bluuebunny/crossref_metadata_2025 huggingface dataset:
La politique internationale du Québec envers les États-Unis
Authors: Paquin Stéphane
Published: September 2014

L’objectif de cet article est de proposer une périodisation de la politique internationale du Québec envers les États-Unis à partir d’une grille d’analyse tirée des travaux de Peter Hall. Cette grille porte sur deux niveaux d’analyse : le premier niveau s’intéresse aux instruments des politiques publiques, alors que le second porte sur le paradigme de l’action publique. À partir de ces deux grands critères, nous proposons une périodisation en cinq périodes. La première période (1867-1960) est caractérisée par l’absence de paradigmes structurés et la quasi-absence d’instruments, à l’exception d’un bureau commercial et touristique à New York. La deuxième période (1960-1976) témoigne d’une volonté de développer la présence québécoise aux États-Unis par la création de nombreux instruments au moment où le paradigme de l’action publique se construit progressivement. La troisième période (1976 à 1980) est caractérisée par une prise de conscience par les souverainistes québécois de l’importance des États-Unis. Cette période se caractérise par un changement de paradigme notable. La quatrième période (1980-2001) est marquée par le virage libre-échangiste. Durant la dernière période (de 2000 à nos jours), on prend la mesure de nouveaux enjeux qui élargissent le paradigme de l’action publique, comme les questions de sécurité après les attentats du 11 septembre 2001, mais aussi les questions énergétiques et environnementales.
Les politiques de présence des États occidentaux au sein des organisations internationales
Authors: David-Ismayil Meryll
Published: September 2014

Depuis leurs débuts, les organisations internationales connaissent un déséquilibre en ce qui a trait à la nationalité des fonctionnaires internationaux. Bien que le principe de répartition géographique, énoncé dès 1920, soit l’un des principes fondateurs de la fonction publique internationale, il n’a jamais réussi à être appliqué strictement. Aujourd’hui encore, les Occidentaux sont surreprésentés au sein des secrétariats internationaux dans des proportions qu’on ne connaît toujours pas précisément. Cet article revient sur les politiques de présence des États occidentaux au sein des organisations internationales qui permettent d’expliquer le maintien de cette domination, laquelle n’est pas seulement numérique. Puisque près d’un fonctionnaire international sur dix est français, le cas de la France est particulièrement étudié, ce pays constituant en outre un modèle pour ses voisins, proches comme lointains.
Performance of Secondary Schools from 2005-2012: An Input to Implementation of Education for All (EFA) in Region 10
Authors: Madrid-Garabato Melinda , Dela Rama Juana M.
Published: September 2014

The educational system of the Philippines aims to empower all Filipino children with access, equity and quality education. Thus, the conduct of this study gathers the profile of the public secondary schools in Region 10 in terms of enrolment both male and female, number of drop outs, number of graduates and NAT MPS Scores as an input to evaluate the performance of secondary schools on its implementation of Education for All (EFA) from year 2005-2012 in comparison to the EFA targets geared towards 2015. Data subjects for statistical treatment using Mean and Percentage rate to determine the average performance of the secondary schools in Region 10. Results have shown that the schools showed drastic increase in enrolment with a greater number of females than males. Meanwhile, NAT MPS Scores increased with 55.46 MPS in year 2012, however, secondary schools still have to work out to reach the regional EFA target of 75 with a difference of 19.54 from the actual score in 2012. Dropout Rate decreased to 4.32 and yet to work for to attain 0 dropout rate in 2015. Number of Graduates generally increased but showed a slight decrease in some school years. This shows that secondary schools in Region 10 have performed well compared to previous years, but still have to work out more towards achieving the goals of Education for All (EFA) by 2015.
Two contrasting views of multidecadal climate variability in the twentieth century
Authors: Kravtsov Sergey , Wyatt Marcia G. , Curry Judith A. , Tsonis Anastasios A.
Published: September 2014

The bulk of our knowledge about causes of twentieth century climate change comes from simulations using numerical models. In particular, these models seemingly reproduce the observed nonuniform global warming, with periods of faster warming in 1910–1940 and 1970–2000, and a pause in between. However, closer inspection reveals some differences between the observations and model simulations. Here we show that observed multidecadal variations of surface climate exhibited a coherent global‐scale signal characterized by a pair of patterns, one of which evolved in sync with multidecadal swings of the global temperature, and the other in quadrature with them. In contrast, model simulations are dominated by the stationary—single pattern—forced signal somewhat reminiscent of the observed “in‐sync” pattern most pronounced in the Pacific. While simulating well the amplitude of the largest‐scale—Pacific and hemispheric—multidecadal variability in surface temperature, the model underestimates variability in the North Atlantic and atmospheric indices.
Insight into the Mechanism and Stereochemistry of the Transformations of Alkyltitanium Ate‐Complexes. An Enhanced Enantioselectivity in the Cyclopropanation of the Carboxylic Esters with Titanacyclopropane Reagents
Authors: Kulinkovich Oleg G. , Kananovich Dzmitry G. , Lopp Margus , Snieckus Victor
Published: September 2014

The dependence of the stereoselectivity of the cyclopropanation reaction of γ,γ‐diphenyl‐γ‐butyrolactone and carboxylic esters with alkylmagnesium bromides in the presence of titanium(IV) TADDOLates on the structure of the reactants has been examined in detail. It has been found that the enantioselectivity in the formation of cis‐1,2‐disubstituted cyclopropanols is a function of the structure of the carboxylic ester alkoxy group and leads, in the case of cyclopropanation of hexafluoroisopropyl alkanoates, to 84% ee. To rationalize these observations, as well as the NMR data on the structures of the TADDOL‐derived alkyltitanium species, a new mechanistic model for the formation of the five‐coordinated chiral titanacyclopropane reactive intermediates and their subsequent reorganization in the reactions with esters is proposed. The essential features of this model consist in the generation of configurationally stable TADDOL derived titanacyclopropane species with an apical or equatorial position of the stereogenic carbanion center which is followed by retention or inversion of absolute configuration in course of the displacement of the carboxylic ester alkoxy group.

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Asymmetric Aldol Reaction of Thiazole‐Carbaldehydes: Regio‐ and Stereoselective Synthesis of Tubuvalin Analogues
Authors: Paladhi Sushovan , Das Joydeb , Samanta Mousumi , Dash Jyotirmayee
Published: September 2014

The first organocatalytic enantioselective approach to precursors of tubuvaline (pre‐Tuv) is presented employing a prolinamide‐catalyzed aldol reaction of easily accessible thiazole‐carbaldehyde with methyl isopropyl ketone “on water” in excellent yield as well as regio‐ and enantioselectivities. The analogues of pre‐Tuv were achieved using an L‐proline‐catalyzed direct asymmetric aldol reaction of substituted thiazole‐carbaldehydes with acetone. A direct and flexible approach to the tubavaline (Tuv) core of tubusylins has been established employing the reductive amination of the pre‐Tuv species. The key aldol reaction should greatly expand the potential of this strategy to the synthesis of natural product tubulysins and a range of analogues.

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Total Syntheses of Dendrodolides A, B, and E
Authors: Mohapatra Debendra K. , Pulluri Karthik , Bhimireddy Eswar , Reddy D. Prabhakar , Yadav Jhillu S.
Published: September 2014

Convergent total syntheses of dendrodolides A, B, and E comprising 12‐membered macrolactones are described. The syntheses of dendrodolides A and B were accomplished in 11 linear steps with 24 % and 25 % overall yield, respectively, starting from commercially available homoallyl alcohol 19 and enantiomerically pure epoxide 20. Dendrodolide E was subsequently obtained from dendrodolides A or B in 81 % yield by treatment with BCl3. Key steps were Maruoka asymmetric allylation, Corey‐Chaykovsky reaction, Yamaguchi esterification, and ring‐closing metathesis.
Transition‐Metal‐Free Syntheses of Pyridine‐Containing Thioethers Through Two‐Fold CS Bond Formation
Authors: Badsara Satpal Singh , Chan Chien‐Ching , Lee Chin‐Fa
Published: September 2014

A transition‐metal‐free, two‐fold CS bond cross‐coupling reaction of dihalopyridines with different thiols is described, which provides the resulting dithioethers in good to excellent yields.
A Basic Germanodecatungstate with a −7 Charge: Efficient Chemoselective Acylation of Primary Alcohols
Authors: Sugahara Kosei , Satake Naoto , Kamata Keigo , Nakajima Takahito , Mizuno Noritaka
Published: September 2014

The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ‐Keggin germanodecatungstate, [γ‐HGeW10O36]7− (A), having a −7 charge was, for the first time, successfully synthesized by the reaction of [γ‐H2GeW10O36]6− with one equivalent of [(n‐C4H9)4N]OH under non‐aqueous conditions. The activities of germanodecatungstates for base‐catalyzed reactions dramatically increased with increase in the number negative charges from −6 to −7. In the presence of A, various combinations of acylating agents and primary alcohols including those with acid‐sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.
Stable Small Quantum Dots for Synaptic Receptor Tracking on Live Neurons
Authors: Cai En , Ge Pinghua , Lee Sang Hak , Jeyifous Okunola , Wang Yong , Liu Yanxin , Wilson Katie M. , Lim Sung Jun , Baird Michelle A. , Stone John E. , Lee Kwan Young , Davidson Michael W. , Chung Hee Jung , Schulten Klaus , Smith Andrew M. , Green William N. , Selvin Paul R.
Published: September 2014

We developed a coating method to produce functionalized small quantum dots (sQDs), about 9 nm in diameter, that were stable for over a month. We made sQDs in four emission wavelengths, from 527 to 655 nm and with different functional groups. AMPA receptors on live neurons were labeled with sQDs and postsynaptic density proteins were visualized with super‐resolution microscopy. Their diffusion behavior indicates that sQDs access the synaptic clefts significantly more often than commercial QDs.
A Hexameric Peptide Barrel as Building Block of Amyloid‐β Protofibrils
Authors: Lendel Christofer , Bjerring Morten , Dubnovitsky Anatoly , Kelly Robert T. , Filippov Andrei , Antzutkin Oleg N. , Nielsen Niels Chr. , Härd Torleif
Published: September 2014

Oligomeric and protofibrillar aggregates formed by the amyloid‐β peptide (Aβ) are believed to be involved in the pathology of Alzheimer’s disease. Central to Alzheimer pathology is also the fact that the longer Aβ42 peptide is more prone to aggregation than the more prevalent Aβ40. Detailed structural studies of Aβ oligomers and protofibrils have been impeded by aggregate heterogeneity and instability. We previously engineered a variant of Aβ that forms stable protofibrils and here we use solid‐state NMR spectroscopy and molecular modeling to derive a structural model of these. NMR data are consistent with packing of residues 16 to 42 of Aβ protomers into hexameric barrel‐like oligomers within the protofibril. The core of the oligomers consists of all residues of the central and C‐terminal hydrophobic regions of Aβ, and hairpin loops extend from the core. The model accounts for why Aβ42 forms oligomers and protofibrils more easily than Aβ40.
Eine niedermolekulare Verbindung inhibiert die Proteindisulfidisomerase und sensibilisiert Krebszellen für die Chemotherapie
Authors: Eirich Jürgen , Braig Simone , Schyschka Liliana , Servatius Phil , Hoffmann Judith , Hecht Sabrina , Fulda Simone , Zahler Stefan , Antes Iris , Kazmaier Uli , Sieber Stephan A. , Vollmar Angelika M.
Published: September 2014

Die Entwicklung von Resistenzen gegen Chemotherapeutika stellt eine der größten Herausforderungen der Krebsforschung dar. Eine Möglichkeit dieses Problem zu umgehen ist, Chemotherapeutika zusammen mit Verbindungen zu verabreichen, die Zellen gegen die Medikamente sensibilisieren und Apoptose induzieren. Wir beschreiben die Entdeckung einer neuen Substanzklasse (T8), die verschiedene Krebszellen gegen subtoxische Konzentrationen von Etoposid sensibilisiert. Durch Proteomanalysen konnte gezeigt werden, dass die Proteindisulfidisomerase (PDI) das alleinige Ziel der T8‐Verbindungen ist. Detaillierte biologische und chemische Studien wie die Optimierung der Molekülstrukturen, Docking‐Analysen, Fluoreszenzmikroskopie und Apoptoseuntersuchungen belegen den Wirkmechanismus der reversiblen Inhibition der PDI und zeigen eine erhöhte Stressantwort im endoplasmatischen Retikulum durch T8.
Dynamic Mirror‐Symmetry Breaking in Bicontinuous Cubic Phases
Authors: Dressel Christian , Liu Feng , Prehm Marko , Zeng Xiangbing , Ungar Goran , Tschierske Carsten
Published: September 2014

Chiral segregation of enantiomers or chiral conformers of achiral molecules during self‐assembly in well‐ordered crystalline superstructures has fascinated chemists since Pasteur. Here we report spontaneous mirror‐symmetry breaking in cubic phases formed by achiral multichain‐terminated diphenyl‐2,2′‐bithiophenes. It was found that stochastic symmetry breaking is a general phenomenon observed in bicontinuous cubic liquid crystal phases of achiral rod‐like compounds. In all compounds studied the ${{\it Im}\bar 3m}$ cubic phase is always chiral, while the ${Ia\bar 3d}$ phase is achiral. These intriguing observations are explained by propagation of homochiral helical twist across the entire networks through helix matching at network junctions. In the ${Ia\bar 3d}$ phase the opposing chiralities of the two networks cancel, but not so in the three‐networks ${{\it Im}\bar 3m}$ phase. The high twist in the ${{\it Im}\bar 3m}$ phase explains its previously unrecognized chirality, as well as the origin of this complex structure and the transitions between the different cubic phases.
Enhancing Fullerene‐Based Solar Cell Lifetimes by Addition of a Fullerene Dumbbell
Authors: Schroeder Bob C. , Li Zhe , Brady Michael A. , Faria Gregório Couto , Ashraf Raja Shahid , Takacs Christopher J. , Cowart John S. , Duong Duc T. , Chiu Kar Ho , Tan Ching‐Hong , Cabral João T. , Salleo Alberto , Chabinyc Michael L. , Durrant James R. , McCulloch Iain
Published: September 2014

Cost‐effective, solution‐processable organic photovoltaics (OPV) present an interesting alternative to inorganic silicon‐based solar cells. However, one of the major remaining challenges of OPV devices is their lack of long‐term operational stability, especially at elevated temperatures. The synthesis of a fullerene dumbbell and its use as an additive in the active layer of a PCDTBT:PCBM‐based OPV device is reported. The addition of only 20 % of this novel fullerene not only leads to improved device efficiencies, but more importantly also to a dramatic increase in morphological stability under simulated operating conditions. Dynamic secondary ion mass spectrometry (DSIMS) and TEM are used, amongst other techniques, to elucidate the origins of the improved morphological stability.
Unprecedented Chain‐Length‐Dependent Conformational Conversion Between 11/9 and 18/16 Helix in α/β‐Hybrid Peptides
Authors: Legrand Baptiste , André Christophe , Moulat Laure , Wenger Emmanuel , Didierjean Claude , Aubert Emmanuel , Averlant‐Petit Marie Christine , Martinez Jean , Calmes Monique , Amblard Muriel
Published: September 2014

α,β‐Hybrid oligomers of varying lengths with alternating proteogenic α‐amino acid and the rigid β2,3,3‐trisubstituted bicyclic amino acid ABOC residues were studied using both X‐ray crystal and NMR solution structures. While only an 11/9 helix was obtained in the solid state regardless of the length of the oligomers, conformational polymorphism as a chain‐length‐dependent phenomenon was observed in solution. Consistent with DFT calculations, we established that short oligomers adopted an 11/9 helix, whereas an 18/16 helix was favored for longer oligomers in solution. A rapid interconversion between the 11/9 helix and the 18/16 helix occurred for oligomers of intermediate length.
Chirality in Ordered Porous Organosilica Hybrid Materials
Authors: MacLean Michael W. A. , Reid Lacey M. , Wu Xiaowei , Crudden Cathleen M.
Published: September 2014

The ever‐growing demand for chiral small molecules on a global scale has set a precedent for the proliferation of cost‐effective and reliable methods for their synthesis and separation. Of these methods, those based on heterogeneous platforms present an unparalleled opportunity as they allow for the source of the chirality to be recycled. Chiral hybrid organosilica materials are one particularly interesting class of chiral heterogeneous platforms that creates a synergy between well‐understood individual chiral molecules and the structural stability and inertness of the inorganic silicon scaffolds. This Focus Review summarizes the recent advances towards the incorporation of chirality into organosilica scaffolds, the synthesis of the chiral building blocks, and their promising applications towards facilitating asymmetric heterogeneous catalysis as well as chiral chromatography.
Robust Sliding Mode Observer based Fault Estimation for Certain Class of Uncertain Nonlinear Systems
Authors: Zhang Jian , Swain Akshya Kumar , Nguang Sing Kiong
Published: September 2014

This paper proposes a new scheme for estimating the actuator and sensor fault for Lipschitz nonlinear systems with unstructured uncertainties using the sliding mode observer (SMO) technique. Initially, a coordinate transformation is introduced to transform the original state vector into two parts such that the actuator faults only appear in the dynamics of the second state vector. The concept of equivalent output error injection is then employed to estimate the actuator fault. The effects of system uncertainties on the estimation errors of states and faults are minimized by integrating an
uncertainty attenuation level into the observer. The sufficient conditions for the state estimation error to be bounded and satisfy a prescribed
performance are derived and expressed as a linear matrix inequality (LMI) optimization problem. Furthermore, the proposed actuator fault estimation method is extended to sensor fault estimation. Finally, the effectiveness of the proposed scheme in estimating actuator and sensor faults has been illustrated considering an example of a single‐link flexible joint robot system.
Efficient in vitro gene therapy with PEG siRNA lipid nanocapsules for passive targeting strategy in melanoma
Authors: Resnier Pauline , LeQuinio Pierre , Lautram Nolwenn , André Emilie , Gaillard Cédric , Bastiat Guillaume , Benoit Jean‐Pierre , Passirani Catherine
Published: September 2014

Small interfering RNA (siRNA)‐mediated gene therapy is a promising strategy to temporarily inhibit the expression of proteins implicated in carcinogenesis or chemotherapy resistance. Although intra‐tumoral administration can be envisaged, studies currently focus on formulating nanomedicines for intravenous injection to target tumor sites as well as metastases. The development of synthetic nanoparticles and liposomes has advanced greatly during the last decade. The objective of this work consists in formulating and optimizing the encapsulation of siRNA into lipid nanocapsules (LNCs) for efficient gene therapy to target melanoma cells. SiRNA LNCs were prepared from DOTAP/DOPE lipoplexes, and the siRNA amount and lipid/siRNA charge ratio were assayed to improve the stability and the encapsulation yield. Cryo‐TEM imaging of the siRNA lipoplexes and LNC morphology revealed specific organization of the siRNA DOTAP/DOPE lipoplexes as well as specific lipid microstructures that can be eliminated by purification. No cytotoxicity of the siRNA LNCs against the melanoma SK‐Mel28 cell line was observed at concentrations of up to 500 ng/mL siRNA. In vitro siRNA transfection experiments, compared to Oligofectamine™, demonstrated interesting targeted gene silencing effects. Finally, complement activation assays confirmed the feasibility of the PEGylation of siRNA LNCs as part of a passive targeting strategy for future in vivo melanoma‐ and metastasis‐targeting experiments.
Stacking interactions in RNA and DNA: Roll‐slide energy hyperspace for ten unique dinucleotide steps
Authors: Mukherjee Sanchita , Kailasam Senthilkumar , Bansal Manju , Bhattacharyya Dhananjay
Published: September 2014

Understanding dinucleotide sequence directed structures of nuleic acids and their variability from experimental observation remained ineffective due to unavailability of statistically meaningful data. We have attempted to understand this from energy scan along twist, roll, and slide degrees of freedom which are mostly dependent on dinucleotide sequence using ab initio density functional theory. We have carried out stacking energy analysis in these dinucleotide parameter phase space for all ten unique dinucleotide steps in DNA and RNA using DFT‐D by ωB97X‐D/6‐31G(2d,2p), which appears to satisfactorily explain conformational preferences for AU/AU step in our recent study. We show that values of roll, slide, and twist of most of the dinucleotide sequences in crystal structures fall in the low energy region. The minimum energy regions with large twist values are associated with the roll and slide values of B‐DNA, whereas, smaller twist values correspond to higher stability to RNA and A‐DNA like conformations. Incorporation of solvent effect by CPCM method could explain the preference shown by some sequences to occur in B‐DNA or A‐DNA conformations. Conformational preference of BII sub‐state in B‐DNA is preferentially displayed mainly by pyrimidine–purine steps and partly by purine–purine steps. The purine–pyrimidine steps show largest effect of 5‐methyl group of thymine in stacking energy and the introduction of solvent reduces this effect significantly. These predicted structures and variabilities can explain the effect of sequence on DNA and RNA functionality. © 2014 Wiley Periodicals, Inc. Biopolymers 103: 134–147, 2015.
Harnessing the Synthetic Capabilities of Glycopeptide Antibiotic Tailoring Enzymes: Characterization of the UK‐68,597 Biosynthetic Cluster
Authors: Yim Grace , Kalan Lindsay , Koteva Kalinka , Thaker Maulik N. , Waglechner Nicholas , Tang Irene , Wright Gerard D.
Published: September 2014

In this study, a draft genome sequence of Actinoplanes sp. ATCC 53533 was assembled, and an 81‐kb biosynthetic cluster for the unusual sulfated glycopeptide UK‐68,597 was identified. Glycopeptide antibiotics are important in the treatment of infections caused by Gram‐positive bacteria. Glycopeptides contain heptapeptide backbones that are modified by many tailoring enzymes, including glycosyltransferases, sulfotransferases, methyltransferases, and halogenases, generating extensive chemical and functional diversity. Several tailoring enzymes in the cluster were examined in vitro for their ability to modify glycopeptides, resulting in the synthesis of novel molecules. Tailoring enzymes were also expressed in the producer of the glycopeptide aglycone A47934, generating additional chemical diversity. This work characterizes the biosynthetic program of UK‐68,597 and demonstrates the capacity to expand glycopeptide chemical diversity by harnessing the unique chemistry of tailoring enzymes.
NuMED covered cheatham‐platinum stent™ for the treatment or prevention of right ventricular outflow tract conduit disruption during transcatheter pulmonary valve replacement
Authors: Bishnoi Ram N. , Jones Thomas K. , Kreutzer Jacqueline , Ringel Richard E.
Published: September 2014

Objective

Retrospectively assess the frequency of right ventricular outflow tract (RVOT) conduit disruption during transcatheter pulmonary valve replacement (TPVR) and the effectiveness and safety of NuMED Covered Cheatham‐Platinum Stents™ (CCPS) for its prevention or treatment.

Background

There have been no published reports to date describing the safety and effectiveness of covered stents to prevent or treat RVOT conduit disruption during TPVR.

Methods

Data regarding 251 TPVR procedures performed at multiple US investigational sites were retrospectively reviewed to explore the incidence and potential predictors of conduit disruption. In addition, data on the use of 69 CCPS implanted in 50 patients during TPVR was reviewed.

Results

The overall incidence of conduit disruption requiring intervention was 6%. The only predictor identified was a very elevated RVOT conduit systolic pressure gradient. A pre‐existing conduit tear was present in nine, while 31 developed tears after conduit dilation and three, after TPVR. The CCPS was used prophylactically in seven. Conduit tears were prevented or repaired in 49/50 patients. No CCPS‐related acute complications were reported. At 6‐month follow‐up, no patient had more than mild pulmonary regurgitation and the mean Doppler RVOT gradient (12.7 ± 5.8 mm Hg) comparing favorably with that reported in the Melody TPV® IDE trial (20.0 ± 8.6 mm Hg).

Conclusion

CCPS implantation can successfully treat RVOT conduit disruption without negative impact on the TPV function. This retrospective analysis suggests high RVOT conduit systolic pressure gradient is a risk factor for conduit tears during TPVR. © 2014 Wiley Periodicals, Inc.
Implantation of the new Nit‐Occlud PDA‐R device in children below 10 kilogram
Authors: Moysich Axel , Happel Christoph M. , Laser Kai T. , Kececioglu Deniz , Haas Nikolaus A.
Published: September 2014

Background

Interventional closure of patent ductus arteriosus (PDA) has become a common and safe procedure in most pediatric cath labs. Interventional treatment of PDAs still remains a challenge in those children with low body weight and a large PDA. The Nit‐Occlud PDA‐R® device was developed and especially designed for large PDAs. We report our most recent experience in children with a body weight lower than 10 kg.

Materials and Methods

The PDA‐R® device was used in seven children (age 1–10, median 6 months) with a body weight from 4.1 to 9.7 kg (median 5.9 kg): ductal length was 12 mm (median), with a large ampulla (median 9 mm) which exceeded the diameter of the aorta (median 6 mm) and large diameter (median minimal diameter 4 mm). In six cases, the Nit‐Occlud PDA‐R was selected with an aortic disc of 12 mm and in one case an occluder with an aortic disc of 14 mm.

Results

Occlusion of the PDA was documented by angiography and/or echocardiography in all cases. At a mean follow‐up of 21.4 months, no flow obstruction to the left or right pulmonary artery or new onset coarctation of the aorta was noted.

Conclusions

The Nit‐Occlud PDA‐R® device is suitable in children with a body weight below 10 kg when a relative large PDA is present. © 2015 Wiley Periodicals, Inc.
Magnetically Encoded Luminescent Composite Nanoparticles through Layer‐by‐Layer Self‐Assembly
Authors: Song Erqun , Han Weiye , Xu Hongyan , Jiang Yunfei , Cheng Dan , Song Yang , Swihart Mark T.
Published: September 2014

Sensitive and rapid detection of multiple analytes and the collection of components from complex samples are important in fields ranging from bioassays/chemical assays, clinical diagnosis, to environmental monitoring. A convenient strategy for creating magnetically encoded luminescent CdTe@SiO2@n Fe3O4 composite nanoparticles, by using a layer‐by‐layer self‐assembly approach based on electrostatic interactions, is described. Silica‐coated CdTe quantum dots (CdTe@SiO2) serve as core templates for the deposition of alternating layers of Fe3O4 magnetic nanoparticles and poly(dimethyldiallyl ammonium chloride), to construct CdTe@SiO2@n Fe3O4 (n=1, 2, 3, …︁) composite nanoparticles with a defined number (n) of Fe3O4 layers. Composite nanoparticles were characterized by zeta‐potential analysis, fluorescence spectroscopy, vibrating sample magnetometry, and transmission electron microscopy, which showed that the CdTe@SiO2@n Fe3O4 composite nanoparticles exhibited excellent luminescence properties coupled with well‐defined magnetic responses. To demonstrate the utility of these magnetically encoded nanoparticles for near‐simultaneous detection and separation of multiple components from complex samples, three different fluorescently labeled IgG proteins, as model targets, were identified and collected from a mixture by using the CdTe@SiO2@n Fe3O4 nanoparticles.
A Peptide Dendron‐Based Shrinkable Metallo‐Hydrogel for Charged Species Separation and Stepwise Release of Drugs
Authors: Qin Long , Xie Fan , Duan Pengfei , Liu Minghua
Published: September 2014

A shrinkable supramolecular metallo‐hydrogel based on the L‐glutamic acid dendron and magnesium showed reversible volume‐phase transition depending on pH changes. The hydrogel further showed selective shrinkage upon addition of positively charged species, while it remained in the gel state when negatively charged species were incorporated. Based on this property, the gel could be used as the matrix to efficiently separate ionic dye mixtures, in which the cationic dye was incorporated predominantly in the shrunken gel, while the negatively charged dye was released into the aqueous solution. More interestingly, the shrinkable gel can be used as a model drug‐delivery vehicle for the stepwise release of a two‐component drug system, in which the negatively charged drug is released first and then the second component is released with a pH trigger.
Label‐Free Photoelectrochemical Detection of Double‐Stranded HIV DNA by Means of a Metallointercalator‐Functionalized Electrogenerated Polymer
Authors: Haddache Fatima , Le Goff Alan , Reuillard Bertrand , Gorgy Karine , Gondran Chantal , Spinelli Nicolas , Defrancq Eric , Cosnier Serge
Published: September 2014

The design of photoactive functionalized electrodes for the sensitive transduction of double‐stranded DNA hybridization is reported. Multifunctional complex [Ru(bpy‐pyrrole)2(dppn)]2+ (bpy‐pyrrole=4‐methyl‐4′‐butylpyrrole‐2,2′‐bipyridine, dppn=benzo[i]dipyrido[3,2‐a:2′,3′‐c]phenazine) exhibiting photosensitive, DNA‐intercalating, and electropolymerizable properties was synthesized and characterized. The pyrrole groups undergo oxidative electropolymerization on planar electrodes forming a metallopolymer layer on the electrode. Thanks to the photoelectrochemical and intercalating properties of the immobilized RuII complex, the binding of a double‐stranded HIV DNA target was photoelectrochemically detected on planar electrodes. Photocurrent generation through visible irradiation was correlated to the interaction between double‐stranded DNA and the metallointercalator polymer. These interactions were well fitted by using a Langmuir isotherm, which allowed a dissociation constant of 2×106 L mol−1 to be estimated. The low detection limit of 1 fmol L−1 and sensitivity of 0.01 units per decade demonstrate excellent suitability of these modified electrodes for detection of duplex DNA.
Batch versus Flow Photochemistry: A Revealing Comparison of Yield and Productivity
Authors: Elliott Luke D. , Knowles Jonathan P. , Koovits Paul J. , Maskill Katie G. , Ralph Michael J. , Lejeune Guillaume , Edwards Lee J. , Robinson Richard I. , Clemens Ian R. , Cox Brian , Pascoe David D. , Koch Guido , Eberle Martin , Berry Malcolm B. , Booker‐Milburn Kevin I.
Published: September 2014

The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20 % lower than that of batch, whereas three‐layer reactors were 20 % more productive. Finally, the utility of flow chemistry was demonstrated in the scale‐up of the ring‐opening reaction of a potentially explosive [1.1.1] propellane with butane‐2,3‐dione.
Ring‐Shaped Silafluorene Derivatives as Efficient Solid‐State UV‐Fluorophores: Synthesis, Characterization, and Photoluminescent Properties
Authors: Cai Yuanjing , Samedov Kerim , Dolinar Brian S. , Albright Haley , Guzei Ilia A. , Hu Rongrong , Zhang Chaocan , West Robert
Published: September 2014

Four ring‐shaped silafluorene‐containing compounds (1–4) were synthesized and characterized as potentially promising monomers for fluorescent polymers. Their optical properties in solution and solid state (thin film and powder) were studied. These compounds have low quantum yields in solution (Φfl=0.13‐0.15) with fluorescence maxima at about 355 nm, but high quantum yields in the solid state (powder, Φfl=0.35‐0.54) with fluorescence maxima at about 377 and 488 nm. Influence of the substituents and the number of silafluorene units in 1–4 on their optical properties was investigated. Extensive study of the X‐ray crystal structures of 1–4 was undertaken to analyze and qualitatively estimate the role, extent, and influence of silafluorene moieties’ interactions on solid‐state fluorescent properties. Excited state UV/Vis and theoretical molecular orbital (MO) calculations were performed to explore possible fluorescence mechanisms and differences in quantum yields among these compounds.
Thermodynamic and Kinetic Origins of Au250 Nanocluster Electrochemiluminescence
Authors: Hesari Mahdi , Workentin Mark S. , Ding Zhifeng
Published: September 2014

Au clusters with protecting organothiolate ligands and core diameters less than 2 nm are molecule‐like structures, suitable for catalysis, optoelectronics and biology applications. The spectroscopy and electrochemistry of Au250 (Au25[(SCH2CH2Ph)18], SCH2CH2Ph=2‐phenylethanethiol) allowed us to construct a Latimer‐type diagram for the first time, which revealed a rich photoelectrochemistry of the cluster and the unique relationship to its various oxidation states and corresponding excited states. The occurrence of cluster electrochemiluminescence (ECL) was examined in the presence of tri‐n‐propylamine (TPrA) as a co‐reactant and was discovered to be in the near‐infrared (NIR) region with peak wavelengths of 860, 865, and 960 nm, emitted by Au25+*, Au250*, and Au25−*, respectively. The light emissions, with an efficiency up to 103 % relative to that of the efficient Ru(bpy)32+/TPrA system, depended on the kinetics of the reactions between the electrogenerated TPrA radical and Au25z (z=2+, 1+, 1−, and 2−) in the vicinity of the electrode or the bulk Au250. These thermodynamic and kinetic origins were further explored by means of spooling ECL and photoluminescence spectroscopy during a sweep of the potential or at a constant potential applied to the working electrode. NIR‐ECL emissions of the cluster can be tuned in wavelength and intensity by adjusting the applied potential and TPrA concentration based on the above discoveries.
A Review of the Iron–Air Secondary Battery for Energy Storage
Authors: McKerracher R. D. , Ponce de Leon Carlos , Wills R. G. A. , Shah A. A. , Walsh Frank C.
Published: September 2014

Recent interest in the iron–air flow battery, known since the 1970s, has been driven by incentives to develop low‐cost, environmentally friendly and robust rechargeable batteries. With a predicted open‐circuit potential of 1.28 V, specific charge capacity of <300 A h kg−1 and reported efficiencies of 96, 40 and 35 % for charge, voltage and energy, respectively, the iron–air system could be well suited for a range of applications, including automotive. A number of challenges still need to be resolved, including: efficient and moderate‐cost bifunctional oxygen electrodes, low‐cost iron electrodes able to decrease corrosion and hydrogen evolution, new cell designs using additive manufacturing technologies and mathematical models to improve battery performance. This Minireview considers the thermodynamics and kinetics aspects of the iron–air battery, the operational variables and cell components, thereby highlighting current challenges and assessing recent developments.
The unfolding water drama in the Anthropocene: towards a resilience‐based perspective on water for global sustainability
Authors: Rockström J. , Falkenmark M. , Allan T. , Folke C. , Gordon L. , Jägerskog A. , Kummu M. , Lannerstad M. , Meybeck M. , Molden D. , Postel S. , Savenije H.H.G. , Svedin U. , Turton A. , Varis O.
Published: September 2014

The human influence on the global hydrological cycle is now the dominant force behind changes in water resources across the world and in regulating the resilience of the Earth system. The rise in human pressures on global freshwater resources is in par with other anthropogenic changes in the Earth system (from climate to ecosystem change), which has prompted science to suggest that humanity has entered a new geological epoch, the Anthropocene. This paper focuses on the critical role of water for resilience of social‐ecological systems across scales, by avoiding major regime shifts away from stable environmental conditions, and in safeguarding life‐support systems for human wellbeing. It highlights the dramatic increase of water crowding: near‐future challenges for global water security and expansion of food production in competition with carbon sequestration and biofuel production. It addresses the human alterations of rainfall stability, due to both land‐use changes and climate change, the ongoing overuse of blue water, reflected in river depletion, expanding river basin closure, groundwater overexploitation and water pollution risks. The rising water turbulence in the Anthropocene changes the water research and policy agenda, from a water‐resource efficiency to a water resilience focus. This includes integrated land and water stewardship to sustain wetness‐dependent ecological functions at the landscape scale and a stronger emphasis on green water management for ecosystem services. A new paradigm of water governance emerges, encouraging land‐use practices that explicitly take account of the multifunctional roles of water, with adequate attention to planetary freshwater boundaries and cross‐scale interactions. © 2014 The Authors. Ecohydrology published by John Wiley & Sons, Ltd.
Modular Access to Highly Functionalised Tetrahydroquinolines
Authors: Cordero Franca M. , Khairnar Bhushan B. , Brandi Alberto
Published: September 2014

Highly functionalised tetrahydroquinolines have been obtained by a modular approach consisting of a nitrone 1,3‐dipolar cycloaddition to 2‐bromostyrene followed by isoxazolidine N–O cleavage and copper‐catalysed aromatic N‐substitution/cyclisation. A 1,2,3,4‐tetrahydro‐1,8‐naphthyridine was obtained in the same way.
Simulation‐based design of a microfabricated pneumatic electrospray nebulizer
Authors: Jarvas Gabor , Grym Jakub , Foret Frantisek , Guttman Andras
Published: September 2014

A microfabricated pneumatic electrospray nebulizer has been developed and evaluated using computer simulations and experimental measurements of the MS signals. The microdevice under development is designed for electrospray MS interfacing without the need to fabricate an electrospray needle and can be used as a disposable or an integral part of a reusable system. The design of the chip layout was supported by computational fluid dynamics simulations. The tested microdevices were fabricated in glass using conventional photolithography, followed by wet chemical etching and thermal bonding. The performance of the microfabricated nebulizer was evaluated by means of TOF‐MS with a peptide mixture. It was demonstrated that the nebulizer, operating at supersonic speed of the nebulizing gas, produced very stable nanospray (900 nL/min) as documented by less than 0.1% (SE) fluctuation in total mass spectrometric signal intensity.
On Medical Progress and Health Care Demand: A Ces Perspective Using the Grossman Model of Health Status
Authors: Batinti Alberto
Published: September 2014

I propose an application of the pure‐consumption version of the Grossman model of health care demand, where utility depends on consumption and health status and health status on medical care and health technology. I derive the conditions under which an improvement in health care technology leads to an increase/decrease in health care consumption. In particular, I show how the direction of the effect depends on the relationship between the constant elasticity of substitution parameters of the utility and health production functions. I find that, under the constancy assumption, the ratio of the two elasticity of substitution parameters determines the direction of a technological change on health care demand. On the other hand, the technology share parameter in the health production function contributes to the size but not to the direction of the technological effect. I finally explore how the ratio of the elasticity of substitution parameters work in measurement and practice and discuss how future research may use the theoretical insight provided here. Copyright © 2014 John Wiley & Sons, Ltd.
Meat and fish consumption and the risk of renal cell carcinoma in the European prospective investigation into cancer and nutrition
Authors: Rohrmann Sabine , Linseisen Jakob , Overvad Kim , Lund Würtz Anne Mette , Roswall Nina , Tjonneland Anne , Boutron‐Ruault Marie‐Christine , Racine Antoine , Bastide Nadia , Palli Domenico , Agnoli Claudia , Panico Salvatore , Tumino Rosario , Sacerdote Carlotta , Weikert Steffen , Steffen Annika , Kühn Tilman , Li Kuanrong , Khaw Kay‐Tee , Wareham Nicholas J. , Bradbury Kathryn E. , Peppa Eleni , Trichopoulou Antonia , Trichopoulos Dimitrios , Bueno‐de‐Mesquita H.B(as) , Peeters Petra H.M. , Hjartåker Anette , Skeie Guri , Weiderpass Elisabete , Jakszyn Paula , Dorronsoro Miren , Barricarte Aurelio , Santiuste de Pablos Carmen , Molina‐Montes Esther , de la Torre Ramón Alonso , Ericson Ulrika , Sonestedt Emily , Johansson Mattias , Ljungberg Börje , Freisling Heinz , Romieu Isabelle , Cross Amanda J. , Vergnaud Anne‐Claire , Riboli Elio , Boeing Heiner
Published: September 2014

Renal cell cancer (RCC) incidence varies worldwide with a higher incidence in developed countries and lifestyle is likely to contribute to the development of this disease. We examined whether meat and fish consumption were related to the risk of RCC in the European Prospective Investigation into Cancer and Nutrition (EPIC). The analysis included 493,179 EPIC participants, recruited between 1992 and 2000. Until December 2008, 691 RCC cases have been identified. Meat and fish consumption was assessed at baseline using country‐specific dietary assessment instruments; 24‐hour recalls were applied in an 8% subsample for calibration purposes. Cox proportional hazards regression was used to calculate multivariable‐adjusted hazard ratios (HR) and 95% confidence intervals (CI). Women with a high consumption of red meat (HR = 1.36, 95% CI 1.14–1.62; calibrated, per 50 g/day) and processed meat (HR = 1.78, 95% CI 1.05–3.03; calibrated, per 50 g/day) had a higher risk of RCC, while no association existed in men. For processed meat, the association with RCC incidence was prominent in premenopausal women and was lacking in postmenopausal women (p interaction = 0.02). Neither poultry nor fish consumption were statistically significantly associated with the risk of RCC. The results show a distinct association of red and processed meat consumption with incident RCC in women but not in men. A biological explanation for these findings remains unclear.
ILL‐STRUCTURED PROBLEMS AS MULTIPLE‐CHOICE ITEMS
Authors: Ward William C. , Carlson Sybil B. , Woisetschlaeger Erich
Published: September 2014

A new item type was developed, incorporating features of “ill‐structured” problems in a multiple‐choice format. The problems are similar to previously developed scientific thinking tasks in requiring the examinee to go beyond the information provided; they resemble a variant of the logical reasoning item type, but demand somewhat more structuring by the examinee of the set of assumptions needed to solve the problem.

A pretest was carried out to compare the new item type with two variants of the logical reasoning item type; a second study, using preexisting data, compared these two variants with one another. In neither case was there any indication that problems identified as “ill‐structured” measured different aspects of ability than do “well‐structured” problems. The new item type might be employed in tests of reasoning for the sake of increasing the variety of item types available for test construction, but would not be expected to extend the range of cognitive skills assessed by the tests.
THE SEARCH FOR COMMUNICATION SKILLS
Authors: Baird Leonard L.
Published: September 2014

This review attempts to identify generic competencies in communication that may be amenable to assessment. Concentrating on research based literature, the review examines the models, methods, and research reviews that have been used to study communication. From these sources four areas of skill were identified: listening, empathy, non‐verbal communication, and expressive abilities. The research relating to the definitions of subskills within these areas is discussed, as well as the difficulties in assessing the skills.
COMPARISON OF IRT OBSERVED‐SCORE AND TRUE‐SCORE ‘EQUATINGS’*
Authors: Lord Frederic M. , Wingersky Marilyn S.
Published: September 2014

Two methods of ‘equating’ tests using item response theory are compared, one using true scores, the other using the estimated distribution of observed scores. On the data studied, they yield almost indistinguishable results. This is a reassuring result for users of IRT equating methods.
PREDICTING PREDICTABILITY: THE INFLUENCE OF STUDENT AND INSTITUTIONAL CHARACTERISTICS ON THE PREDICTION OF GRADES
Authors: Baird Leonard L.
Published: September 2014

This is a report of a study that examined the statistical and institutional influences on the prediction of first‐year college grades. The basic sources of information were the Validity Study Services file which summarizes the results of College Board validity studies and the College Handbook file which includes data about college characteristics. The criterion was the size of the multiple correlation between academic predictors and first‐year college grades. The independent variables were the statistical data of the validity study and college characteristics. In general it was found, as expected, that the extent of the variation of the academic ability of the students was positively related to the size of the multiple correlation. In addition, several variables suggested the interpretation that the heterogeneity of the programs and experience of college were negatively related to the size of the multiple correlation.

Further analyses investigated the characteristics that were associated with the greater or lesser efficiency of sat‐verbal scores and sat‐mathematical scores in the prediction of grades. Similar analyses examined the characteristics associated with greater or lesser efficiency of sat scores and the high school record. Finally, the prediction of grades at colleges of different selectivity was examined. In all of these analyses evidence was provided for the influence of institutional characteristics on the prediction of grades, an influence that needs to be taken into account when interpreting the “validity” of tests like the sat.