bluuebunny/crossref_metadata_2025 huggingface dataset:
L’essayiste discret
Authors: Daunais Isabelle
Published: May 2017

Si l’oeuvre de Gilles Marcotte est reconnue comme celle d’un critique majeur de la littérature québécoise, elle est beaucoup moins souvent lue comme celle d’un essayiste. Il est vrai que cette oeuvre ne correspond pas tout à fait aux critères par lesquels l’essai est généralement identifié, et qui tiennent à la position de distinction ou de distance de l’essayiste face au monde. Gilles Marcotte écrit au contraire depuis la conscience forte d’une communauté – une communauté qui inclut les vivants et les morts, les lecteurs ordinaires –, sans laquelle il ne saurait y avoir pour lui ni art ni littérature. Par cette position au sein du monde, il pratique une forme plus discrète d’essai, mais aussi, à bien des égards, plus singulière.
Gilles Marcotte, Montréaliste
Authors: Cambron Micheline
Published: May 2017

Cet article s’attache aux divers sens et usages liés dans oeuvre de Gilles Marcotte à Montréal comme lieu polymorphe, à la fois thème et structure, temps et espace. Proche en cela de la notion d’« espace habité » de Michel de Certeau, l’idée selon laquelle on écrit et lit différemment selon les lieux est déjà présente dans La littérature et le reste et réunit les essais du volume Écrire à Montréal. Dans l’oeuvre de Marcotte, ville et écriture se rejoignent dans une commune ouverture aux possibles, dans la pluralité et le mélange, et la radicalité du partage du sens qu’ils induisent. En témoigne le rôle heuristique de Montréal qui apparaît dans Le roman à l’imparfait tandis que d’autres textes de Marcotte, notamment sa contribution à Montréal imaginaire, montrent que le désordre montréalais trouve plutôt à loger dans les oeuvres faiblement légitimées de la littérature populaire ; mystères urbains, récits journalistiques, romans obscurs. Les villes, dans l’oeuvre essayistique, critique et fictionnelle de Gilles Marcotte, n’ont pas la fermeté ontologique qu’une conception réaliste tendrait à leur attribuer, elles relèvent plutôt du mouvement de l’esprit qui les fait advenir dans l’ordre du discours et sont indissociables du projet intellectuel qu’elles manifestent. Ce faisant Gilles Marcotte rend la ville habitable.
LA ACOMODACIÓN POR MOTIVOS RELIGIOSOS EN EL MODELO PERUANO DE RELACIONES IGLESIA ESTADO
Authors:   Universidad de Piura (Perú), Mosquera Susana
Published: May 2017

Este trabajo quiere presentar el sistema jurí­dico peruano de relaciones iglesia estado, un modelo de colaboración que evoluciona no sin dificultades por el peso que arrastra de una anterior etapa de confesionalidad estatal católica. En esa evolución, la diversidad religiosa de la sociedad peruana actual desempeña un papel esencial pero obliga a encontrar respuesta a las posibles dificultades que presenta la convivencia religiosa plural. Las reglas de acomodación tienen la naturaleza adecuada para dar solución a esos problemas, pero veremos que son todaví­a poco conocidas y las oportunidades judiciales para haberlas aplicado han sido desperdiciadas.
EVALUACIÓN DEL SISTEMA JURÍDICO DE RECONOCIMIENTO DEL FENÓMENO RELIGIOSO EN CHILE 1999-2013
Authors:   Universidad de Talca, Del Picó Jorge
Published: May 2017

El artí­culo analiza los resultados del estudio de campo aplicado el año 2016 para evaluar la eficacia de la normativa jurí­dica que rige en Chile a las confesiones organizadas como entidades religiosas, teniendo como horizonte verificador de su efectividad cualitativa el asentamiento de los principios de igualdad y libertad religiosa, en la perspectiva de contribuir al análisis multidisciplinario del modo en que el Estado ha reconocido la relevancia de la religión en la sociedad chilena a partir de la aprobación de la Ley de Cultos de 1999, dando cuenta del grado de conocimiento del régimen legal vigente aplicable al reconocimiento jurí­dico o constitución legal de las organizaciones religiosas, la percepción de satisfacción sobre su contenido preceptivo por parte de sus destinatarios y una aproximación a una tipologí­a de las entidades religiosas chilenas
ÓRGANOS DE REFERENCIA IBÉRICOS E IBEROAMERICANOS EN LA GESTIÓN PÚBLICA DEL HECHO RELIGIOSO
Authors:   Universidad Autónoma de Madrid (España), Sánchez Isidoro Martín
Published: May 2017

ÓRGANOS DE REFERENCIA IBÉRICOS E IBEROAMERICANOS EN LA GESTIÓN PÚBLICA DEL HECHO RELIGIOSO M. GONZÁLEZ S., 1a ed. Pamplona, Editorial Thomson Reuters-Aranzadi, Cizur Menor, 2017, 226 pp. ISBN: 978-84-915217-4-7
Testing the capability of ORCHIDEE land surface model to simulate Arctic ecosystems: Sensitivity analysis and site‐level model calibration
Authors: Dantec‐Nédélec S. , Ottlé C. , Wang T. , Guglielmo F. , Maignan F. , Delbart N. , Valdayskikh V. , Radchenko T. , Nekrasova O. , Zakharov V. , Jouzel J.
Published: May 2017

The ORCHIDEE land surface model has recently been updated to improve the representation of high‐latitude environments. The model now includes improved soil thermodynamics and the representation of permafrost physical processes (soil thawing and freezing), as well as a new snow model to improve the representation of the seasonal evolution of the snow pack and the resulting insulation effects. The model was evaluated against data from the experimental sites of the WSibIso‐Megagrant project (www.wsibiso.ru). ORCHIDEE was applied in stand‐alone mode, on two experimental sites located in the Yamal Peninsula in the northwestern part of Siberia. These sites are representative of circumpolar‐Arctic tundra environments and differ by their respective fractions of shrub/tree cover and soil type. After performing a global sensitivity analysis to identify those parameters that have most influence on the simulation of energy and water transfers, the model was calibrated at local scale and evaluated against in situ measurements (vertical profiles of soil temperature and moisture, as well as active layer thickness) acquired during summer 2012. The results show how sensitivity analysis can identify the dominant processes and thereby reduce the parameter space for the calibration process. We also discuss the model performance at simulating the soil temperature and water content (i.e., energy and water transfers in the soil‐vegetation‐atmosphere continuum) and the contribution of the vertical discretization of the hydrothermal properties. This work clearly shows, at least at the two sites used for validation, that the new ORCHIDEE vertical discretization can represent the water and heat transfers through complex cryogenic Arctic soils—soils which present multiple horizons sometimes with peat inclusions. The improved model allows us to prescribe the vertical heterogeneity of the soil hydrothermal properties.
Impact of detrained cumulus on climate simulated by the Community Atmosphere Model Version 5 with a unified convection scheme
Authors: Park Sungsu , Baek Eun‐Hyuk , Kim Baek‐Min , Kim Seong‐Joong
Published: May 2017

Cumulus elements generated by detraining convective condensate–detrained cumulus–are added to the Community Atmosphere Model Version 5 (CAM5) combined with a Unified Convection Scheme (UNICON). Instead of evaporating convective liquids detrained into clear portions, we diagnosed a new detrained cumulus that is horizontally nonoverlapped with cumulus and stratus in each layer by assuming a steady state balance between the detrainment rate of cumulus condensates and the dissipation rate of detrained condensates by entrainment mixing with environmental air. The addition of detrained cumulus was found to substantially improve the simulation of low‐level clouds and the associated shortwave cloud radiative forcing, particularly in the subtropical trade cumulus regime. In addition to the mean climate, successful simulations of the diurnal cycle of precipitation, Madden‐Julian Oscillation, and Kelvin wave were also well maintained.
Valuing environmental services provided by local stormwater management
Authors: Brent Daniel A. , Gangadharan Lata , Lassiter Allison , Leroux Anke , Raschky Paul A.
Published: May 2017

The management of stormwater runoff via distributed green infrastructures delivers a number of environmental services that go beyond the reduction of flood risk, which has been the focus of conventional stormwater systems. Not all of these services may be equally valued by the public, however. This paper estimates households' willingness to pay (WTP) for improvements in water security, stream health, recreational and amenity values, as well as reduction in flood risk and urban heat island effect. We use data from nearly 1000 personal interviews with residential homeowners in Melbourne and Sydney, Australia. Our results suggest that the WTP for the highest levels of all environmental services is A$799 per household per year. WTP is mainly driven by residents valuing improvements in local stream health, exemptions in water restrictions, the prevention of flash flooding, and decreased peak urban temperatures respectively at A$297, A$244, A$104 and A$65 per year. We further conduct a benefit transfer analysis and find that the WTP and compensating surplus are not significantly different between the study areas. Our findings provide additional support that stormwater management via green infrastructures have large nonmarket benefits and that, under certain conditions, benefit values can be transferred to different locations.
Validating a universal model of particle transport lengths with laboratory measurements of suspended grain motions
Authors: Naqshband Suleyman , McElroy Brandon , Mahon Robert C.
Published: May 2017

The mechanics of sediment transport are of fundamental importance for fluvio‐deltaic morphodynamics. The present study focuses on quantifying particle motions and trajectories across a wide range of flow conditions. In particular, a continuous model is presented that predicts particle travel distances for saltation and suspension based on Rouse number and relative grain roughness. By utilizing a series of eight video cameras in a plexiglass flume direct measurements of the distributions of particle travel distances (excursion lengths) were obtained. To this end, experiments were carried out in dark under black lights with fluorescent painted plastic and quartz sand particles. For relatively high Rouse numbers indicating bed load dominant transport regime (
), particle motion is governed by the effect of gravitational forces (settling velocities) and measured excursion lengths closely follow a Gaussian distribution. For
, particle motion is equally subjected to both gravitational and turbulent forces. Consequently, measured excursion lengths exhibit a bimodal distribution with two distinct peaks. As turbulent fluctuations increase and dominate particle motion over gravity (
), distributions of excursion lengths become unimodal and negative‐skewed with mean values deviating from the modes. The predicted trend of linearly increasing excursion lengths with decreasing Rouse numbers is consistent with measured excursion lengths across a wide range of Rouse numbers
). Furthermore, measured excursion lengths are observed to fit within the predicted range of excursion lengths with no significant difference between measured excursion lengths of plastic and quartz sand particles.
The role of rating curve uncertainty in real‐time flood forecasting
Authors: Ocio David , Le Vine Nataliya , Westerberg Ida , Pappenberger Florian , Buytaert Wouter
Published: May 2017

Data assimilation has been widely tested for flood forecasting, although its use in operational systems is mainly limited to a simple statistical error correction. This can be due to the complexity involved in making more advanced formal assumptions about the nature of the model and measurement errors. Recent advances in the definition of rating curve uncertainty allow estimating a flow measurement error that includes both aleatory and epistemic uncertainties more explicitly and rigorously than in the current practice. The aim of this study is to understand the effect such a more rigorous definition of the flow measurement error has on real‐time data assimilation and forecasting. This study, therefore, develops a comprehensive probabilistic framework that considers the uncertainty in model forcing data, model structure, and flow observations. Three common data assimilation techniques are evaluated: (1) Autoregressive error correction, (2) Ensemble Kalman Filter, and (3) Regularized Particle Filter, and applied to two locations in the flood‐prone Oria catchment in the Basque Country, northern Spain. The results show that, although there is a better match between the uncertain forecasted and uncertain true flows, there is a low sensitivity for the threshold exceedances used to issue flood warnings. This suggests that a standard flow measurement error model, with a spread set to a fixed flow fraction, represents a reasonable trade‐off between complexity and realism. Standard models are therefore recommended for operational flood forecasting for sites with well‐defined stage‐discharge curves that are based on a large range of flow observations.
Mercury concentrations and pools in four adjacent coniferous and deciduous upland forests in Beijing, China
Authors: Zhou Jun , Wang Zhangwei , Zhang Xiaoshan , Gao Yu
Published: May 2017

Understanding of forest mercury (Hg) pools is important for quantifying the global atmospheric Hg removal. We studied gaseous elemental Hg (GEM) concentrations, litterfall Hg depositions, and pool sizes in four adjacent stands at Mount Dongling to assess Hg dynamics in the forested catchment and the potential of Hg release during wildfires. The average GEM concentration was 2.5 ± 0.5 ng m−3, about 1.5 times of the background levels in the Northern Hemisphere. In all four stands, Hg concentrations increase in the following order: bole wood < branch/twig < bark < mineral soil < needles/leaves < litterfall < Oi litter < Oe soil < Oa organic soil. The Hg pools of aboveground biomass were comparable in the forests of larch, oak, and Chinese pine, which were much greater than that of mixed broadleaf stands due to lower biomass. The total Hg pools in ecosystems were similar in the four stands, because of the comparable Hg pool in the soil horizons (0–40 cm), which accounted for over 97% of the total ecosystem Hg storage in the four stands. Although Hg pools of the forest ecosystem in north China were comparable to North America and North Europe, Hg storage in forests constituted a high threat for large Hg emission pulses to the atmosphere by wildfires. The potential Hg emissions from the combustion at the four stands were ranged from 0.675 to 1.696 mg m−2.
Changes in the structure and propagation of the MJO with increasing CO2
Authors: Adames Ángel F. , Kim Daehyun , Sobel Adam H. , Del Genio Anthony , Wu Jingbo
Published: May 2017

Changes in the Madden‐Julian Oscillation (MJO) with increasing CO2 concentrations are examined using the Goddard Institute for Space Studies Global Climate Model (GCM). Four simulations performed with fixed CO2 concentrations of 0.5, 1, 2, and 4 times preindustrial levels using the GCM coupled with a mixed layer ocean model are analyzed in terms of the basic state, rainfall, moisture and zonal wind variability, and the structure and propagation of the MJO. The GCM simulates basic state changes associated with increasing CO2 that are consistent with results from earlier studies: column water vapor increases at ∼7.1% K−1, precipitation also increases but at a lower rate (∼3% K−1), and column relative humidity shows little change. Moisture and rainfall variability intensify with warming while zonal wind variability shows little change. Total moisture and rainfall variability increases at a rate this is similar to that of the mean state change. The intensification is faster in the MJO‐related anomalies than in the total anomalies, though the ratio of the MJO band variability to its westward counterpart increases at a much slower rate. On the basis of linear regression analysis and space‐time spectral analysis, it is found that the MJO exhibits faster eastward propagation, faster westward energy dispersion, a larger zonal scale, and deeper vertical structure in warmer climates.
Curcumin suppresses gastric cancer by inhibiting gastrin‐mediated acid secretion
Authors: Zhou Shufen , Yao Dongjie , Guo Ling , Teng Ling
Published: May 2017

Hyperacidity in the stomach is known to promote the progression of gastric cancer. The plant‐derived chemotherapeutic curcumin is used to treat gastric cancer. The objective of this study was to investigate whether curcumin regulates gastrin‐mediated acid secretion in suppressing gastric cancer. Gastric cancer cells were treated with 25 μm curcumin, followed by Annexin V/propidium iodide double‐staining assay to evaluate cell apoptosis. Western blot analysis was used to analyze caspase‐3 expression in response to curcumin treatment. Gastrin levels in culture medium were also monitored. Mice bearing gastric cancers were treated with curcumin, followed by analysis of tumor caspase‐3 expression, gastric acid pH, and gastric secretion in serum. Curcumin prominently inhibited gastric cancer cell proliferation and promoted cell apoptosis. Caspase‐3 was upregulated by curcumin treatment. Curcumin also reduced gastrin secretion. Curcumin dramatically inhibited tumor growth, increased gastric pH, and reduced gastric secretion. In gastric cancer, curcumin suppresses gastrin‐mediated acid secretion, which inhibits gastric cancer progression.
Metabolic Reprogramming of Macrophages Exposed to Silk, Poly(lactic‐co‐glycolic acid), and Silica Nanoparticles
Authors: Saborano Raquel , Wongpinyochit Thidarat , Totten John D. , Johnston Blair F. , Seib F. Philipp , Duarte Iola F.
Published: May 2017

Monitoring macrophage metabolism in response to nanoparticle exposure provides new insights into biological outcomes, such as inflammation or toxicity, and supports the design of tailored nanomedicines. This paper describes the metabolic signature of macrophages exposed to nanoparticles ranging in diameter from 100 to 125 nm and made from silk, poly(lactic‐co‐glycolic acid) or silica. Nanoparticles of this size and type are currently at various stages of preclinical and clinical development for drug delivery applications. 1H NMR analysis of cell extracts and culture media is used to quantify the changes in the intracellular and extracellular metabolomes of macrophages in response to nanoparticle exposure. Increased glycolytic activity, an altered tricarboxylic acid cycle, and reduced ATP generation are consistent with a proinflammatory phenotype. Furthermore, amino acids possibly arising from autophagy, the creatine kinase/phosphocreatine system, and a few osmolytes and antioxidants emerge as important players in the metabolic reprogramming of macrophages exposed to nanoparticles. This metabolic signature is a common response to all nanoparticles tested; however, the direction and magnitude of some variations are clearly nanoparticle specific, indicating material‐induced biological specificity. Overall, metabolic reprogramming of macrophages can be achieved with nanoparticle treatments, modulated through the choice of the material, and monitored using 1H NMR metabolomics.
Injectable Supramolecular Hydrogels as Delivery Agents of Bcl‐2 Conversion Gene for the Effective Shrinkage of Therapeutic Resistance Tumors
Authors: Liu Xuan , Chen Xiaohong , Chua Ming Xuan , Li Zibiao , Loh Xian Jun , Wu Yun‐Long
Published: May 2017

Injectable hydrogels to deliver therapeutic genes in a minimally invasive manner and to achieve long term sustained release at tumor sites to minimize side effects are attractive for cancer therapy and precision medicine, but its rational design remains a challenge. In this report, an injectable supramolecular hydrogel system is designed based on the polypesudorotaxane formation between α‐cyclodextrin (α‐CD) and cationic methoxy‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone)‐b‐poly(ethylene imine) (MPEG–PCL–PEI) copolymer, with the ability to form polyplexes with anionic plasmid DNA for effective sustained gene delivery. To be mentioned, the MPEG–PCL–PEI copolymers show similar pDNA binding ability, better gene transfection efficiency, lower cytotoxicity than nonviral gene transfection gold standard PEI (25 kDa), due to the formation of micelles and more stable polyplexes. More importantly, this MPEG–PCL–PEI/α‐CD/pDNA supramolecular hydrogel shows a sustained release of pDNA in form of polyplex for up to 7 d. By taking these advantages, this supramolecular hydrogel system is applied as an injectable carrier for sustained Bcl‐2 conversion gene release, in an in vivo rodent model of therapeutic resistant hepatocarcinoma with high expression of antiapoptotic Bcl‐2 protein. This work represents the first time that injectable MPEG–PCL–PEI/α‐CD supramolecular hydrogels possess good controllable release effect of Bcl‐2 conversion genes in the form of polyplex to effectively inhibit in vivo tumor growth and this “enemy to friend” strategy will benefit various applications, including on‐demand gene delivery and personalized medicine.
Europium‐Doped Cerium Oxide Nanoparticles Limit Reactive Oxygen Species Formation and Ameliorate Intestinal Ischemia–Reperfusion Injury
Authors: Gubernatorova Ekaterina O. , Liu Xiaobo , Othman Ali , Muraoka Wayne T. , Koroleva Ekaterina P. , Andreescu Silvana , Tumanov Alexei V.
Published: May 2017

Accumulating evidence suggests that ischemia–reperfusion‐induced injury is associated with the formation of reactive oxygen species (ROS). This study demonstrates the therapeutic effectiveness of novel europium‐doped cerium oxide nanoparticles (Eu‐doped Ceria NPs) as ROS scavengers in a mouse model of intestinal ischemia–reperfusion‐induced injury. An increased production of superoxide radicals is detected in the intestine throughout the ischemia stage and again after initiating reperfusion. These changes in superoxide radical formation are associated with the induction of inflammatory cytokines in the intestine. This study further shows that Eu‐Ceria NPs exhibit superoxide scavenging activity in vitro. Importantly, administration of Eu‐Ceria NPs into the intestinal lumen during the onset of ischemia effectively blocks superoxide accumulation, reduces the expression of IL‐1b, and ameliorates the intestinal pathology. These results suggest that early increased production of ROS during the ischemia–reperfusion promotes intestinal pathology and that mucosal delivery of Eu‐Ceria NPs may be a potential therapeutic approach to block ROS accumulation and ameliorate the severity of intestinal disease.
Origami‐Based Reconfigurable Metamaterials for Tunable Chirality
Authors: Wang Zuojia , Jing Liqiao , Yao Kan , Yang Yihao , Zheng Bin , Soukoulis Costas M. , Chen Hongsheng , Liu Yongmin
Published: May 2017

Origami is the art of folding two‐dimensional (2D) materials, such as a flat sheet of paper, into complex and elaborate three‐dimensional (3D) objects. This study reports origami‐based metamaterials whose electromagnetic responses are dynamically controllable via switching the folding state of Miura‐ori split‐ring resonators. The deformation of the Miura‐ori unit along the third dimension induces net electric and magnetic dipoles of split‐ring resonators parallel or anti‐parallel to each other, leading to the strong chiral responses. Circular dichroism as high as 0.6 is experimentally observed while the chirality switching is realized by controlling the deformation direction and kinematics. In addition, the relative density of the origami metamaterials can be dramatically reduced to only 2% of that of the unfolded structure. These results open a new avenue toward lightweight, reconfigurable, and deployable metadevices with simultaneously customized electromagnetic and mechanical properties.
Ultrathin Cs3Bi2I9 Nanosheets as an Electronic Memory Material for Flexible Memristors
Authors: Hu Yanqiang , Zhang Shufang , Miao Xiaoliang , Su Liushuai , Bai Fan , Qiu Ting , Liu Jizi , Yuan Guoliang
Published: May 2017

Methylammonium lead halide (MAPbX3) perovskites have attracted tremendous attention due to their remarkable performances in solar cells, light‐emitting diodes, photodetectors, lasers, and electronic memories. However, the issue of toxicity still greatly restricts their further large‐scale applications. Here, this study presents a series of nontoxic and stable methylammonium (or cesium) bismuth halides A3Bi2I9 (A = Cs+ and MA+) nanosheets for using in flexible memories. The ultrathin A3Bi2I9 nanosheets can be easily prepared by a dissolution–recrystallization process. This is the first attempt that reports the ultrathin bismuth halides and explores their potential applications in flexible electronic devices. The flexible memristors based on such ultrathin Cs3Bi2I9 nanosheets exhibit typical bipolar resistive switching behavior and remarkable characteristics such as high Ron/Roff ratio (≈103), very low working voltage (≈0.3 V), and long data retention (>104 s), as well as excellent endurability, reproducibility, environmental stability, and flexibility. With such appealing characteristics, the cesium bismuth halide memristors have great potential for practical applications. The results of this work demonstrate that cesium bismuth halide ultrathin nanosheets will be promising candidates for more emerging applications in electronics and optoelectronics such as memories, photodetectors, photovoltaics, and light‐emitting diodes.
Near‐Infrared Organic Single‐Crystal Lasers with Polymorphism‐Dependent Excited State Intramolecular Proton Transfer
Authors: Wang Xuedong , Li Zhi‐Zhou , Li Shi‐Feng , Li Hui , Chen Jianwei , Wu Yishi , Fu Hongbing
Published: May 2017

Organic solid‐state lasers (OSSLs) are broadly tunable coherent sources, potentially compact, convenient, and manufactured at low costs. As compared with conventional organic materials, organic molecules with excited state intramolecular proton‐transfer (ESIPT) process are excellent active laser medium candidates due to their inherent four‐level system. This study demonstrates the effect of the polymorphism‐dependent ESIPT on the OSSLs. It is found the α‐phase crystals with a low photoluminescence quantum efficiency of ≈2% emit two components: the tautomer A emissions and the tautomer B emissions, which indicate the noncomplete ESIPT case. For comparison, the β‐phase crystals with moderate intramolecular hydrogen‐bonding emitting near‐infrared photoluminescence have all tautomer B emissions, which are of relatively high photoluminescence quantum efficiency (≈15%) and are red‐shifted by an average of ≈250 nm from the corresponding absorptions. The complete ESIPT process of the β‐phase crystals contributes to the amplified spontaneous near‐infrared emission (λ ≈ 730 nm) with a low threshold of ≈1.86 µJ cm−2. This work has provided the platform for the investigation of the ESIPT lasers, which contributes to the high‐performance organic solid‐state near‐infrared laser devices.
Significant Influence of the Methoxyl Substitution Position on Optoelectronic Properties and Molecular Packing of Small‐Molecule Electron Acceptors for Photovoltaic Cells
Authors: Li Sunsun , Ye Long , Zhao Wenchao , Zhang Shaoqing , Ade Harald , Hou Jianhui
Published: May 2017

Molecular engineering of nonfullerene electron acceptors is of great importance for the development of organic photovoltaics. In this study, a series of methoxyl‐modified dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐based small‐molecule acceptor (SMA) isomers are synthesized and characterized to determine the effect of substitution position of the terminal group in these acceptor–donor–acceptor‐type SMAs. Minor changes in the substitution position are demonstrated to greatly influence the optoelectronic properties and molecular packing of the isomers. Note that SMAs with planar molecular backbones show more ordered molecular packing and smaller π–π stacking distances, thus dramatically higher electron mobilities relative to their counterparts with distorted end‐groups. By utilizing polymer poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophen)‐co‐(1,3‐di(5‐thiophene‐2‐yl)‐5,7‐bis(2‐ethylhexyl)benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione)] (PBDB‐T) as an electron donor, an optimum power conversion efficiency (PCE) of 11.9% is achieved in the device based on PBDB‐T:IT‐OM‐2, which is among the top efficiencies reported as of yet. Moreover, the PCE stays above 10% as the film thickness increases to 250 nm, which is very advantageous for large‐area printing. Overall, the intrinsic molecular properties as well as the morphologies of blends can be effectively modulated by manipulating the substituent position on the terminal groups, and the structure–property relationships gleaned from this study will aid in designing more efficient SMAs for versatile applications.
Review on High‐Loading and High‐Energy Lithium–Sulfur Batteries
Authors: Peng Hong‐Jie , Huang Jia‐Qi , Cheng Xin‐Bing , Zhang Qiang
Published: May 2017

Owing to high specific energy, low cost, and environmental friendliness, lithium–sulfur (Li–S) batteries hold great promise to meet the increasing demand for advanced energy storage beyond portable electronics, and to mitigate environmental problems. However, the application of Li–S batteries is challenged by several obstacles, including their short life and low sulfur utilization, which become more serious when sulfur loading is increased to the practically accepted level above 3–5 mg cm−2. More and more efforts have been made recently to overcome the barriers toward commercially viable Li–S batteries with a high sulfur loading. This review highlights the recent progress in high‐sulfur‐loading Li–S batteries enabled by hierarchical design principles at multiscale. Particularly, basic insights into the interfacial reactions, strategies for mesoscale assembly, unique architectures, and configurational innovation in the cathode, anode, and separator are under specific concerns. Hierarchy in the multiscale design is proposed to guide the future development of high‐sulfur‐loading Li–S batteries.
Acne conglobata in a long‐term survivor with trisomy 13, accompanied by selective IgM deficiency
Authors: Inoue Chiyoko N. , Tanaka Yoshiko , Tabata Nobuko
Published: May 2017

Trisomy 13 (T13) is a congenital chromosomal disorder that is usually fatal within 2 years of birth, and only a few patients have been reported to reach adolescence. Here, we report a male long‐term survivor of T13, currently 15 years of age, with a several‐year history of extensive acne conglobata (AC) with abscesses on the face and neck. Methicillin‐resistantStaphylococcus aureuswas consistently isolated from the pustular lesions. Serum IgM levels were extremely low at 10 mg/dl. There were no abnormalities in neutrophil and total B cell number, or in serum IgA and IgG levels. Increased CD8+ T cell counts and inversion of the CD4/CD8 ratio were observed repeatedly. The patient's clinical features and laboratory data support a diagnosis of selective IgM deficiency (SIgMD) with concurrent AC. Immunoglobulin replacement therapy elevated serum IgM levels to the normal range and reduced the severity of AC. We suggest that T13 may represent a syndromic disorder associated with multiple organ malformation and a risk of developing immunodeficiency involving SIgMD. Because pediatric SIgMD is rare and an immunological abnormality in T13 patients has not previously been reported, we describe the patient's clinical course.
Efficient Brønsted‐Acid‐Catalyzed Deuteration of Arenes and Their Transformation to Functionalized Deuterated Products
Authors: Liang Xuewei , Duttwyler Simon
Published: May 2017

A convenient method to perdeuterate aromatic compounds is reported. Commercially available nonaflic acid (C4F9SO3H) in combination with C6D6 as the deuterium source provided access to a series of highly labeled arenes. Some of them were then used as building blocks for the preparation of functionalized deuterated products. A wide range of synthetic procedures were investigated. They involved traditional methods such as halogenation or nucleophilic substitution, but also metal‐catalyzed cross coupling and C−X bond activation. The transformations comprised redox‐neutral, oxidative as well as reductive reactions, and mechanistically, ionic, radical and pericyclic processes were covered. Under many conditions, the overall degree of deuteration remained high; in C−X activation reactions, a more pronounced re‐protonation was observed.
Kartierung des Hydratwassers um Alkoholketten mittels THz‐Kalorimetrie
Authors: Böhm Fabian , Schwaab Gerhard , Havenith Martina
Published: May 2017

Änderungen im Wasserstoffbrückennetzwerk von in Wasser gelösten Alkoholketten wurden mithilfe der THz‐Spektroskopie gemessen. Die THz‐Spektren wurden zerlegt und die einzelnen Komponenten normalem Wasser, tetraedrisch angeordnetem Hydratwasser und ungeordneterem Hydratwasser zugeordnet. Das tetraedrisch angeordnete Wasser erzeugt eine Bande bei 195 cm−1 und ist am hydrophoben Teil des Alkohols lokalisiert. Die zweite Komponente zeigt eine Bande bei 165 cm−1 und wird dem Hydratwasser in der ersten Solvatationsschale zugeordnet. Die vermessenen, temperaturabhängigen Änderungen im THz‐Spektrum von gelösten Alkoholketten können direkt mit Änderungen von Wärmekapazität, Entropie und freier Energie korreliert werden. Dabei ist überraschenderweise nicht das tetraedrisch angeordnete Wasser, sondern hauptsächlich das ungeordnete Hydratwasser für die temperaturabhängigen Änderungen von ΔCp und ΔG verantwortlich. Der für den gelösten Stoff spezifische Unterschied in der freien Energie ist auf die Bildung von Kavitäten zurückzuführen und skaliert linear mit der Kettenlänge der Alkohole.
Dynamic Modulation of Enzyme Activity by Near‐Infrared Light
Authors: Wang Changping , Zhang Qiang , Wang Xinyu , Chang Hong , Zhang Sanjun , Tang Yuankai , Xu Jianhua , Qi Ruijuan , Cheng Yiyun
Published: May 2017

Engineering near‐infrared (NIR) light‐sensitive enzymes remains a huge challenge. A photothermal effect‐associated method is developed for tailoring the enzymatic activity of enzymes by exposure to NIR light. An ultrasmall platinum nanoparticle was anchored in an enzyme to generate local heating upon NIR irradiation, which enhanced the enzyme activity without increasing bulk temperature. Following NIR irradiation, the enzyme activity was tailored rapidly and reversibly, and was modulated by varying laser power density and irradiation time. Four enzymes were engineered, including glucoamylase, glucose oxidase, catalase, and proteinase K with NIR‐light sensitivity, and demonstrated their utility in practical applications such as photolithography and NIR light‐responsive antibacterial or anticancer actions. Our investigation suggests that this approach could be broadly used to engineer enzymes with NIR‐light sensitivity for many biological applications.
Differences between G‐Protein‐Stabilized Agonist–GPCR Complexes and their Nanobody‐Stabilized Equivalents
Authors: Saleh Noureldin , Ibrahim Passainte , Clark Timothy
Published: May 2017

Protein nanobodies have been used successfully as surrogates for unstable G‐proteins in order to crystallize G‐protein‐coupled receptors (GPCRs) in their active states. We used molecular dynamics (MD) simulations, including metadynamics enhanced sampling, to investigate the similarities and differences between GPCR–agonist ternary complexes with the α‐subunits of the appropriate G‐proteins and those with the protein nanobodies (intracellular binding partners, IBPs) used for crystallization. In two of the three receptors considered, the agonist‐binding mode differs significantly between the two alternative ternary complexes. The ternary‐complex model of GPCR activation entails enhancement of ligand binding by bound IBPs: Our results show that IBP‐specific changes can alter the agonist binding modes and thus also the criteria for designing GPCR agonists.
The Effect of Water upon Deep Eutectic Solvent Nanostructure: An Unusual Transition from Ionic Mixture to Aqueous Solution
Authors: Hammond Oliver S. , Bowron Daniel T. , Edler Karen J.
Published: May 2017

The nanostructure of a series of choline chloride/urea/water deep eutectic solvent mixtures was characterized across a wide hydration range by neutron total scattering and empirical potential structure refinement (EPSR). As the structure is significantly altered, even at low hydration levels, reporting the DES water content is important. However, the DES nanostructure is retained to a remarkably high level of water (ca. 42 wt % H2O) because of solvophobic sequestration of water into nanostructured domains around cholinium cations. At 51 wt %/83 mol % H2O, this segregation becomes unfavorable, and the DES structure is disrupted; instead, water–water and DES–water interactions dominate. At and above this hydration level, the DES–water mixture is best described as an aqueous solution of DES components.
One‐Dimensionally Disordered Chiral Sorting by Racemic Tiling in a Surface‐Confined Supramolecular Assembly of Achiral Tectons
Authors: Zhang Yi‐Qi , Lin Tao , Cirera Borja , Hellwig Raphael , Palma Carlos‐Andres , Chen Zhi , Ruben Mario , Barth Johannes V. , Klappenberger Florian
Published: May 2017

The aggregation of (pro)chiral/achiral molecules into crystalline structures at interfaces forms conglomerates, racemates, and solid solutions, comparable to known bulk phases. Scanning tunneling microscopy and Monte Carlo simulations were employed to uncover a distinct racemic phase, expressing 1D disordered chiral sorting through random tiling in surface‐confined supramolecularly assembled achiral 4,4′′‐diethynyl‐1,1′:4′,1′′‐terphenyl molecules. The configurational entropy of the 1D disordered racemic tiling phase was verified by analytical modeling, and found to lie between that of a perfectly ordered 2D racemate and a racemic solid solution.
Preparation of microencapsulated aluminum hypophosphite and flame retardancy and mechanical properties of flame‐retardant ABS composites
Authors: Wu Ningjing , Xiu Zhaoxia , Du Jiyu
Published: May 2017

Microencapsulated aluminum hypophosphite (MFAHP) with a shell of melamine–formaldehyde resin (MF) was prepared via in situ condensation polymerization. The presence of MFAHP increased the water resistance of flame‐retarded (FR) acrylonitrile–butadiene–styrene (ABS) composites after hot water treatment. The mechanical properties indicate that the tensile strength and flexural strength of the FR ABS/MFAHP composites is enhanced with the incorporation of MFAHP. Cone calorimeter test results demonstrated that the peak heat release rate, total heat release, and total smoke release values of the ABS/MFAHP composites were significantly decreased. Digital photos and scanning electron microscopy images of the residues of ABS/25 wt % MFAHP2 composites exhibited compact char layer structures, with many cobweb‐like nanoparticle arrangements formed on the surface by the burning process. The investigation of flame‐retardant mechanisms of ABS/MFAHP composites using infrared spectroscopy and energy‐dispersive X‐ray spectroscopy indicated that both the formation of char residue in the condensed phase and the release of inert gases by the MF shell in the gas phase led to the formation of compact and stable char layers containing carbon/pyrophosphate and aluminum polyphosphate, consequently leading to the good flame‐retardant performance of MFAHP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45008.
Ultraviolet–visible/fluorescence behaviors of a spiropyran/polydimethylsiloxane composite film under acid vapors
Authors: Zhao Zhixun , Tian Jintao
Published: May 2017

A spiropyran (SP)/polydimethylsiloxane (PDMS) composite film was prepared in this study, and its ultraviolet–visible/fluorescence behaviors under acid vapors were investigated. With UV irradiation, the ring‐closed SP in the PDMS matrix transformed to a ring‐opened merocyanine, which contained phenolate oxygen and could be further protonated by the hydrogen offered by the acid vapor. Such a protonation process endowed the composite film with not only an obvious color change from purple to yellow but also a strong fluorescent emission. As a result, some common volatile acids, hydrochloric acid, hydrofluoric acid, nitric acid, trifluoroacetic acid, formic acid, acetic acid, and propionic acid, could be distinguished with this method either via color or fluorescent emission. Meanwhile, the film showed good recyclability during the processes of irradiation and protonation. The method, therefore, displayed good processing in real time and was fast and recyclable; this makes it suitable as an alternative for applications related to environmental and safety monitoring of acid vapors. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45199.
Effects of methylene diphenyl diisocyanate on the physical, mechanical, and vulcanization properties of nitrile rubber
Authors: Razavizadeh Mahmoud , Jamshidi Masoud
Published: May 2017

In this research, methylene diphenyl diisocyanate (MDI) was added to an acrylonitrile–butadiene rubber (NBR) compound as an additive, and its effects on the vulcanization of the rubber investigated. For this purpose, MDI was added at different concentrations (5, 10, and 20 phr) to the rubber compound. The rubber properties, including the rheometry and tensile strength, were investigated. Differential scanning calorimetry and swelling tests were used to assess the vulcanization mechanism and chemical reactions in the presence of MDI. Finally, Fourier transform infrared spectroscopy analysis was used to study the chemical structure of the NBR–MDI cured compounds. We found that MDI played a more important role than the additive in the NBR compound. It acted as a covulcanizing agent along with the sulfur groups. The 10 phr MDI content was found to be the optimum content for achieving the best NBR–MDI properties. This content increased the crosslinking density of the compound and decreased the swelling of NBR in toluene. We also found that MDI adsorbed the accelerator agents and sulfur groups, so it decreased the rate of vulcanization, especially at early ages. Furthermore, it reacted with NBR and produced strong urea (i.e., NHCONH) and thiourethane groups (i.e., SCONH), and this increased NBR's structural strength. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45200.
Free‐volume effects on the thermomechanical performance of epoxy–SiO2 nanocomposites
Authors: Lizundia Erlantz , Serna Iñaki , Axpe Eneko , Vilas José Luis
Published: May 2017

In this study, free‐volume effects on the thermal and mechanical properties of epoxy–SiO2 nanocomposites were investigated. SiO2 particles ranging from 15 nm to 2 µm were used, and the nature of the matrix–filler interphase was modified by surface grafting. Nanoparticles 15 nm in diameter yielded an increase in the glass‐transition temperature (Tg) of the composites up to 5 °C; at the same time, they increased the storage modulus (E′) from 2340 to 2725 MPa. Conversely, large particles markedly decreased both Tg and E′; this suggested the pivotal role of nanoparticle size on the final properties of the nanocomposite. The functionalization of SiO2 nanoparticles markedly improved their dispersion within the epoxy matrix. The positron annihilation lifetime spectroscopy results indicate that the free volume strongly depended on the interphase. These experimental findings obtained here could be extrapolated to industrially relevant nanocomposites and could provide a rationale for the comprehension of free‐volume effects on the thermal and mechanical properties of nanocomposite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45216.
Maillard reaction in natural rubber latex: Improvement of concentration process
Authors: Kongkaew Chaveewan , Poonsrisawat Aphisit , Champreda Verawat , Loykulnant Surapich
Published: May 2017

Maillard reaction in natural rubber (NR) latex was studied by treating fresh latex with formaldehyde and glutaraldehyde. Volatile fatty acid number of the treated latex could be lower than acceptable limit (< 0.08) for more than 20 days. Attenuated total reflectance infrared spectroscopy and sodium dodecyl sulfate polyacrylamide gel electrophoresis revealed the occurrence of protein crosslinks in the treated latex. NR treated with glutaraldehyde has much higher nitrogen content than NR treated with formaldehyde and untreated NR, respectively. Colloidal stability of rubber particles, represented by pH, zeta potential, viscosity, and particle size distribution information, were unchanged after treating the latex with formaldehyde. Treatment of the fresh latex with glutaraldehyde 100 and 200 mmol/kg of latex led to the aggregation of rubber particles. Interestingly, the Maillard crosslinking of proteins in fresh latex could efficiently promote the transfer of rubber particles from the serum phase into the cream phase during centrifugation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45224.
Mechanism of Nickel‐Catalyzed Suzuki–Miyaura Coupling of Amides
Authors: Xu Zheng‐Yang , Yu Hai‐Zhu , Fu Yao
Published: May 2017

The Ni‐catalyzed Suzuki–Miyaura coupling of N‐tert‐butoxycarbonyl (N‐Boc)‐protected amides provides a versatile strategy for the construction of C−C bonds. In this study, density functional theory (DFT) methods have been used to elucidate the mechanism of this reaction, with particular emphasis on the roles of N‐Boc, K3PO4 and H2O. Our results corroborated those of previous reports, indicating that the overall catalytic cycle consists of three steps, including oxidative addition, transmetalation, and reductive elimination. Three of the possible transmetalation mechanisms were examined to interpret the effects of K3PO4 and H2O. According to the most feasible of these transmetalation mechanisms, K3PO4 (acting as a Lewis base) would initially interact with the Lewis acid PhBpin to give a K3PO4‐PhBpin complex, which would readily undergo a hydrogen transfer step with H2O. The H transfer in the transmetalation step was determined to be the rate‐determining step. Notably, the theoretical results showed good agreement with the experimental data.
Core–Shell‐structured Dendritic Mesoporous Silica Nanoparticles for Combined Photodynamic Therapy and Antibody Delivery
Authors: Abbaraju Prasanna Lakshmi , Yang Yannan , Yu Meihua , Fu Jianye , Xu Chun , Yu Chengzhong
Published: May 2017

Multifunctional core–shell‐structured dendritic mesoporous silica nanoparticles with a fullerene‐doped silica core, a dendritic silica shell and large pores have been prepared. The combination of photodynamic therapy and antibody therapeutics significantly inhibits the cancer cell growth by effectively reducing the level of anti‐apoptotic proteins.
Stabilization of Time‐Varying and Disturbed Complex Dynamical Networks with Different‐Dimensional Nodes and Uncertain Nonlinearities
Authors: Zhang Lili , Lei Youfa , Wang Yinhe , Chen Baoying
Published: May 2017

This paper investigates the stabilization problem for time‐varying and disturbed complex dynamical networks (CDNs) with different‐dimensional nodes and uncertain nonlinearities. To be consistent with the properties of real‐world networks, both the disturbances of our networks and the nonlinear structures of the nodes permit are completely unknown but bounded. Furthermore, the norm bounds of the uncertain nonlinearities and disturbances (NBUND) are applied to design the stabilization controllers. When the NBUND are known in advance, some decentralized state feedback controllers are proposed to stabilize our networks. And when they are unknown, adaptive decentralized stabilization schemes are brought forward for our network models. The effectiveness and feasibility of our theoretical results are verified by two simulation examples.