bluuebunny/crossref_metadata_2025_split huggingface dataset:
Représentation et atrophie politiques des métropoles : le cas du Brésil
Authors: Carvalho Nelson Rojas de , Ribeiro Luiz Cesar de Queiroz , Malo Isabelle 
Published: March 2014

De récentes réflexions sur les enjeux liés à la construction identitaire de la gouvernance métropolitaine ont surtout mis l’accent sur l’analyse des effets politico-institutionnels d’un processus double : celui de la mondialisation et du néolibéralisme. Associé à une dynamique de répartition du pouvoir vers le haut et vers le bas, le processus de mondialisation des économies métropolitaines se traduit par un renforcement et une autonomisation des acteurs politiques locaux et supranationaux ainsi que par un affaiblissement des autorités intermédiaires, c’est-à-dire l’État national et le gouvernement métropolitain. Quant à lui, le processus de libéralisation implique une désactivation des mécanismes de réglementation des conflits liés à la distribution et des externalités du marché actuelles. Il a également un effet dissuasif quant à la mise en oeuvre des mécanismes de réglementation des nouveaux conflits et externalités inhérents à la politique métropolitaine. La combinaison des deux processus impliquerait une reconfiguration des métropoles, lesquelles comportent des lacunes en matière de gouvernance, au sens strict, et en matière de politique, au sens large. Si les effets pervers de ce double processus sur l’établissement de la gouvernance métropolitaine semblent incontestables, dans le présent article, nous adoptons un point de vue analytique complémentaire en mettant l’accent sur le processus de métropolisation brésilien. Nous tentons de vérifier dans quelle mesure les variables internes de la dynamique métropolitaine brésilienne sont également génératrices de blocages politico-institutionnels dans la mise en place de la gouvernance métropolitaine.
« J’habite… enfin…, je me comprends » : l’appropriation territoriale des adolescents placés en question
Authors: Guy Fleur 
Published: March 2014

Le rapport à l’espace des adolescents, et plus particulièrement leur mobilité, est souvent appréhendé à travers le prisme de la famille et d’un lieu de résidence unique. Pourtant, certains individus vivent dès l’adolescence des situations de multirésidentialité, en lien notamment avec une prise en charge fondée sur le déplacement géographique. L’analyse des situations résidentielles des enfants placés montre une diversité de configurations, impliquant les parents, mais aussi la famille élargie et l’entourage. L’appropriation territoriale des adolescents intègre alors de multiples espaces : entre le domicile familial et le lieu de placement apparaissent des espaces tiers, révélateurs d’un rapport affectif au territoire.
Cosmogenic 35S measurements in the Tibetan Plateau to quantify glacier snowmelt
Authors: Priyadarshi Antra , Hill‐Falkenthal Jason , Thiemens Mark , Zhang Zhisheng , Lin Mang , Chan Chuen‐yu , Kang Shichang 
Published: March 2014

AbstractThe cosmogenic radionuclide 35S (t1/2 ~ 87 days) is a unique tracer for high‐altitude air mass and has been used extensively to understand stratospheric air mass mixing. In this paper, we investigate if 35S can be utilized as an independent tracer to quantify glacier melt. We report the first measurements of 35S in samples collected from the Tibetan Plateau during 2009–2012 with an aim to interpret 35S in atmospheric particles and their deposition over glacier and snowmelts. Our measurements show that 35S activity in the aerosol phase varies from 116 ± 13 to 2229 ± 52 atoms/m3 resulting in higher values during winter–spring and lower values during summer–autumn. This seasonality is likely due to higher mixing of 35S‐rich stratospheric air masses during winter–spring and 35S‐poor air masses from the Bay of Bengal during the Asian summer monsoon. The average 35S activity in the Zhadang glacier was found to be 3–8 times higher relative to the nearby lake water. The main source of 35S activity in the Zhadang glacier is atmospheric deposition, whereas both atmospheric deposition and glacier snowmelt are the primary sources in the Nam Co Lake. The focus of this study is to quantitatively determine the spatial and temporal variations in glacier snowmelt. In the future, extensive sampling of aerosols and snow is required for determining 35S in combination with stable oxygen isotopes in sulfate to better understand the glacier melt process and hydrological cycle on the Tibetan Plateau.
Performance characteristics of the NLDN for return strokes and pulses superimposed on steady currents, based on rocket‐triggered lightning data acquired in Florida in 2004–2012
Authors: Mallick S. , Rakov V. A. , Hill J. D. , Ngin T. , Gamerota W. R. , Pilkey J. T. , Biagi C. J. , Jordan D. M. , Uman M. A. , Cramer J. A. , Nag A. 
Published: March 2014

AbstractWe present a detailed evaluation of performance characteristics of the U.S. National Lightning Detection Network (NLDN) using, as ground truth, Florida rocket‐triggered lightning data acquired in 2004–2012. The overall data set includes 78 flashes containing both the initial stage and leader/return‐stroke sequences and 2 flashes composed of the initial stage only. In these 80 flashes, there are a total of 326 return strokes (directly measured channel‐base currents are available for 290 of them) and 173 kiloampere‐scale (≥1 kA) superimposed pulses, including 58 initial continuous current pulses and 115 M components. All these events transported negative charge to the ground. The NLDN detected 245 return strokes and 9 superimposed pulses. The resultant NLDN flash detection efficiency is 94%, return‐stroke detection efficiency is 75%, and detection efficiency for superimposed pulses is 5% for peak currents ≥1 kA and 32% for peak currents ≥5 kA. For return strokes, the median location error is 334 m and the median value of absolute peak current estimation error is 14%. The percentage of misclassified events is 4%, all of them being return strokes. The median value of absolute event‐time mismatch (the difference in times at which the event is reported to occur by the NLDN and recorded at the lightning triggering facility) for return strokes is 2.8 µs. For two out of the nine superimposed pulses detected by the NLDN, we found optical evidence of a reilluminated branch (recoil leader) coming in contact with the existing grounded channel at an altitude of a few hundred meters above ground.
Asymmetric Diels–Alder Reactions of 2,4,6‐Trienals via Tetraenamine Catalysis
Authors: Zhou Qing‐Qing , Xiao You‐Cai , Yuan Xin , Chen Ying‐Chun 
Published: March 2014

AbstractWhile significant progress has been made in Diels–Alder cycloadditions of 2,4‐dienals by the formation of trienamine intermediates, we report that the further extended tetraenamine species can be generated from 2,4,6‐trienal substrates, which subsequently act as 3,6‐regioselective diene partners in asymmetric Diels–Alder reaction with 3‐olefinic oxindole dienophiles. An array of highly functionalized spirocyclic compounds were produced in good stereoselectivity up to 96 % ee and greater than 19:1 d.r., and with fair to moderate yields of 40–67 %.
Fluorogel Elastomers with Tunable Transparency, Elasticity, Shape‐Memory, and Antifouling Properties
Authors: Yao Xi , Dunn Stuart S. , Kim Philseok , Duffy Meredith , Alvarenga Jack , Aizenberg Joanna 
Published: March 2014

AbstractOmniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resistance to wetting by various liquids and anti‐biofouling behavior, while maintaining cytocompatiblity.
Molecular Ionization from Carbon Nanotube Paper
Authors: Narayanan Rahul , Sarkar Depanjan , Cooks R. Graham , Pradeep Thalappil 
Published: March 2014

AbstractAmbient ionization is achieved by spraying from a carbon nanotube (CNT)‐impregnated paper surface under the influence of small voltages (≥3 V). Organic molecules give simple high‐quality mass spectra without fragmentation in the positive or negative ion modes. Conventional field ionization is ruled out, and it appears that field emission of microdroplets occurs. Microscopic examination of the CNT paper confirms that the nanoscale features at the paper surface are responsible for the high electric fields. Raman spectra imply substantial current flows in the nanotubes. The performance of this analytical method was demonstrated for a range of volatile and nonvolatile compounds and a variety of matrices.
Bestimmung transienter Konformationszustände von Proteinen durch Festkörper‐R1ρ‐Relaxationsdispersions‐NMR‐Spektroskopie
Authors: Ma Peixiang , Haller Jens D. , Zajakala Jérémy , Macek Pavel , Sivertsen Astrid C. , Willbold Dieter , Boisbouvier Jérôme , Schanda Paul 
Published: March 2014

AbstractDie Funktion von Proteinen basiert auf der Fähigkeit, eine Vielfalt an Zuständen einzunehmen, die sich in ihren Strukturen und freien Energien unterscheiden. Um eine Proteinfunktion zu verstehen, gilt es daher herauszufinden, wie die verschiedenen, thermisch zugänglichen Konformationen miteinander verbunden sind und welche Strukturen und relativen Energien sie aufweisen. Viele biomolekulare Reaktionen laufen innerhalb von Mikro‐ bis Millisekunden ab, weshalb diese Zeitskala von zentraler (und funktioneller) Bedeutung ist. Wir zeigen hier, dass R1ρ‐Relaxationsdispersionsexperimente in Festkörper‐NMR mit Rotation am magischen Winkel Einblicke in die Thermodynamik und Kinetik solcher Austauschprozesse gibt, und dass auch strukturelle Parameter über kurzlebige Zustände erhalten werden können.
Structure of a Reactive Gold Carbenoid
Authors: Seidel Günter , Fürstner Alois 
Published: March 2014

AbstractA formal gold‐for‐chromium transmetalation allowed the gold carbenoid species [Cy3PAuCAr2]NTf2 (11) (Ar=pMeOC6H4‐) to be obtained in crystalline form. The structure in the solid state suggests that there is only little back donation of electron density from gold to the carbene center of 11 and hence very modest AuC double‐bond character; rather, it is the organic ligand framework that is responsible for stabilizing this species by resonance delocalization of the accumulated positive charge. Because 11 is capable of cyclopropanating p‐methoxystyrene even at low temperature, the discussion of its structure is deemed relevant for a better understanding of the mechanisms of π‐acid catalysis in general.
Convenient and Mild Epoxidation of Alkenes Using Heterogeneous Cobalt Oxide Catalysts
Authors: Banerjee Debasis , Jagadeesh Rajenahally V. , Junge Kathrin , Pohl Marga‐Martina , Radnik Jörg , Brückner Angelika , Beller Matthias 
Published: March 2014

AbstractA general epoxidation of aromatic and aliphatic olefins has been developed under mild conditions using heterogeneous CoxOy–N/C (x=1,3; y=1,4) catalysts and tert‐butyl hydroperoxide as the terminal oxidant. Various stilbenes and aliphatic alkenes, including renewable olefins, and vitamin and cholesterol derivatives, were successfully transformed into the corresponding epoxides with high selectivity and often good yields. The cobalt oxide catalyst can be recycled up to five times without significant loss of activity or change in structure. Characterization of the catalyst by XRD, TEM, XPS, and EPR analysis revealed the formation of cobalt oxide nanoparticles with varying size (Co3O4 with some CoO) and very few large particles with a metallic Co core and an oxidic shell. During the pyrolysis process the nitrogen ligand forms graphene‐type layers, in which selected carbon atoms are substituted by nitrogen.
Probing Transient Conformational States of Proteins by Solid‐State R1ρ Relaxation‐Dispersion NMR Spectroscopy
Authors: Ma Peixiang , Haller Jens D. , Zajakala Jérémy , Macek Pavel , Sivertsen Astrid C. , Willbold Dieter , Boisbouvier Jérôme , Schanda Paul 
Published: March 2014

AbstractThe function of proteins depends on their ability to sample a variety of states differing in structure and free energy. Deciphering how the various thermally accessible conformations are connected, and understanding their structures and relative energies is crucial in rationalizing protein function. Many biomolecular reactions take place within microseconds to milliseconds, and this timescale is therefore of central functional importance. Here we show that R1ρ relaxation dispersion experiments in magic‐angle‐spinning solid‐state NMR spectroscopy make it possible to investigate the thermodynamics and kinetics of such exchange process, and gain insight into structural features of short‐lived states.
Metal‐ and Reagent‐Free Highly Selective Anodic Cross‐Coupling Reaction of Phenols
Authors: Elsler Bernd , Schollmeyer Dieter , Dyballa Katrin Marie , Franke Robert , Waldvogel Siegfried R. 
Published: March 2014

AbstractThe direct oxidative cross‐coupling of phenols is a very challenging transformation, as homo‐coupling is usually strongly preferred. Electrochemical methods circumvent the use of oxidizing reagents or metal catalysts and are therefore highly attractive. Employing electrolytes with a high capacity for hydrogen bonding, such as methanol with formic acid or 1,1,1,3,3,3‐hexafluoro‐2‐propanol, a direct electrolysis in an undivided cell provides mixed 2,2′‐biphenols with high selectivity. This mild method tolerates a variety of moieties, for example, tert‐butyl groups, which are not compatible with other strong electrophilic media but vital for later catalytic applications of the formed products.
Nanosized cellulose derivatives as green reinforcing agents at higher loadings in natural rubber
Authors: Thakore Sonal 
Published: March 2014

ABSTRACTCellulose nanoparticles (CelNPs) prepared by an acid hydrolysis process were acetylated under ambient conditions to retain the nanosize and to obtain hydrophobic nanosized derivatives. Green nanocomposites of natural rubber (NR) with more than 50 phr of cellulosic fillers were successfully developed by a commercial dry mixing process. The incorporation of cellulose acetate nanofiller up to 40 phr led to an almost linear increase in both the tensile and elongation properties, which were higher than even those of a composite with the conventional filler carbon black (CB). This was further supported by the almost uniform single‐phase morphology of the nanobiocomposite revealed by scanning electron microscopy and the high thermal stability. The results indicate the high degree of compatibility between the hydrophobic nanosized filler and the NR matrix. Although a drop in the mechanical strength was observed above 50 phr, the cellulose derivatives were expected to prove to be promising substitutes for the hazardous filler CB even at higher loadings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40632.
Determination of moisture content of polyamide 66 directly from combination region near‐infrared spectra
Authors: Kuda‐Malwathumullage Chamathca P. S. , Small Gary W. 
Published: March 2014

ABSTRACTThe hygroscopic nature of polyamide (PA) polymers motivates the development of analysis tools for use in assessing their moisture content. Among possible analysis techniques, near‐infrared (near‐IR) spectroscopy is non‐destructive, requires little or no sample preparation, and is compatible with sample thicknesses on the order of mm. The work reported here makes use of transmission near‐IR spectroscopy in the combination region (5000–4000 cm−1) to develop a protocol for assessing the moisture content of PA 66 samples directly from their spectral intensities after preprocessing with the standard normal variate transform and partial least‐squares. The method is compatible with online or continuous monitoring applications and can be calibrated without the use of destructive reference measurements such as thermogravimetric analysis. The long‐term calibration performance of the technique is evaluated, and on a scale of 0–100% moisture uptake, the standard error of prediction is found to average 1.4% over 6 months. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40645.
Star‐shaped POSS–methacrylate copolymers with phenyl–triazole as terminal groups, synthesis, and the pyrolysis analysis
Authors: Qiang Xiu , Chen Fang , Ma Xiao‐Yan , Hou Xian‐Bing 
Published: March 2014

ABSTRACTStar‐shaped polyhedral oligomeric silsesquioxane (POSS)–methacrylate hybrid copolymers with phenyl–triazole as terminal groups had been designed and synthesized via sequential atom transfer radical polymerization (ATRP), azidation, and phenylacetylene‐terminated procedures, and the hybrid copolymers here could be denoted as POSS–(PXMA‐Pytl)8, where X can be M, B, L, and S, represented four different methacrylate monomers, such as methacrylate (MMA), butyl methacrylate (BMA), lauryl methacrylate (LMA), and stearyl methacrylate (SMA), respectively. Thermal gravimetric analysis (TGA) and in situ Fourier transform infrared spectroscopy (FTIR) were applied for studying the thermal stability and degradation mechanism, and it was found that all of the POSS–(PXMA‐Cl)8 and POSS–(PXMA‐Pytl)8 copolymers exhibited excellent thermal stabilities, which had great potential in heat‐resistant material application. Different tendencies of decomposition temperatures at 5% and 10% weight loss (T5 and T10) dependent on the side‐chain length and terminal group species were investigated respectively. The longer alkyl side chains of the monomers, the lower thermal stabilities, and enhanced T5 and T10 were also shown with the introduction of phenyl–triazole groups instead of chlorine groups. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40652.
Modular Transcriptional Repertoire Analyses of Adults With Systemic Lupus Erythematosus Reveal Distinct Type I and Type II Interferon Signatures
Authors: Chiche Laurent , Jourde‐Chiche Noémie , Whalen Elizabeth , Presnell Scott , Gersuk Vivian , Dang Kristen , Anguiano Esperanza , Quinn Charlie , Burtey Stéphane , Berland Yvon , Kaplanski Gilles , Harle Jean‐Robert , Pascual Virginia , Chaussabel Damien 
Published: March 2014

ObjectiveThe role of interferon‐α (IFNα) in the pathogenesis of systemic lupus erythematosus (SLE) is strongly supported by gene expression studies. The aim of this study was to improve characterization of the blood IFN signature in adult SLE patients.MethodsConsecutive patients were enrolled and followed up prospectively. Microarray data were generated using Illumina BeadChips. A modular transcriptional repertoire was used as a framework for the analysis.ResultsOur repertoire of 260 modules, which consisted of coclustered gene sets, included 3 IFN‐annotated modules (M1.2, M3.4, and M5.12) that were strongly up‐regulated in SLE patients. A modular IFN signature was observed in 54 of 62 patients (87%) or 131 of all 157 samples (83%). The IFN signature was more complex than expected, with each module displaying a distinct activation threshold (M1.2 < M3.4 < M5.12), thus providing a modular score by which to stratify SLE patients based on the presence of 0, 1, 2, or 3 active IFN modules. A similar gradient in modular IFN signature was observed within patients with clinically quiescent disease, for whom moderate/strong modular scores (2 or 3 active IFN modules) were associated with higher anti–double‐stranded DNA titers and lower lymphocyte counts than those in patients with absent/mild modular scores (0 or 1 active IFN modules). Longitudinal analyses revealed both stable (M1.2) and variable (M3.4 and M5.12) components of modular IFN signature over time in single patients. Interestingly, mining of other data sets suggested that M3.4 and M5.12 could also be driven by IFNβ and IFNγ.ConclusionModular repertoire analysis reveals complex IFN signatures in SLE, which are not restricted to the previous IFNα signature, but which also involve IFNβ and IFNγ.
Brief Report: In Search of a Candidate Pathogen for Giant Cell Arteritis: Sequencing‐Based Characterization of the Giant Cell Arteritis Microbiome
Authors: Bhatt Ami S. , Manzo Veronica E. , Pedamallu Chandra Sekhar , Duke Fujiko , Cai Diana , Bienfang Don C. , Padera Robert F. , Meyerson Matthew , Docken William P. 
Published: March 2014

ObjectiveTo characterize the microbiome of the temporal artery in patients with giant cell arteritis (GCA), and to apply an unbiased and comprehensive shotgun sequencing‐based approach to determine whether there is an enrichment of candidate pathogens in the affected tissue.MethodsTemporal artery biopsy specimens were collected from patients at a single institution over a period of 4 years, and unbiased DNA sequencing was performed on 17 formalin‐fixed, paraffin‐embedded specimens. Twelve of the 17 patients fulfilled the clinical and histopathologic criteria for GCA, and the other 5 patients served as controls. Using PathSeq software, human DNA sequences were computationally subtracted, and the remaining non‐human DNA sequences were taxonomically classified using a comprehensive microbial sequence database. The relative abundance of microbes was inferred based on read counts assigned to each organism. Comparison of the microbial diversity between GCA cases and controls was carried out using hierarchical clustering and linear discriminant analysis of effect size.ResultsPropionibacterium acnes and Escherichia coli were the most abundant microorganisms in 16 of the 17 samples, and Moraxella catarrhalis was the most abundant organism in 1 control sample. Pathogens previously described to be correlated with GCA were not differentially abundant in cases compared to controls. There was not a significant burden of likely pathogenic viruses.ConclusionDNA sequencing of temporal artery biopsy specimens from GCA cases, in comparison with non‐GCA controls, showed no evidence of previously identified candidate GCA pathogens. A single pathogen was not clearly and consistently associated with GCA in this case series.
Tear Cathepsin S as a Candidate Biomarker for Sjögren's Syndrome
Authors: Hamm‐Alvarez Sarah F. , Janga Srikanth R. , Edman Maria C. , Madrigal Sara , Shah Mihir , Frousiakis Starleen E. , Renduchintala Kavita , Zhu Jay , Bricel Seth , Silka Kimberly , Bach Dianne , Heur Martin , Christianakis Stratos , Arkfeld Daniel G. , Irvine John , Mack Wendy J. , Stohl William 
Published: March 2014

ObjectiveThe diagnosis of Sjögren's syndrome (SS) in routine practice is largely a clinical one and requires a high index of suspicion by the treating physician. This great dependence on clinical judgment frequently leads to delayed diagnosis or misdiagnosis. Tear protein profiles have been proposed as simple and reliable biomarkers for the diagnosis of SS. Given that cathepsin S activity is increased in the lacrimal glands and tears of NOD mice (a murine model of SS), the aim of this study was to explore the clinical utility of using tear cathepsin S (CTSS) activity as a biomarker for SS.MethodsA method to measure CTSS activity in tears eluted from Schirmer's test strips was developed and validated. Schirmer's tests were performed and CTSS activity measurements were obtained in 278 female subjects, including 73 with SS, 79 with rheumatoid arthritis, 40 with systemic lupus erythematosus, 10 with blepharitis, 31 with nonspecific dry eye disease, and 12 with other autoimmune diseases, as well as 33 healthy control subjects.ResultsThe median tear CTSS activity in patients with SS was 4.1‐fold higher than that in patients with other autoimmune diseases, 2.1‐fold higher than that in patients with nonspecific dry eye disease, and 41.1‐fold higher than that in healthy control subjects. Tear CTSS levels were equally elevated in patients with primary SS and those with secondary SS, independent of the Schirmer's test strip values or the levels of circulating anti‐SSA or anti‐SSB antibodies.ConclusionMarkedly high levels of tear CTSS activity are suggestive of SS. CTSS activity in tears can be measured in a simple, quick, economical, and noninvasive manner and may serve as a novel biomarker for autoimmune dacryoadenitis during the diagnostic evaluation for SS.