969 resultados para Positions
Resumo:
Five anthranilic acid derivatives, a mixture I of three new compounds 11′-hexadecenoylanthranilic acid (1), 9′-hexadecenoylanthranilic acid (2), and 7′-hexadecenoylanthranilic acid (3), as well as a new compound 9,12,15-octadecatrienoylanthranilic acid (4) together with a new natural product, hexadecanoylanthranilic acid (5), were isolated from Geijera parviflora Lindl. (Rutaceae). Their structures were elucidated by extensive spectroscopic measurements, and the positions of the double bonds in compounds 1-3 of the mixture I were determined by tandem mass spectrometry employing ozone-induced dissociation. The mixture I and compound 5 showed good antibacterial activity against several Gram-positive strains. © 2013 Elsevier B.V.
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Large scale screening of libraries consisting of natural and small molecules led to the identification of many small molecule inhibitors repressing Wnt/β-Catenin signaling. However, targeted synthesis of novel Wnt pathway inhibitors has been rarely described. We developed a modular and expedient way to create the aromatic ring system with an aliphatic ring in between. Our synthesis opens up the possibility, in principle, to substitute all positions at the ring system with any desired substituent. Here, we tested five different haloquinone analogs carrying methoxy- and hydroxy-groups at different positions. Bona fide Wnt activity assays in cell culture and in Xenopus embryos revealed that two of these compounds act as potent inhibitors of aberrant activated Wnt/β-Catenin signaling.
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Disjoint top-view networked cameras are among the most commonly utilized networks in many applications. One of the open questions for these cameras' study is the computation of extrinsic parameters (positions and orientations), named extrinsic calibration or localization of cameras. Current approaches either rely on strict assumptions of the object motion for accurate results or fail to provide results of high accuracy without the requirement of the object motion. To address these shortcomings, we present a location-constrained maximum a posteriori (LMAP) approach by applying known locations in the surveillance area, some of which would be passed by the object opportunistically. The LMAP approach formulates the problem as a joint inference of the extrinsic parameters and object trajectory based on the cameras' observations and the known locations. In addition, a new task-oriented evaluation metric, named MABR (the Maximum value of All image points' Back-projected localization errors' L2 norms Relative to the area of field of view), is presented to assess the quality of the calibration results in an indoor object tracking context. Finally, results herein demonstrate the superior performance of the proposed method over the state-of-the-art algorithm based on the presented MABR and classical evaluation metric in simulations and real experiments.
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Previous studies have shown that the human lens contains glycerophospholipids with ether linkages. These lipids differ from conventional glycerophospholipids in that the sn-1 substituent is attached to the glycerol backbone via an 1-O-alkyl or an 1-O-alk-1'-enyl ether rather than an ester bond. The present investigation employed a combination of collision-induced dissociation (CID) and ozone-induced dissociation (OzID) to unambiguously distinguish such 1-O-alkyl and 1-O-alk-1'-enyl ethers. Using these methodologies the human lens was found to contain several abundant 1-O-alkyl glycerophos-phoethanolamines, including GPEtn(16:0e/9Z-18:1), GPEtn(11Z-18:1e/9Z-18:1), and GPEtn(18:0e/9Z-18:1), as well as a related series of unusual 1-O-alkyl glycerophosphoserines, including GPSer(16:0e/9Z-18:1), GPSer(11Z-18:1e/9Z-18:1), GPSer(18:0e/9Z-18:1) that to our knowledge have not previously been observed in human tissue. Isomeric 1-O-alk-1'-enyl ethers were absent or in low abundance. Examination of the double bond position within the phospholipids using OzID revealed that several positional isomers were present, including sites of unsaturation at the n-9, n-7, and even n-5 positions. Tandem CID/OzID experiments revealed a preference for double bonds in the n-7 position of 1-O-ether linked chains, while n-9 double bonds predominated in the ester-linked fatty acids [e.g., GPEtn(11Z-18:1e/9Z-18:1) and GPSer(11Z-18:1e/9Z-18:1)]. Different combinations of these double bond positional isomers within chains at the sn-1 and sn-2 positions point to a remarkable molecular diversity of ether-lipids within the human lens.
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Contemporary lipidomics protocols are dependent on conventional tandem mass spectrometry for lipid identification. This approach is extremely powerful for determining lipid class and identifying the number of carbons and the degree of unsaturation of any acyl-chain substituents. Such analyses are however, blind to isomeric variants arising from different carbon carbon bonding motifs within these chains including double bond position, chain branching, and cyclic structures. This limitation arises from the fact that conventional, low energy collision-induced dissociation of even-electron lipid ions does not give rise to product ions from intrachain fragmentation of the fatty acyl moieties. To overcome this limitation, we have applied radical-directed dissociation (RDD) to the study of lipids for the first time. In this approach, bifunctional molecules that contain a photocaged radical initiator and a lipid-adducting group, such as 4-iodoaniline and 4-iodobenzoic acid, are used to form noncovalent complexes (i.e., adduct ions) with a lipid during electrospray ionization. Laser irradiation of these complexes at UV wavelengths (266 nm) cleaves the carbon iodine bond to liberate a highly reactive phenyl radical. Subsequent activation of the nascent radical ions results in RDD with significant intrachain fragmentation of acyl moieties. This approach provides diagnostic fragments that are associated with the double bond position and the positions of chain branching in glycerophospholipids, sphingomyelins and triacylglycerols and thus can be used to differentiate isomeric lipids differing only in such motifs. RDD is demonstrated for well-defined lipid standards and also reveals lipid structural diversity in olive oil and human very-low density lipoprotein.
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This paper explores the emotional life of fly‑in fly‑out (FIFO) workers and their families, through an analysis of more than 500 postings made on an online chat forum for mining families. Building on literature on fly‑in fly‑out workers and understandings of emotions as socially constructed, analysis shows how posters to the forum, typically women whose male partners are FIFO workers, construct gendered emotional identities for their partners (sometimes referred to as 'Mr Miner'), and for themselves, as 'mining women', 'mining widows' or the 'mining missus'. Inherent in the creation of gendered emotional subject positions is the process of women undertaking emotion work on and behalf of themselves, their male partners and their children. The findings demonstrate the overarching normative dimensions of women's emotional self‑transformations in the service of their mining partners' careers and the attendant reproduction of everyday patriarchal relations in the private lives of mining families.
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The Comment by Mayers and Reiter criticizes our work on two counts. Firstly, it is claimed that the quantum decoherence effects that we report in consequence of our experimental analysis of neutron Compton scattering from H in gaseous H2 are not, as we maintain, outside the framework of conventional neutron scatteringtheory. Secondly, it is claimed that we did not really observe such effects, owing to a faulty analysis of the experimental data, which are claimed to be in agreement with conventional theory. We focus in this response on the critical issue of the reliability of our experimental results and analysis. Using the same standard Vesuvio instrument programs used by Mayers et al., we show that, if the experimental results for H in gaseous H2 are in agreement with conventional theory, then those for D in gaseous D2 obtained in the same way cannot be, and vice-versa. We expose a flaw in the calibration methodology used by Mayers et al. that leads to the present disagreement over the behaviour of H, namely the ad hoc adjustment of the measured H peak positions in TOF during the calibration of Vesuvio so that agreement is obtained with the expectation of conventional theory. We briefly address the question of the necessity to apply the theory of open quantum systems.
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Unsaturated lipids deposited onto a range of materials are observed to react with the low concentrations of ozone present in normal laboratory air. Parent lipids and ozonolysis cleavage products are both detected directly from surfaces by desorption electrospray ionisation mass spectrometry (DESI-MS) with the resulting mass spectra providing clear evidence of the double bond position within these molecules. This serendipitous process has been coupled with thin-layer chromatography (TLC) to provide a simple but powerful approach for the detailed structural elucidation of lipids present in complex biological extracts. Lipid extracts from human lens were deposited onto normal phase TLC plates and then developed to separate components according to lipid class. Exposure of the developed plates to laboratory air for ca. 1 h prior to DESI-MS analysis gave rise to ozonolysis products allowing for the unambiguous identification of double bond positions in even low abundant, unsaturated lipids. In particular, the co-localization of intact unsaturated lactosylceramides (LacCer) with products from their oxidative cleavage provide the first evidence for the presence of three isomeric LacCer (d18:0/24:1) species in the ocular lens lipidome, i.e., variants with double bonds at the n-9, n-7 and n-5 positions.
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Light of Extinction presents a diverse series of views into the complex antics of a semi-autonomous gaggle of robotic actants. Audiences initially enter into the 'backend' of the experience to be rudely confronted with the raw, messy operations of a horde of object-manipulating robotic forms. Seen through viewing apertures these ‘things’ deny any opportunity to grasp their imagined order. Audiences then flow on into the 'front end' of the work where now, seen through another aperture, the very same forms seemingly coordinate a stunning deep-field choreography, floating lusciously within inky landscapes of media, noise and embodied sound. As one series of conceptions slip into extinction, so others flow on in. The idea of the 'extinction of human experience' expresses a projected fear for that which will disappear when biodiverse worlds have descended into an era of permanent darkness. ‘Light Of Extinction' re-positions this anthropomorphic lament in order to suggest a more rounded acknowledgement of what might still remain - suggesting the previously unacknowledged power and place of autonomous, synthetic creation. Momentary disbelief gives way to a relieving celebration of the imagined birth of ‘things’ – without need for staples such as conventional light or the harmonious lullabies of long-extinguished sounds.
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An in vivo screen has been devised for NF-κB p50 activity in Escherichia coli exploiting the ability of the mammalian transcription factor to emulate a prokaryotic repressor. Active intracellular p50 was shown to repress the expression of a green fluorescent protein reporter gene allowing for visual screening of colonies expressing active p50 on agar plates. A library of mutants was constructed in which the residues Y267, L269, A308 and V310 of the dimer interface were simultaneously randomised and twenty-five novel functional interfaces were selected which repressed the reporter gene to similar levels as the wild-type protein. The leucine-269 alanine-308 core was repeatedly, but not exclusively, selected from the library whilst a diversity of predominantly non-polar residues were selected at positions 267 and 310. These results indicate that L269 and A308 may form a hot spot of interaction and allow an insight into the processes of dimer selectivity and evolution within this family of transcription factors.
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This volume introduces a collective approach that positions transmedia as a dynamic phenomenon which undergoes constant innovation as it absorbs current trends and advances in its constituent disciplines. The first section, 'Sustaining Future Practices', explores emerging models for defining stakeholder needs, understanding resource requirements and measuring the value and success of transmedia productions. The focus then shifts to 'Intersecting Contexts of Transmedia Practices', which uses the juxtaposition of a diverse collection of case studies to transcend not only the debates about how to define transmedia, but also the professional and disciplinary boundaries that impose artificial constraints upon the way transmedia projects are approached and understood. This inter-disciplinary dialogue aims to promote an ongoing conversation on the challenges and opportunities associated with sustaining this vital creative industry.
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The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X=H), nitroperbenzoates (X=para-, meta-, ortho-NO2), and methoxyperbenzoates (X=para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting-at least initially-in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.
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Facial expression recognition (FER) has been dramatically developed in recent years, thanks to the advancements in related fields, especially machine learning, image processing and human recognition. Accordingly, the impact and potential usage of automatic FER have been growing in a wide range of applications, including human-computer interaction, robot control and driver state surveillance. However, to date, robust recognition of facial expressions from images and videos is still a challenging task due to the difficulty in accurately extracting the useful emotional features. These features are often represented in different forms, such as static, dynamic, point-based geometric or region-based appearance. Facial movement features, which include feature position and shape changes, are generally caused by the movements of facial elements and muscles during the course of emotional expression. The facial elements, especially key elements, will constantly change their positions when subjects are expressing emotions. As a consequence, the same feature in different images usually has different positions. In some cases, the shape of the feature may also be distorted due to the subtle facial muscle movements. Therefore, for any feature representing a certain emotion, the geometric-based position and appearance-based shape normally changes from one image to another image in image databases, as well as in videos. This kind of movement features represents a rich pool of both static and dynamic characteristics of expressions, which playa critical role for FER. The vast majority of the past work on FER does not take the dynamics of facial expressions into account. Some efforts have been made on capturing and utilizing facial movement features, and almost all of them are static based. These efforts try to adopt either geometric features of the tracked facial points, or appearance difference between holistic facial regions in consequent frames or texture and motion changes in loca- facial regions. Although achieved promising results, these approaches often require accurate location and tracking of facial points, which remains problematic.
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As the first academically rigorous interrogation of the generation of performance within the global frame of the motion capture volume, this research presents a historical contextualisation and develops and tests a set of first principles through an original series of theoretically informed, practical exercises to guide those working in the emergent space of performance capture. It contributes a new understanding of the framing of performance in The Omniscient Frame, and initiates and positions performance capture as a new and distinct interdisciplinary discourse in the fields of theatre, animation, performance studies and film.
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In 2005, governments around the world unanimously agreed to the principle of the responsibility to protect (R2P), which holds that all states have a responsibility to protect their populations from genocide and mass atrocities, that the international community should assist them to fulfil this duty, and that the international community should take timely and decisive measures to protect populations from such crimes when their host state fails to do so. Progressing R2P from words to deeds requires international consensus about the principle’s meaning and scope. To achieve a global consensus on this, we need to better understand the position of governments around the world, including in the Asia-Pacific region, which has long been associated with an enduring commitment to a traditional concept of sovereignty. The present article contributes to such an endeavour through its three sections. The first part charts the nature of the international consensus on R2P and examines the UN secretary-general’s approach. The second looks in detail at the positions of the Asia-Pacific region’s governments on the R2P principle. The final part explores the way forward for progressing the R2P principle in the Asia-Pacific region.