bluuebunny/crossref_metadata_2025 huggingface dataset:
Apprendre et guérir
Authors: Papillon Joëlle
Published: July 2017

Cet article traite des rapports intergénérationnels dans l’oeuvre de trois auteures autochtones. Tandis qu’An Antane Kapesh (Innue) dénonce de façon virulente le démembrement des familles causé, entre autres raisons, par la scolarisation forcée des enfants dans le système des pensionnats, Virginia Pésémapéo Bordeleau (métisse crie) et Naomi Fontaine (Innue) illustrent chacune à leur façon des remembrements. Dans leurs romans, des personnes autochtones trouvent des façons de se réenraciner dans la suite des générations et sur le territoire, entre autres grâce à une pratique du soin de l’autre qui mène à la réconciliation avec soi-même.
Sur les routes/roots1
Authors: Laporte David
Published: July 2017

Cette contribution explore les représentations de l’espace dans le roman de la routeOurse bleuede Virginia Pésémapéo Bordeleau. L’hypothèse de l’auteur tend à démontrer la cohabitation de deux réseaux de représentations spatiales, tributaires de la culture métissée du personnage principal, Victoria, métisse d’origine crie dont la spiritualité emprunte à la fois au catholicisme de sa jeunesse et à un animisme refoulé avec lequel elle tente de renouer. Le retour vers le pays natal (Baie James) offre ainsi une vision empreinte de syncrétisme où se juxtaposent les mythes de la Terre promise et de la Terre-Mère. Tous deux rendent compte du double mouvement de détérioration/réappropriation de la mémoire et des repères culturels : le premier se construit autour du motif de la perte, qui habite les paysages désertés de l’enfance ; le second exploite une herméneutique de la trace, où la reconquête identitaire est en bonne partie fonction de la capacité de Victoria à interpréter les indices liés au territoire.
La constitution de la mémoire des pensionnats indiens au Québec
Authors: Bousquet Marie-Pierre
Published: July 2017

L’intégration de l’histoire des pensionnats autochtones dans l’histoire collective nationale est-elle plus difficile au Québec qu’ailleurs au Canada ? Cet article se penche sur la constitution de la mémoire des pensionnats indiens au Québec, puis sur la transformation de cette mémoire en une histoire censée devenir collective et nationale. Alimentée par la lecture d’intellectuels français ayant réagi aux lois mémorielles de leur gouvernement, la réflexion de l’auteure s’attache à trois phases par lesquelles transitent des événements du passé pour atteindre une large reconnaissance et entrer dans un récit national : la collection d’un ensemble de témoignages ; le passage de récits personnels à une mémoire collective par la commémoration ; le partage de ces commémorations par un public plus large. Constatant le manque actuel d’inclusion de l’histoire particulière des pensionnats autochtones dans l’histoire collective québécoise, l’auteure analyse les écueils dans la réception de cette histoire par les Québécois, puis elle propose des pistes pour y remédier.
El valor de superarse. Deporte y humanismo, por Guillem Turró Ortega
Authors: López Frías Francisco Javier
Published: July 2017

Reseña de Turró Ortega, Guillem (2013) El valor de superarse. Deporte y humanismo
El nominalisme en metafísica
Authors: Rodríguez-Pereyra Gonzalo
Published: July 2017

El nominalisme té almenys dues varietats. Una consisteix en el rebuig dels objectes abstractes; l’altra, en el rebuig dels universals. Les dues varietats del nominalisme són independents entre si i cadascuna pot defensar-se consistentment sense l’altra, per bé que comparteixen algunes motivacions i arguments. Aquest article exposa les teories nominalistes de les dues varietats.
Ficción y compromiso ontológico
Authors: Orlando Eleonora
Published: July 2017

En este trabajo me ocupo de la semántica de los términos de ficción, en el marco de una posición de tipo abstractista (Kripke 2011 y 2013, van Inwagen 1977, Salmon 1998 y 2002, Thomasson 1999, Predelli 1997, 2002 y 2005 y Voltolini 2011). En particular, me concentro en dos problemas que afectan a este tipo de posiciones: el primero de ellos es dar cuenta de la verdad intuitiva de enunciados como “Ulises duerme en la playa de Ithaca”; el segundo es explicar la aceptación, también intuitiva, de que “Ulises no existe” es un enunciado verdadero.
Two Regioisomeric π‐Conjugated Small Molecules: Synthesis, Photophysical, Packing, and Optoelectronic Properties
Authors: Li Yuxiang , Lee Dae Hee , Lee Joungphil , Nguyen Thanh Luan , Hwang Sungu , Park Moon Jeong , Choi Dong Hoon , Woo Han Young
Published: July 2017

Two regioisomeric D1‐A‐D‐A‐D1 type π‐conjugated molecules (1,4‐bis{5‐[4‐(5‐fluoro‐7‐(5‐hexylthiophen‐2‐yl)benzo[c][1,2,5]thiadiazole)]­thiophen‐2‐yl}‐2,5‐bis(hexyldecyloxy)benzene (Prox‐FBT) and 1,4‐bis{5‐[4‐(6‐fluoro‐7‐(5‐hexylthiophen‐2‐yl)benzo[c][1,2,5]thiadiazole)]­thiophen‐2‐yl}‐2,5‐bis(hexyldecyloxy)benzene (Dis‐FBT)) are synthesized, by controlling the fluorine topology to be proximal or distal relative to the central core. The different F geometries are confirmed by the 1H–1H nuclear Overhauer effect spectroscopy (NOESY). Clearly different optical, electrochemical, and thermal transition behaviors are obtained, i.e., stronger absorption, deeper valance band (by ≈0.2 eV), and higher melting/recrystallization temperatures (by 7–20 °C) are observed for Dis‐FBT. The different intermolecular packing and unit cell structures are also calculated for the two regioisomers, based on the powder X‐ray diffraction and 2D grazing‐incidence wide‐angle X‐ray diffraction measurements. A tighter π–π packing with a preferential monoclinic face‐on orientation is extracted for Dis‐FBT, compared to Prox‐FBT with bimodal orientations. Different topological structures significantly affect the electrical and photovoltaic properties, where Prox‐FBT shows higher parallel hole mobility (2.3 × 10−3 cm2 V−1 s−1), but Dis‐FBT demonstrates higher power conversion efficiency (5.47%) with a larger open‐circuit voltage of 0.95 V (vs 0.79 V for Prox‐FBT). The findings suggest that small changes in the topological geometry can affect the electronic structure as well as self‐assembly behaviors, which can possibly be utilized for fine‐adjusting the electrical properties and further optimization of optoelectronic devices.
Precise Manipulation of Multilength Scale Morphology and Its Influence on Eco‐Friendly Printed All‐Polymer Solar Cells
Authors: Ye Long , Xiong Yuan , Li Sunsun , Ghasemi Masoud , Balar Nrup , Turner Johnathan , Gadisa Abay , Hou Jianhui , O'Connor Brendan T. , Ade Harald
Published: July 2017

Significant efforts have lead to demonstrations of nonfullerene solar cells (NFSCs) with record power conversion efficiency up to ≈13% for polymer:small molecule blends and ≈9% for all‐polymer blends. However, the control of morphology in NFSCs based on polymer blends is very challenging and a key obstacle to pushing this technology to eventual commercialization. The relations between phases at various length scales and photovoltaic parameters of all‐polymer bulk‐heterojunctions remain poorly understood and seldom explored. Here, precise control over a multilength scale morphology and photovoltaic performance are demonstrated by simply altering the concentration of a green solvent additive used in blade‐coated films. Resonant soft X‐ray scattering is used to elucidate the multiphasic morphology of these printed all‐polymeric films and complements with the use of grazing incidence wide‐angle X‐ray scattering and in situ spectroscopic ellipsometry characterizations to correlate the morphology parameters at different length scales to the device performance metrics. Benefiting from the highest relative volume fraction of small domains, additive‐free solar cells show the best device performance, strengthening the advantage of single benign solvent approach. This study also highlights the importance of high volume fraction of smallest domains in printed NFSCs and organic solar cells in general.
pH‐Responsive Nanoscale Coordination Polymer for Efficient Drug Delivery and Real‐Time Release Monitoring
Authors: Han Kai , Zhang Wei‐Yun , Zhang Jin , Ma Zhao‐Yu , Han He‐You
Published: July 2017

Both excess dosages of drug and unwanted drug carrier can lead to severe side effects as well as the failure of tumor therapy. Here, an Fe3+–gallic acid based drug delivery system is designed for efficient monitoring of drug release in tumor. Fe3+ and polyphenol gallic acid can form polygonal nanoscale coordination polymer in aqueous solution, which exhibits certain antitumor effect. Importantly, this coordination polymer possesses extremely high doxorubicin (DOX) loading efficacy (up to 48.3%). In vitro studies demonstrate that the fluorescence of DOX can be quenched efficiently when DOX is loaded on the coordination polymer. The acidity in lysosome also triggers the release of DOX and fluorescence recovery simultaneously, which realizes real‐time monitoring of drug release in tumor cells. In vivo studies further indicate that this polyphenol‐rich drug delivery system can significantly inhibit tumor growth with negligible heart toxicity of DOX. This system with minimal side effects should be a promising nanoplatform for tumor treatment.
Stretchable Dry Electrodes with Concentric Ring Geometry for Enhancing Spatial Resolution in Electrophysiology
Authors: Wang Kaiping , Parekh Udit , Pailla Tejaswy , Garudadri Harinath , Gilja Vikash , Ng Tse Nga
Published: July 2017

The multichannel concentric‐ring electrodes are stencil printed on stretchable elastomers modified to improve adhesion to skin and minimize motion artifacts for electrophysiological recordings of electroencephalography, electromyography, and electrocardiography. These dry electrodes with a poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate interface layer are optimized to show lower noise level than that of commercial gel disc electrodes. The concentric ring geometry enables Laplacian filtering to pinpoint the bioelectric potential source with spatial resolution determined by the ring distance. This work shows a new fabrication approach to integrate and create designs that enhance spatial resolution for high‐quality electrophysiology monitoring devices.
Multifunctional Nanotube–Mucoadhesive Poly(methyl vinyl ether‐co‐maleic acid)@Hydroxypropyl Methylcellulose Acetate Succinate Composite for Site‐Specific Oral Drug Delivery
Authors: Kerdsakundee Nattha , Li Wei , Martins João Pedro , Liu Zehua , Zhang Feng , Kemell Marianna , Correia Alexandra , Ding Yaping , Airavaara Mikko , Hirvonen Jouni , Wiwattanapatapee Ruedeekorn , Santos Hélder A.
Published: July 2017

An advanced oral drug delivery system that can effectively deliver drugs with poor oral bioavailability is strongly desirable. Herein, a multifunctional nano‐in‐micro structured composite is developed by encapsulation of the mucoadhesive poly(methyl vinyl ether‐co‐maleic acid) modified halloysite nanotubes (HNTs) with the pH‐responsive hydroxypropyl methylcellulose acetate succinate by the microfluidics to control the drug release, increase cell–particle interaction, and improve drug absorption. The microparticles show spherical shape, homogeneous particle size distribution (58 ± 1 µm), and pH‐responsive dissolution behavior at pH > 6, and they prevent the premature release of curcumin in simulated pH conditions of the stomach and immediately release the curcumin in simulated pH conditions of the small intestine. The surface modification of HNT with mucoadhesive poly(methyl vinyl ether‐co‐maleic acid) significantly enhances its interactions with the intestinal Caco‐2/HT29‐MTX cells and the mouse small intestines, and increases the permeability of curcumin across the co‐cultured Caco‐2/HT29‐MTX cell monolayers by about 13 times compared to the free curcumin. Therefore, the developed multifunctional nanotube–mucoadhesive poly(methyl vinyl ether‐co‐maleic acid)@hydroxypropyl methylcellulose acetate succinate composite is a promising oral drug delivery system for drugs with poor oral bioavailability.
Wet‐Spun Superelastic Graphene Aerogel Millispheres with Group Effect
Authors: Zhao Xiaoli , Yao Weiquan , Gao Weiwei , Chen Hao , Gao Chao
Published: July 2017

Graphene aerogel has attracted great attention due to its unique properties, such as ultralow density, superelasticity, and high specific surface area. It shows huge potential in energy devices, high‐performance pressure sensors, contaminates adsorbents, and electromagnetic wave absorbing materials. However, there still remain some challenges to further promote the development and real application of graphene aerogel including cost‐effective scalable fabrication and miniaturization with group effect. This study shows millimeter‐scale superelastic graphene aerogel spheres (GSs) with group effect and multifunctionality. The GSs are continuously fabricated on a large scale by wet spinning of graphene oxide liquid crystals followed by facile drying and thermal annealing. Such GS has an unusual core–shell structure with excellent elasticity and specific strength. Significantly, both horizontally and vertically grouped spheres exhibit superelasticity comparable to individual spheres, enabling it to fully recover at 95% strain, and even after 1000 compressive cycles at 70% strain, paving the way to wide applications such as pressure‐elastic and adsorbing materials. The GS shows a press‐fly behavior with an extremely high jump velocity up to 1.2 m s−1. For the first time, both free and oil‐adsorbed GSs are remotely manipulated on water by electrostatic charge due to their ultralow density and hydrophobic properties.
Disordered Conformation with Low Pii Helix in Phosphoproteins Orchestrates Biomimetic Apatite Formation
Authors: Sarem Melika , Lüdeke Steffen , Thomann Ralf , Salavei Pavel , Zou Zhaoyong , Habraken Wouter , Masic Admir , Shastri V. Prasad
Published: July 2017

The interplay between noncollagenous proteins and biomineralization is widely accepted, yet the contribution of their secondary structure in mineral formation remains to be clarified. This study demonstrates a role for phosvitin, an intrinsically disordered phosphoprotein, in chick embryo skeletal development, and using circular dichroism and matrix least‐squares Henderson–Hasselbalch global fitting, unravels three distinct pH‐dependent secondary structures in phosvitin. By sequestering phosvitin on a biomimetic 3D insoluble cationic framework at defined pHs, access is gained to phosvitin in various conformational states. Induction of biomimetic mineralization at near physiological conditions reveals that a disordered secondary structure with a low content of PII helix is remarkably efficient at promoting calcium adsorption, and results in the formation of biomimetic hydroxyapatite through an amorphous calcium phosphate precursor. By extending this finding to phosphorylated full‐length human recombinant dentin matrix protein‐1 (17‐513 AA), this bioinspired approach provides compelling evidence for the role of a disordered secondary structure in phosphoproteins in bone‐like apatite formation.
Recent Progress in the Preparation, Assembly, Transformation, and Applications of Layer‐Structured Nanodisks beyond Graphene
Authors: Zhang Xiao , Cheng Hongfei , Zhang Hua
Published: July 2017

Layered nanodisks with confined thickness and lateral size have been emerging as a unique type of two‐dimensional (2D) nanomaterials in recent years. Inheriting some properties of 2D nanosheets and meanwhile possessing the size‐confinement effect, these layered nanodisks exhibit unique optical, electronic, and chemical properties, which endow them with great promise in a wide range of applications. Here, the recent progress of layered nanodisks is introduced. The synthetic strategies, assembly, structural/compositional transformation, and applications of layered nanodisks are systematically described and discussed, with emphasis on their new appealing structures and functions. Finally, some perspectives and future research directions of this promising field are given.
An All‐Solution‐Based Hybrid CMOS‐Like Quantum Dot/Carbon Nanotube Inverter
Authors: Shulga Artem G. , Derenskyi Vladimir , Salazar‐Rios Jorge Mario , Dirin Dmitry N. , Fritsch Martin , Kovalenko Maksym V. , Scherf Ullrich , Loi Maria A.
Published: July 2017

The development of low‐cost, flexible electronic devices is subordinated to the advancement in solution‐based and low‐temperature‐processable semiconducting materials, such as colloidal quantum dots (QDs) and single‐walled carbon nanotubes (SWCNTs). Here, excellent compatibility of QDs and SWCNTs as a complementary pair of semiconducting materials for fabrication of high‐performance complementary metal‐oxide‐semiconductor (CMOS)‐like inverters is demonstrated. The n‐type field effect transistors (FETs) based on I− capped PbS QDs (Vth = 0.2 V, on/off = 105, SS‐th = 114 mV dec−1, µe = 0.22 cm2 V−1 s−1) and the p‐type FETs with tailored parameters based on low‐density random network of SWCNTs (Vth = −0.2 V, on/off > 105, SS‐th = 63 mV dec−1, µh = 0.04 cm2 V−1 s−1) are integrated on the same substrate in order to obtain high‐performance hybrid inverters. The inverters operate in the sub‐1 V range (0.9 V) and have high gain (76 V/V), large maximum‐equal‐criteria noise margins (80%), and peak power consumption of 3 nW, in combination with low hysteresis (10 mV).
Encoding Random Hot Spots of a Volume Gold Nanorod Assembly for Ultralow Energy Memory
Authors: Dai Qiaofeng , Ouyang Min , Yuan Weiguang , Li Jinxiang , Guo Banghong , Lan Sheng , Liu Songhao , Zhang Qiming , Lu Guang , Tie Shaolong , Deng Haidong , Xu Yi , Gu Min
Published: July 2017

Data storage with ultrahigh density, ultralow energy, high security, and long lifetime is highly desirable in the 21st century and optical data storage is considered as the most promising way to meet the challenge of storing big data. Plasmonic coupling in regularly arranged metallic nanoparticles has demonstrated its superior properties in various applications due to the generation of hot spots. Here, the discovery of the polarization and spectrum sensitivity of random hot spots generated in a volume gold nanorod assembly is reported. It is demonstrated that the two‐photon‐induced absorption and two‐photon‐induced luminescence of the gold nanorods adjacent to such hot spots are enhanced significantly because of plasmonic coupling. The polarization, wavelength, and spatial multiplexing of the hot spots can be realized by using an ultralow energy of only a few picojoule per pulse, which is two orders of magnitude lower than the value in the state‐of‐the‐art technology that utilizes isolated gold nanorods. The ultralow recording energy reduces the cross‐talk between different recording channels and makes it possible to realize rewriting function, improving significantly both the quality and capacity of optical data storage. It is anticipated that the demonstrated technology can facilitate the development of multidimensional optical data storage for a greener future.
Hierarchical VS2 Nanosheet Assemblies: A Universal Host Material for the Reversible Storage of Alkali Metal Ions
Authors: Zhou Junhua , Wang Lu , Yang Mingye , Wu Jinghua , Chen Fengjiao , Huang Wenjing , Han Na , Ye Hualin , Zhao Feipeng , Li Youyong , Li Yanguang
Published: July 2017

Reversible electrochemical storage of alkali metal ions is the basis of many secondary batteries. Over years, various electrode materials are developed and optimized for a specific type of alkali metal ions (Li+, Na+, or K+), yet there are very few (if not none) candidates that can serve as a universal host material for all of them. Herein, a facile solvothermal method is developed to prepare VS2 nanosheet assemblies. Individual nanosheets are featured with a few atomic layer thickness, and they are hierarchically arranged with minimized stacking. Electrochemical measurements show that VS2 nanosheet assemblies enable the rapid and durable storage of Li+, Na+, or K+ ions. Most remarkably, the large reversible specific capacity and great cycling stability observed for both Na+ and K+ are extraordinary and superior to most existing electrode materials. The experimental results of this study are further supported by density functional theory calculations showing that the layered structure of VS2 has large adsorption energy and low diffusion barriers for the intercalation of alkali metal ions.
Strongly Enhanced Photovoltaic Performance and Defect Physics of Air‐Stable Bismuth Oxyiodide (BiOI)
Authors: Hoye Robert L. Z. , Lee Lana C. , Kurchin Rachel C. , Huq Tahmida N. , Zhang Kelvin H. L. , Sponseller Melany , Nienhaus Lea , Brandt Riley E. , Jean Joel , Polizzotti James Alexander , Kursumović Ahmed , Bawendi Moungi G. , Bulović Vladimir , Stevanović Vladan , Buonassisi Tonio , MacManus‐Driscoll Judith L.
Published: July 2017

Bismuth‐based compounds have recently gained increasing attention as potentially nontoxic and defect‐tolerant solar absorbers. However, many of the new materials recently investigated show limited photovoltaic performance. Herein, one such compound is explored in detail through theory and experiment: bismuth oxyiodide (BiOI). BiOI thin films are grown by chemical vapor transport and found to maintain the same tetragonal phase in ambient air for at least 197 d. The computations suggest BiOI to be tolerant to antisite and vacancy defects. All‐inorganic solar cells (ITO|NiOx|BiOI|ZnO|Al) with negligible hysteresis and up to 80% external quantum efficiency under select monochromatic excitation are demonstrated. The short‐circuit current densities and power conversion efficiencies under AM 1.5G illumination are nearly double those of previously reported BiOI solar cells, as well as other bismuth halide and chalcohalide photovoltaics recently explored by many groups. Through a detailed loss analysis using optical characterization, photoemission spectroscopy, and device modeling, direction for future improvements in efficiency is provided. This work demonstrates that BiOI, previously considered to be a poor photocatalyst, is promising for photovoltaics.
Well‐Designed Hierarchical Co3O4 Architecture as a Long‐Life and Ultrahigh Rate Capacity Anode for Advanced Lithium‐Ion Batteries
Authors: Liu Mengting , Deng Xia , Ma Yaodong , Xie Wenhe , Hou Xiaoyi , Fu Yujun , He Deyan
Published: July 2017

In a simple strategy of mild heat‐assistant precipitation followed by annealing in air, hierarchical Co3O4 flower‐like microspheres self‐constructed by porous nanosheets are synthesized in bulk and tested as an anode material for advanced lithium‐ion batteries (LIBs). Benefited from its high porosity and specific surface area as well as a necessary short activation, the as‐prepared architecture shows an enhanced lithium storage performance of high capacity, long‐life cycle, and ultrahigh rate capacity compared with the great majority of reported and commercial Co3O4 materials. Especially, it delivers a reversible capacity of 715 mAh g−1 after 1000 cycles under a current density of 1000 mA g−1 with a coulombic efficiency of more than 99%. When the electrode is laid aside for 5 d and recycled again, it can reach upward of 680 mAh g−1 for another 150 cycles. Such an impressive electrochemical performance indicates that the hierarchical Co3O4 flower‐like microspheres can be a promising electrode material of advanced LIBs in future.
Annulated 1,3,4‐Azadiphospholides: Heterocycles with Widely Tunable Optical Properties
Authors: Suter Riccardo , Benkő Zoltán , Bispinghoff Mark , Grützmacher Hansjörg
Published: July 2017

Phosphorus heterocycles find applications in the synthesis of π‐conjugated compounds and as precursors for optoelectronic materials such as organic light‐emitting diodes (OLEDs), electronic switches, and transistors. A high‐yield, one‐pot synthesis of anionic annulated 1,3,4‐azadiphospholides from Na(OCP) and 2‐chloropyridines is presented. The synthesis proceeds without the use of transition metals and tolerates a wide range of substrates. Cyano‐substituted compounds are especially deeply colored and have absorption maxima which range from λmax=525 to 596 nm. The optical properties are dominated by the spatial separation of an electron acceptor and donor unit within one molecule (push–pull chromophore). The anionic 1,3,4‐azadiphospholides are silylated to neutral siloxy compounds with a strong blue‐shifted absorption. This reaction can be reversed by addition of fluoride ions, which allows fluoride ions to be detected in optically low concentrations.
Bioinspired, Size‐Tunable Self‐Assembly of Polymer–Lipid Bilayer Nanodiscs
Authors: Ravula Thirupathi , Ramadugu Sudheer Kumar , Di Mauro Giacomo , Ramamoorthy Ayyalusamy
Published: July 2017

Polymer‐based nanodiscs are valuable tools in biomedical research that can offer a detergent‐free solubilization of membrane proteins maintaining their native lipid environment. Herein, we introduce a novel ca. 1.6 kDa SMA‐based polymer with styrene:maleic acid moieties that can form nanodiscs containing a planar lipid bilayer which are useful to reconstitute membrane proteins for structural and functional studies. The physicochemical properties and the mechanism of formation of polymer‐based nanodiscs are characterized by light scattering, NMR, FT‐IR, and TEM. A remarkable feature is that nanodiscs of different sizes, from nanometer to sub‐micrometer diameter, can be produced by varying the lipid‐to‐polymer ratio. The small‐size nanodiscs (up to ca. 30 nm diameter) can be used for solution NMR spectroscopy studies whereas the magnetic‐alignment of macro‐nanodiscs (diameter of > ca. 40 nm) can be exploited for solid‐state NMR studies on membrane proteins.
Eigenschaften von Wasser in den Poren von periodisch mesoporösen Organosilicas – Nanoabprägung der lokalen Struktur
Authors: Mietner J. Benedikt , Brieler Felix J. , Lee Young Joo , Fröba Michael
Published: July 2017

Die Eigenschaften von Gastmolekülen in den Poren poröser Materialien sind sowohl aus wissenschaftlicher wie auch aus technologischer Perspektive hochinteressant. Entscheidenden Einfluss auf die durch eine geometrische Beschränkung hervorgerufenen Effekte haben insbesondere die Topologie, Größe und Oberflächenpolarität der Poren. Allerdings ist über die Kontaktfläche zwischen Gastmolekül und Porenwand noch zu wenig bekannt. Hier wird gezeigt, dass die Mobilität von Wassermolekülen in den Poren von periodisch mesoporösen Organosilicas (PMOs) stark von der Polarität der organischen Einheit abhängt. Mithilfe mehrdimensionaler Festkörper‐NMR‐Spektroskopie wurde die räumliche Anordnung von Wasser im Inneren von Poren bestimmt. Wassermoleküle interagieren, abhängig von der alternierenden Oberflächenpolarität, entweder nur mit den anorganischen Silicatschichten oder auch mit den organischen Schichten. Als Ergebnis wird in Abhängigkeit von den PMO‐Typen entweder eine modulierte oder eine gleichmäßige Porenfüllung mit Wasser vorgeschlagen.
Cyclodextrin Cavity‐Induced Mechanistic Switch in Copper‐Catalyzed Hydroboration
Authors: Zhang Pinglu , Meijide Suárez Jorge , Driant Thomas , Derat Etienne , Zhang Yongmin , Ménand Mickaël , Roland Sylvain , Sollogoub Matthieu
Published: July 2017

N‐heterocyclic carbene‐capped cyclodextrin (ICyD) ligands, α‐ICyD and β‐ICyD derived from α‐ and β‐cyclodextrin, respectively give opposite regioselectivities in a copper‐catalyzed hydroboration. The site‐selectivity results from two different mechanisms: the conventional parallel one and a new orthogonal mechanism. The shape of the cavity was shown not only to induce a regioselectivity switch but also a mechanistic switch. The scope of interest of the encapsulation of a reactive center is therefore broadened by this study.
Intermediate Product Regulation in Tandem Solid Catalysts with Multimodal Porosity for High‐Yield Synthetic Fuel Production
Authors: Duyckaerts Nicolas , Bartsch Mathias , Trotuş Ioan‐Teodor , Pfänder Norbert , Lorke Axel , Schüth Ferdi , Prieto Gonzalo
Published: July 2017

Tandem catalysis is an attractive strategy to intensify chemical technologies. However, simultaneous control over the individual and concerted catalyst performances poses a challenge. We demonstrate that enhanced pore transport within a Co/Al2O3 Fischer–Tropsch (FT) catalyst with hierarchical porosity enables its tandem integration with a Pt/ZSM‐5 zeolitic hydrotreating catalyst in a spatially distant fashion that allows for catalyst‐specific temperature adjustment. Nevertheless, this system resembles the case of close active‐site proximity by mitigating secondary reactions of primary FT α‐olefin products. This approach enables the combination of in situ dewaxing with a minimum production of gaseous hydrocarbons (18 wt %) and an up to twofold higher (50 wt %) selectivity to middle distillates compared to tandem pairs based on benchmark mesoporous FT catalysts. An overall 80 % selectivity to liquid hydrocarbons from syngas is attained in one step, attesting to the potential of this strategy for increasing the carbon efficiency in intensified gas‐to‐liquid technologies.
Polyladderane Constructed from a Gemini Monomer through Photoreaction
Authors: Wang Zhihan , Miller Benjamin , Butz Jonathan , Randazzo Katelyn , Wang Zijun D. , Chu Qianli R.
Published: July 2017

Polyladderane, the first polymer to contain the ladderane functional group, was synthesized from a gemini monomer through photoreaction in the solid state. The modular design of the gemini monomers used to create polyladderane allowed specific structural modification, resulting in the formation of two distinct polymer products. Monomers were synthesized by connecting two photoreactive units, either sorbic acids (monomer I) or 2‐furanacrylic acids (monomer II), with a 1,4‐butanediol linker. Single‐crystal X‐ray diffraction analysis of the monomers confirmed that they packed in the desired head‐to‐tail orientation and within a viable distance for photoreaction by electronically complementary interaction. Pre‐organized gemini monomers were irradiated with UV light and monitored by FT‐IR. Two polyladderanes with cis,anti,cis‐[3]‐ladderane as a characteristic functional group were constructed stereospecifically in 24–36 hours.
Antidepressants, Antipsychotics, and Mood Stabilizers in Pregnancy: What Do We Know and How Should We Treat Pregnant Women with Depression
Authors: Ornoy Asher , Weinstein‐Fudim Liza , Ergaz Zivanit
Published: July 2017

Depression is generally treated with antidepressants, but may often need antipsychotics and mood stabilizers. We discuss the updated data regarding the safety in pregnancy of antidepressants and antipsychotics, except selective serotonin reuptake inhibitors, and their possible impact on the long‐term development of the offspring. Several earlier studies demonstrated a slight increase in the rate of major anomalies following maternal tricyclic antidepressant treatment, but most current literature shows their relative safety in pregnancy. Data on the development of the offspring are also reassuring. The antipsychotic drugs are also safe for the developing fetus and do not seem to induce developmental delay. Both groups of drugs may cause perinatal withdrawal symptoms and difficulties in neonatal adaptation. The mood stabilizers, lithium, and several anti‐epileptic drugs, may adversely affect the developing embryo and fetus. While valproic acid, carbamazepine, and topiramate are teratogenic and may also affect postnatal development, the newer antiepileptic and mood stabilizers, lamotrigine and levetiracetam, seem to be safe in pregnancy and apparently have no long‐term neurodevelopmental damage. Lithium may increase the rate of cardiac anomalies, especially of Ebstein's anomaly, and may warrant a mid‐trimester fetal echocardiography. Although data on the development of the offspring are reassuring, we should remember that most studies were carried out during early childhood, at a time when inattention, learning difficulties, behavioral and psychiatric problems are not yet identifiable. When considering medical treatment for depression in women at child‐bearing age, we have to weigh the severity of the symptoms and their impact on the developing fetus and child. Birth Defects Research 109:933–956, 2017.© 2017 Wiley Periodicals, Inc.
Enzymatic mechanisms of biological magnetic sensitivity
Authors: Letuta Ulyana G. , Berdinskiy Vitaly L. , Udagawa Chikako , Tanimoto Yoshifumi
Published: July 2017

Primary biological magnetoreceptors in living organisms is one of the main research problems in magnetobiology. Intracellular enzymatic reactions accompanied by electron transfer have been shown to be receptors of magnetic fields, and spin‐dependent ion‐radical processes can be a universal mechanism of biological magnetosensitivity. Magnetic interactions in intermediate ion‐radical pairs, such as Zeeman and hyperfine (HFI) interactions, in accordance with proposed strict quantum mechanical theory, can determine magnetic‐field dependencies of reactions that produce biologically important molecules needed for cell growth. Hyperfine interactions of electrons with nuclear magnetic moments of magnetic isotopes can explain the most important part of biomagnetic sensitivities in a weak magnetic field comparable to the Earth's magnetic field. The theoretical results mean that magnetic‐field dependencies of enzymatic reaction rates in a weak magnetic field that can be independent of HFI constant a, if H << a, and are determined by the rate constant of chemical transformations in the enzyme active site. Both Zeeman and HFI interactions predict strong magnetic‐field dependence in weak magnetic fields and magnetic‐field independence of enzymatic reaction rate constants in strong magnetic fields. The theoretical results can explain the magnetic sensitivity of E. coli cell and demonstrate that intracellular enzymatic reactions are primary magnetoreceptors in living organisms. Bioelectromagnetics. 38:511–521, 2017. © 2017 Wiley Periodicals, Inc.
A critique of utilitarian and instrumentalist concepts for the teaching of gross anatomy to medical and dental students: Provoking debate
Authors: Moxham Bernard J. , Pais Diogo
Published: July 2017

Medical and dental curricula, together with anatomical sciences courses, are increasingly having to change, mainly because there is a drive to being what is termed, without adequate definition, “clinically relevant.” The concept of “clinical anatomy” has accordingly been invented and it is expected that, at all times, the teaching of anatomy is directly focused on clinical scenarios, meaning almost invariably the disease‐based model of medicine and dentistry. Furthermore, students are not expected to have a detailed knowledge of gross anatomy and the time devoted to teaching and learning the subject has decreased significantly. The notion being fostered is that knowledge is not required “just in case” but “just in time.” However, the absence of agreed core syllabuses that are internationally accepted complicates a discussion about what is relevant practically and what does not need to be taught. In this article, we critique such an utilitarian and instrumentalist approach to the teaching of gross anatomy within medical and dental curricula. We draw attention to the need to embrace the functionality‐based model of medicine and dentistry by returning to an understanding that the role of the medical or dental practitioner is to value health and to restore to functionality the ill person or the pathologically affected region/organ/system. A fuller knowledge of anatomy than is presently taught is regarded as a prerequisite for appreciating normality and health. A further problem with the instrumentalist approach to medical education is that, by concentrating on what is seen to be at the time “useful” or “clinically relevant,” there is the danger of undermining, or discouraging, future developments that rely on what contemporaneously seems “useless” and “irrelevant” knowledge. Finally, the reliance instrumentalism has on just what is pragmatic and regardless of scientific validity is contrary to the ethos and practice of a university education that values deep learning and the development of learnèd professions. Clin. Anat. 30:912–921, 2017. © 2017 Wiley Periodicals, Inc.
Selectivity in the Cyclization of Citronellal Introduced by Squalene Hopene Cyclase Variants
Authors: Bastian Silke A. , Hammer Stephan C. , Kreß Nico , Nestl Bettina M. , Hauer Bernhard
Published: July 2017

The squalene hopene cyclase from Alicyclobacillus acidocaldarius (AacSHC) is a highly efficient enzyme catalyst for stereoselective Brønsted acid catalysis. We engineered AacSHC to catalyze the selective Prins cyclization of citronellal. Four active site variants were identified for the diastereoselective cyclization of (S)‐citronellal to stereoisomers (−)‐iso‐isopulegol, (+)‐isopulegol and (−)‐neo‐isopulegol, respectively. The replacement of active site residues resulted in two triple variants that catalyzed the transformation of (R)‐citronellal to give the isomers (+)‐neo‐isopulegol and (−)‐isopulegol with up to >99 % de, respectively. The newly designed library of functionally diverse active site geometries exhibits high selective control during citronellal cyclization, leading exclusively to a single diastereomer of the desired isopulegol. Whereas the cyclization of citronellal with chemical catalysts was observed to produce the isopulegol isomer with the lowest energy, the reaction with AacSHC variants proceeded with higher product selectivity. The results of this study show that variants of AacSHC are excellent catalysts for the highly selective formation of isopulegol stereoisomers.
Embedding Reduced Graphene Oxide in Bacterial Cellulose‐Derived Carbon Nanofibril Networks for Supercapacitors
Authors: Chang Yanhong , Zhou Lu , Xiao Zhichang , Liang Jiaxu , Kong Debin , Li Zihao , Zhang Xinghao , Li Xianglong , Zhi Linjie
Published: July 2017

A simple, effective, eco‐friendly, and scalable reduced graphene oxide embedding strategy is developed to construct self‐supported carbon electrode material networks for supercapacitors from a naturally occurring biomaterial−bacterial cellulose. The thus‐engineered self‐supported carbon nanofibril networks exhibit superior supercapacitive performance compared to their counterparts, thus opening up an avenue to design self‐supported high‐capacitance carbon electrode materials toward high‐class supercapacitors.
Magnetic Shielding Studies of C2 and C2H2 Support Higher than Triple Bond Multiplicity in C2
Authors: Karadakov Peter B. , Kirsopp Josh
Published: July 2017

The carbon–carbon bonds in the ground states of C2 and C2H2, at their equilibrium geometries, are compared by analysing the changes in the off‐nucleus magnetic shielding tensor within the space surrounding each of these molecules. A wide range of quantum‐chemical approaches, including full‐valence CASSCF‐GIAO, CCSD(T)‐GIAO and CCSDT‐GIAO, all with the cc‐pVQZ basis set, as well as HF‐GIAO and MP2‐GIAO, with the cc‐pVQZ, cc‐pV5Z and cc‐pV6Z basis sets, show that the surroundings of the carbon–carbon bond in C2 are more shielded than those of the carbon–carbon bond in C2H2. The additional shielding of the carbon–carbon bond in C2 is found to be due to a larger paramagnetic contribution to the component of the shielding tensor which is perpendicular to the molecular axis. The analysis of the off‐nucleus shielding data indicates that the carbon–carbon bond in C2 is “bulkier” and, therefore, of a higher multiplicity, but weaker than the corresponding bond in C2H2. According to the results of the shielding calculations, the carbon nuclei in C2 should be much more shielded than those in C2H2, with 13C isotropic magnetic shieldings in the ranges of around 224–227 ppm and around 123–125 ppm for C2 and C2H2, respectively.
MacroEvoLution: A New Method for the Rapid Generation of Novel Scaffold‐Diverse Macrocyclic Libraries
Authors: Saupe Jörn , Kunz Oliver , Haustedt Lars Ole , Jakupovic Sven , Mang Christian
Published: July 2017

Macrocycles are a structural class bearing great promise for future challenges in medicinal chemistry. Nevertheless, there are few flexible approaches for the rapid generation of structurally diverse macrocyclic compound collections. Here, an efficient method for the generation of novel macrocyclic peptide‐based scaffolds is reported. The process, named here as “MacroEvoLution”, is based on a cyclization screening approach that gives reliable access to novel macrocyclic architectures. Classification of building blocks into specific pools ensures that scaffolds with orthogonally addressable functionalities are generated, which can easily be used for the generation of structurally diverse compound libraries. The method grants rapid access to novel scaffolds with scalable synthesis (multi gram scale) and the introduction of further diversity at a late stage. Despite being developed for peptidic systems, the approach can easily be extended for the synthesis of systems with a decreased peptidic character.
Asymmetric Alkynylation of β‐Ketoesters and Naphthols Promoted by New Chiral Biphenylic Iodanes
Authors: Companys Simon , Peixoto Philippe A. , Bosset Cyril , Chassaing Stefan , Miqueu Karinne , Sotiropoulos Jean‐Marc , Pouységu Laurent , Quideau Stéphane
Published: July 2017

The preparation of new chiral biphenylic λ3‐iodane reagents bearing transferable alkynyl ligands is described. These reagents transfer their carbon‐based ligands onto β‐ketoesters with an enantiomeric excess (ee) up to 68 %, and most remarkably, enable the dearomative alkynylation of naphthols in good to high yields up to 84 % ee.
Cesium Removal from Human Blood by Poly(ethylene glycol)‐Decorated Prussian Blue Magnetic Nanoparticles
Authors: Qian Jun , Xu Jiaying , Kuang Liangju , Hua Daoben
Published: July 2017

The current oral administration of drugs for cesium (Cs) decorporation treatment are often subject to side effects and low efficiency. Therefore, it is of great significance, yet challenging, to develop novel materials and techniques for efficient removal of Cs from the human body. We report herein a new method for directly removing cesium from blood by poly(ethylene glycol)‐decorated Prussian blue magnetic nanoparticles (PEG‐PB MNs). The nanoparticles have been successfully synthesized by one‐pot hydrothermal reaction. The adsorption of cesium in aqueous solution is a highly selective process and kinetically follows a pseudo‐second‐order model, which can reach equilibrium with a large capacity of 274.7 mg Cs g−1 within one hour at 298.15 K. PEG‐PB MNs were also efficiently regenerated and reused with high adsorption efficiency after five cycles. The nanoparticles successfully removed cesium ions from human blood with improved biocompatibility. The removal efficiency achieved 64 % in the blood with an initial Cs concentration of 168.4 ppb. This study provides a new approach to directly remove cesium ions from the human body by utilizing biocompatible Prussian blue magnetic nanoparticles.
In‐Situ Observation of Nanoparticle Formation Under Different Power of Microwave Irradiation
Authors: Asakuma Yusuke , Matsumura Shungo , Saptoro Agus
Published: July 2017

Microwave technology has emerged as one of the useful methods for nanoparticle synthesis. Despite many studies on this area, its underlying mechanism has not been clearly understood. In this study, in‐situ observation of nanoparticle growth was carried out and the profiles and behaviors of produced bubbles and particles under microwave effect were reported. Sizes of bubble and nanoparticle particle were measured during and after microwave irradiation using a DLS apparatus and behavior of particle growth and superheating effect were observed. From the experimental data, it is apparent that the maximum bubble sizes were greatly influenced by the irradiation power and solute concentration. Particle number density, which is related to the initial solute concentration, is also an important factor for the bubble size produced during the irradiation. Finally, through in‐situ observation of superheating effect, the behavior was frequently caused by the irradiation at higher power. To prevent superheating effect, influencing factors such as the irradiation power and number density should be controlled to ensure a stable operation of particle formation process.
A Multiobjective Optimization Including Results of Life Cycle Assessment in Developing Biorenewables‐Based Processes
Authors: Helmdach Daniel , Yaseneva Polina , Heer Parminder K. , Schweidtmann Artur M. , Lapkin Alexei A.
Published: July 2017

A decision support tool has been developed that uses global multiobjective optimization based on 1) the environmental impacts, evaluated within the framework of full life cycle assessment; and 2) process costs, evaluated by using rigorous process models. This approach is particularly useful in developing biorenewable‐based energy solutions and chemicals manufacturing, for which multiple criteria must be evaluated and optimization‐based decision‐making processes are particularly attractive. The framework is demonstrated by using a case study of the conversion of terpenes derived from biowaste feedstocks into reactive intermediates. A two‐step chemical conversion/separation sequence was implemented as a rigorous process model and combined with a life cycle model. A life cycle inventory for crude sulfate turpentine was developed, as well as a conceptual process of its separation into pure terpene feedstocks. The performed single‐ and multiobjective optimizations demonstrate the functionality of the optimization‐based process development and illustrate the approach. The most significant advance is the ability to perform multiobjective global optimization, resulting in identification of a region of Pareto‐optimal solutions.
Tetrakis{[(p‐dodecacarboranyl)methyl]stilbenyl}ethylene: A Luminescent Tetraphenylethylene (TPE) Core System
Authors: Cabrera‐González Justo , Bhattacharyya Santanu , Milián‐Medina Begoña , Teixidor Francesc , Farfán Norberto , Arcos‐Ramos Rafael , Vargas‐Reyes Verónica , Gierschner Johannes , Núñez Rosario
Published: July 2017

The synthesis and spectroscopic characterization of the first set of tetrakis{[(p‐dodecacarboranyl)methyl]stilbenyl}ethylenes (TDSE), substituted either with a methyl or a phenyl group in the 2‐position (Ccluster) of the ortho‐carborane, are described. The complex absorption properties are elucidated by TD‐DFT calculations, stressing the importance of through‐bond conjugation. Enhanced conjugation and restriction of the conformational space are identified as the main factors for boosted luminescence properties in solution, compared with the tetraphenylethylene (TPE) core, effectively reducing internal conversion (IC). IC is further reduced when aggregate suspensions of our compounds are formed in water, providing highly luminescent materials of quasi‐isolated (very weakly interacting) emitters.