bluuebunny/crossref_metadata_2025 huggingface dataset:
Possibilidades de gestão compartilhada na perspectiva de um olhar sistêmico sobre a cultura
Authors: F. Rodrigues Luiz Augusto , Souza Ana Clarissa Fernandes de
Published: February 2017

O artigo apresenta reflexões e discussões sobre algumas possibilidades de compartilhamento na construção e gestão pública de sistemas de cultura no Brasil. Aborda o Sistema Nacional de Cultura, articulando-o com sistemas estadual e municipais, a partir de exemplos do estado do Rio de Janeiro, trazendo algumas reflexões sobre a construção compartilhada de planos de cultura e de conselhos municipais de políticas culturais, assim como da realização de conferências municipais de cultura.
Desenvolvimento de Competências Gerenciais de Gestores Públicos em Instituições Federais de Educaçã
Authors: Brito-de-Jesus Kelly Cristina , Dos-Santos Marcos Gilberto , Souza-Silva Jader Cristino De , Rivera-Castro Miguel Angel
Published: February 2017

A defesa de gestores públicos competentes para gerenciar tornou-se uma questão emergente no processo de transformações que a agenda reformista propunha. O objetivo desta pesquisa é analisar como gestores públicos de Instituições Federais de Educação – IFEs desenvolvem as competências gerenciais. Adotou-se, nesta investigação, uma metodologia quantitativa, com a participação de 110 gestores públicos de IFEs. Dessa forma, para atender à estrutura da metodologia quantitativa, foram construídas duas escalas – escala de modalidades da aprendizagem organizacional e escala de competências gerenciais. As escalas foram validadas a partir de análise fatorial exploratória. Para identificar a relação entre as variáveis, foi realizada análise de regressão múltipla.  Os resultados sinalizam que as competências gerenciais cognitivas funcionais são explicadas pelas modalidades leitura de textos/banco de dados e mentoria e as competências gerenciais comportamentais políticas são mais influenciadas pelas modalidades leitura de textos/banco de dados e comunidades de prática. Os resultados apontam também que os gestores públicos desenvolvem as competências utilizando modalidades da aprendizagem que se aproximam de pressupostos mais cognitivistas e, em menor relevância, por meio de processos participativos e baseados na prática. 
O Destino das Cidades ou as Cidades como Destino: Uma Reflexão sobre Cidades Criativas a partir de Políticas Públicas Culturais
Authors: Leitão Claudia Sousa
Published: February 2017

O urbanista Peter Hall, quando descreve o período áureo das chamadas “cidades eternas” (Atenas, Florença, Londres, Paris, Viena e Berlim), constata a existência de alguns pontos convergentes entre elas: criatividade, cosmopolitismo e inovação. O século XXI será o século das cidades, apesar da presença insatisfatória de políticas públicas transversais capazes de oferecer a necessária complexidade aos estudos e pesquisas sobre as mesmas. No discurso da indústria turística, por exemplo, as cidades que recebem grande fluxo turístico são chamadas de “destinos”. Mas, o que significaria, na perspectiva da economia criativa, uma cidade ser um “destino”? Se ampliássemos os significados da palavra “destino”, a partir da intersecção das políticas do turismo com as políticas culturais, certamente avançaríamos em políticas transversais para a economia criativa brasileira, assim como na (re) significação das nossas cidades. Afinal, o “destino de uma cidade” é muito mais significativo e estratégico para as políticas públicas do que a “cidade como um destino”, pois cidades são menos mercadorias a serem consumidas por turistas vorazes do que espaços privilegiados de inclusão, socialização e humanização dos indivíduos. Este artigo tem por objetivo refletir sobre a contribuição da cultura no fortalecimento das políticas públicas para a economia criativa brasileira, e seu impacto sobre as cidades.
 
O Turismo como Prática Cultural Organizativa, Sociomaterial e Estética
Authors: Bispo Marcelo De Souza
Published: February 2017

O “turismo como prática cultural organizativa” é uma proposta de um novo olhar para os estudos turísticos, o qual refuta a ontologia hegemônica na compreensão de que o turismo é um fenômeno centrado nos indivíduos, no qual o deslocamento das pessoas é protagonista no entendimento do que vem a ser turismo. Assume-se uma ontologia societal, na qual a construção social é resultado da inter(ação) de humanos e não humanos, no caso do turismo, os humanos sendo os turistas e visitantes, moradores locais e profissionais da área, enquanto os não humanos são todos os elementos que também constituem a atividade turística como os hotéis, aeroportos, praias, montanhas, músicas, traços e ritos culturais, gastronomia, entre outros. Assim, nesta posição filosófica em que não há protagonismo nem de humanos ou mesmo dos não humanos, assume-se uma postura pós-estruturalista e póshumanista, na qual o fenômeno turístico é compreendido como uma prática social geradora de cultura e identidade, fruto de um processo organizativo (organizing), sociomaterial e estético. Destacam-se como possibilidades metodológicas as várias abordagens etnográficas, a etnometodologia e a teoria fundamentada (grounded theory).
The United States “warming hole”: Quantifying the forced aerosol response given large internal variability
Authors: Banerjee A. , Polvani L. M. , Fyfe J. C.
Published: February 2017

Twenty‐five years of large summer cooling over the southeastern United States ending in the mid‐1970s coincided with rapidly increasing anthropogenic aerosol emissions. Here we assess the claim that the cooling in that period was predominantly due to such aerosols. We utilize two 50‐member sets of coupled climate model simulations, one with only anthropogenic aerosol forcings and another with all known natural and anthropogenic forcings, together with a long control integration. We show that, in the absence of aerosol forcing, none of the model simulations capture the observed surface cooling rate (∼0.56°C decade−1), whereas with increasing aerosol emissions 2 (of 50) of the simulations do. More importantly, however, we find that the cooling from aerosols (0.20°C decade−1) is insufficient to explain the observation. Our results therefore suggest that, while aerosols may have played a role, the observed cooling was a rare event that contained a large contribution from unforced internal variability.
Influence of grain size heterogeneity on strength and microcracking behavior of crystalline rocks
Authors: Peng Jun , Wong Louis Ngai Yuen , Teh Cee Ing
Published: February 2017

This study numerically investigates the influence of material heterogeneity on the strength and deformation behavior and the associated microcracking process of a felsic crystalline rock using a grain‐based modeling approach in two‐dimensional Particle Flow Code. By using a heterogeneity index defined in this study, the heterogeneity induced by variation of grain size distribution can be explicitly incorporated into the numerical specimen models quantitatively. Under compressive loading, the peak strength and the elastic modulus are found to increase as the numerical model gradually changes from heterogeneous to homogeneous, i.e., a decrease of heterogeneity index. Meanwhile, the number of grain boundary tensile cracks gradually decreases and the number of intragrain cracks increases at the moment of failure. However, the total number of generated microcracks seems not to be significantly influenced by heterogeneity. The orientation of grain boundary microcracks is mainly controlled by the geometry of assembled grain structure of the numerical specimen model, while the orientation of intragrain microcracks is to a large degree influenced by the confinement. In addition, the development of intragrain cracks (both tensile and shear) is much more favored in quartz than in other minerals. Under direct tensile loading, heterogeneity is found to have no significant influence on the simulated stress‐strain responses and rock strength. Only grain boundary tensile cracks are generated when the numerical models are loaded in direct tension, and the position of generated macroscopic fracture developed upon failure of the specimen is largely affected by heterogeneity.
Iron partitioning between ferropericlase and bridgmanite in the Earth's lower mantle
Authors: Xu Shenzhen , Lin Jung‐Fu , Morgan Dane
Published: February 2017

Earth's lower mantle is generally believed to be seismically and chemically homogeneous because most of the key seismic parameters can be explained using a simplified mineralogical model at expected pressure‐temperature conditions. However, recent high‐resolution tomographic images have revealed seismic and chemical stratification in the middle‐to‐lower parts of the lower mantle. Thus far, the mechanism for the compositional stratification and seismic inhomogeneity, especially their relationship with the speciation of iron in the lower mantle, remains poorly understood. We have built a complete and integrated thermodynamic model of iron and aluminum chemistry for lower mantle conditions and from this model has emerged a stratified picture of the valence, spin, and composition profile in the lower mantle. Within this picture the lower mantle has an upper region with Fe3+‐enriched bridgmanite with high‐spin ferropericlase and metallic Fe and a lower region with low‐spin, iron‐enriched ferropericlase coexisting with iron‐depleted bridgmanite and almost no metallic Fe. The transition between the regions occurs at a depth of around 1600 km and is driven by the spin transition in ferropericlase, which significantly changes the iron partitioning and speciation to one that favors Fe2+ in ferropericlase and suppresses Fe3+ and metallic iron formation. These changes lead to lowered bulk sound velocity by 3–4% around the middle‐lower mantle and enhanced density by ~1% toward the lowermost mantle. The predicted chemically and seismically stratified lower mantle differs dramatically from the traditional homogeneous model.
Ultramylonite generation via phase mixing in high‐strain experiments
Authors: Cross A. J. , Skemer P.
Published: February 2017

Dynamic recrystallization and phase mixing are considered to be important processes in ductile shear zone formation, as they collectively enable a permanent transition to the strain‐weakening, grain‐size sensitive deformation regime. While dynamic recrystallization is well understood, the underlying physical processes and timescales required for phase mixing remain enigmatic. Here, we present results from high‐strain phase mixing experiments on calcite‐anhydrite composites. A poorly mixed starting material was synthesized from fine‐grained calcite and anhydrite powders. Samples were deformed in the Large Volume Torsion apparatus at 500°C and shear strain rates of 5 × 10−5 to 5 × 10−4 s−1, to finite shear strains of up to γ = 57. Microstructural evolution is quantified through analysis of backscattered electron images and electron backscatter diffraction data. During deformation, polycrystalline domains of the individual phases are geometrically stretched and thinned, causing an increase in the spatial density of interphase boundaries. At moderate shear strains (γ ≥ 6), domains are so severely thinned that they become “monolayers” of only one or two grain's width and form a thin compositional layering. Monolayer formation is accompanied by a critical increase in the degree of grain boundary pinning and, consequently, grain‐size reduction below the theoretical limit established by the grain‐size piezometer or deformation mechanism field boundary. Ultimately, monolayers neck and disaggregate at high strains (17 <γ <57) to complete the phase mixing process. This “geometric” phase mixing mechanism is consistent with observations of mylonites, where layer (i.e., foliation) formation is associated with strain localization, and layers are ultimately destroyed at the mylonite‐ultramylonite transition.
Zooplankton community response to the winter 2013 deep convection process in the NWMediterranean Sea
Authors: Donoso Katty , Carlotti François , Pagano Marc , Hunt Brian P. V. , Escribano Rubén , Berline Léo
Published: February 2017

The Gulf of Lion is an important area of deep convection, where intense winter vertical mixing brings nutrients up from deeper layers, promoting the largest bloom in the Mediterranean at the end of winter/early spring. The DEWEX program conducted cruises in February and April 2013 to investigate the ecosystem level impacts of deep water convection. Zooplankton data were collected through net sampling and imaging with an Underwater Vision Profiler. In winter, low zooplankton abundance and biomass were observed in the Deep Convection Zone (DCZ) and higher values on its periphery. In spring, this pattern reversed with high biomass in the DCZ and lower values on the periphery. On average for the whole area, the potential grazing impact was estimated to increase by one order of magnitude from winter to spring. In April, all areas except the DCZ incurred top‐down control by zooplankton on the phytoplankton stock. In the DCZ, the chlorophyll‐a values remained high despite the high zooplankton biomass and carbon demand, indicating a sustained bottom‐up control. The zooplankton community composition was comparable for both periods, typified by high copepod dominance, but with some differences between the DCZ and peripheral regions. In spring the DCZ was characterized by a strong increase in herbivorous species such as Centropages typicus and Calanus helgolandicus, and an increase in the number of large zooplankton individuals. Our study indicates that the DCZ is likely an area of both enhanced energy transfer to higher trophic levels and organic matter export in the North Western Mediterranean Sea.
Revisiting global fossil fuel and biofuel emissions of ethane
Authors: Tzompa‐Sosa Z. A. , Mahieu E. , Franco B. , Keller C. A. , Turner A. J. , Helmig D. , Fried A. , Richter D. , Weibring P. , Walega J. , Yacovitch T. I. , Herndon S. C. , Blake D. R. , Hase F. , Hannigan J. W. , Conway S. , Strong K. , Schneider M. , Fischer E. V.
Published: February 2017

Recent measurements over the Northern Hemisphere indicate that the long‐term decline in the atmospheric burden of ethane (C2H6) has ended and the abundance increased dramatically between 2010 and 2014. The rise in C2H6atmospheric abundances has been attributed to oil and natural gas extraction in North America. Existing global C2H6emission inventories are based on outdated activity maps that do not account for current oil and natural gas exploitation regions. We present an updated global C2H6emission inventory based on 2010 satellite‐derived CH4fluxes with adjusted C2H6emissions over the U.S. from the National Emission Inventory (NEI 2011). We contrast our global 2010 C2H6emission inventory with one developed for 2001. The C2H6difference between global anthropogenic emissions is subtle (7.9 versus 7.2 Tg yr−1), but the spatial distribution of the emissions is distinct. In the 2010 C2H6inventory, fossil fuel sources in the Northern Hemisphere represent half of global C2H6emissions and 95% of global fossil fuel emissions. Over the U.S., unadjusted NEI 2011 C2H6emissions produce mixing ratios that are 14–50% of those observed by aircraft observations (2008–2014). When the NEI 2011 C2H6emission totals are scaled by a factor of 1.4, the Goddard Earth Observing System Chem model largely reproduces a regional suite of observations, with the exception of the central U.S., where it continues to underpredict observed mixing ratios in the lower troposphere. We estimate monthly mean contributions of fossil fuel C2H6emissions to ozone and peroxyacetyl nitrate surface mixing ratios over North America of ~1% and ~8%, respectively.
A modern Sr/Ca‐δ18O‐sea surface temperature calibration for Isopora corals on the Great Barrier Reef
Authors: Brenner Logan D. , Linsley Braddock K. , Potts Donald C.
Published: February 2017

Isopora (Acroporidae) is a genus of often encrusting, branching to submassive corals that are common in many shallow habitats on modern and fossil Indo‐West Pacific reefs. Although abundant, Isopora is largely absent from paleoceanographic literature. The scarcity of large Porites and the abundance of Isopora retrieved from the Great Barrier Reef (GBR) on Integrated Ocean Drilling Program Expedition 325 focused paleoceanographic attention on Isopora. Here we provide the first independent high‐resolution calibration of both Sr/Ca and δ18O for temperature analyses based on Isopora and demonstrate its consistency with Porites records. We developed modern skeletal Sr/Ca‐ and δ18O‐sea surface temperature (SST) calibrations based on five modern Isopora colonies from Heron Island in the southern GBR. Pairing the coral Sr/Ca record with monthly SST data yielded Sr/Ca‐SST sensitivities from −0.061 ± 0.004 (centered) to −0.083 ± 0.007 (raw) mmol/mol °C−1 based on reduced major axis regressions. These sensitivities are in the middle of the range of published Porites values and overlap most published values for Isopora, −0.075 ± 0.011 to −0.065 ± 0.011 mmol/mol °C−1. The δ18O‐SST sensitivities range from −0.184 ± 0.014 (centered) to −0.185 ± 0.014 (raw) ‰ °C−1, assuming that all seasonal variation in δ18O was due to SST. These δ18O‐SST sensitivities are smaller than the widely accepted value of −0.23‰ °C−1 for biogenic aragonite but are at the upper end of high‐resolution Porites‐defined sensitivities that are consistently less than the aforementioned established value. Our results validate the use of Isopora as an alternative source of paleoceanographic records in habitats where large massive Porites are scarce or absent.
A new record of Atlantic sea surface salinity from 1896 to 2013 reveals the signatures of climate variability and long‐term trends
Authors: Friedman Andrew R. , Reverdin Gilles , Khodri Myriam , Gastineau Guillaume
Published: February 2017

Sea surface salinity (SSS) is a major ocean circulation component and indicator of the hydrological cycle. Here we investigate an unprecedented Atlantic SSS compilation from 1896 to 2013 and analyze the main modes of SSS decadal variability. Using principal component analysis, we find that the low‐latitude (tropical and subtropical) Atlantic and the subpolar Atlantic have distinct variability. Subpolar and low‐latitude SSS are negatively correlated, with subpolar anomalies leading low‐latitude anomalies by about a decade. Subpolar SSS varies in phase with the Atlantic Multidecadal Oscillation (AMO), whereas low‐latitude SSS varies in phase with the North Atlantic Oscillation (NAO). Additionally, northern tropical SSS is anticorrelated with Sahel rainfall, suggesting that SSS reflects the Intertropical Convergence Zone latitude. The 1896–2013 SSS trend shows amplification of the mean SSS field, with subpolar freshening and low‐latitude salinification. The AMO and NAO have little effect on the long‐term trend but contribute to the trend since 1970.
Facile Fabrication, Structures, and Properties of Laser‐Marked Polyacrylamide/Bi2O3 Hydrogels
Authors: Cao Zheng , Hu Yanchao , Yu Qiang , Lu Ying , Wu Dun , Zhou An , Ma Wenzhong , Xia Yanping , Liu Chunlin , Loos Katja
Published: February 2017

Laser marking of wet and soft polyacrylamide/bismuth oxide (PAM/Bi2O3) hydrogel materials can be achieved by simply embedding Bi2O3 particles inside PAM hydrogels and a subsequent laser treatment with a Nd: YAG laser beam at 1064 nm. In comparison with the pure hydrogel, the marking properties of the laser‐marked PAM/Bi2O3 hydrogel samples vary as the Bi2O3 content increase from 0.17 to 3.0 wt% and as the laser power increase from 23.5 to 47.0 W. SEM, XPS, XRD, TGA, Raman spectroscopy, water contact angle and mechanical property tests are performed to characterize the laser‐marked PAM/Bi2O3 hydrogels. The results herein indicate that the marking contrast and visual appearance on the surface of the PAM/Bi2O3 hydrogels after laser irradiation are mainly due to the decomposition of Bi2O3 to black bismuth metal.
High‐Performance Photodetectors Based on Organometal Halide Perovskite Nanonets
Authors: Wang Wenhui , Ma Yurong , Qi Limin
Published: February 2017

The booming development of organometal halide perovskites has prompted the exploration of morphology‐engineering strategies to improve their performance in optoelectronic applications. However, the preparation of optoelectronic devices of perovskites with complex architectures and desirable properties is still highly challenging. Herein, novel CH3NH3PbI3 nanonets and nanobowl arrays are fabricated facilely by using monolayer colloidal crystal (MCC) templates on different substrates. Specifically, highly ordered CH3NH3PbI3 nanonets with high crystallinity are fabricated on a variety of flat substrates, whereas regular CH3NH3PbI3 nanobowl arrays are produced on a coarse substrate. The photodetection performance of the CH3NH3PbI3 nanonet‐based photodetectors is significantly enhanced compared to the photodetectors based on conventional CH3NH3PbI3 compact films. Particularly, the nanonet photodetectors exhibit a high responsivity (10.33 A W−1 under 700 nm monochromatic light), which is six times higher than that for the compact CH3NH3PbI3 film devices, fast response speed, and good stability. Owing to the two‐dimensional arrayed structure, the CH3NH3PbI3 nanonets exhibit an enhanced light harvesting ability and offer direct carrier transport pathways. Meanwhile, the MCC template brings about larger grain sizes with enhanced crystallinity. Furthermore, the perovskite nanonets can be formed on a flexible polyethylene terephthalate substrate for the fabrication of promising flexible nanonet photodetectors.
Synthesis of Fluorenes with an All‐Carbon Quaternary Center via Palladium‐Catalyzed Dual Arylation using Cyclic Diaryliodonium Triflates
Authors: Peng Xiaopeng , Luo Hongwen , Wu Fuhai , Zhu Daqian , Ganesan A. , Huang Peng , Wen Shijun
Published: February 2017

Catalyzed by palladium species, cyclic diaryliodonium salts underwent dual C‐aryl functionalization smoothly with activated methylene sources. With this new finding, a series of diversified fluorenes with an all‐carbon quaternary center was quickly constructed. Moreover, our approach also provided various novel spirofluorenes containing barburate acid or indane motifs which are featured in medicinal drugs and functional materials.

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Synthesis of 2‐Substituted Quinolines via Rhodium(III)‐Catalyzed C–H Activation of Imidamides and Coupling with Cyclopropanols
Authors: Zhou Xukai , Qi Zisong , Yu Songjie , Kong Lingheng , Li Yang , Tian Wan‐Fa , Li Xingwei
Published: February 2017

An efficient synthesis of 2‐substituted quinolines from readily available cyclopropanols and imidamides has been developed, where the cyclopropanol acts as a C3 synthon. With the assistance of a bifunctional imidamide directing group, the reaction occurred via sequential C–H/C–C cleavage and C–C/C–N bond formation.

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Modeling the membrane formation of novel PVA membranes for predicting the composition path and their final morphology
Authors: Bouyer Denis , M'Barki Oualid , Pochat‐Bohatier Céline , Faur Catherine , Petit Eddy , Guenoun Patrick
Published: February 2017

Herein, a numerical model is developed for investigating the appropriate operating conditions for obtaining porous membranes from PVA/water system. The main interest of such novel polymeric system lies in the use of water as solvent instead of classical organic solvent. In that context, the membrane formation involves three coupled and interdependent phenomena: phase inversion, crosslinking, and solvent evaporation. The mass transfer model involves thermodynamic description by Flory‐Huggins theory, specific diffusion formalism for dilute system and external mass transfers in free convection. Since the system evolves from monophasic to diphasic region during membrane formation, the diffusion formalisms were adjusted depending on the composition path to simulate the solvent and catalyzer evaporation. The simulations exhibit that due to mass transfers occurring concomitantly to phase inversion and crosslinking, the operating conditions (final temperature, catalyzer, initial solution thickness) must be carefully chosen to ensure the formation of a porous membrane with PVA/water system. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3035–3047, 2017
One‐particle density matrix characterization of many‐body localization
Authors: Bera Soumya , Martynec Thomas , Schomerus Henning , Heidrich‐Meisner Fabian , Bardarson Jens H.
Published: February 2017

We study interacting fermions in one dimension subject to random, uncorrelated onsite disorder, a paradigmatic model of many‐body localization (MBL). This model realizes an interaction‐driven quantum phase transition between an ergodic and a many‐body localized phase, with the transition occurring in the many‐body eigenstates. We propose a single‐particle framework to characterize these phases by the eigenstates (the natural orbitals) and the eigenvalues (the occupation spectrum) of the one‐particle density matrix (OPDM) in individual many‐body eigenstates. As a main result, we find that the natural orbitals are localized in the MBL phase, but delocalized in the ergodic phase. This qualitative change in these single‐particle states is a many‐body effect, since without interactions the single‐particle energy eigenstates are all localized. The occupation spectrum in the ergodic phase is thermal in agreement with the eigenstate thermalization hypothesis, while in the MBL phase the occupations preserve a discontinuity at an emergent Fermi edge. This suggests that the MBL eigenstates are weakly dressed Slater determinants, with the eigenstates of the underlying Anderson problem as reference states. We discuss the statistical properties of the natural orbitals and of the occupation spectrum in the two phases and as the transition is approached. Our results are consistent with the existing picture of emergent integrability and localized integrals of motion, or quasiparticles, in the MBL phase. We emphasize the close analogy of the MBL phase to a zero‐temperature Fermi liquid: in the studied model, the MBL phase is adiabatically connected to the Anderson insulator and the occupation‐spectrum discontinuity directly indicates the presence of quasiparticles localized in real space. Finally, we show that the same picture emerges for interacting fermions in the presence of an experimentally‐relevant bichromatic lattice and thereby demonstrate that our findings are not limited to a specific model.

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Total Synthesis of the Cytotoxic Marine Triterpenoid Isodehydrothyrsiferol Reveals Partial Enantiodivergency in the Thyrsiferol Family of Natural Products
Authors: Hoshino Akihiro , Nakai Haruka , Morino Miyako , Nishikawa Keisuke , Kodama Takeshi , Nishikibe Kento , Morimoto Yoshiki
Published: February 2017

Recently, the phenomenon of enantiodivergence was uncovered as a new phenomenon in the biosynthesis of natural products. In nature, chiral natural products are usually produced in optically active form, but both enantiomers sometimes arise in different genera and/or species or in a single species. Here we show through enantioselective total synthesis that the natural product isodehydrothyrsiferol shows partial enantiodivergency in that six of the nine or ten asymmetric centers are enantiomeric to those of other members of the marine squalene‐derived triterpenoid thyrsiferol family. In addition, isodehydrothyrsiferol and dehydrothyrsiferol, which show partial enantiodivergency, were isolated from the same producer, the red alga Laurencia viridis. These results demonstrate that partial enantiodivergence can develop even between natural products originating from a single species.
C,O‐Chelated BINOL/Gold(III) Complexes: Synthesis and Catalysis with Tunable Product Profiles
Authors: Cui Jian‐Fang , Ko Hok‐Ming , Shing Ka‐Pan , Deng Jie‐Ren , Lai Nathanael Chun‐Him , Wong Man‐Kin
Published: February 2017

Unprecedented stable BINOL/gold(III) complexes, adopting a novel C,O‐chelation mode, were synthesized by a modular approach through combination of 1,1′‐binaphthalene‐2,2′‐diols (BINOLs) and cyclometalated gold(III) dichloride complexes [(C^N)AuCl2]. X‐ray crystallographic analysis revealed that the bidentate BINOL ligands tautomerized and bonded to the AuIII atom through C,O‐chelation to form a five‐membered ring instead of the conventional O,O′‐chelation giving a seven‐membered ring. These gold(III) complexes catalyzed acetalization/cycloisomerization and carboalkoxylation of ortho‐alkynylbenzaldehydes with trialkyl orthoformates.
Syntheses, characterization, antibacterial activity and molecular modelling of phenylantimony(III) heteroleptic derivatives containing substituted oximes and piperidine dithiocarbamate
Authors: Beniwal Savita , Chhimpa Sunil , Gaur Deepti , John P.J. , Singh Yashpal , Sharma Jyoti
Published: February 2017

Six new heteroleptic phenylantimony(III) derivatives containing substituted oximes and dithiocarbamate moieties of the type (where R = ─C6H5, X = ─CH3 (2a); R = ─C6H4CH3, X = ─CH3 (2b); R = ─C6H4Cl, X = ─CH3 (2c); R = ─C6H4Br, X = ─CH3 (2d); R = ─C6H4OH, X = ─H (2e); R(X)C = (2f)) have been synthesized by the reactions of phenylantimony(III) dichloride with the sodium salt of substituted oximes and dithiocarbamate moiety in unimolar ratio with stirring in dichloromethane. All these newly synthesized derivatives have been characterized using physicochemical and elemental analyses. Structures have been proposed on the basis of infrared, 1H NMR, 13C NMR and LC–MS spectral studies and molecular modelling. In these derivatives the oxime behaves in an unidentate manner whereas dithiocarbamate behaves in a monofunctional anisobidentate manner. Pseudo‐trigonal bipyramidal (ψ‐TBP) geometry around the antimony metal centre is proposed for these phenylantimony(III) heteroleptic derivatives. The geometry of a representative complex has been optimized through molecular modelling. These newly synthesized derivatives were screened against Bacillus subtilis (Gram‐positive) and Escherichia coli (Gram‐negative) bacteria to evaluate their antibacterial potential. The structure–activity relationship for antibacterial activity among the four derivatives 2a, 2c, 2e and 2f is discussed.
Eco‐friendly synthesis of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐tetrazole and benzodiazepine‐2‐carboxamide derivatives with the aid of MCM‐48/H5PW10V2O40
Authors: Vessally Esmail , Hosseinzadeh‐Khanmiri Rahim , Ghorbani‐Kalhor Ebrahim , Es'haghi Moosa , Ejlali Ladan
Published: February 2017

A heterogeneous material composed of MCM‐48/H5PW10V2O40 was produced and used as an efficient, eco‐friendly and highly recyclable catalyst for the one‐pot and multicomponent synthesis of 3,4‐dihydroquinoxalin‐2‐amine, diazepine‐tetrazole and benzodiazepine‐2‐carboxamide derivatives in aqueous media and at room temperature with high yields in short reaction times (40–60 min). The recoverable catalyst was easily recycled at least five times without any loss of catalytic activity. The structures of obtained products were confirmed using 1H NMR and 13C NMR spectra.
Ethaline and Glyceline binary eutectic mixtures: characteristics and intermolecular interactions
Authors: Mjalli F.S. , Ahmed O.U.
Published: February 2017

Deep eutectic solvents (DESs) are ionic liquids analogs that have been the subject of a growing interest in the scientific community. Governed by their favorable chemical and physical properties, they were utilized in a wide variety of fields. DESs possessing both desirable and undesirable properties for a specific application are not uncommon. As such, investigation into the variation of their properties upon mixing, in order to understand and improve their properties for a specific application, seems promising. In this study, the measurement of the physical and selected excess thermodynamic properties of Ethaline upon addition of Glyceline was carried out. The deviation of excess molar volume as a function of Glyceline molar fraction was observed to be alternating between negative and positive. This implies that the predominant interactions is due to either the difference in the sizes and shapes of the constituent molecules or to the effect dispersion forces. The highest deviations of the excess molar volume were observed at 30 and 90 mol% Glyceline. Density, viscosity, pH, RI and conductivity of the pure and DES mixtures were measured at different Glyceline molar fractions within the temperature range of 20 to 80 °C. © 2017 Curtin University of Technology and John Wiley & Sons, Ltd.
Efficient Color‐Tunable Copper(I) Complexes and Their Applications in Solution‐Processed Organic Light‐Emitting Diodes
Authors: So Gary Kwok‐Ming , Cheng Gang , Wang Jian , Chang Xiaoyong , Kwok Chi‐Chung , Zhang Hongxing , Che Chi‐Ming
Published: February 2017

A series of dppnc‐ and neocuproine‐based CuI complexes (dppnc=7,8‐bis(diphenylphosphino)‐7,8‐dicarba‐nido‐undecaborate) are synthesized and the emission color of these CuI complexes can be tuned from green to deep red via rational modification of the neocuproine ligand structure. The molecular structures of the emissive CuI complexes, Cu(dppnc)‐G (green emitting), Cu(dppnc)‐Y (yellow emitting), and Cu(dppnc)‐R (red emitting), are characterized and their electronic structures and related transition properties are elucidated by photo‐physical and computational (density functional theory) studies. The calculation results suggest that thermally activated delayed fluorescence (TADF) is the emission mechanism for these CuI complexes. Efficient solution‐processed green‐, yellow‐, and red‐emitting OLEDs are fabricated based on the emissive complexes as the dopants. High external quantum efficiency (EQE) of 15.20 % and current efficiency of 48.15 cd A−1 at 1000 cd m−2 are achieved in the green‐emitting device with Cu(dppnc)‐G. A maximum EQE of 10.17 %, CIE coordinates of (0.61, 0.38) and a maximum electroluminescent peak of 631 nm are achieved in the red device based on Cu(dppnc)‐R.
Semi‐Global Exquisite Disturbance Attenuation Control for Perturbed Uncertain Nonlinear Systems
Authors: Yang Jun , Zhang Chuanlin , Li Shihua , Niu Xitong
Published: February 2017

Motivated by the design of disturbance observers with active elimination of the adverse effects caused by system uncertainties and disturbances, the problem of semi‐global exquisite disturbance attenuation control for a class of perturbed nonlinear systems is investigated in this paper. A feedback domination technique is utilized to integrate with the disturbance observer design and then a general composite active anti‐disturbance control law is proposed. With a recursive design procedure, the mismatched lumped disturbances are compensated in a novel step‐by‐step way while the non‐vanishing nonlinearities are treated via a feedback domination approach, rather than utilizing the straightforward feedback linearization method. The closed‐loop control performance and disturbance rejection ability now can be improved. A rigorous stability analysis assures the effectiveness of the proposed strategy. Numerical simulation results affirm the improved control and disturbance rejection performances with respect to several related existing results.
Short‐term highway traffic flow prediction based on a hybrid strategy considering temporal–spatial information
Authors: Li Linchao , He Shanglu , Zhang Jian , Ran Bin
Published: February 2017

Short‐term traffic flow prediction is fundamental for the intelligent transportation system and is proved to be a challenge. This paper proposed a hybrid strategy that is general and can make use of a large number of underlying machine learning or time‐series prediction models to capture the complex patterns beneath the traffic flow. With the strategy, four different combinations were implemented. To consider the spatial features of traffic phenomenon, several different state vectors including different observations were built. The performance of the proposed strategy was investigated using the traffic flow measurements from the Traffic Operation and Safety Laboratory in Wisconsin, USA. The results show the overall performance of hybrid strategy is better than a single model. Also, incorporating observations from adjacent junctions can improve prediction accuracy. Copyright © 2017 John Wiley & Sons, Ltd.
Neubau einer integralen Spannbetonbrücke
Authors: Fuchs Maximilian , Blank Gregor , Schneider Andreas , Paukner Florian
Published: February 2017

Der Neubau des Überführungsbauwerks BW 03 über die B20 im Zuge des dreistreifigen Ausbaus der Bundesstraße im Abschnitt Burghausen – Marktl am Inn stellte eine spannende Ingenieuraufgabe dar. Der gestalterische Anspruch und die vielfältigen Anforderungen aus Nutzung und Trassierung der sich kreuzenden Verkehrswege erforderten eine unkonventionelle Entwurfslösung. Der Beitrag beschreibt den Entwurf, die Konstruktion und die Ausführung der aufgelösten Rahmenbrücke als integrale Spannbetonkonstruktion.
Messtechnische Dauerüberwachung zur Absicherung der Restnutzungsdauer eines spannungsrisskorrosionsgefährdeten Brückenbauwerks
Authors: Bolle Guido , Mertzsch Olaf , Marx Steffen
Published: February 2017

Ausgangspunkt für die Dauerüberwachung der Brücke über die Bahn in Waren (Müritz) bilden die Ergebnisse der Nachrechnung und der Spannstahluntersuchungen. Entsprechend diesen war davon auszugehen, dass das Bauwerk zwar spannungsrisskorrosionsgefährdeten Spannstahl enthält, jedoch eine ausreichende Ankündigung bezüglich eines duktilen Versagens besitzt. Damit ist der Weiterbetrieb der Brücke unter Voraussetzung eines verkürzten Inspektionsintervalls möglich. Wegen der stark eingeschränkten Inspizierbarkeit des Bauwerks im laufenden Betrieb wurde die erforderliche zeitlich engmaschige visuelle Begutachtung durch ein Bauwerksmonitoring ersetzt. Im Fokus stand dabei nicht die ganzheitliche messtechnische Observation des Bauwerks, sondern die zielgerichtete und wirtschaftliche Registrierung einer eventuell auftretenden Biegerissbildung.

Innerhalb des bisher zweijährigen Messzeitraums wurde das Auftreten eines Biegerisses unter Gebrauchslasten und damit das tatsächliche Eintreten des Riss‐vor‐Bruch‐Kriteriums detektiert. Der Beitrag zeigt die prinzipielle Vorgehensweise beim zielgerichteten Sammeln von Informationen als Grundlage für eine sichere Entscheidungsfindung sowie bei der Planung, Ausführung und Bewertung der Dauermessungen und deren Einordnung in den Begutachtungsprozess des Bauwerks.
ATF6β‐based fine‐tuning of the unfolded protein response enhances therapeutic antibody productivity of Chinese hamster ovary cells
Authors: Pieper Lisa A. , Strotbek Michaela , Wenger Till , Olayioye Monilola A. , Hausser Angelika
Published: February 2017

The dynamics of protein folding and secretion are key issues in improving the productivity and robustness of Chinese hamster ovary (CHO) producer cells. High recombinant protein secretion in CHO producer clones triggers the activation of the unfolded protein response (UPR), an intracellular response to the accumulation of unfolded and misfolded proteins in the endoplasmic reticulum (ER). We previously reported that the human microRNA (miRNA) miR‐1287 enhances productivity in IgG‐expressing CHO cells (CHO‐IgG). Here, through next‐generation sequencing (NGS), we identified the activating transcription factor 6 beta (ATF6β), a repressor of the pro‐survival and UPR promoting factor ATF6α, as a direct target gene of miR‐1287 in CHO‐IgG cells. We show that the transient depletion of ATF6β resulted in enhanced specific productivity comparable to that of miR‐1287‐expressing CHO‐IgG cells. Strikingly, stable  ATF6β knockdown in CHO‐IgG cells significantly improved antibody titer and viable cell density under fed‐batch conditions. This was associated with the elevated expression of the UPR genes glucose‐regulated protein 78 (GRP78), homocysteine inducible ER protein with ubiquitin like domain 1 (Herpud1) and CCAAT/enhancer‐binding protein homologous protein (CHOP). We hence demonstrate that ATF6β‐based cell line engineering is a promising strategy to improve the productivity of CHO producer cells by activating an optimally balanced UPR program. Biotechnol. Bioeng. 2017;114: 1310–1318. © 2017 Wiley Periodicals, Inc.
Simultaneous densitometric determination of anthelmintic drug albendazole and its metabolite albendazole sulfoxide by HPTLC in human plasma and pharmaceutical formulations
Authors: Pandya Jui J. , Sanyal Mallika , Shrivastav Pranav S.
Published: February 2017

A new, simple, accurate and precise high‐performance thin‐layer chromatographic method has been developed and validated for simultaneous determination of an anthelmintic drug, albendazole, and its active metabolite albendazole, sulfoxide. Planar chromatographic separation was performed on aluminum‐backed layer of silica gel 60G F254 using a mixture of toluene–acetonitrile–glacial acetic acid (7.0:2.9:0.1, v/v/v) as the mobile phase. For quantitation, the separated spots were scanned densitometrically at 225 nm. The retention factors (Rf) obtained under the established conditions were 0.76 ± 0.01 and 0.50 ± 0.01 and the regression plots were linear (r2 ≥ 0.9997) in the concentration ranges 50–350 and 100–700 ng/band for albendazole and albendazole sulfoxide, respectively. The method was validated for linearity, specificity, accuracy (recovery) and precision, repeatability, stability and robustness. The limit of detection and limit of quantitation found were 9.84 and 29.81 ng/band for albendazole and 21.60 and 65.45 ng/band for albendazole sulfoxide, respectively. For plasma samples, solid‐phase extraction of analytes yielded mean extraction recoveries of 87.59 and 87.13% for albendazole and albendazole sulfoxide, respectively. The method was successfully applied for the analysis of albendazole in pharmaceutical formulations with accuracy ≥99.32%.
Structural Changes of Binary/Ternary Spinel Oxides During Ethanol Anaerobic Decomposition
Authors: Vozniuk Olena , Bazzo Cristian , Albonetti Stefania , Tanchoux Nathalie , Bosselet Françoise , Millet Jean‐Marc M. , Di Renzo Francesco , Cavani Fabrizio
Published: February 2017

Several M‐modified iron oxides of the spinel family have proven to be effective electron and O2− vectors for the production of hydrogen in the chemical‐loop reforming of bio‐alcohols. The present work is specifically focused on investigation of ethanol anaerobic decomposition over spinel oxides, which results in significant structural changes of the oxygen carrier material itself and corresponds to a first step of the chemical‐loop reforming process. In particular, a series of binary/ternary M‐modified ferrospinels were prepared by a co‐precipitation method and tested in terms of both redox properties and intrinsic catalytic activity in addition to a complex ex situ study that encompasses the solid‐state chemistry investigations of the fresh and reduced oxygen carrier materials. It was found that Co/Cu incorporation facilitates total/partial oxidation of ethanol, giving rise to high yields of H2, COx, and H2O; whereas Mn incorporation predominantly favored dehydrogenation and condensation reactions, leading to the formation of acetaldehyde and acetone. In addition, the incorporation of Mn contributed to significantly reduce the amount of coke formed; however, it caused a lower intrinsic reducibility, which was explained by the formation of a thermodynamically stable and hardly reducible layer of MnxFeyO solid solution.
Free‐Standing Phytantriol Q224 Cubic‐Phase Films: Resistivity Monitoring and Switching
Authors: Brown Rosemary , Madrid Elena , Castaing Remi , Stone James M. , Squires Adam M. , Edler Karen J. , Takashina Kei , Marken Frank
Published: February 2017

Phytantriol Q224 cubic phase, as a bicontinuous meso‐structured material stable in contact with aqueous electrolyte, has found applications in drug delivery and cosmetics and is employed here as a free‐standing film separating two aqueous compartments in order to study i) ion conductivity (at low potential bias within ±0.8 V), ii) conductivity switching effects (at high potential bias beyond ±0.8 V), and iii) phase switching effects (as a function of temperature). A microhole of approximately 20 μm diameter in a 6 μm thick poly‐ethylene‐terephthalate film is employed as the support coated with phytantriol (on a single side or on both sides) in contact with aqueous electrolyte phase on both sides in a classic four‐electrode measurement cell. The conductivity of the phytantriol phase within the microhole is shown to be ionic strength, applied potential, time/history, and temperature dependent. The experimental data for asymmetric phytantriol deposits are indicative of a microhole resistance that can be switched between two states (high and low resistance associated with a filled or empty microhole, respectively). When heating symmetrically applied films of phytantriol, Q224‐to‐HII phase transition linked to a jump to a higher specific resistivity is observed, which is consistent with differential scanning calorimetry data for this phase transition.
Fe and N Co‐doped Carbons Derived from an Ionic Liquid as Active Bifunctional Oxygen Catalysts
Authors: Xu Jun , Shi Liang , Liang Cong , Wu Hui , Lei Jiaheng , Liu Dan , Qu Deyu , Xie Zhizhong , Li Junsheng , Tang Haolin
Published: February 2017

A high‐performance electrocatalyst that could effectively catalyze the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is required in important energy conversion devices such as metal–air batteries. Herein, we report the template‐free synthesis of a Fe and N co‐doped carbon catalyst, using a novel ionic liquid as the precursor. The Fe−N−C catalyst prepared at 800 °C exhibits comparable ORR performance but significantly improved OER activity compared to the commercial Pt/C catalyst as well as good stability. We demonstrate that the excellent performance of the catalyst is caused by its high heteroatom content, large surface area, and high degree of graphitization.
Synthesis of Unique Flowerlike Bi2O2(OH)(NO3) Hierarchical Microstructures with High Surface Area and Superior Photocatalytic Performance
Authors: Han Qiaofeng , Pang Jiawei , Wang Xin , Wu Xiaodong , Zhu Junwu
Published: February 2017

Unique flowerlike Bi2O2(OH)(NO3) (denoted as BION) hierarchical microstructures assembled by ultrathin nanosheets were hydrothermally synthesized from incomplete hydrolysis of anhydrous bismuth nitrate (Bi(NO3)3) after adsorption of glacial acetic acid (HAc). The structure, composition, and optical properties of the products were characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, etc. The as‐prepared flowerlike BION possessed an ultra‐high surface area and thus exhibited exceptional photocatalytic activity for rhodamine B (RhB) degradation under UV light irradiation with an efficiency of about 17; 6 and 2.5 times higher than spherical, aggregated sheet‐like BION and P25 TiO2, respectively, and also superior to the reported sheet‐like BION. It also showed good photocatalytic activity for crystal violet (CV) degradation. This work opens new routes for the rational design and synthesis of nontoxic basic bismuth nitrates with a facile synthetic approach, controllable morphology, and excellent photoreactivity.
A Stable Aminyl Radical Coordinated to Cobalt
Authors: Rodríguez‐Lugo Rafael E. , de Bruin Bas , Trincado Monica , Grützmacher Hansjörg
Published: February 2017

A family of cobalt complexes bearing the trop2NH [bis(5‐H‐dibenzo[a,d]cyclohepten‐5‐yl)‐amine] and 2,2’‐bpy (2,2’‐bipyridine) chelate ligands were prepared and fully characterized. The compounds [Co(trop2N)(bpy)], [Co(trop2NH)(bpy)]+, and [Co(trop2N)(bpy)]+ are cobalt complexes interrelated by one‐electron redox processes and/or proton transfer. Two limiting resonance structures can be used to describe the paramagnetic complex [Co(trop2N)(bpy)]+: [CoII(trop2N−)(bpy)]+ (CoII amido) and [CoI(trop2N⋅)(bpy)]+ (CoI‐aminyl radical). Structural data, DFT calculations, and reactivity toward H‐abstraction indicate a slightly higher contribution of the aminyl radical form to the ground state of [Co(trop2N)(bpy)]+. The results described here complete the series of Group 9 metal aminyl radical complexes bearing the diolefin amine ligand trop2NH.