bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photographie, un objet du pouvoir
Authors: Jewsiewicki Bogumil 
Published: August 2016

Ce texte examine les effets sociaux des usages congolais de la photographie comme medium de production et de circulation de l’identité et du corps modernes. Au cours du XXe siècle, la représentation photographique témoigne de la nouvelle identité mise en circulation dans l’univers moderne. L’image « mécaniquement reproduite » constitue un artefact tenant lieu et place d’une personne moderne. Pour ce numéro spécial, l’intérêt du texte proposé ici est surtout comparatif. L’analyse d’un processus de représentation de soi par la photographie éclaire ce que fait à la représentation de soi la circulation sur Internet des images autoproduites. Certes, les deux situations sont opposées : dans le cas congolais l’image fixe est bidimensionnelle, sa production par un tiers et sa circulation sont commodifiées ; sur Internet l’image animée est autoproduite pour la circulation dans l’espace non commodifié. Néanmoins, dans un cas comme dans l’autre, il y a coïncidence entre le changement de médium et la volonté du sujet de mettre en circulation une autre représentation de soi, de contrôler l’image de son corps. Au Congo, l’identité moderne est en construction permanente, elle semble graviter autour de la personne plutôt que faire partie du corps. Socialement acceptée, la représentation du corps noir féminin « moderne » s’inscrit dans la mémoire culturelle de la domination, y compris au plan de l’érotisme. Par contre, lorsque des femmes s’emparent de l’image de leur corps pour défier le système social, le corps nu est représenté en tant que bien commodifié. Il est alors inscrit dans un mode de jouissance « moderne » et dans l’offre de satisfaction du désir masculin individuel contre l’accès aux réseaux de pouvoir. Faut-il y voir un désir de pouvoir ou une tentative de libération de la domination masculine ? La distinction est difficile à opérer. En effet, sur le sexe féminin exposé plane la mémoire d’une autre conception selon laquelle ce sexe est autant le lieu d’où vient la vie que le siège d’une puissance sorcière. Exposer/regarder le sexe féminin est ainsi un acte de pouvoir.
L’institutionnalisation des fat studies : l’impensé des « corps gros » comme modes de subjectivation politique et scientifique
Authors: Rousseau Audrey 
Published: August 2016

Cet article discute de l’institutionnalisation croissante du champ de recherche desfat studies. Entremêlant savoirs militants et connaissances universitaires, ce courant interdisciplinaire et intersectionnel veut dénoncer la discrimination basée sur le poids dans les sociétés occidentales en mettant en avant le vécu des personnesfat. Puisque ces théories et ces pratiques sont peu connues des communautés féministes francophones, en raison d’un déficit de traduction, l’auteure a choisi de présenter certains enjeux liés à la construction sociale des discours sur la « corpulence » et la reconnaissance des « corps gros » comme sujets épistémiques.
Entre science et politique : la question épistémologique dans l’histoire de la psychologie féministe
Authors: Pache Stéphanie 
Published: August 2016

L’expertise psychologique a acquis durant leXXe siècle un statut social qui en a fait la cible des critiques des féministes de la deuxième vague. Cet article présente l’histoire de la façon dont cette critique politique et épistémologique se développe en une approche féministe de la psychologie. Il discute également le processus qui fait de la psychologie féministe une nouvelle expertise.
Propagation of rating curve uncertainty in design flood estimation
Authors: Steinbakk G. H. , Thorarinsdottir T. L. , Reitan T. , Schlichting L. , Hølleland S. , Engeland K. 
Published: August 2016

AbstractStatistical flood frequency analysis is commonly performed based on a set of annual maximum discharge values which are derived from stage measurements via a stage‐discharge rating curve model. Such design flood estimation techniques often ignore the uncertainty in the underlying rating curve model. Using data from eight gauging stations in Norway, we investigate the effect of curve and sample uncertainty on design flood estimation by combining results from a Bayesian multisegment rating curve model and a Bayesian flood frequency analysis. We find that sample uncertainty is the main contributor to the design flood estimation uncertainty. However, under extrapolation of the rating curve, the uncertainty bounds for both the rating curve model and the flood frequency analysis are highly skewed and ignoring these features may underestimate the potential risk of flooding. We expect this effect to be even more pronounced in arid and semiarid climates with a higher variability in floods.
The anthropogenic perturbation of the marine nitrogen cycle by atmospheric deposition: Nitrogen cycle feedbacks and the 15N Haber‐Bosch effect
Authors: Yang Simon , Gruber Nicolas 
Published: August 2016

AbstractOver the last 100 years, anthropogenic emissions have led to a strong increase of atmospheric nitrogen deposition over the ocean, yet the resulting impacts and feedbacks are neither well understood nor quantified. To this end, we run a suite of simulations with the ocean component of the Community Earth System Model v1.2 forced with five scenarios of nitrogen deposition over the period from 1850 through 2100, while keeping all other forcings unchanged. Even though global oceanic net primary production increases little in response to this fertilization, the higher export and the resulting expansion of the oxygen minimum zones cause an increase in pelagic and benthic denitrification and burial by about 5%. In addition, the enhanced availability of fixed nitrogen in the surface ocean reduces global ocean N2 fixation by more than 10%. Despite the compensating effects through these negative feedbacks that eliminate by the year 2000 about 60% of the deposited nitrogen, the anthropogenic nitrogen input forced the upper ocean N budget into an imbalance of between 9 and 22 Tg N yr−1 depending on the deposition scenario. The excess nitrogen accumulates to highly detectable levels and causes in most areas a distinct negative trend in the δ15N of the oceanic fixed nitrogen pools—a trend we refer to as the 15N Haber‐Bosch effect. Changes in surface nitrate utilization and the nitrogen feedbacks induce further changes in the δ15N of
, making it a good but complex recorder of the overall impact of the changes in atmospheric deposition.
Iron‐Based Imidazolium Salts as Versatile Catalysts for the Synthesis of Quinolines and 2‐ and 4‐Allylanilines by Allylic Substitution of Alcohols
Authors: Trillo Paz , Pastor Isidro M. 
Published: August 2016

AbstractReadily available iron(III)‐based imidazolium salts have proven to be very versatile catalysts for the allylic substitution reaction of alcohols with anilines, allowing the synthesis of quinolines, 2‐allylanilines and 4‐allylanilines just by modulating the reaction conditions. Noteworthy, the formation of quinoline derivatives proceeds by ortho‐allylation of the corresponding aniline and subsequent oxidative cyclization mediated by atmospheric oxygen. The reaction using anilines as nucleophiles is selective to the C‐alkylation versus the N‐alkylation, under any reaction conditions studied.magnified image
Efficient Biosynthesis of (R)‐ or (S)‐2‐Hydroxybutyrate from l‐Threonine through a Synthetic Biology Approach
Authors: Yao Peiyuan , Cui Yunfeng , Yu Shanshan , Du Yuncheng , Feng Jinhui , Wu Qiaqing , Zhu Dunming 
Published: August 2016

AbstractAn efficient multi‐enzyme cascade reaction for the synthesis of (R)‐ or (S)‐2‐hydroxybutyric acid [(R)‐ or (S)‐2‐HB] from l‐threonine was developed by using recombinant Escherichia coli cells expressing separately or co‐expressing l‐threonine deaminase from Escherichia coli K‐12 (ilvA), formate dehydrogenase (FDH) from Candida boidinii and l‐lactate dehydrogenase (l‐LDH) from Oryctolagus cuniculus or d‐lactate dehydrogenase (d‐LDH) from Staphylococcus epidermidis ATCC 12228. Up to 750 mM of l‐threonine were completely transformed to (R)‐ or (S)‐2‐HB in optically pure form (>99% ee) with high isolated yields. This one‐pot multi‐enzyme transformation provides a new practical method for the synthesis of these important optically pure compounds.magnified image
Aerobic Copper Catalysis for Tandem Oxy‐N‐alkenylation of [1,2,3]Triazolo[1,5‐a]pyridines
Authors: Pankajakshan Sreekumar , Ang Wei Li , Sreejith Sivarampanicker , Stuparu Mihaiela Corina , Loh Teck‐Peng 
Published: August 2016

AbstractN‐Alkenylated triazolinone ylides were generated through copper‐catalyzed oxy‐N‐alkenylation of triazolopyridines. The mechanistic course of this aerobic tandem reaction has been experimentally elucidated and primary photophysical data of the ylide products are also given.magnified image
Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether‐Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure–Reactivity Relationship and Mechanistic DFT Study
Authors: Della Monica Francesco , Vummaleti Sai V. C. , Buonerba Antonio , Nisi Assunta De , Monari Magda , Milione Stefano , Grassi Alfonso , Cavallo Luigi , Capacchione Carmine 
Published: August 2016

AbstractA series of dinuclear iron(III)I complexes supported by thioether‐triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron‐based catalysts (5200 h−1; 120 °C, 2 MPa, 1 h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle.magnified image
Access to Polycyclic Alkaloid‐Like Structures by Coupling the Passerini and Ugi Reactions with Two Sequential Metal‐Catalyzed Cyclizations
Authors: Spallarossa Martina , Banfi Luca , Basso Andrea , Moni Lisa , Riva Renata 
Published: August 2016

AbstractComplex polycyclic compounds resembling some natural alkaloids have been prepared in only three high yielding steps by combining the Ugi or Passerini multicomponent reactions with two metal‐catalyzed cyclizations: an intramolecular Tsuji–Trost reaction of the isocyanide‐derived amide followed by a ring‐closing metathesis. Scaffold diversity may be explored by the appropriate choice of starting unsaturated isocyanides. The Tsuji–Trost cyclization proceeds with moderate to good diastereoselectivity, and the major diastereomer was in most cases isolated in the pure form.magnified image
Prediction of the originating site of sinonasal inverted papilloma by preoperative magnetic resonance imaging and computed tomography
Authors: Fang Gaoli , Lou Hongfei , Yu Wenling , Wang Xiangdong , Yang Bentao , Xian Junfang , Song Xiaohong , Fan Erzhong , Li Ying , Wang Chengshuo , Zhang Luo 
Published: August 2016

BackgroundPrecise localization and excision of the originating site of a sinonasal inverted papilloma (SNIP) is essential for decreasing tumor recurrence. In this study we evaluated the use of preoperative computed tomography (CT) and magnetic resonance imaging (MRI) to pinpoint the attachment/originating sites of SNIPs in 143 patients.MethodsOsteitis signs in CTs and convoluted cerebriform pattern (CCP)–based reverse tracings from MRIs of 143 SNIP patients were analyzed preoperatively to predict the originating site of SNIPs. The predicted sites were compared with actual SNIP attachment sites determined by surgery, and patients were followed‐up for evaluation of SNIP recurrence rates over a mean period of about 4 years.ResultsOsteitis signs in CT accurately predicted the actual tumor attachment site in 49.7% of all patients. In comparison, convoluted cerebriform pattern (CCP)–based reverse tracings in MRI and combination CT plus MRI accurately predicted the SNIP originating sites in 84.1% and 86% of the patients, respectively. Sensitivity and specificity in predicting the SNIP originating site were: CT, 54.6% and 69.2%; MRI, 93.1% and 76.9%; and CT+MRI, 94.6% and 92.3%, respectively. A single postoperative recurrence occurred in 4.2% of the patients.ConclusionsPreoperative combination of MRI and CT provides a better option to accurately predict the SNIP originating site, and thus may facilitate accurate and complete excision of the SNIP.
{[CuSn5Sb3]2−}2: Ein Dimer inhomogener Superatome
Authors: Wilson Robert J. , Broeckaert Lies , Spitzer Fabian , Weigend Florian , Dehnen Stefanie 
Published: August 2016

AbstractDie Reaktion des binären Zintl‐Anions (Sn2Sb2)2− mit dem β‐Diketiminato‐Komplex [LCu(NCMe)] (L=nacnac=[(N(C6H3iPr2‐2,6)C(Me))2CH]−) in Ethylendiamin oder DMF führt zur Bildung des ternären Cluster‐Dimers {[CuSn5Sb3]2−}2 (1) in Form seines [K(crypt‐222)]+‐Salzes. Die Elementzusammensetzung von 1 wurde mithilfe energiedispersiver Röntgenspektroskopie (EDX) und quantenchemischer Rechnungen verifiziert. Das Dimer besteht aus monomeren, trimetallischen Einheiten “[CuSn5Sb3]2−”, deren Struktur zwischen der des dreifach überdachten trigonalen Prismas und der des einfach überdachten quadratischen Antiprismas angesiedelt ist. Das Cluster‐Monomer lässt sich infolge der Anwesenheit von Sb‐Atomen und insbesondere der eines Cu‐Atoms (anstelle von ausschließlich Sn‐Atomen) als inhomogenes Superatom beschreiben, das – wie quantenchemische Rechnungen zeigen – durch Dimerisierung stabilisiert wird. Dabei resultiert ein relativ kleiner Cu⋅⋅⋅Cu‐Abstand, allerdings ohne signifikante bindende Wechselwirkung.
Biomimetic Hybrid Nanocontainers with Selective Permeability
Authors: Messager Lea , Burns Jonathan R. , Kim Jungyeon , Cecchin Denis , Hindley James , Pyne Alice L. B. , Gaitzsch Jens , Battaglia Giuseppe , Howorka Stefan 
Published: August 2016

AbstractChemistry plays a crucial role in creating synthetic analogues of biomacromolecular structures. Of particular scientific and technological interest are biomimetic vesicles that are inspired by natural membrane compartments and organelles but avoid their drawbacks, such as membrane instability and limited control over cargo transport across the boundaries. In this study, completely synthetic vesicles were developed from stable polymeric walls and easy‐to‐engineer membrane DNA nanopores. The hybrid nanocontainers feature selective permeability and permit the transport of organic molecules of 1.5 nm size. Larger enzymes (ca. 5 nm) can be encapsulated and retained within the vesicles yet remain catalytically active. The hybrid structures constitute a new type of enzymatic nanoreactor. The high tunability of the polymeric vesicles and DNA pores will be key in tailoring the nanocontainers for applications in drug delivery, bioimaging, biocatalysis, and cell mimicry.
Decarbonylative Silylation of Esters by Combined Nickel and Copper Catalysis for the Synthesis of Arylsilanes and Heteroarylsilanes
Authors: Guo Lin , Chatupheeraphat Adisak , Rueping Magnus 
Published: August 2016

AbstractAn efficient nickel/copper‐catalyzed decarbonylative silylation reaction of carboxylic acid esters with silylboranes is described. This reaction provides access to structurally diverse silanes with high efficiency and excellent functional‐group tolerance starting from readily available esters.
Prediction of Protein Structure Using Surface Accessibility Data
Authors: Hartlmüller Christoph , Göbl Christoph , Madl Tobias 
Published: August 2016

AbstractAn approach to the de novo structure prediction of proteins is described that relies on surface accessibility data from NMR paramagnetic relaxation enhancements by a soluble paramagnetic compound (sPRE). This method exploits the distance‐to‐surface information encoded in the sPRE data in the chemical shift‐based CS‐Rosetta de novo structure prediction framework to generate reliable structural models. For several proteins, it is demonstrated that surface accessibility data is an excellent measure of the correct protein fold in the early stages of the computational folding algorithm and significantly improves accuracy and convergence of the standard Rosetta structure prediction approach.
A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}8–10
Authors: Chalkley Matthew J. , Peters Jonas C. 
Published: August 2016

AbstractGiven the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein a redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand is described. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark–Feltham numbers: {FeNO}8, {FeNO}9, and {FeNO}10. These {FeNO}8–10 compounds are each low‐spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopy, in conjunction with DFT calculations, provides insight into the electronic structures of this uncommon redox series of iron nitrosyl complexes. In particular, the data collectively suggest that {TPBFeNO}8–10 are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark–Feltham numbers.
From 0 to II in One‐Electron Steps: A Series of Ruthenium Complexes Supported by TropPPh2
Authors: Yang Xiuxiu , Gianetti Thomas L. , Harbort Joshua , Wörle Michael D. , Tan Lilin , Su Cheng‐Yong , Jurt Pascal , Harmer Jeffrey R. , Grützmacher Hansjörg 
Published: August 2016

AbstractWe report the synthesis of a series of ruthenium complexes supported by the phosphine olefin ligand tropPPh2 (trop=5‐H‐dibenzo‐[a,d]cyclohepten‐5‐yl) in the oxidation states 0, +I, and +II, formed via successive one‐electron oxidization steps from Ru0(tropPPh2)2. The bidentate character of the tropPPh2 ligand and its steric hindrance force the complexes to adopt uncommon geometries, which were investigated by X‐ray diffraction analysis. EPR data of the mononuclear RuI complex reveal couplings of the unpaired spin with the ruthenium and two phosphorus nuclei, as well as the olefinic protons which show that the spin is mainly localized on the RuI center.
5‐Formylcytosin ist vermutlich eine semipermanente Base an definierten Genompositionen
Authors: Su Meng , Kirchner Angie , Stazzoni Samuele , Müller Markus , Wagner Mirko , Schröder Arne , Carell Thomas 
Published: August 2016

AbstractDie epigenetische Base 5‐Formyl‐2′‐desoxycytosin (fdC) wurde kürzlich im Genom von Stammzellen entdeckt. Ihre Funktion ist bisher jedoch unbekannt. Daten aus Genomsequenzierungen zeigen eine Anreicherung in CpG‐Inseln von Promotoren, weshalb eine Beteiligung an der Regulation der Transkription während der zellulären Differenzierung angenommen wird. Auch ist fdC dafür bekannt, von dem Enzym Thymin‐DNA‐Glykosylase (Tdg) erkannt und ausgeschnitten zu werden. Folglich wird angenommen, dass fdC als Intermediat während der aktiven Demethylierung auftritt. Um die Funktion von fdC zu verstehen, ist es von großer Bedeutung, seine Bildung und Entfernung an definierten genomischen Positionen analysieren zu können. Im Folgenden beschreiben wir eine neue derartige Methode, die sequenzspezifische chemische Derivatisierung von fdC mit Droplet Digital PCR kombiniert. Erste Ergebnisse zeigen, dass das Reparaturprotein Tdg nur 50 % der fdCs an einer bestimmten Position im Genom entfernt, was auf semipermanente Eigenschaften dieser Base hinweist.
Ruthenium(II)‐Catalyzed C−H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate‐Controlled Synthesis of Indoles and 3H‐Indoles
Authors: Li Yunyun , Qi Zisong , Wang He , Yang Xifa , Li Xingwei 
Published: August 2016

AbstractIndoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor–acceptor diazo compounds were developed that afforded NH indoles and 3H‐indoles under ruthenium catalysis. The coupling of α‐diazoketoesters afforded NH indoles by cleavage of the C(N2)−C(acyl) bond whereas α‐diazomalonates gave 3H‐indoles by C−N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium‐catalyzed C−H activation.
Hydrogen Peroxide Coordination to Cobalt(II) Facilitated by Second‐Sphere Hydrogen Bonding
Authors: Wallen Christian M. , Palatinus Lukáš , Bacsa John , Scarborough Christopher C. 
Published: August 2016

AbstractM(H2O2) adducts have been postulated as intermediates in biological and industrial processes; however, only one observable M(H2O2) adduct has been reported, where M is redox‐inactive zinc. Herein, direct solution‐phase detection of an M(H2O2) adduct with a redox‐active metal, cobalt(II), is described. This CoII(H2O2) compound is made observable by incorporating second‐sphere hydrogen‐bonding interactions between bound H2O2 and the supporting ligand, a trianionic trisulfonamido ligand. Thermodynamics of H2O2 binding and decay kinetics of the CoII(H2O2) species are described, as well as the reaction of this CoII(H2O2) species with Group 2 cations.
{[CuSn5Sb3]2−}2: A Dimer of Inhomogeneous Superatoms
Authors: Wilson Robert J. , Broeckaert Lies , Spitzer Fabian , Weigend Florian , Dehnen Stefanie 
Published: August 2016

AbstractReaction of the binary Zintl anion (Sn2Sb2)2− with the β‐diketiminato complex [LCu(NCMe)] (L=nacnac=[(N(C6H3iPr2‐2,6)C(Me))2CH]−) in ethylenediamine or DMF affords the ternary cluster dimer {[CuSn5Sb3]2−}2 (1) as its [K(crypt‐222)]+ salt. The chemical formulation of 1 is supported by energy‐dispersive X‐ray spectroscopy (EDX) and quantum chemical calculations. Each monomeric part of the dimer represents a trimetallic “[CuSn5Sb3]2−” cluster, with an architecture in between a tricapped trigonal prism and a capped square antiprism. As shown by quantum chemical investigations, the presence of Sb atoms and, in particular, of Cu atoms in the cluster skeleton makes the monomeric unit behave like an inhomogeneous superatom, which clearly prefers to dimerize, thereby producing a relatively short, yet virtually non‐bonding Cu⋅⋅⋅Cu distance.
From Gold Nanoseeds to Nanorods: The Microscopic Origin of the Anisotropic Growth
Authors: Meena Santosh Kumar , Sulpizi Marialore 
Published: August 2016

AbstractDirectly manipulating and controlling the size and shape of metal nanoparticles is a key step for their tailored applications. In this work, molecular dynamics simulations were applied to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. Different factors influencing the growth were selectively included in the models to unravel the role of the surfactants and ions. In the early stage of the growth, when the seed is only a few nanometers large, a dramatic symmetry breaking occurs as the surfactant layer preferentially covers the (100) and (110) facets, leaving the (111) facets unprotected. This anisotropic surfactant layer in turn promotes anisotropic growth with the less protected tips growing faster. When silver salt is added to the growth solution, the asymmetry of the facets is preserved, but the Br− concentration at the interface increases, resulting in increased surface passivation.