bluuebunny/crossref_metadata_2025_split huggingface dataset:
A new era of treatment for patients with haemophilia A?
Authors: Klamroth Robert 
Published: November 2016

SummaryTreatment and prevention of bleeding episodes in patients with severe haemophilia A require frequent intravenous injection of factor VIII. Inhibitory antibodies against factor VIII occur in approximately 30 % of these patients during the first exposure days and immune tolerance induction to eradicate the inhibitor is challenging. Prevention of bleeds in patients with haemophilia A and inhibitors is less effective and there is ongoing research for alternative treatment options. A promising approach in 2016 is the development of emicizumab (ACE910), a bispecific IgG antibody to factor IXa and factor X, that mimics the cofactor function of factor VIII. Due to the different structure of this antibody it cannot be neutralized by factor VIII inhibitors and has the possibility to achieve haemostasis in patients with severe haemophilia A with and without inhibitors. First studies in healthy volunteers and in patients showed a shortened activated partial thromboplastin time and increased peak height of thrombin generation in a dose-dependent manner. The halflife of the drug was 4 to 5 weeks. There were no clinical signs of thrombosis and no laboratory abnormalities indicating hypercoagulability. In a first study with 18 patients with severe haemophilia A with and without inhibitors a remarkable reduction in the annualised bleeding rate occurred. Safety of the drug has to be proven in ongoing research. Mimicking the cofactor activity of factor VIII by a bispecific antibody for the treatment of severe haemophilia A is so far safe and seems to be effective and is one highlight in haemostasis 2016.
Computable Error Bounds for a Class of Boundary Value Problems: a Coefficients Perturbation Approach
Authors: El Daou Mohamed K. , Al-Hamdan Ahmad R. 
Published: November 2016

This paper is concerned with computing upper and lower bounds for the error committed when some boundary value problems are approximated by means of numerical techniques based on the Coefficients Perturbation Methods. These computed bounds are expressed in terms of the perturbations introduced in the differential equation and in the prescribed boundary conditions associated with it. Numerical examples demonstrating the sharpness of our results are given.
La richesse floristique des friches du Parc national de Frontenac
Authors: Pellerin Stéphanie , Duquesne Théo , Omelczuk Walter Clarissa , Pasquet Salomé 
Published: November 2016

La plupart des parcs nationaux situés dans le sud du Québec comportent des vestiges des anciennes activités agricoles, et notamment de nombreuses friches. Afin de connaître la richesse floristique des friches du Parc national de Frontenac (situé à la jonction des Cantons-de-l’Est et de Chaudière-Appalaches) et d’identifier les facteurs régissant leur composition, leur flore a été inventoriée à la fin de l’été 2012 au sein de 165 placettes d’échantillonnage réparties dans 40 parcelles de friches. Des analyses d’espèces indicatrices de l’âge des friches ont été réalisées ainsi que des analyses de redondance. Au total, 209 espèces ont été identifiées, dont seulement 37 étaient d’origine exotique. Cette richesse correspond à plus de la moitié de toutes les espèces recensées pour l’ensemble du parc. Les espèces indicatrices des jeunes friches (< 25 ans) étaient toutes des herbacées exotiques, tandis que celles indicatrices des vieilles friches (≥ 25 ans) étaient surtout des herbacées indigènes. La composition floristique des friches était surtout expliquée par le temps depuis l’arrêt des activités agricoles et le pH du sol. Nous recommandons de favoriser le retour des friches vers la forêt, mais d’en conserver quelques-unes à un stade herbacé pour maintenir la richesse floristique du secteur.
Extension de l’aire de répartition connue du campagnol sylvestre (Microtus pinetorum) : mention la plus nordique au Québec
Authors: Brouillette Patricia , Boulet Monique 
Published: November 2016

Le campagnol sylvestre (Microtus pinetorum) occupe la partie est de l’Amérique du Nord. Au Canada, on le trouve dans le sud-ouest de l’Ontario et dans le sud-est du Québec. Compte tenu de sa répartition restreinte et fragmentée ainsi que de sa rareté relative, il a obtenu un statut d’espèce préoccupante au Canada en 1998. Il se caractérise notamment par le fait qu’il soit le seul campagnol fouisseur au pays. Le 28 août 2013, un spécimen a été capturé au lac Mondor à Saint-Jean-de-Matha, dans la région de Lanaudière, au Québec. Cette observation est la plus septentrionale à ce jour, et constitue la première et unique mention de l’espèce au nord du fleuve Saint-Laurent. Cet article propose un état de la situation de cette espèce au Québec et décrit le spécimen capturé ainsi que l’environnement où il a été trouvé afin de bonifier les connaissances scientifiques sur ce micromammifère peu commun.
Facteurs environnementaux associés à la prolifération de la méduse d’eau douce Craspedacusta sowerbii dans les lacs du Québec
Authors: El Moussaoui Nadia , Beisner Beatrix E. 
Published: November 2016

Les proliférations (aussi appelées pullulations ou « blooms ») de la méduse d’eau douce Craspedacusta sowerbii semblent de plus en plus fréquentes dans les lacs d’Amérique du Nord. Cependant, puisqu’elles apparaissent sporadiquement, de façon discontinue dans le temps et l’espace, on connaît mal leur répartition, leur écologie et les facteurs environnementaux qui les influencent. Les objectifs du présent projet étaient de déterminer la répartition spatiale et les facteurs environnementaux responsables de la prolifération de C. sowerbii au Québec en vue de prévoir de nouvelles proliférations. À l’aide des données recueillies, nous avons cartographié la répartition des lacs québécois envahis par C. sowerbii jusqu’en 2014 et colligé des données sur les variables environnementales de ceux-ci : leur profondeur maximale, leur superficie, leur périmètre et leur altitude, ainsi que la transparence de l’eau et sa concentration en chlorophylle a, en carbone organique dissous (COD) et en phosphore total. En tout, l’espèce a été répertoriée dans 88 lacs au Québec, principalement dans les régions des Laurentides, de l’Outaouais et de l’Estrie, où les lacs sont particulièrement abondants. Selon nos analyses statistiques, les proliférations de cette méduse exotique au Québec ont été observées plus fréquemment dans les lacs dont la superficie est supérieure à 2,8 km² et dont l’eau a une concentration en phosphore total inférieure à 14,77 µg/l.
Relationship between sensitizer concentration and resist performance of chemically amplified extreme ultraviolet resists in sub-10 nm half-pitch resolution region
Authors: Kozawa Takahiro , Santillan Julius Joseph , Itani Toshiro 
Published: November 2016

Abstract
The development of lithography processes with sub-10 nm resolution is challenging. Stochastic phenomena such as line width roughness (LWR) are significant problems. In this study, the feasibility of sub-10 nm fabrication using chemically amplified extreme ultraviolet resists with photodecomposable quenchers was investigated from the viewpoint of the suppression of LWR. The relationship between sensitizer concentration (the sum of acid generator and photodecomposable quencher concentrations) and resist performance was clarified, using the simulation based on the sensitization and reaction mechanisms of chemically amplified resists. For the total sensitizer concentration of 0.5 nm−3 and the effective reaction radius for the deprotection of 0.1 nm, the reachable half-pitch while maintaining 10% critical dimension (CD) LWR was 11 nm. The reachable half-pitch was 7 nm for 20% CD LWR. The increase in the effective reaction radius is required to realize the sub-10 nm fabrication with 10% CD LWR.
Decomposition of Al2.7Fe0.3Ti in heated Al–Al2.7Fe0.3Ti refiner fabricated by spark plasma sintering and its refining performance
Authors: Watanabe Yoshimi , Hamada Takayuki , Sato Hisashi 
Published: November 2016

Abstract
In our previous study, a novel Al-L12-type Al2.7Fe0.3Ti refiner was fabricated by spark plasma sintering (SPS) and its refining performance was studied. It was found that L12-type Al2.7Fe0.3Ti particles can be favorable heterogeneous nucleation sites for Al casts, since the lattice matching between Al2.7Fe0.3Ti and Al is good. It was also found that the thermal stability of heterogeneous nucleation sites affects the grain-refining performance. In this study, the decomposition phenomena of the Al2.7Fe0.3Ti phase in a refiner are studied by heating an Al–Al2.7Fe0.3Ti refiner fabricated by SPS. In addition, the refining performance of a heated Al–Al2.7Fe0.3Ti refiner is investigated.
Modeled Martian subsurface elemental composition measurements with the Probing In situ with Neutron and Gamma ray instrument
Authors: Nowicki Suzanne F. , Evans Larry G. , Starr Richard D. , Schweitzer Jeffrey S. , Karunatillake Suniti , McClanahan Timothy P. , Moersch Jeffrey E. , Parsons Ann M. , Tate Christopher G. 
Published: November 2016

AbstractThe Probing In situ with Neutron and Gamma ray (PING) instrument is an innovative application of active neutron‐induced gamma ray technology. The objective of PING is to measure the elemental composition of the Martian regolith. This manuscript presents PING's sensitivities as a function of the Martian regolith depth and PING's uncertainties in the measurements as a function of observation time in passive and active mode. The modeled sensitivities show that in PING's active mode, where both a pulsed neutron generator (PNG) and a gamma ray spectrometer (GRS) are used, PING can interrogate the material below the rover to about 20 cm due to the penetrating nature of the high‐energy neutrons and the resulting secondary gamma rays observed with the GRS. PING is capable of identifying most major and minor rock‐forming elements, including H, O, Na, Mn, Mg, Al, Si, P, S, Cl, Cr, K, Ca, Ti, Fe, and Th. The modeled uncertainties show that PING's use of a PNG reduces the required observation times by an order of magnitude over a passive operating mode where the PNG is turned off. While the active mode allows for more complete elemental inventories with higher sensitivity, the gamma ray signatures of some elements are strong enough to detect in passive mode. We show that PING can detect changes in key marker elements and make thermal neutron measurements in about 1 min that are sensitive to H and Cl.
Inherited crustal deformation along the East Gondwana margin revealed by seismic anisotropy tomography
Authors: Pilia S. , Arroucau P. , Rawlinson N. , Reading A. M. , Cayley R. A. 
Published: November 2016

AbstractThe mechanisms of continental growth are a crucial part of plate tectonic theory, yet a clear understanding of the processes involved remains elusive. Here we determine seismic Rayleigh wave phase anisotropy variations in the crust beneath the southern Tasmanides of Australia, a Paleozoic accretionary margin. Our results reveal a complex, thick‐skinned pervasive deformation that was driven by the tectonic interaction between the proto‐Pacific Ocean and the ancient eastern margin of Gondwana. Stress‐induced effects triggered by the collision and entrainment of a microcontinent into the active subduction zone are evident in the anisotropy signature. The paleofracturing trend of failed rifting between Australia and Antarctica is also recorded in the anisotropy pattern as well as a tightly curved feature in central Tasmania. The observed patterns of anisotropy correlate well with recent geodynamic and kinematic models of the Tasmanides and provide a platform from which the spatial extent of deformational domains can be refined.
GDGT and alkenone flux in the northern Gulf of Mexico: Implications for the TEX86 and UK'37 paleothermometers
Authors: Richey Julie N. , Tierney Jessica E. 
Published: November 2016

AbstractThe TEX86 and
molecular biomarker proxies have been broadly applied in downcore marine sediments to reconstruct past sea surface temperature (SST). Although both TEX86 and
have been interpreted as proxies for mean annual SST throughout the global ocean, regional studies of glycerol dibiphytanyl glycerol tetraethers (GDGTs) and alkenones in sinking particles are required to understand the influence of seasonality, depth distribution, and diagenesis on downcore variability. We measure GDGT and alkenone flux, as well as the TEX86 and
indices in a 4 year sediment trap time series (2010–2014) in the northern Gulf of Mexico (nGoM), and compare these data with core‐top sediments at the same location. GDGT and alkenone fluxes do not show a consistent seasonal cycle; however, the largest flux peaks for both occurs in winter.
covaries with SST over the 4 year sampling interval, but the
‐SST relationship in this data set implies a smaller slope or nonlinearity at high temperatures when compared with existing calibrations. Furthermore, the flux‐weighted
value from sinking particles is significantly lower than that of underlying core‐top sediments, suggesting preferential diagenetic loss of the tri‐unsaturated alkenone in sediments. TEX86 does not covary with SST, suggesting production in the subsurface upper water column. The flux‐weighted mean TEX86 matches that of core‐top sediments, confirming that TEX86 in the nGoM reflects local planktonic production rather than allochthonous or in situ sedimentary production. We explore potential sources of uncertainty in both proxies in the nGoM but demonstrate that they show nearly identical trends in twentieth century SST, despite these factors.
Chiral Aluminum Catalyst System for the Enantioselective Addition of Vinylaluminum Reagents to Aldehydes: Metal Controlled Reversal of Enantioselectivity
Authors: Adate Priyanka A. , Matsunaga Takuya , Shin Hirata , Harada Toshiro 
Published: November 2016

AbstractA chiral aluminum catalyst system has been developed for the enantioselective vinylation of aldehydes. β,β‐Disubstituted (E)‐vinylaluminum reagents, generated regio‐ and stereoselectively by the carboalumination of terminal alkynes with trimethylalumunim (Me3Al), were used straightforwardly without transmetalation to vinyltitanium reagents in the subsequent enantioselective addition to aldehydes with a DPP‐H8‐BINOL‐derived chiral aluminum catalyst at low catalyst loading (5 mol%). The reaction afforded the corresponding enantiomerically enriched secondary allylic alcohols with a reversal of the selectivity observed in closely related reactions catalyzed by a chiral titanium complex derived from the same ligand.magnified image
Iron‐Catalyzed Direct Alkylamination of Phenols with O‐Benzoyl‐N‐alkylhydroxylamines under Mild Conditions
Authors: Jia Lei , Gao Sen , Xie Junyao , Luo Meiming 
Published: November 2016

AbstractA novel iron‐catalyzed direct alkylamination reaction of phenols has been achieved with O‐benzoyl‐N‐alkylhydroxylamines as aminating agents. This protocol provides a facile access to N‐alkyl‐substituted aminophenols though a radical reaction from phenols. The catalytic direct alkylamination operates at room temperature without the need of any ligands and additives to afford the desired products with excellent regioselectivity and functional group tolerance.magnified image
Ligand‐Free Heck Reactions of Aryl Iodides: Significant Acceleration of the Rate through Visible Light Irradiation at Ambient Temperature
Authors: Zhang Heng , Huang Xueliang 
Published: November 2016

AbstractA mild Heck reaction of aryl iodides and olefins was realized by the cooperation of a palladium and a photoredox catalyst under the irradiation of visible light. This protocol works well to synthesize stilbenes with high Z/E ratios and (E)‐cinnamates in the absence of ligands at ambient temperature. Control experiments revealed that palladium salt, visible light and photoredox catalyst were all crucial for the achievement of this cross‐coupling under mild conditions.magnified image
Perfluoroalkanesulfonylation of Alkynyl(phenyl)iodonium Tosylates by the Weakly Nucleophilic Sodium Perfluoroalkanesulfinates
Authors: Han Jia‐Bin , Yang Lian , Chen Xing , Zha Gao‐Feng , Zhang Cheng‐Pan 
Published: November 2016

AbstractAn additive‐ and transition metal‐free perfluoroalkanesulfonylation of alkynyl(phenyl)iodonium tosylates with sodium perfluoroalkanesulfinates (RfnSO2Na) is described. The poorly nucleophilic RfnSO2Na reacted with alkynyl(phenyl)iodonium salts in dichloromethane at room temperature under a nitrogen atmosphere for 5–60 minutes to afford a variety of acetylenic triflones and alkynyl perfluoroalkyl sulfones in good to quantitative yields. The position of substituents on the phenyl rings of the arylethynyl moiety in the iodonium salts had a big influence on the reaction. The formation of five‐membered cyclic vinyl sulfones suggested that the reaction proceeds via an alkylidene carbene intermediate. Furthermore, successful scaling‐up of the reaction demonstrates the practicality of the new method. Advantages of the method include short reaction times, mild conditions, and the easy access to perfluoroalkanesulfonylation reagents (RfnSO2Na).magnified image
Sulfination of Alcohols with p‐Toluenesulfonylmethyl Isocyanide under Metal‐Free Conditions: A Mitsunobu Approach
Authors: Kadari Lingaswamy , Radha Krishna Palakodety , Lakshmi Prapurna Y. 
Published: November 2016

AbstractA Mitsunobu approach for the synthesis of sulfinate esters by direct nucleophilic substitution of alcohols is described. The salient features of this strategy include neutral and metal‐free conditions for the rapid synthesis of sulfinates in high yields. The present protocol using p‐toluenesulfonylmethyl isocyanide (TosMIC) and the triphenylphosphine (TPP)/diisopropyl azodicarboxylate (DIAD) reagent system represents the general synthetic route to this important class of compounds.magnified image
Die Molekülstruktur des pentagonal‐pyramidalen Hexamethylbenzol‐Dikations C6(CH3)62+ im Kristall
Authors: Malischewski Moritz , Seppelt K. 
Published: November 2016

AbstractGegenüber dem bekannten 2‐Norbornylkation, dessen Struktur bis zum kürzlich erfolgten kristallographischen Nachweis der Fünffach‐Koordination eines Kohlenstoffatoms lange umstritten war, hat das pentagonal‐pyramidale Hexamethylbenzol‐Dikation deutlich weniger Aufmerksamkeit erfahren. Es wurde zuerst 1973 bei tiefen Temperaturen in magischer Säure (HSO3F/SbF5) von Hogeveen erzeugt, der für die Verbindung auf Basis von NMR‐Spektroskopie und Reaktivitätsstudien eine nicht‐klassische Struktur mit sechsfach koordiniertem Kohlenstoff vorschlug. Die Isolierung und Bestimmung der Kristallstruktur gelangen jedoch nicht. C6(CH3)62+ wird bei der Reaktion von Hexamethyldewarbenzolepoxid mit HSO3F/SbF5 erhalten und kann durch einen Überschuss von wasserfreiem HF als SbF6−‐Salz auskristallisiert werden. Die Molekülstruktur von C6(CH3)62+(SbF6−)2⋅HSO3F belegt die pentagonal‐pyramidale Struktur des Dikations. Das apikale Kohlenstoffatom ist an eine Methylgruppe (Bindungslänge 1.479(3) Å) sowie an die fünf basalen Kohlenstoffatome gebunden (Bindungslängen 1.694(2)–1.715(3) Å).
Cyclic Amino(Ylide) Silylene: A Stable Heterocyclic Silylene with Strongly Electron‐Donating Character
Authors: Alvarado‐Beltran Isabel , Baceiredo Antoine , Saffon‐Merceron Nathalie , Branchadell Vicenç , Kato Tsuyoshi 
Published: November 2016

AbstractAn isolable heterocyclic silylene (4) with two different π‐donating substituents, namely a classical amino group and a more electropositive and stronger carbon‐based π‐donating phosphonium ylide, was synthesized and fully characterized. The combination of these two different π‐donating substituents confers high thermal stability and an unusual nucleophilic character on silylene 4. Therefore, silylene 4 behaves as a strong donor ligand toward transition metals with a donating character comparable to N‐heterocyclic carbenes, in contrast to classical N‐heterocyclic silylenes, which generally present a weak donating character.
Gram‐Scale Synthesis of Chiral Cyclopropane‐Containing Drugs and Drug Precursors with Engineered Myoglobin Catalysts Featuring Complementary Stereoselectivity
Authors: Bajaj Priyanka , Sreenilayam Gopeekrishnan , Tyagi Vikas , Fasan Rudi 
Published: November 2016

AbstractEngineered hemoproteins have recently emerged as promising systems for promoting asymmetric cyclopropanations, but variants featuring predictable, complementary stereoselectivity in these reactions have remained elusive. In this study, a rationally driven strategy was implemented and applied to engineer myoglobin variants capable of providing access to 1‐carboxy‐2‐aryl‐cyclopropanes with high trans‐(1R,2R) selectivity and catalytic activity. The stereoselectivity of these cyclopropanation biocatalysts complements that of trans‐(1S,2S)‐selective variants developed here and previously. In combination with whole‐cell biotransformations, these stereocomplementary biocatalysts enabled the multigram synthesis of the chiral cyclopropane core of four drugs (Tranylcypromine, Tasimelteon, Ticagrelor, and a TRPV1 inhibitor) in high yield and with excellent diastereo‐ and enantioselectivity (98–99.9% de; 96–99.9% ee). These biocatalytic strategies outperform currently available methods to produce these drugs.
Crystal Structure Determination of the Pentagonal‐Pyramidal Hexamethylbenzene Dication C6(CH3)62+
Authors: Malischewski Moritz , Seppelt K. 
Published: November 2016

AbstractIn contrast to the well‐known 2‐norbornyl cation, the structure of which was a matter of long debate until its pentacoordinated nature was recently proven by an X‐ray structure, the pentagonal‐pyramidal dication of hexamethylbenzene has received considerably less attention. This species was first prepared by Hogeveen in 1973 at low temperatures in magic acid (HSO3F/SbF5), for which he proposed a non‐classical structure (containing a hexacoordinated carbon) based on NMR spectroscopy and reactivity studies, but no X‐ray crystal structure has been reported. C6(CH3)62+ can be obtained through the dissolution of hexamethyl Dewar benzene epoxide in HSO3F/SbF5 and crystallized as the SbF6− salt upon addition of excess anhydrous hydrogen fluoride. The crystal structure of C6(CH3)62+ (SbF6−)2⋅HSO3F confirms the pentagonal pyramidal structure of the dication. The apical carbon is bound to one methyl group (distance 1.479(3) Å) and to the five basal carbon atoms (distances 1.694(2)–1.715(3) Å).
Conversion of the Native 24‐mer Ferritin Nanocage into Its Non‐Native 16‐mer Analogue by Insertion of Extra Amino Acid Residues
Authors: Zhang Shengli , Zang Jiachen , Wang Wenming , Chen Hai , Zhang Xiaorong , Wang Fudi , Wang Hongfei , Zhao Guanghua 
Published: November 2016

AbstractProtein assemblies with high symmetry are widely distributed in nature. Most efforts so far have focused on repurposing these protein assemblies, a strategy that is ultimately limited by the structures available. To overcome this limitation, methods for fabricating novel self‐assembling proteins have received intensive interest. Herein, by reengineering the key subunit interfaces of native 24‐mer protein cage with octahedral symmetry through amino acid residues insertion, we fabricated a 16‐mer lenticular nanocage whose structure is unique among all known protein cages. This newly non‐native protein can be used for encapsulation of bioactive compounds and exhibits high uptake efficiency by cancer cells. More importantly, the above strategy could be applied to other naturally occurring protein assemblies with high symmetry, leading to the generation of new proteins with unexplored functions.