bluuebunny/crossref_metadata_2025 huggingface dataset:
De quelques usages sociologiques des récits en édition numérique
Authors: Dardy Claudine
Published: November 2016

Le site éditeur Raconter la vie a constitué en deux ans d’existence une collection de six cents récits. L’abondance narrative ainsi suscitée déploie une mosaïque faite des fragments de vies multiples qui peut se prêter au regard sociologique au gré des angles de vue décelant tel ou tel motif ou thème. On peut encore s’essayer à identifier des types de récits : témoignage, récit de vie sociale ou même performance artistique. On a choisi, par l’enquête, de rencontrer quelques protagonistes de cette scène numérique, à commencer par la web éditrice pivot du site, ses collaborateurs, dits éditeurs communautaires, et les auteurs. L’intention était de situer la production de ces récits et leur proposition à l’édition numérique au regard des pratiques d’écriture et de lecture de leurs auteurs, prenant acte d’une culture de l’écrit, voire d’une culture littéraire en référence. Les auteurs évoquent des pratiques variées des carnets personnels à l’expérience d’ateliers d’écriture, en passant par les écrits professionnels. Beaucoup sont habiles à utiliser les ressources du numérique, blog, réseaux, plateforme. L’ombre d’une maison d’édition traditionnelle prestigieuse, l’engagement d’un professeur au collège de France, la compétence éditoriale — double lecture des textes, aide à la mise en forme technique — servent un désir latent de publication largement partagé par les auteurs. De quoi, pour ces derniers, se concevoir comme auteurs amateurs et caresser l’espoir d’une reconnaissance d’écrivain. À défaut d’impulser un impossible parlement des invisibles, le site éditeur préserve la forme narrative en même temps qu’il promeut une figure d’auteur amateur. Il pourrait s’apparenter à un atelier d’écriture grand format aux prismes du numérique ; on y est privé d’une sociabilité de lectures partagées mais autorisé aux jeux d’identités multiples, celles de ces personnages et auteurs appelés à raconter le roman vrai de la société et si fort en quête d’éditeurs.
Assessment and Treatment of Psychiatric Distress, Sexual Dysfunction, Sleep Disturbances, and Pain in Multiple Sclerosis
Authors: Gromisch Elizabeth S. , Schairer Laura C. , Pasternak Eliana , Kim Stella H. , Foley Frederick W.
Published: November 2016

Background: Psychiatric distress (depression and anxiety), sexual dysfunction, sleep disturbances, and pain are frequent comorbidities in multiple sclerosis (MS) that have the potential to interfere with functioning and quality of life. Often, patients benefit from a combination of medical and psychotherapeutic interventions. However, the literature suggests that many of these issues have been underdiagnosed or undertreated. To better understand current practices, this study aimed to gain a multidisciplinary perspective on how MS providers assess and treat these five problems.

Methods: An online questionnaire was completed by 42 members of the Consortium of Multiple Sclerosis Centers on their assessment procedures, treatment recommendations, and prevalence rates of these issues in their practices.

Results: More than 80% of participants reported routinely assessing for depression, anxiety, sleep, and pain, but only slightly more than half ask about sexual dysfunction. Most of these health-care providers endorsed using a general question in their assessments and recommending a pharmaceutical intervention.

Conclusions: Health-care providers are aware of the prevalence of these issues in their patients with MS. Promoting the use of validated screening measures and increased research on psychotherapeutic interventions for sleep and pain are two potential avenues for improving patient care.
How Open Access Affects Competition in Scholarly Publishing Markets: A Tale of Good Intentions, Big Deals and Uncertain Outcomes
Authors: McCabe Mark J.
Published: November 2016

Watch the VIDEO of the presentation.Since the 1990s a wave of innovation has transformed media markets, including those involving scientific communication.  Expectations that the internet might improve access to the scientific literature while lowering costs to users have only been partially fulfilled.  Using a modern economic framework I identify the historical, structural sources of market power in publishing markets and discuss the role that OA can play on a stage populated by publishers, authors, readers, and institutional actors of various types.  For example, efforts to “flip” journals from a reader to author pay basis can follow a number of paths.  At least one of these paths is efficient, lower cost, and plausible.
The Management of Voluntary Ingestion of Razor Blades by Inmates
Authors: Elghali Mohamed amine , Ghrissi Rafik , Fadhl Houssem , Mahjoub Mohamed , Jarrar Mohamed Salah , Jedidi Maher , Letaief Rached , Hamila Fehmi
Published: November 2016

Ingestion of sharp objects is a rare event. We report our experience in the care of prisoners who ingested razor blades and the in-time evolution of our management. This is a descriptive study including all detainees ingesting a razor blade, transferred from the prison to Farhat Hached University Hospital of Sousse, from January 1, 2014 to December 31, 2015. Thus, we counted 19 cases of swallowed razor blades in 16 prisoners; indeed, 1 prisoner ingested a razor blade three times and another had ingested a blade twice. Our study includes 19 episodes of swallowed razor blades. In 2 cases, these events were secondary to suicide attempts. In the other cases, it was an expression of discontent and rejection of the situation in the prison. Three patients had a psychiatric history. The mean age of the patients is 24 years. The initial clinical examination had not objectified signs of gastrointestinal perforation. Thoraco-abdomino-pelvic computed tomography scans allowed specifying the blade location in all cases. It also objectified a pneumo-mediastinum in 2 cases. The blade location was esophageal in 1 case, gastric in 6 cases, and in the small bowel in the other cases. The first 4 patients had surgical removal of the blade. In subsequent cases, surgical abstention was the rule, and spontaneous blade expulsion was observed. The average time of expulsion was 4 days. In our experience, surgical removal of sharp foreign bodies should not be performed systematically without complications.
A quantitative assessment of methane cycling in Hikurangi Margin sediments (New Zealand) using geophysical imaging and biogeochemical modeling
Authors: Luo Min , Dale Andrew W. , Haffert Laura , Haeckel Matthias , Koch Stephanie , Crutchley Gareth , De Stigter Henko , Chen Duofu , Greinert Jens
Published: November 2016

Takahe seep, located on the Opouawe Bank, Hikurangi Margin, is characterized by a well‐defined subsurface seismic chimney structure ∼80,500 m2 in area. Subseafloor geophysical data based on acoustic anomaly layers indicated the presence of gas hydrate and free gas layers within the chimney structure. Reaction‐transport modeling was applied to porewater data from 11 gravity cores to constrain methane turnover rates and benthic methane fluxes in the upper 10 m. Model results show that methane dynamics were highly variable due to transport and dissolution of ascending gas. The dissolution of gas (up to 3761 mmol m−2 yr−1) dwarfed the rate of methanogenesis within the simulated sediment column (2.6 mmol m−2 yr−1). Dissolved methane is mainly consumed by anaerobic oxidation of methane (AOM) at the base of the sulfate reduction zone and trapped by methane hydrate formation below it, with maximum rates in the central part of the chimney (946 and 2420 mmol m−2 yr−1, respectively). A seep‐wide methane budget was constrained by combining the biogeochemical model results with geophysical data and led to estimates of AOM rates, gas hydrate formation, and benthic dissolved methane fluxes of 3.68 × 104 mol yr−1, 73.85 × 104 mol yr−1, and 1.19 × 104 mol yr−1, respectively. A much larger flux of methane probably escapes in gaseous form through focused bubble vents. The approach of linking geochemical model results with spatial geophysical data put forward here can be applied elsewhere to improve benthic methane turnover rates from limited single spot measurements to larger spatial scales.
A strong phase reversal of the Arctic Oscillation in midwinter 2015/2016: Role of the stratospheric polar vortex and tropospheric blocking
Authors: Cheung Hoffman H. N. , Zhou Wen , Leung Marco Y. T. , Shun C. M. , Lee S. M. , Tong H. W.
Published: November 2016

In January 2016, Asia and North America experienced unusual cold temperatures, although the global average of surface air temperature broke the warmest record during a strong El Niño event. This was closely related to the remarkable phase transition of the Arctic Oscillation (AO), which can be explained by stratosphere‐troposphere interactions. First, the quasi‐biennial oscillation changed to its westerly phase in summer 2015 and the stratospheric polar vortex was stronger in early to midwinter 2015/2016. As blocking did not occur in December, the associated downward propagation signal resulted in a strongly positive AO in late December 2015. Second, after late December, the positive phase of Pacific‐North America pattern became apparent in El Niño event, which strengthened the Aleutian anticyclone in the stratosphere. In addition, an equivalent barotropic (“blocking”) anticyclone was established in the troposphere over Asia. The coexistence of blocking over Asia and North America characterized the negative AO and a strong zonal wave number 2 pattern. Due to stronger zonal wave number 2 signals from the troposphere, the stronger stratospheric polar vortex was elongated, with two cyclonic centers over Asia and the North Atlantic in January. The resultant southward displacement of polar vortices was followed by rare snowfall in the subtropical region of East Asia and a heavy snowstorm on the East Coast of the United States.
Toward understanding the physical link between turbines and microclimate impacts from in situ measurements in a large wind farm
Authors: Rajewski Daniel A. , Takle Eugene S. , Prueger John H. , Doorenbos Russell K.
Published: November 2016

Recent wind farm studies have revealed elevated nighttime surface temperatures but have not validated physical mechanisms that create the observed effects. We report measurements of concurrent differences in surface wind speed, temperature, fluxes, and turbulence upwind and downwind of two turbine lines at the windward edge of a utility‐scale wind farm. On the basis of these measurements, we offer a conceptual model based on physical mechanisms of how wind farms affect their own microclimate. Periods of documented curtailment and zero‐power production of the wind farm offer useful opportunities to rigorously evaluate the microclimate impact of both stationary and operating turbines. During an 80 min nighttime wind farm curtailment, we measured abrupt and large changes in turbulent fluxes of momentum and heat leeward of the turbines. At night, wind speed decreases in the near wake when turbines are off but abruptly increases when turbine operation is resumed. Our measurements are compared with Moderate Resolution Imaging Spectroradiometer Terra and Aqua satellite measurements reporting wind farms to have higher nighttime surface temperatures. We demonstrate that turbine wakes modify surface fluxes continuously through the night, with similar magnitudes during the Terra and Aqua transit periods. Cooling occurs in the near wake and warming in the far wake when turbines are on, but cooling is negligible when turbines are off. Wind speed and surface stratification have a regulating effect of enhancing or decreasing the impact on surface microclimate due to turbine wake effects.
The influence of local sea surface temperatures on Australian east coast cyclones
Authors: Pepler Acacia S. , Alexander Lisa V. , Evans Jason P. , Sherwood Steven C.
Published: November 2016

Cyclones are a major cause of rainfall and extreme weather in the midlatitudes and have a preference for genesis and explosive development in areas where a warm western boundary current borders a continental landmass. While there is a growing body of work on how extratropical cyclones are influenced by the Gulf Stream and Kuroshio Current in the Northern Hemisphere, there is little understanding of similar regions in the Southern Hemisphere including the Australian east coast, where cyclones that develop close to the coast are the main cause of severe weather and coastal flooding. This paper quantifies the impact of east Australian sea surface temperatures (SSTs) on local cyclone activity and behavior, using three different sets of sea surface temperature boundary conditions during the period 2007–2008 in an ensemble of Weather Research and Forecasting Model physics parameterizations. Coastal sea surface temperatures are demonstrated to have a significant impact on the overall frequency of cyclones in this region, with warmer SSTs acting as a trigger for the intensification of weak or moderate cyclones, particularly those of a subtropical nature. However, sea surface temperatures play only a minor role in the most intense cyclones, which are dominated by atmospheric conditions.
A clear‐sky radiation closure study using a one‐dimensional radiative transfer model and collocated satellite‐surface‐reanalysis data sets
Authors: Dolinar Erica K. , Dong Xiquan , Xi Baike , Jiang Jonathan H. , Loeb Norman G.
Published: November 2016

Earth's climate is largely determined by the planet's energy budget, i.e., the balance of incoming and outgoing radiation at the surface and top of atmosphere (TOA). Studies have shown that computing clear‐sky radiative fluxes are strongly dependent on atmospheric state variables, such as temperature and water vapor profiles, while the all‐sky fluxes are greatly influenced by the presence of clouds. NASA‐modeled vertical profiles of temperature and water vapor are used to derive the surface radiation budget from Clouds and Earth Radiant Energy System (CERES), which is regarded as one of the primary sources for evaluating climate change in climate models. In this study, we evaluate the Modern‐Era Retrospective Analysis for Research and Applications version 2 (MERRA‐2) reanalyzed clear‐sky temperature and water vapor profiles with newly generated atmospheric profiles from Department of Energy Atmospheric Radiation Measurement (ARM)‐merged soundings and Aura Microwave Limb Sounder retrievals at three ARM sites. The temperature profiles are well replicated in MERRA‐2 at all three sites, whereas tropospheric water vapor is slightly dry below ~700 hPa. These profiles are then used to calculate clear‐sky surface and TOA radiative fluxes from the Langley‐modified Fu‐Liou radiative transfer model (RTM). In order to achieve radiative closure at both the surface and TOA, the ARM‐measured surface albedos and aerosol optical depths are adjusted to account for surface inhomogeneity. In general, most of the averaged RTM‐calculated surface downward and TOA upward shortwave and longwave fluxes agree within ~5 W/m2 of the observations, which is within the uncertainties of the ARM and CERES measurements. Yet still, further efforts are required to reduce the bias in calculated fluxes in coastal regions.
Timing of the faulting on the Wispy Terrain of Dione based on stratigraphic relationships with impact craters
Authors: Hirata Naoyuki
Published: November 2016

The trailing hemisphere of Dione is characterized by the Wispy Terrain, where it exhibits a hemispheric‐scale network of extensional tectonic faults superposed on the moon's cratered surface. The faults likely reflect past endogenic activity and Dione's interior thermal history. Although fresh exposures of pristine scarps indicate that the timing of the faulting is relatively recent, the absolute age of the faulting remains uncertain. To estimate the timing of the faulting, we investigated stratigraphic relationships between impact craters and faults. Using high‐resolution images obtained by the ISS camera onboard the Cassini spacecraft, we investigated craters with diameters exceeding or equal to 10 km that coincide spatially with the faults and classified the craters as crosscut craters or superposed craters. As a result, at least 82% of the craters were interpreted as clear examples of crosscut craters and 12% of the craters were interpreted to be candidates of superposed craters, although stratigraphic relationships are often ambiguous. The paucity of superposed craters and a predicted cratering rate indicate that the faulting of the Wispy Terrain is 0.30–0.79 Ga. If 12–18% of the craters are assumed to be superposed, the timing of the faulting could be in the range 0.30–0.79 Ga. However, it is possible that the faulting of the Wispy Terrain is still ongoing.
Identification of the vascular endothelial growth factor signalling pathway by quantitative proteomic analysis of rat condylar cartilage
Authors: Jiang Liting , Xie Yinyin , Wei Li , Zhou Qi , Shen Xing , Jiang Xinquan , Gao Yiming
Published: November 2016

Angiogenesis mediated by vascular endothelial growth factor (VEGF) is known to play an important role in regulating cartilage remodelling and endochondral ossification. However, the details of how VEGF signalling mechanisms affect condyle remodelling in response to alterations in functional loading remains unclear. To explore this, eighty 16‐day‐old male SD rats were divided into two equal groups which were fed either a soft/powdery diet or a hard diet for 4 weeks; the stiffness of the diet results in alteration of mastication force and hence temporomandibular joint (TMJ) development. We performed a proteomic analysis of rat condylar cartilage using isobaric tags for relative and absolute quantification (iTRAQ) labelling, followed by 2D nano‐high performance liquid chromatography and MALDI‐TOF/time‐of‐flight technology. After protein identification, we used biological information analysis to identify the differentially expressed proteins associated with the VEGF signalling pathway. Among the identified differentially expressed proteins, we found VEGF signalling mainly via the p44/42 MAPK and p38 mitogen‐activated protein kinase (MAPK) pathways in condylar cartilage, including VEGFD, VGFR2, KPCB, KPCT, KPCZ, ARAF, RASN, PLCG2, PLCG1, JUN and M3K12. Furthermore, four representative protein candidates, VEGF, p38 MAPK and p44/42 MAPK/phospho‐p44/42 MAPK, were confirmed by immunohistochemical staining and western blot. Our data suggest that VEGF might play an important role in TMJ development and remodelling in response to alterations in functional loading through the p44/42 MAPK and p38 MAPK signalling pathway. This study provides new clues to the understanding of the signalling mechanism responsible for VEGF production in response to different masticatory functions at the protein level.
An Engineered Breast Cancer Model on a Chip to Replicate ECM‐Activation In Vitro during Tumor Progression
Authors: Gioiella Filomena , Urciuolo Francesco , Imparato Giorgia , Brancato Virginia , Netti Paolo A.
Published: November 2016

In this work, a new model of breast cancer is proposed featuring both epithelial and stromal tissues arranged on a microfluidic chip. The main task of the work is the in vitro replication of the stromal activation during tumor epithelial invasion. The activation of tumor stroma and its morphological/compositional changes play a key role in tumor progression. Despite emerging evidences, to date the activation of tumor stroma in vitro has not been achieved yet. The tumor‐on‐chip proposed in this work is built in order to replicate the features of its native counterpart: multicellularity (tumor epithelial cell and stromal cell); 3D engineered stroma compartment composed of cell‐assembled extracellular matrix (ECM); reliable 3D tumor architecture. During tumor epithelial invasion the stroma displayed an activation process at both cellular and ECM level. Similarly of what repeated in vivo, ECM remodeling is found in terms of hyaluronic acid and fibronectin overexpression in the stroma compartment. Furthermore, the cell‐assembled ECM featuring the stromal tissue, allowed on‐line monitoring of collagen remodeling during stroma activation process via real time multiphoton microscopy. Also, trafficking of macromolecules within the stromal compartment has been monitored in real time.
Flexible and Stretchable Energy Storage: Recent Advances and Future Perspectives
Authors: Liu Wei , Song Min‐Sang , Kong Biao , Cui Yi
Published: November 2016

Energy‐storage technologies such as lithium‐ion batteries and supercapacitors have become fundamental building blocks in modern society. Recently, the emerging direction toward the ever‐growing market of flexible and wearable electronics has nourished progress in building multifunctional energy‐storage systems that can be bent, folded, crumpled, and stretched while maintaining their electrochemical functions under deformation. Here, recent progress and well‐developed strategies in research designed to accomplish flexible and stretchable lithium‐ion batteries and supercapacitors are reviewed. The challenges of developing novel materials and configurations with tailored features, and in designing simple and large‐scaled manufacturing methods that can be widely utilized are considered. Furthermore, the perspectives and opportunities for this emerging field of materials science and engineering are also discussed.
Extraordinary Figure‐of‐Merit of Magnetic Resonance from Ultrathin Silicon Nanohole Membrane as All‐Dielectric Metamaterial
Authors: Park Sang‐Gil , Lee Youngseop , Kwon Seyong , Yoo SeokJae , Park Q‐Han , Park Je‐Kyun , Jeong Ki‐Hun
Published: November 2016

Metamaterial allows novel nanophotonic applications such as negative permeability, negative refractive index, and near‐zero index. In particular, all‐dielectric metamaterials recently create new opportunities for manipulating electromagnetic fields, taking full advantage of low‐loss, bandwidth enhancement, and isotropic responses. Here a silicon dielectric metamaterial is reported in near‐infrared region, exhibiting extraordinarily figure‐of‐merit, defined by sensitivity (resonance shift/refractive index change) over full width at half maximum, from magnetic resonance shift depending on index changes of surrounding medium. This silicon dielectric metamaterial comprises subwavelength nanohole arrays in a square lattice on an ultrathin amorphous silicon membrane. The ultrathin silicon nanohole membrane is fabricated on a glass wafer by using e‐beam lithography, silicon reactive ion etching, and hydrogen fluoride wet etching. This all‐dielectric metamaterial successfully demonstrates exceptional figure‐of‐merit of 29, which is 7.6 times higher than those values of conventional metamaterials. This novel metamaterial enables not only the label‐free detection of chemical and biological molecules with different mass concentrations but also the in situ reaction monitoring of biochemical molecules.
Current‐Induced Joule Heating and Electrical Field Effects in Low Temperature Measurements on TIPS Pentacene Thin Film Transistors
Authors: Nikiforov Gueorgui O. , Venkateshvaran Deepak , Mooser Sebastian , Meneau Aurélie , Strobel Thomas , Kronemeijer Auke , Jiang Lang , Lee Mi Jung , Sirringhaus Henning
Published: November 2016

The channel temperature (Tch) of solution‐processed 6,13‐bis(triisopropylsilylethynyl)‐pentacene (TIPS pentacene) thin film transistors (TFTs) is closely monitored in real time during current–voltage (I–V) measurements carried out in a He exchange gas cryostat at various base temperatures (Tb) between 300 K and 20 K. This is done using a platinum (Pt) resistance temperature sensor embedded within the transistor channel. Under large gate (Vg) and source‐drain (Vds) voltage biases, an increase inTchis observed, the magnitude of which depends on the thermal conductivity of the substrate. The increase inTchis associated with a simultaneous increase in the transistor drain current (Id) and becomes particularly pronounced at cryogenicTb. These experimental observations are rationalized using a 1D theoretical model and are attributed to current‐induced Joule heating. However, even though the heating of the channel unquestionably plays an important role, the corresponding amount of increase inIdat cryogenicTband large voltage biases cannot be fully accounted for unless at low temperatures μTIPSis enhanced in the presence of strong electrical fields. Therefore it is concluded that theI–Vcharacteristics of TIPS pentacene TFTs at lowTband large voltage biases are a result of a complex interplay between current‐induced Joule heating and electrical field effects.
Highly Sensitive Pressure Sensor Based on Bioinspired Porous Structure for Real‐Time Tactile Sensing
Authors: Kang Subin , Lee Jaehong , Lee Sanggeun , Kim SeulGee , Kim Jae‐Kang , Algadi Hassan , Al‐Sayari Saleh , Kim Dae‐Eun , Kim DaeEun , Lee Taeyoon
Published: November 2016

A flexible pressure sensor with high performances is one of the promising candidates for achieving electronic skins (E‐skin) related to various applications such as wearable devices, health monitoring systems, and artificial robot arms. The sensitive response for external mechanical stimulation is fundamentally required to develop the E‐skin which imitates the function of human skin. The performance of capacitive pressure sensors can be improved using morphologies and structures occurring in nature. In this work, highly sensitive capacitive pressure sensors based on a porous structure of polydimethylsiloxane (PDMS) thin film, inspired on the natural multilayered porous structures seen in mushrooms, diatoms, and spongia offilinalis, have been developed and evaluated. A bioinspired porous dielectric layer is used, resulting in high‐performance pressure sensors with high sensitivity (0.63 kPa−1), high stability over 10 000 cycles, fast response and relaxation times, and extremely low‐pressure detection of 2.42 Pa. Additionally, the resulting pressure sensors are demonstrated to fabricate multipixel arrays, thus achieving successful real‐time tactile sensing of various touch shapes. The developed high‐performance flexible pressure sensors may open new opportunities for innovative applications in advanced human‐machine interface systems, robotic sensory systems, and various wearable health monitoring devices.
Toward High‐Temperature Stability of PTB7‐Based Bulk Heterojunction Solar Cells: Impact of Fullerene Size and Solvent Additive
Authors: Dkhil Sadok Ben , Pfannmöller Martin , Saba Maria Ilenia , Gaceur Meriem , Heidari Hamed , Videlot‐Ackermann Christine , Margeat Olivier , Guerrero Antonio , Bisquert Juan , Garcia‐Belmonte Germa , Mattoni Alessandro , Bals Sara , Ackermann Jörg
Published: November 2016

The use of fullerene as acceptor limits the thermal stability of organic solar cells at high temperatures as their diffusion inside the donor leads to phase separation via Ostwald ripening. Here it is reported that fullerene diffusion is fully suppressed at temperatures up to 140 °C in bulk heterojunctions based on the benzodithiophene‐based polymer (the poly[[4,8‐bis[(2‐ethylhexyl)oxy]‐benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]‐thieno[3,4‐b]thiophenediyl]], (PTB7) in combination with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC70BM). The blend stability is found independently of the presence of diiodooctane (DIO) used to optimize nanostructuration and in contrast to PTB7 blends using the smaller fullerene derivative PC70BM. The unprecedented thermal stability of PTB7:PC70BM layers is addressed to local minima in the mixing enthalpy of the blend forming stable phases that inhibit fullerene diffusion. Importantly, although the nanoscale morphology of DIO processed blends is thermally stable, corresponding devices show strong performance losses under thermal stress. Only by the use of a high temperature annealing step removing residual DIO from the device, remarkably stable high efficiency solar cells with performance losses less than 10% after a continuous annealing at 140 °C over 3 days are obtained. These results pave the way toward high temperature stable polymer solar cells using fullerene acceptors.
A case for cannabidiol in Wolf–Hirschhorn syndrome seizure management
Authors: Ho Karen S. , Wassman E. Robert
Published: November 2016

Complex, and sometimes intractable, seizures affect the quality of life and cognitive development of over 90% of individuals with Wolf–Hirschhorn syndrome (WHS). Fine resolution genotype–phenotype mapping of the WHS locus recently identified a candidate gene whose probable function has led to insights into a mechanism connecting WHS seizures with those of Dravet syndrome, a distinct condition caused by mutations in SCN1A and SCN1B. In addition to this possible molecular mechanistic connection, these disorders' seizures share a strikingly similar constellation of features, including clinical presentation, seizure types, early age of onset, EEG pattern, and responses to specific anti‐epileptic drugs. Based in part on these similarities, we suggest that a highly successful Phase III clinical trial of a formulation of cannabidiol for Dravet syndrome seizures may be directly translatable into possible benefits for WHS individuals with challenging seizure patterns. © 2016 Wiley Periodicals, Inc.
Nickel‐Catalyzed C(Aryl)−O Bond Activation/Cross‐Coupling Reaction of Carbazoles with Methyl Grignard: Synthesis of Ellipticine
Authors: Rasheed Sk. , Rao Desaboini Nageswar , Das Parthasarathi
Published: November 2016

A nickel‐catalyzed cross‐coupling reaction between methoxy‐substituted carbazoles and MeMgBr has been developed. This protocol for the cleavage of the C(aryl)−OMe was used to efficiently assemble various methyl‐substituted carbazoles and successfully applied to the total synthesis of the antitumor agent ellipticine.
Aerobic Oxidation of Benzylic sp3 C−H Bonds through Cooperative Visible‐Light Photoredox Catalysis of N‐Hydroxyimide and Dicyanopyrazine
Authors: Liu Xinfei , Lin Lu , Ye Xinyi , Tan Choon‐Hong , Jiang Zhiyong
Published: November 2016

A visible‐light‐driven cooperative catalysis between dicyanopyrazine‐derived chromophore (DPZ) and N‐hydroxyimide has been developed. Under irradiation with a low‐energy and operationally convenient visible light, the cooperative catalytic system could facilitate the aerobic oxygenation of a series of benzylic sp3 C−H bonds through a photoredox pathway. The method provides a novel approach to access valuable carbonyls from benzylic methylenes and benzylic alcohols in moderate to excellent yields (up to 93 %).
Total Synthesis of Lingzhiol and its Analogues through the Wittig Reaction of an Oxocyclopentane Carboxylate
Authors: Rengarasu Rathikrishnan , Maier Martin E.
Published: November 2016

The biosynthesis of polycyclic natural product lingzhiol (1) through an intramolecular Friedel–Crafts alkylation reaction of an aryl‐substituted cyclopentane epoxide (22) was attempted. The synthesis of this endocyclic epoxide involved the alkylation of cyclopentane carboxylate 14 with alkyl iodide 25 to afford ketoester 26. Subsequent Wittig olefination led to exocyclic alkene exo‐15 in good yield. Epoxidation, opening of the epoxide to generate allyl alcohol 29, and a second epoxidation reaction afforded compounds 22 and 31. However, presumably owing to stereoelectronic effects, the cyclization of these substrates into polycycles 17 and 32, respectively, was unsuccessful. Nevertheless, the Wittig reaction to afford exo‐15 allowed us to converge with the previously reported route of Qin et al., which featured the cyclization of spiro epoxide 16. Thus, lingzhiol is now available in only nine steps. Various analogues of lingzhiol were also prepared, including desoxy derivative 37, quinone 38, mono‐methoxy‐deoxy derivative 39, and ketone 40.
Computed tomography–based quantification of lesion water uptake identifies patients within 4.5 hours of stroke onset: A multicenter observational study
Authors: Minnerup Jens , Broocks Gabriel , Kalkoffen Judith , Langner Soenke , Knauth Michael , Psychogios Marios Nikos , Wersching Heike , Teuber Anja , Heindel Walter , Eckert Bernd , Wiendl Heinz , Schramm Peter , Fiehler Jens , Kemmling André
Published: November 2016

Objective

Many patients with stroke cannot receive intravenous thrombolysis because the time of symptom onset is unknown. We tested whether computed tomography (CT)‐based quantification of water uptake in the ischemic tissue can identify patients with stroke onset within 4.5 hours, the time window of thrombolysis.

Methods

Perfusion CT was used to identify ischemic brain tissue, and its density was measured in native CT and related to the density of the corresponding area of the contralateral hemisphere to quantify lesion water uptake. The optimal cutoff value of water uptake distinguishing stroke onset within and beyond 4.5 hours was calculated in patients with proximal middle cerebral artery occlusion (derivation cohort) with known time of symptom onset. The so‐derived cutoff value was validated in a prospective cohort from other stroke centers.

Results

Of 178 patients of the derivation cohort, 147 (82.6%) had CT within 4.5 hours. Percentage water uptake was significantly lower in patients with stroke onset within compared to beyond 4.5 hours. The area under the receiver operating characteristic curve for distinguishing these patient groups according to percentage water uptake was 0.999 (95% confidence interval = 0.996–1.000, p < 0.001) with an optimal cutoff value of 11.5%. Applying this cutoff to the validation cohort of 240 patients, sensitivity was 98.6%, specificity 90.5%, positive predictive value 99.1%, and negative predictive value 86.4%.

Interpretation

Quantification of brain water uptake identifies stroke patients with symptom onset within 4.5 hours with high accuracy and may guide the decision to use thrombolysis in patients with unknown time of stroke onset. Ann Neurol 2016;80:924–934
Redox‐Flow‐Batterien: von metallbasierten zu organischen Aktivmaterialien
Authors: Winsberg Jan , Hagemann Tino , Janoschka Tobias , Hager Martin D. , Schubert Ulrich S.
Published: November 2016

Die Forschung auf dem Gebiet der Redox‐Flow‐Batterie (RFB) erlebt momentan einen signifikanten Aufschwung, der durch den wachsenden Bedarf angetrieben wird, immer größere Elektrizitätsmengen aus erneuerbaren Quellen zwischenzuspeichern. RFBs sind vielversprechende Kandidaten, um in Kombination mit Photovoltaik‐ und Windkraftanlagen sogenannte “Smart Grids” (d. h. intelligente Stromnetze) aufzubauen. Um das Ziel eines “grünen”, sicheren und kostengünstigen Energiespeichers zu erreichen, wurde in den vergangen Jahren der Fokus von metallbasierten Materialien mehr und mehr auf organische Aktivmaterialien verlagert. In diesem Aufsatz wird eine Übersicht über verschiedene Flow‐Batterie‐Systeme gegeben. Dafür werden relevante Beiträge über die Geschichte dieser Systeme diskutiert und die Entwicklung innerhalb der letzten Jahre von klassischen, anorganischen über organisch/anorganische hin zu Redox‐Flow‐Batterien, welche innerhalb des Katholyten und Anolyten redoxaktive organische Materialien nutzen, aufgezeigt. Wir analysieren die verfügbaren Technologien in Bezug auf deren technische, ökonomische und umweltbezogene Aspekte und diskutieren Vorteile und Beschränkungen dieser Systeme. Zum Abschluss werden weitere technologische Herausforderungen und potenzielle Forschungsmöglichkeiten erörtert.
Zuckerseitige Wechselwirkungen in einem DNA‐RNA‐G‐Quadruplex: Hinweise auf sequentielle C−H⋅⋅⋅O‐Wasserstoffbrücken als Beitrag zur RNA‐Quadruplex‐Faltung
Authors: Dickerhoff Jonathan , Appel Bettina , Müller Sabine , Weisz Klaus
Published: November 2016

DNA‐G‐Quadruplexe wurden systematisch an anti‐dG‐Positionen mit einzelnen Riboguanosin‐Bausteinen (rG) modifiziert. Zirkulardichroismus‐ und NMR‐Experimente bestätigen den Erhalt der nativen Quadruplex‐Topologie für den Großteil der DNA‐RNA‐Hybridstrukturen. Veränderungen in der C8‐chemischen Verschiebung von Guanosinen an der 3′‐Seite einer rG‐Substitution im Quadruplex‐Kern legen C8‐H⋅⋅⋅O‐Wasserstoffbrücken mit dem O2′ des C2′‐endo‐Ribonukleotids nahe. Eine geometrische Analyse bekannter, hochaufgelöster Strukturen deutet darauf hin, dass entsprechende Wechselwirkungen ein allgemeineres Merkmal in RNA‐Quadruplexen sind und möglicherweise zur beobachteten Präferenz für parallele Topologien beitragen.
Der Einsatz von N‐heterocyclischen Vinylliganden zur Isolierung stabiler Divinylgermylene und eines Germylium‐Kations
Authors: Hering‐Junghans Christian , Andreiuk Patricia , Ferguson Michael J. , McDonald Robert , Rivard Eric
Published: November 2016

Es werden zwei effiziente Methoden präsentiert, um σ‐ und π‐Elektronen‐donierende N‐heterocyclische Vinylgruppen an Hauptgruppenelementen (E) zu installieren: Halogensilan‐Eliminierung und baseninduzierte E‐C Bindungsbildung. Die Platzierung von zwei NHC=CH−‐Liganden (NHC=N‐heterocyclisches Carben) an einem GeII‐Zentrum resultiert in einem zweifach koordinierten Germylen, einem schweren Kongener der flüchtigen Divinylcarbene. Die Fähigkeit dieses vinylischen Ligandengerüstes, als π‐Donor hochreaktive Spezies zu stabilisieren wurde des Weiteren durch die Synthese eines dreifach koordinierten Germylium‐Kations R3Ge+ gezeigt.
A Million Turnover Molecular Anode for Catalytic Water Oxidation
Authors: Creus Jordi , Matheu Roc , Peñafiel Itziar , Moonshiram Dooshaye , Blondeau Pascal , Benet‐Buchholz Jordi , García‐Antón Jordi , Sala Xavier , Godard Cyril , Llobet Antoni
Published: November 2016

Molecular ruthenium‐based water oxidation catalyst precursors of general formula [Ru(tda)(Li)2] (tda2− is [2,2′:6′,2′′‐terpyridine]‐6,6′′‐dicarboxylato; L1=4‐(pyren‐1‐yl)‐N‐(pyridin‐4‐ylmethyl)butanamide, 1 b; L2=4‐(pyren‐1‐yl)pyridine), 1 c), have been prepared and thoroughly characterized. Both complexes contain a pyrene group allowing ready and efficiently anchoring via π interactions on multi‐walled carbon nanotubes (MWCNT). These hybrid solid state materials are exceptionally stable molecular water‐oxidation anodes capable of carrying out more than a million turnover numbers (TNs) at pH 7 with an Eapp=1.45 V vs. NHE without any sign of degradation. XAS spectroscopy analysis before, during, and after catalysis together with electrochemical techniques allow their unprecedented oxidative ruggedness to be monitored and verified.
Redox‐Flow Batteries: From Metals to Organic Redox‐Active Materials
Authors: Winsberg Jan , Hagemann Tino , Janoschka Tobias , Hager Martin D. , Schubert Ulrich S.
Published: November 2016

Research on redox‐flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of “green”, safe, and cost‐efficient energy storage, research has shifted from metal‐based materials to organic active materials in recent years. This Review presents an overview of various flow‐battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox‐active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted.
Nickel‐Catalyzed Alkoxy–Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers
Authors: Guo Lin , Liu Xiangqian , Baumann Christoph , Rueping Magnus
Published: November 2016

A nickel‐catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B‐alkyl 9‐BBN and trialkylborane reagents that involves the cleavage of stable C(sp2)−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp2)−C(sp3) bonds that does not suffer from β‐hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method.
Arsole‐Containing π‐Conjugated Polymer by the Post‐Element‐Transformation Technique
Authors: Matsumura Yoshimasa , Ishidoshiro Makoto , Irie Yasuyuki , Imoto Hiroaki , Naka Kensuke , Tanaka Kazuyoshi , Inagi Shinsuke , Tomita Ikuyoshi
Published: November 2016

A synthetic method to obtain an arsole‐containing π‐conjugated polymer by the post‐transformation of the organotitanium polymer titanacyclopentadiene‐2,5‐diyl unit with an arsenic‐containing building block is described. The UV/Vis absorption maximum and onset of the polymer were observed at 517 nm and 612 nm, respectively. The polymer exhibits orange photoluminescence with an emission maximum (Emax) of 600 nm and the quantum yield (Φ) of 0.05. The polymer proved to exhibit a quasi‐reversible redox behavior in its cyclic voltammetric (CV) analysis. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were estimated to be −5.43 and −3.24 eV, respectively, from the onsets for oxidation and reduction signals in the CV analysis. Further chemical modification of the arsole unit in the π‐conjugated polymer by complexation of gold(I) chloride occurred smoothly resulting in the bathochromic shift of the UV/Vis absorption and lowering of the LUMO energy level.
Using N‐Heterocyclic Vinyl Ligands to Access Stable Divinylgermylenes and a Germylium Cation
Authors: Hering‐Junghans Christian , Andreiuk Patricia , Ferguson Michael J. , McDonald Robert , Rivard Eric
Published: November 2016

Two efficient methods are presented to install σ‐ and π‐electron‐donating N‐heterocyclic vinyl groups onto main‐group elements (E): halosilane elimination and base‐induced E−C bond formation. Placement of two NHC=CH− ligands (NHC=N‐heterocyclic carbene) onto a GeII center affords a two‐coordinate germylene, a heavy congener of the elusive divinyl carbenes. The π‐donating ability of this vinylic ligand scaffold was further demonstrated by the synthesis of a three‐coordinate germylium cation R3Ge+.
The first oxalamide‐bridged ferrocene: Facile synthesis, preliminary conformational analysis and biological evaluation
Authors: Kovač Veronika , Radošević Kristina , Bebek Anica , Makarević Janja , Štefanić Zoran , Barišić Lidija , Žinić Mladen , Rapić Vladimir
Published: November 2016

tert‐Butyl‐1′‐methoxycarbonyl‐1‐ferrocenecarbamate (1) was Boc‐deprotected to give free amine which underwent oxalyl chloride‐mediated dimerization. The structure of the so‐obtained oxalamide‐bridged ferrocene 2 was elucidated using infrared and NMR (1H, 13C, COSY, NOESY, HSQC, HMBC) spectroscopies, crystal structure analysis, and electrospray ionization and high‐resolution mass spectrometry. The preliminary conformational analysis in solution suggested the intramolecular engagement of oxalamide protons, while single‐crystal analysis revealed an intermolecular hydrogen‐bonding pattern. Also, the effect of oxalamide‐bridged ferrocene 2 on cell viability of three human cell lines (HEK293T, HeLa and HepG2) was tested. In vitro screening revealed proliferative as well as cytotoxic effects of the tested compound in the applied concentration range (1–350 μM) on HEK293T and HepG2 cells. Stimulatory effect on cell growth was the most pronounced for normal HEK293T cells, while the highest cytotoxic effect was observed towards HeLa tumour cells and it was dose‐dependent. The observed dual biological activity of 2 implies its potential application in drug development.
Morphological evolution and mechanical property enhancement of natural rubber/polypropylene blend through compatibilization by nanoclay
Authors: Masa Abdulhakim , Saito Hiromu , Sakai Tadamoto , Kaesaman Azizon , Lopattananon Natinee
Published: November 2016

Nanocomposites of natural rubber (NR)/polypropylene (PP) (80/20 wt %) blends filled with 5 phr pristine clay were prepared by melt‐mixing process. Effects of clay incorporation technique via conventional melt‐mixing (CV) and masterbatch mixing (MB) methods on nanostructure and properties of the blend nanocomposites were investigated. The XRD, SAXS, WAXD, and TEM results showed that the clays in the NR/PP blend nanocomposites were presented in different states of dispersion and were locally existed at the interface between NR and PP as well as dispersed in the NR matrix. The presence of clay caused unique morphological evolution such as fine fibrillar PP domains. The tensile strength was improved over the unfilled NR/PP blends by 53% and 224%, and the storage modulus at 25 °C was increased by 78% and 120% for the NR/PP/clay nanocomposites prepared by CV and MB methods, respectively. Significant improvement in both properties was particularly obtained from the MB method due to finer dispersion fibrillar PP phase in the NR matrix and stronger interfacial adhesion between NR and PP fibers, as suggested from DMA. The oil resistance of blend nanocomposites was also improved over that of the unfilled NR/PP blend, and this property was further progressed by the masterbatch mixing method. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2017,134, 44574.
Electro‐conductive cotton fabric prepared by electron beam induced graft polymerization and electroless deposition technology
Authors: Krishnanand Kumar , Thite Amol , Mukhopadhyay Anjan K.
Published: November 2016

Cotton fabric has been made electro‐conductive by electroless deposition of silver from its salt solution. Preparation process involved radical graft polymerization of glycidyl methacrylate monomer on plain woven cotton fabric using 10 kGy dose of electron beam irradiation, and then hydrazination of the epoxy ring of the monomer to introduce reducing agents into the fibre chemical structure. These reducing agents are sites for metal particle deposition. The chemical modifications were characterized by infrared spectroscopic studies. From X‐ray diffraction pattern analysis, the average size of these deposited silver metallic particles is 41 nm. These are observed as heterogeneous deposition on the fibre surface in scanning electron images. From thermogravimetric analysis, around 7.5% of the metal plated fabric weight is silver. The deposited silver nanoparticles make a conductive pathway through contact network, and this network brings a drop in average value of surface resistivity of the cotton fabric from 109 Ω/sq to 3.63 Ω/sq for the metallised fabric. Such prepared electro‐conductive fabric showed very good wash durability of electrical conductivity up to 15 washing cycles when carried out as per ISO‐105‐C10:2006 (E) test no. A (1) standard, indicating firm adherence of silver nanoparticles to the fabric surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44576.