listric fault from Albian to Santonian times, when it evolved as an extensional rollover associated with the Aulet salt roller. The ~3km thick Cenomanian-Campanian succession filling the Sant Gervàs flap displays 130° bed fanning attitude from overturned Cenomanian carbonate platform strata to upright Campanian turbidite beds. The Sant Gervàs flap development since Cenomanian times was related to the fall of a large salt pillow after the main Soperia minibasin stage. Jurassic-Campanian diachronous subsidence is also observed in the adjacent Montiberri, Faiada, and Tamurcia depocenters. Correlation with the Pedraforca, Cotiella, and Basque-Cantabrian Basins along the southern Pyrenees suggests that a significant segment of the Iberian side of the Pyrenean rift experienced a gravity-driven extension from Albian to late Santonian. The Ribagorça Basin provides an excellent field analogue for presently buried salt-related structures of extended passive margins.This research was carried out with the aid of grants by CSIC-ESF 2007–2013
JAE-Doc postdoctoral research contract (E.S.) and with funding from the Spanish
Research Agency through projects CGL2009-1355, CGL2011-26670, and
CGL2010-15416. Additional funding was provided by Atlas Project and
Statoil Research CenterPeer reviewe
Reproducibility of lateral excursive tooth contact in a semi-adjustable articulator depending on the type of lateral guidance
The purposes of this study were (i) to compare the reproducibility of lateral tooth contacts of casts mounted in a semi-adjustable articulator when condylar guidance was set by different methods and (ii) to assess the margin of error of the variations of condylar guidance without changing lateral tooth contacts, depending on the type of lateral guidance. In subjects with different types of lateral guidance, intraoral lateral tooth contacts identified with occlusal registration strips were compared with those identified by use of a semi-adjustable articulator, setting the condylar guidance in four different ways: using protrusive wax wafers, by axiography and by adding and subtracting 5 degrees from the value of condylar guidance obtained by protrusive wax wafers. Tolerance to variations of condylar guidance without changing lateral tooth contacts was determined by increasing and decreasing the value of condylar guidance until lateral tooth contacts changed. Different ways of setting condylar guidance on a semi-adjustable articulator give rise to different values of condylar guidance in the same subject. The occlusal repercussions of these variations of condylar guidance values depend on the type of lateral guidance. Canine protection had the greatest tolerance to variations in the setting of condylar guidance without changing lateral occlusal contacts
The architectures of media power: editing, the newsroom, and urban public space
This paper considers the relation of the newsroom and the city as a lens into the more general relation of production spaces and mediated publics. Leading theoretically from Lee and LiPuma’s (2002) notion of ‘cultures of circulation’, and drawing on an ethnography of the Toronto Star, the paper focuses on how media forms circulate and are enacted through particular practices and material settings. With its attention to the urban milieus and orientations of media organizations, this paper exhibits both affinities with but also differences to current interests in the urban architectures of media, which describe and theorize how media get ‘built into’ the urban experience more generally. In looking at editing practices situated in the newsroom, an emphasis is placed on the phenomenological appearance of media forms both as objects for material assembly as well as more abstracted subjects of reflexivity, anticipation and purposiveness. Although this is explored with detailed attention to the settings of the newsroom and the city, the paper seeks to also provide insight into the more general question of how publicness is material shaped and sited
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Patterns of media coverage repeated in online abuse on high-profile criminal cases
What relationship do the mainstream media have with online abuse on high-profile criminal cases? This article hopes to make a start at answering this question by examining tweets containing the #McCann hashtag, utilised by a highly engaged community of users to comment on all matters related to the disappearance of British child Madeleine McCann. On #McCann, the child’s parents and other players are often singled out as the perpetrators of her disappearance and other crimes, in a blend of harassment, defamation and insults with conspiracy theories, disinformation and a strong anti-establishment vein typical of the posttruth era. Through an experimental digital ethnography blending elements of content and discourse analysis, this research has observed the #McCann conversation and analysed 500 tweets with the hashtag, observing that some of the most offensive theories posted by users on Twitter reprised themes seen in the mainstream media at the time of the disappearance, which resulted in defamation lawsuits by the McCanns and in complaints about unethical reporting at the Leveson Inquiry. This raises questions about the mainstream media’s responsibility and duty of care towards people they report on in the digital age, and showcases a symbiotic yet diffident relationship between anti-establishment online users and traditional news media
New interpretation of the Gran Dolina-TD6 bearing Homo antecessor deposits through sedimentological analysis
Gran Dolina is a cavity infilled by at least 25m of Pleistocene sediments.This sequence contains the TD6 stratigraphic unit, whose records include around 170 hominin bones that have allowed the definition of a new species, Homo antecessor. This fossil accumulation was studied as a single assemblage and interpreted as a succession of several human home bases. We propose a complete stratigraphic context and sedimentological interpretation for TD6, analyzing the relationships between the sedimentary facies, the clasts and archaeo-palaeontological remains. The TD6 unit has been divided into three subunits and 13 layers. Nine sedimentary facies have been defined. Hominin remains appear related to three different sedimentary facies: debris flow facies, channel facies and floodplain facies. They show three kinds of distribution: first a group of scattered fossils, then a group with layers of fossils in fluvial facies, and third a group with a layer of fossils in mixed fluvial and gravity flow facies. The results of this work suggest that some of these hominin remains accumulated in the cave by geological processes, coming from the adjacent slope above the cave or the cave entry, as the palaeogeography and sedimentary characteristics of these allochthonous facies suggest
SNi from SN2: a front-face mechanism ‘synthase’ engineered from a retaining hydrolase
SNi or SNi-like mechanisms, in which leaving group departure and nucleophile approach occur on the same ‘front’ face, have been observed previously experimentally and computationally in both the chemical and enzymatic (glycosyltransferase) substitution reactions of α-glycosyl electrophiles. Given the availability of often energetically comparable competing pathways for substitution (SNi vs SN1 vs SN2) the precise modulation of this archetypal reaction type should be feasible. Here, we show that the drastic engineering of a protein that catalyzes substitution, a retaining β-glycosidase (from Sulfolobus solfataricus SSβG), apparently changes the mode of reaction from “SN2” to “SNi”. Destruction of the nucleophilic Glu387 of SSβG-WT through Glu387Tyr mutation (E387Y) created a catalyst (SSβG-E387Y) with lowered but clear transglycosylation substitution activity with activated substrates, altered substrate and reaction preferences and hence useful synthetic (‘synthase’) utility by virtue of its low hydrolytic activity with unactivated substrates. Strikingly, the catalyst still displayed retaining β stereoselectivity, despite lacking a suitable nucleophile; pH-activity profile, mechanism-based inactivators and mutational analyses suggest that SSβG-E387Y operates without either the use of nucleophile or general acid/base residues, consistent with a SNi or SNi-like mechanism. An x-ray structure of SSβG-E387Y and subsequent metadynamics simulation suggest recruitment of substrates aided by a π-sugar interaction with the introduced Tyr387 and reveal a QM/MM free energy landscape for the substitution reaction catalyzed by this unnatural enzyme similar to those of known natural, SNi-like glycosyltransferase (GT) enzymes. Proton flight from the putative hydroxyl nucleophile to the developing p-nitrophenoxide leaving group of the substituted molecule in the reactant complex creates a hydrogen bond that appears to crucially facilitate the mechanism, mimicking the natural mechanism of SNi-GTs. An oxocarbenium ion-pair minimum along the reaction pathway suggests a step-wise SNi-like DN*ANss rather than a concerted SNi DNAN mechanism. This first observation of a front face mechanism in a β-retaining glycosyl transfer enzyme highlights, not only that unusual SNi reaction pathways may be accessed through direct engineering of catalysts with suitable environments, but also suggests that ‘β-SNi’ reactions are also feasible for glycosyl transfer enzymes and the more widespread existence of SNi or SNi-like mechanism in nature
Two distinct catalytic pathways for GH43 xylanolytic enzymes unveiled by X-ray and QM/MM simulations
Xylanolytic enzymes from glycoside hydrolase family 43 (GH43) are involved in the breakdown of hemicellulose, the second most abundant carbohydrate in plants. Here, we kinetically and mechanistically describe the non-reducing-end xylose-releasing exo-oligoxylanase activity and report the crystal structure of a native GH43 Michaelis complex with its substrate prior to hydrolysis. Two distinct calcium-stabilized conformations of the active site xylosyl unit are found, suggesting two alternative catalytic routes. These results are confirmed by QM/MM simulations that unveil the complete hydrolysis mechanism and identify two possible reaction pathways, involving different transition state conformations for the cleavage of xylooligosaccharides. Such catalytic conformational promiscuity in glycosidases is related to the open architecture of the active site and thus might be extended to other exo-acting enzymes. These findings expand the current general model of catalytic mechanism of glycosidases, a main reaction in nature, and impact on our understanding about their interaction with substrates and inhibitors
Stepwise Catalytic Mechanism via Short-Lived Intermediate Inferred from Combined QM/MM MERP and PES Calculations on Retaining Glycosyltransferase ppGalNAcT2
The glycosylation of cell surface proteins plays a crucial role in a multitude of biological processes, such as cell adhesion and recognition. To understand the process of protein glycosylation, the reaction mechanisms of the participating enzymes need to be known. However, the reaction mechanism of retaining glycosyltransferases has not yet been sufficiently explained. Here we investigated the catalytic mechanism of human isoform 2 of the retaining glycosyltransferase polypeptide UDP-GalNAc transferase by coupling two different QM/MM-based approaches, namely a potential energy surface scan in two distance difference dimensions and a minimum energy reaction path optimisation using the Nudged Elastic Band method. Potential energy scan studies often suffer from inadequate sampling of reactive processes due to a predefined scan coordinate system. At the same time, path optimisation methods enable the sampling of a virtually unlimited number of dimensions, but their results cannot be unambiguously interpreted without knowledge of the potential energy surface. By combining these methods, we have been able to eliminate the most significant sources of potential errors inherent to each of these approaches. The structural model is based on the crystal structure of human isoform 2. In the QM/MM method, the QM region consists of 275 atoms, the remaining 5776 atoms were in the MM region. We found that ppGalNAcT2 catalyzes a same-face nucleophilic substitution with internal return (SNi). The optimized transition state for the reaction is 13.8 kcal/mol higher in energy than the reactant while the energy of the product complex is 6.7 kcal/mol lower. During the process of nucleophilic attack, a proton is synchronously transferred to the leaving phosphate. The presence of a short-lived metastable oxocarbenium intermediate is likely, as indicated by the reaction energy profiles obtained using high-level density functionals
Photo-astrometric distances, extinctions, and astrophysical parameters for Gaia EDR3 stars brighter than G = 18.5
Stars and planetary system
A New Crocodylian from the Late Maastrichtian of Spain: Implications for the Initial Radiation of Crocodyloids
The earliest crocodylians are known primarily from the Late Cretaceous of North America and Europe. The representatives of Gavialoidea and Alligatoroidea are known in the Late Cretaceous of both continents, yet the biogeographic origins of Crocodyloidea are poorly understood. Up to now, only one representative of this clade has been known from the Late Cretaceous, the basal crocodyloid Prodiplocynodon from the Maastrichtian of North America.The fossil studied is a skull collected from sandstones in the lower part of the Tremp Formation, in Chron C30n, dated at -67.6 to 65.5 Ma (late Maastrichtian), in Arén (Huesca, Spain). It is located in a continuous section that contains the K/P boundary, in which the dinosaur faunas closest to the K/P boundary in Europe have been described, including Arenysaurus ardevoli and Blasisaurus canudoi. Phylogenetic analysis places the new taxon, Arenysuchus gascabadiolorum, at the base of Crocodyloidea.The new taxon is the oldest crocodyloid representative in Eurasia. Crocodyloidea had previously only been known from the Palaeogene onwards in this part of Laurasia. Phylogenetically, Arenysuchus gascabadiolorum is situated at the base of the first radiation of crocodyloids that occurred in the late Maastrichtian, shedding light on this part of the cladogram. The presence of basal crocodyloids at the end of the Cretaceous both in North America and Europe provides new evidence of the faunal exchange via the Thulean Land Bridge during the Maastrichtian
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