bluuebunny/crossref_metadata_2025 huggingface dataset:
Contrapondo interpretações de agricultores e pesquisadores sobre possíveis problemas ambientais causados pelo cultivo de eucalipto
Authors: Lima de Aquino Silvia
Published: July 2014

A atuação da indústria fabricante de celulose no Espírito Santo é acompanhada por diversos conflitos e protestos de lideranças comunitárias e sindicais, movimentos sociais, ONGs, etc., em virtude dos problemas sociais e ambientais que estes setores afirmam serem causados pela mesma desde que foi introduzida no Estado. Dentre estes problemas encontram-se, por exemplo, a expulsão de agricultores de base familiar e populações tradicionais, como grupos indígenas e quilombolas, de suas terras; alterações na disponibilidade de emprego no campo; destruição da Mata Atlântica; contaminação das águas de rios e córregos por agrotóxicos e dejetos industriais e homogeneização da paisagem. Diante disso, este trabalho tem o objetivo de estabelecer uma reflexão a respeito das percepções de agricultores de base familiar integrados à indústria de papel e celulose sobre as mudanças ocorridas no ambiente em que residem, vivem e trabalham, tendo em vista a expansão do cultivo de eucalipto para as atividades deste segmento.
Análise da letalidade decorrente de intoxicação por agrotóxicos em agricultores da região Sul do Brasil
Authors: Kirchner Rosane Maria , Silinske Jaqueline , Richter Luciana , Chaves Magda Antunes de , Scherer Mônica Elisa , Benetti Joana Kirchner , Stumm Eniva Miladi Fernandes
Published: July 2014

Os agrotóxicos são utilizados de forma expressiva para combater as doenças e pragas em propriedades rurais. A forma do uso tem gerado danos ao meio ambiente e à saúde do homem, levando muitas vezes a óbito. Esta pesquisa tem por objetivo analisar as circunstâncias e o índice de letalidade decorrente de intoxicação por agrotóxicos em agricultores da região Sul do Brasil. A partir da base de dados do Sistema Nacional de Informações Tóxico-Farmacológicas (SINITOX) para o período de 1999 a 2009, foram construídas séries históricas para casos, óbitos e circunstância de intoxicação (acidental, ocupacional, induzida, ignorada, outros). Para análise e comparação dos resultados, foram utilizados a estatística descritiva e o índice de letalidade. Observou-se que a letalidade no período estudado variou entre 0,9 (RS) e 8,2 (PR), ocorrendo os dois extremos no ano de 2004. Analisando comparativamente os três Estados, o número de óbitos teve percentual maior no PR. Quando observada a circunstância da intoxicação, destaca-se: no RS, de 1999 a 2004, a forma induzida, isto é, premeditada, ocorreu em torno de 30% dos casos, diminuindo gradativamente nos anos seguintes (28,10% a 26,4%); no PR a forma induzida é preocupante, pois oscilou entre 36,23% a 52,01% dos casos, sendo que, nos anos de 2001, 2003, 2004, 2006 e 2007, esta forma ficou em torno de 50%, explicando o maior índice de letalidade neste Estado; em SC, a forma induzida, nos anos de 2005 a 2007, ficou entre 43,5% e 45%. Esta análise demonstra que os agrotóxicos utilizados na lavoura, além de levarem à ocorrência de agravos pelo manuseio inadequado, este também em percentual significativo, servem para atentar sobre a vida de indivíduos.
Atuação pública e privada na gestão de Unidades de Conservação: aspectos socioeconômicos da prestação de serviços de apoio à visitação em parques nacionais
Authors: Rodrigues Camila Gonçalves de Oliveira , Godoy Larissa Ribeiro da Cruz
Published: July 2014

A necessidade de ofertar serviços de apoio à visitação em parques nacionais tem motivado a consolidação de instrumentos de gestão que propiciem a participação de diversos atores no desenvolvimento do turismo, tais como empresas, organizações da sociedade civil, associações e cooperativas de base comunitária. Este artigo visa apontar e discutir, com base em uma revisão teórico-conceitual, alguns dos principais aspectos socioeconômicos associados à prestação de serviços de apoio à visitação em parques nacionais. Dentre esses aspectos, destacam-se o incremento de recursos financeiros para a manutenção dos parques, o equilíbrio econômico-financeiro dos contratos firmados pelo poder público com particulares, a adequação e a qualidade dos serviços prestados, e o potencial efeito dinamizador da economia tendente a favorecer o desenvolvimento socioeconômico local. A análise desses aspectos se baseou no levantamento bibliográfico e de dados secundários sobre a gestão de unidades de conservação e na análise de instrumentos normativos à luz da doutrina do direito administrativo. Uma das principais reflexões do artigo aponta que o aporte de recursos humanos e financeiros por parte das organizações pública e privada na gestão dos parques nacionais requer uma abordagem criteriosa, considerando as funções e responsabilidades no âmbito da gestão dessas áreas. Dessa forma, a convivência entre os regimes público e privado no mesmo espaço, como é o caso da prestação de serviços de apoio à visitação em unidades de conservação, requer o equilíbrio entre os resultados econômico-financeiros privados e os objetivos da função pública relativos à conservação da área e à democratização do seu acesso.
Vulnerabilidade social e a construção de estratégias de enfrentamento e adaptação para pecuaristas de corte no Rio Grande do Sul
Authors: Matte Alessandra , Waquil Paulo Dabdab
Published: July 2014

Este estudo visa compreender como a vulnerabilidade social influencia as capacitações e meios de vida dos pecuaristas de corte da Campanha Meridional e Serra do Sudeste do Rio Grande do Sul e como esses criam estratégias de enfrentamento ou adaptação aos efeitos das situações de vulnerabilidade a que estão expostos. Nesse sentido, o estudo versa sobre o tema da vulnerabilidade desde uma perspectiva social, utilizando as abordagens das capacitações e dos meios de vida para compreender como os pecuaristas de corte têm enfrentado ou se adaptado às situações de vulnerabilidade social. Foram realizadas 60 entrevistas semiestruturadas com pecuaristas de corte, nos municípios de Bagé e Dom Pedrito, localizados na Campanha Meridional, e Piratini e Pinheiro Machado, localizados na Serra do Sudeste. Assim, os principais fatores de vulnerabilidade social identificados são dificuldade de contratação de mão de obra (78%) e ausência de sucessor (77%). Desse modo, a liberdade para escolher a melhor estratégia para enfrentar ou se adaptar às situações de vulnerabilidade fica restrita aos meios de vida de cada família, pois é a disponibilidade de ativos que vai possibilitar aos indivíduos expandir ou restringir suas capacitações individuais.
As atividades turísticas baseadas na alimentação artificial de botos-da-Amazônia (Inia geoffrensis) e a legislação ambiental brasileira
Authors: Alves Luiz Cláudio Pinto de Sá , Machado Carlos José Saldanha , Vilani Rodrigo Machado , Vidal Marcelo Derzi , Andriolo Artur , Azevedo Alexandre De Freitas
Published: July 2014

A atividade turística de interação ser humano-boto-da-Amazônia (Inia geoffrensis), baseada na prática do condicionamento por meio da alimentação artificial, vem aumentando quantitativamente nos últimos anos, assim como a literatura que descreve os seus efeitos negativos. O objetivo deste trabalho é avaliar essa atividade à luz da legislação ambiental, tomando como estudo de caso o Parque Nacional de Anavilhanas (PNA), localizado em Novo Airão, Estado do Amazonas, Brasil. A partir de consultas à literatura especializada, da leitura do arcabouço legal e da análise de material empírico, constata-se que i) legalmente, esta prática está em conflito com alguns aspectos da legislação ambiental, conceitos de ecoturismo e funções das Unidades de Conservação, e ii) administrativamente, os órgãos ambientais responsáveis vêm tomando as medidas necessárias para a mitigação dos impactos negativos e conduzindo ações graduais visando adequar as atividades turísticas à legislação ambiental vigente. Conclui-se afirmando que muito ainda deve ser feito para que o modelo de turismo com botos na Amazônia seja desenvolvido de forma sustentável, sugerindo-se que o conjunto de ações heterogêneas propostas seja implementado para este fim.
Incentivos para a viabilização do biogás a partir dos resíduos da pecuária leiteira no Estado de Minas Gerais
Authors: Alves Gomes Ana Carolina , Macedo Rocha Mariana , Silva Galvão Aziz Da , Murta Baião Albino Pablo
Published: July 2014

O avanço tecnológico apresentado pela pecuária brasileira nos últimos anos trouxe muitos benefícios sociais e econômicos. Porém, junto a esse desenvolvimento são originados sérios problemas ambientais em virtude das grandes quantidades de dejetos que, muitas vezes, são direcionados de forma equivocada em lavouras como adubos e fertilizantes orgânicos, ocasionando diversos tipos de poluição na água, no solo e na atmosfera. Assim, este trabalho buscou, por meio da pesquisa bibliográfica, analisar quais são os incentivos e as políticas públicas existentes no Brasil e no Estado de Minas Gerais para o tratamento da problemática em torno dos dejetos de bovinos de leite, por este estado ter o maior plantel leiteiro do país. Concluiu-se que há ações e esforços realizados pelo Governo Federal e pelo Governo Estadual de Minas Gerais, principalmente, as iniciativas estaduais para a melhoria da competitividade da cadeia produtiva de leite. Contudo, identificou-se uma lacuna entre essas iniciativas estaduais para a produção de leite e os programas governamentais para o tratamento dos dejetos gerados na pecuária leiteira.
Guest Editors’ Introduction Individual and Organizational Reintegration after Ethical or Legal Transgressions: Challenges and Opportunities
Authors: Goodstein Jerry , Butterfield Kenneth D. , Pfarrer Michael D. , Wicks Andrew C.
Published: July 2014

In this article we set the context for this special issue focusing on individual and organizational reintegration in the aftermath of transgressions that violate ethical and legal boundaries. Following a brief introduction to the topic we provide an overview of each of the four articles selected for this special issue. We then present a number of potentially fruitful empirical, theoretical, and normative directions management and ethics scholars might pursue in order to further advance this evolving literature.
Protecting Critical Control Systems
Authors: Dickinson Don
Published: July 2014

Cyber‐security threats, including cyber terrorism, have grown from the esoteric practice of a few specialists to a problem of general concern. National infrastructures have been found to be particularly vulnerable to such attacks. In response to this threat, several standards organizations have produced a wide array of standards and guidelines to help organizations implement security controls to mitigate the risk from cyber‐attacks.
Editorial
Authors: Marzal Felici Javier , Casero Ripollés Andreu
Published: July 2014

Editorial del número 7.
Construcción de la marca en la era de los medios digitales
Authors: Ros Diego Vicente
Published: July 2014

Artículo de la sección Tribuna: investigación y profesión.
La especialización como marca diferencial
Authors: Pardo Baldeón Ramón S.
Published: July 2014

ReseñaEsteve Ramírez, Francisco y Nieto Hernández, Juan Carlos (editores)Nuevos retos del Periodismo EspecializadoColección Universidad. Schedas, S. L.
Hidden Meaning: Andrew Lang, H. Rider Haggard, Sigmund Freud, and Interpretation
Authors: Psomiades Kathy Alexis
Published: July 2014

This essay examines the role Andrew Lang played in the circulation of ideas within and among the fields of anthropology, literature, and psychoanalysis in the late nineteenth and early twentieth centuries. Lang popularized anthropologist Edward Tylor’s theories about myth, and championed them against those of the philologist Max Müller. He provided the occasion for novelist H. Rider Haggard’s engagement with these ideas in the novel She, which Haggard dedicated to him, and he drew upon these theories of myth in essays that explain the value of Haggard’s novels. Finally, both Haggard’s novel and Lang’s anthropological writing shaped the work of Sigmund Freud. Attention to Lang’s role as a transmitter of the ideas of others across genres and disciplines allows us to see how central the problem of interpretation was to the disciplinary formation of anthropology, literature, and psychoanalysis.
Trysting Genres: Andrew Lang’s Fairy Tale Methodologies
Authors: Clark Hillard Molly
Published: July 2014

Andrew Lang represents an alternative model to the cult of the solo literary genius that occupied so much of the Victorian literary landscape, a model that is defined by collaboration and coterie production, and one that troubles the rigidities of discipline and genre. This essay, with Lang at its core, throws into relief the extent to which all authorship is a collective endeavor between forms and across time. While Lang’s entire oeuvre is important, this essay is most interested in his work on the fairy tale. For this essay, Lang is one practitioner of a kind of discourse generated in the wake of the Victorian fairy tale surge—the widespread incorporation of fairy tales into other Victorian literary and cultural forms like theater, fine arts, and literature. What a fairy tale was, and to whom or to what it belonged, were questions that frequently ran through contemporary discourse about literary production, like the copyright debates, the plagiarism debates, and the ongoing discussion about whether social science writing was or was not a kind of creative work. Lang’s treatment of the fairy tale, especially in his popular Colored Fairy Books, places him at the end of this century-long conversation about the nature of originality. This essay considers how Lang’s position at the center of multiple, linked networks might owe something, or everything, to his play with the fairy tale, arguably the most “networked” of forms. Lang’s very interdisciplinarity can help us to understand the extent to which the fairy tale’s language, figures, structure, authors, and methods of production had come to influence other forms of cultural production and consumption.
La perception différenciée de la relation élève-enseignant par les élèves à risque et non à risque de décrochage scolaire
Authors: Poirier Martine , Lessard Anne , Fortin Laurier , Yergeau Éric
Published: July 2014

Cette étude transversale vise à mieux comprendre le lien entre la qualité de la relation élève-enseignant, le risque de décrochage scolaire et le genre des élèves. À l’aide d’un devis descriptif-corrélationnel, nous avons examiné la perception de 756 élèves de deuxième secondaire. Les résultats indiquent que les élèves à risque perçoivent plus négativement la relation avec leur enseignant que les élèves non à risque. De plus, les filles manifestent des attitudes plus positives envers leur enseignant et considèrent que les règlements sont plus clairs que leurs pairs masculins. Cette étude contribue à l’avancement des connaissances en précisant que les différentes dimensions de la relation élève-enseignant (implication émotionnelle et soutien de l’enseignant, encadrement) sont toutes associées au risque de décrochage scolaire.
L’arrimage de l’intervention éducative et socioéducative en contexte de réussite éducative. Empowerment en perspective écosystémique et impact sur l’intervention
Authors: Larose François , Couturier Yves , Bédard Johanne , Larivée Serge J. , Boulanger Dany , Terrisse2 Bernard
Published: July 2014

Il y a une décennie, Lenoir, Larose, Deaudelin, Kalubi et Roy (2002) définissaient l’intervention éducative (IÉ) dans l’univers particulier de l’éducation et du travail enseignant. Dans un article subséquent (Terrisse, Larose et Couturier, 2003), nous réagissions au caractère restrictif du domaine d’application du concept d’IÉ par la proposition d’un construit complémentaire, celui d’intervention socioéducative (ISÉ). Dans cet article, nous resituons le construit d’ISÉ en fonction de la nécessaire complémentarité des intervenants dont l’action éducative se situe auprès de l’enfant dans l’école, dans la famille mais aussi dans la communauté ainsi qu’à la charnière de ces systèmes, tout particulièrement dans un contexte de «réussite éducative». L’articulation des deux construits, l’intervention éducative et socioéducative (IÉSÉ) se caractérise alors par le fondement écosystémique de son déploiement, la nature interdisciplinaire de sa mise en oeuvre et sa visée d’empowerment.
Étude de l’orthographe lexicale à domicile et soutien parental
Authors: Lévesque Jean-Yves , Gaté Jean-Pierre , Mansour Martine , Saint-Pierre Anabel
Published: July 2014

La recherche s’est intéressée au soutien parentalrelativement à l’étude de l’orthographelexicale à domicile chez des élèves du premiercycle primaire. Un entretien téléphonique individuel etstructuré a été réalisé avec 264parents dans sept régions au Québec. L’analyse deces entretiens a révélé que la plupart des parentsoffrent un soutien aux enfants, largement assumé par lesmères. Les élèves qui exercent de larésistance face à la leçon d’orthographeà domicile sont surtout des garçons et desélèves qui manifestent des difficultés enorthographe lexicale. Certaines stratégies d’étudeexemplaires proposées aux enfants sont plus grandementutilisées par des parents dans des écoles de milieufavorisé et ce sont des parents de filles qui ontévoqué le plus grand nombre de stratégiesd’étude proposées aux enfants.
Quelle place est accordée à la composante graphomotrice de l’écriture dans les classes au début du primaire? Enquête auprès d’enseignants québécois
Authors: Labrecque Anne-Marie , Morin Marie-France , Montésinos-Gelet Isabelle
Published: July 2014

Cette enquête traite d’une habileté de base, qui, comme tendent à le démontrer plusieurs recherches, serait nécessaire au développement de la compétence à écrire, mais qui reste pourtant négligée dans le curriculum scolaire actuel, soit l’aspect graphomoteur de l’écriture. Cent quatre-vingt-deux enseignants québécois du 1er cycle du primaire ont répondu à un questionnaire qui a permis de décrire, d’une part, leurs connaissances déclarées au regard de l’enseignement-apprentissage de la composante graphomotrice de l’écriture et, d’autre part, leurs pratiques déclarées en classe relatives à cette composante. L’analyse des résultats a fait ressortir que les connaissances des enseignants ne semblent pas s’appuyer sur une instruction formelle ou sur les connaissances scientifiques actuelles et que leurs pratiques sont assez diversifiées.
Scientists Track Sulfate Emissions Across Time
Authors: Wendel JoAnna
Published: July 2014

Scientists have a precise record of sulfate deposition from volcanoes stretching back 2000 years, a finding that will better inform future climate models and policy decisions. The new reconstruction was detailed in a paper published online on 6 July in Nature Climate Change (doi:10.1038/nclimate2293).
Synthesizing Remote Sensing Data on the Carbon and Water Cycles
Authors: Stavros E. Natasha , Jeong Su‐Jong , Bloom Anthony
Published: July 2014

This year two of NASA's Earth missions, Orbiting Carbon Observatory 2 (OCO‐2; http://oco.jpl.nasa.gov) and Soil Moisture Active Passive (SMAP; http://smap.jpl.nasa.gov), will collect data relating to water and carbon cycles at unprecedented spatial and temporal resolutions. Synthesizing these data provides unique opportunities for understanding interactions, patterns, underlying processes, and variability among climate, carbon, and hydrologic cycles.
Bitz, Ginoux, Jacobson, Nizkorodov, and Yang Receive 2013 Atmospheric Sciences Ascent Awards: Response
Authors: Bitz Cecilia M.
Published: July 2014

I am delighted and honored to receive this award. I am grateful to my nominators and to the AGU Atmospheric Sciences section for this recognition. Many of my students and colleagues have become my friends over the years. It has been a pleasure to share the joy of scientific discovery and companionship with them. I am also fortunate to have had teachers and advisors who inspired me and were generous with their time and encouragement.
Highly elliptical orbit satellites better at observing high‐latitude CO2
Authors: Wendel JoAnna
Published: July 2014

Boreal forests have a significant influence on the global carbon cycle. Arctic permafrost holds about twice the amount of carbon as the Earth's atmosphere. Since the boreal and Arctic region (50°N–90°N) has experienced the largest temperature increases in recent decades, understanding its influence on the global carbon cycle will become increasingly important as the climate continues to warm.
Assessing model representations of stratospheric equatorial waves
Authors: Schultz Colin
Published: July 2014

Some westward‐propagating Rossby‐gravity waves and eastward Kelvin waves can travel up through the atmosphere following their formation in the tropical troposphere. Once they reach the stratosphere, these waves dissipate, releasing their energy. Known as stratospheric equatorial waves, these Rossby‐gravity and Kelvin waves are an important aspect driving the quasi‐biennial oscillation (QBO), a roughly monthly reversal, in the direction of the equatorial stratospheric winds. Similar to other atmospheric systems, such as the El Niño–Southern Oscillation or the North Atlantic Oscillation, the phase of the QBO affects global weather patterns, particularly in North America and western Europe.
Atmospheric transport of mineral dust from the Indo‐Gangetic Plain: Temporal variability, acid processing, and iron solubility
Authors: Srinivas Bikkina , Sarin M. M. , Rengarajan R.
Published: July 2014

Atmospheric transport of chemical constituents from the Indo‐Gangetic Plain (IGP) to the Bay of Bengal is a conspicuous seasonal feature that occurs during the late NE‐monsoon (December–March). With this perspective, aerosol composition and abundance of mineral dust have been studied during November 2009 to March 2010 from a sampling site (Kharagpur: 22.3°N, 87.3°E) in the IGP, representing the atmospheric outflow to the Bay of Bengal. The chemical composition of PM2.5 suggests the dominance of nss‐
(6.9–24.3 µg m−3); whereas the abundance of mineral dust varied from 3 to 18 µg m−3. The concentration of aerosol iron (FeTot) and its fractional solubility (Fews % = Fews/FeTot *100, where Fews is the water‐soluble fraction of FeTot) varied from 60 to 1144 ng m−3 and from 6.7 to 26.5%, respectively. A striking similarity in the temporal variability of total inorganic acidity (TIA = 
 + nss‐
) and Fews (%) provides evidence for acid processing of mineral dust (alluvium) during atmospheric transport from the IGP. The contribution of TIA to water‐soluble inorganic species [(nss‐
 + 
)/ΣWSIS], mass ratios of Ca/Al and Fe/Al, and abundance of dust (%) and Fews (%) in the IGP‐outflow are similar to the aerosol composition over the Bay of Bengal. With the rapid increase in anthropogenic activities over south and south‐east Asia, the enhanced fractional solubility of aerosol iron (attributed to acid processing of mineral dust) has implications to further increase in the air‐sea deposition of Fe to the Ocean surface.
Assessing the temporal variability in extreme storm‐tide time series for coastal flood risk assessment
Authors: Quinn N. , Lewis M. , Wadey M. P. , Haigh I. D.
Published: July 2014

The probability of extreme storm‐tide events has been extensively studied; however, the variability within the duration of such events and implications to flood risk is less well understood. This research quantifies such variability during extreme storm‐tide events (the combined elevation of the tide, surge, and their interactions) at 44 national tide gauges around the UK. Extreme storm‐tide events were sampled from water level measurements taken every 15 min between 1993 and 2012. At each site, the variability in elevation at each time step, relative to a given event peak, was quantified. The magnitude of this time series variability was influenced both by gauge location (and hence the tidal and nontidal residual characteristics) and the time relative to high water. The potential influence of this variability on coastal inundation was assessed across all UK gauge sites, followed by a detailed case study of Portsmouth. A two‐dimensional hydrodynamic model of the Portsmouth region was used to demonstrate that given a current 1 in 200 year storm‐tide event, the predicted number of buildings inundated differed by more than 30% when contrasting simulations forced with the upper and lower bounds of the observed time series variability. The results indicate that variability in the time series of the storm‐tide event can have considerable influence upon overflow volumes, hence with implications for coastal flood risk assessments. Therefore, further evaluating and representing this uncertainty in future flood risk assessments is vital, while the envelopes of variability defined in this research provides a valuable tool for coastal flood modelers.
Intermetallic Layer Growth Kinetics in Sn‐Ag‐Cu System using Diffusion Multiple and Reflow Techniques
Authors: Pawełkiewicz Magdalena , Danielewski Marek , Janczak‐Rusch Jolanta
Published: July 2014

A diffusion multiple (DM) technique was applied to the Sn‐Ag‐Cu ternary system with the aim to determine the kinetics of formation of Cu‐Sn intermetallic compounds (IMCs) and to predict properties of the interface in the solder joints. The formation and growth of the Cu‐Sn intermetallics at the interface between the Cu as a base material and Sn‐Ag‐(Cu) solder was additionally studied during a standard reflow soldering process. Based on the experimental data, the kinetic rate constants and the respective activation energies of the Cu‐Sn IMCs in the temperature range between 150 and 200 °C were calculated and compared with experimental data from the literature. In this way, the mechanism of the pure solid‐state reaction (DM technique) and liquid phase reaction (reflow soldering) were studied. The limitations of DM techniques for the prediction of the IMCs growth during reflow soldering process are discussed as well.
The Influence of Solubilizing Chain Stereochemistry on Small Molecule Photovoltaics
Authors: Zerdan Raghida Bou , Shewmon Nathan T. , Zhu Yu , Mudrick John P. , Chesney Kyle J. , Xue Jiangeng , Castellano Ronald K.
Published: July 2014

Three stereochemically pure isomers and two isomeric mixtures of a solution‐processable diketopyrrolopyrrole‐containing oligothiophene (SMDPPEH) have been used to study the effect of 2‐ethylhexyl solubilizing group stereochemistry on the film morphology and bulk heterojunction (BHJ) solar cell characteristics of small molecule organic photovoltaics. The different SMDPPEH stereoisomer compositions exhibit nearly identical optoelectronic properties in the molecularly dissolved state, as well as in amorphous films blended with PCBM. However, for films in which SMDPPEH crystallization is induced by thermal annealing, significant differences in molecular packing between the different stereoisomer formulations are observed. These differences are borne out in photovoltaic device characteristics for which unannealed devices show very similar behavior, while after annealing the RR‐ and SS‐SMDPPEH enantiomers show blue‐shifted peak EQE relative to the SMDPPEH isomer mixtures. Unannealed devices made from the most crystalline stereoisomer, meso RS‐SMDPPEH, are not completely amorphous, and show improved photocurrent generation as a result. Unlike the other compounds, after thermal annealing the RS‐SMDPPEH devices show reduced device performance. The results reveal that the chirality of commonly used 2‐ethylhexyl solubilizing chains can have a significant effect on the morphology, absorption, and optimum processing conditions of small molecule organic thin films used as photovoltaic device active layers.
Dielectric Spectroscopy of Pristine and O7+ Ion Irradiated NCO‐Terminated Polybutadiene‐Based Liquid Crystalline Polyurethane
Authors: Lal Sohan , Quamara Jitendra K.
Published: July 2014

The dielectric constant (ε′) and loss factor (ε′′) have been measured in NCO‐terminated polybutadiene‐based pristine and 100 MeV O7+ ion irradiated liquid crystalline polyurethane in the temperature region of 80–300 K at frequencies ranging from 1 KHz to 1 MHz. The variation in ε′with temperature in different temperature regions has been analyzed in relation to the dipole structure of the molecules. The ε′′–T plots of pristine liquid crystalline polyurethane (LCPU) reveal the presence of multiple relaxation processes associated with the crankshaft motion of but‐2‐ene groups, dipolar nature of carbonyl groups, and glass transition temperature, respectively. An additional dielectric loss peak is observed in irradiated LCPU samples associated with the Maxwell–Wagner–Sillars (MWS) polarization. There is an overall increase in ε′ in irradiated samples due to the dominance of MWS polarization arising from the large number of radiation‐induced defect sites and free radicals. The loss in γ relaxation due to chain scissions of but‐2‐ene groups and the formation of new subpolar groups providing a new dipolar relaxation process is observed in irradiated LCPU samples. The variation in ε′ with fluence shows the occurrence of a secondary radiation induced crystallization in irradiated LCPU samples. The X‐ray diffraction analysis also shows the effect of fluence on the crystalline nature of LCPU samples.
Preparation of MoS2–MoO3 Hybrid Nanomaterials for Light‐Emitting Diodes
Authors: Yin Zongyou , Zhang Xiao , Cai Yongqing , Chen Junze , Wong Jen It , Tay Yee‐Yan , Chai Jianwei , Wu Jumiati , Zeng Zhiyuan , Zheng Bing , Yang Hui Ying , Zhang Hua
Published: July 2014

A facile strategy to prepare MoS2–MoO3 hybrid nanomaterials is developed, based on the heat‐assisted partial oxidation of lithium‐exfoliated MoS2 nanosheets in air followed by thermal‐annealing‐driven crystallization. The obtained MoS2–MoO3 hybrid nanomaterial exhibits p‐type conductivity. As a proof‐of‐concept application, an n‐type SiC/p‐type MoS2–MoO3 heterojunction is used as the active layer for light‐emitting diodes. The origins of the electroluminescence from the device are theoretically investigated. This facile synthesis and application of hybrid nanomaterials opens up avenues to develop new advanced materials for various functional applications, such as in electrics, optoelectronics, clean energy, and information storage.
Surface‐Confined Self‐Assembled Janus Tectons: A Versatile Platform towards the Noncovalent Functionalization of Graphene
Authors: Du Ping , Jaouen Maud , Bocheux Amandine , Bourgogne Cyril , Han Zheng , Bouchiat Vincent , Kreher David , Mathevet Fabrice , Fiorini‐Debuisschert Céline , Charra Fabrice , Attias André‐Jean
Published: July 2014

A general strategy for simultaneously generating surface‐based supramolecular architectures on flat sp2‐hybridized carbon supports and independently exposing on demand off‐plane functionality with controlled lateral order is highly desirable for the noncovalent functionalization of graphene. Here, we address this issue by providing a versatile molecular platform based on a library of new 3D Janus tectons that form surface‐confined supramolecular adlayers in which it is possible to simultaneously steer the 2D self‐assembly on flat C(sp2)‐based substrates and tailor the external interface above the substrate by exposure to a wide variety of small terminal chemical groups and functional moieties. This approach is validated throughout by scanning tunneling microscopy (STM) at the liquid–solid interface and molecular mechanics modeling studies. The successful self‐assembly on graphene, together with the possibility to transfer the graphene monolayer onto various substrates, should considerably extend the application of our functionalization strategy.
Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp2)H and C(sp3)H Bonds at δ‐ and ε‐Positions
Authors: Wang Chao , Chen Changpeng , Zhang Jingyu , Han Jian , Wang Qian , Guo Kun , Liu Pei , Guan Mingyu , Yao Yingming , Zhao Yingsheng
Published: July 2014

An easily synthesized and accessible N,O‐bidentate auxiliary has been developed for selective CH activation under palladium catalysis. The novel auxiliary showed its first powerful application in CH functionalization of remote positions. Both C(sp2)H and C(sp3)H bonds at δ‐ and ε‐positions were effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium‐catalyzed intramolecular CH amination.
Phosphoric Acid Catalyzed Desymmetrization of Bicyclic Bislactones Bearing an All‐Carbon Stereogenic Center: Total Syntheses of (−)‐Rhazinilam and (−)‐Leucomidine B
Authors: Gualtierotti Jean‐Baptiste , Pasche Delphine , Wang Qian , Zhu Jieping
Published: July 2014

In the presence of a catalytic amount of an imidodiphosphoric acid, enantioselective desymmetrization of bicyclic bislactones by reaction with alcohols took place smoothly to afford enantiomerically enriched monoacids having an all‐carbon stereogenic center. Concise catalytic enantioselective syntheses of both (−)‐rhazinilam and (−)‐leucomidine B were subsequently developed using (S)‐methyl 4‐ethyl‐4‐formylpimelate monoacid as a common starting material.
Evidence‐based decision about test scoring rules in clinical anatomy multiple‐choice examinations
Authors: Severo Milton , Gaio A. Rita , Povo Ana , Silva‐Pereira Fernanda , Ferreira Maria Amélia
Published: July 2014

In theory the formula scoring methods increase the reliability of multiple‐choice tests in comparison with number‐right scoring. This study aimed to evaluate the impact of the formula scoring method in clinical anatomy multiple‐choice examinations, and to compare it with that from the number‐right scoring method, hoping to achieve an evidence‐based decision about test scoring rules. Two hundred and ninety‐eight students completed an examination in clinical anatomy which included 40 multiple‐choice questions with five response options each. Among these, 245 (82.2%) examinees were assessed according to the number‐right scoring method (group A) while 53 (17.8%) were assessed according to the formula scoring method (group B). The prevalence of passing was significantly higher in group A than in group B, after correction of the pass and fail cutoffs for guessing (84.9% vs. 62.3%, P = 0.005), keeping a similar reliability in both groups (0.7 vs. 0.8, P = 0.094). Pearson Correlation coefficients between practical and theoretical examination scores were 0.66 [95%CI = (0.58–0.73)] and 0.72 [95%CI = (0.56–0.83)] for groups A and B, respectively. Based solely on the reliability and validity assessments, the test‐maker could therefore use either scoring rules; however, if the test‐maker also takes into account the students' ability to deduce answers with partial knowledge, then the number‐right score rule is most appropriate. Anat Sci Educ 8: 242–248. © 2014 American Association of Anatomists.
A new approach to measure the scientific strengths of territories
Authors: Abramo Giovanni , D'Angelo Ciriaco Andrea , Di Costa Flavia
Published: July 2014

The current work applies a method for mapping the supply of new knowledge from public research organizations, in this case from Italian institutions at the level of regions and provinces (NUTS2 and NUTS3). Through the analysis of scientific production indexed in the Web of Science for the years 2006–2010, the new knowledge is classified in subject categories and mapped according to an algorithm for the reconciliation of authors' affiliations. Unlike other studies in the literature based on simple counting of publications, the present study adopts an indicator, Scientific Strength, which takes account of both the quantity of scientific production and its impact on the advancement of knowledge. The differences in the results that arise from the 2 approaches are examined. The results of works of this kind can inform public research policies, at national and local levels, as well as the localization strategies of research‐based companies.
A Mix‐and‐Read Fluorescence Strategy for the Switch‐On Probing of Kinase Activity Based on an Aptameric‐Peptide/Graphene‐Oxide Platform
Authors: Lei Chunyang , Xu Xiahong , Zhou Jiang , Liu Xin , Nie Zhou , Qing Meng , Li Pei , Huang Yan , Yao Shouzhuo
Published: July 2014

Protein kinase plays a vital role in regulating signal‐transduction pathways and its simple and quick detection is highly desirable because traditional kinase assays typically rely on a time‐consuming kinase‐phosphorylation process (ca. 1 h). Herein, we report a new and rapid fluorescence‐based sensing platform for probing the activity of protein kinase that is based on the super‐quenching capacity of graphene oxide (GO) nanosheets and specific recognition of the aptameric peptide (FITC‐IP20). On the GO/peptide platform, the fluorescence quenching of FITC‐IP20 that is adsorbed onto GO can be restored by selective binding of active protein kinase to the aptameric peptide, thereby resulting in the fast switch‐on detection of kinase activity (ca. 15 min). The feasibility of this method has been demonstrated by the sensitive measurement of the activity of cAMP‐dependent protein kinase (PKA), with a detection limit of 0.053 mU μL−1. This assay technique was also successfully applied to the detection of kinase activation in cell lysate.
Mechanistic Switching by Hydronium Ion Activity for Hydrogen Evolution and Oxidation over Polycrystalline Platinum Disk and Platinum/Carbon Electrodes
Authors: Shinagawa Tatsuya , Garcia‐Esparza Angel T. , Takanabe Kazuhiro
Published: July 2014

Fundamental electrochemical reactions, namely the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), are re‐evaluated under various pH conditions over polycrystalline Pt disk electrodes and Pt/C electrodes to investigate the overpotential and Tafel relations. Kinetic trends are observed and can be classified into three pH regions: acidic (1–5), neutral (5–9), and alkaline (9–13). Under neutral conditions, in which H2O becomes the primary reactant, substantial overpotential, which is not affected by pH and the supporting electrolyte type, is required for electrocatalysis in both directions. This ion independence, including pH, suggests that HER/HOR performance under neutral conditions solely reflects the intrinsic electrocatalytic activity of Pt in the rate determining steps, which involve electron transfer with water molecules. A global picture of the HER/HOR, resulting from mechanistic switching accompanied by change in pH, is detailed.
Electrodeposition of Zinc Nanorods from Ionic Liquid into Porous Anodic Alumina
Authors: Starykevich Maksim , Lisenkov Aleksey D. , Salak Andrei N. , Ferreira Mario G. S. , Zheludkevich Mikhail L.
Published: July 2014

Electrochemical deposition of zinc nanorods into the anodic aluminium‐oxide template from ionic‐liquid electrolyte is reported. For the first time, the electrodeposition from an ionic liquid is performed in a porous alumina template, anodically grown on the aluminium substrate without complete removal of the barrier layer. The two‐step process was applied; first, with alternating‐current pulse nucleation of zinc nanoparticles on the bottom of the pores, followed by direct‐current growth of the rods. The electrolyte consisted of 0.5 M ZnCl2 in choline chloride and ethylene glycol in a 1:2 molar ratiod. The resulting zinc nanorods are approximately 3 μm in length and 70 nm in diameter. The achieved fill factor of the pores is in the 70–80 % range.
Discovery of New Oxygen Evolution Reaction Electrocatalysts by Combinatorial Investigation of the Ni–La–Co–Ce Oxide Composition Space
Authors: Haber Joel A. , Guevarra Dan , Jung Suho , Jin Jian , Gregoire John M.
Published: July 2014

We report a new family of earth‐abundant electrocatalysts for the oxygen evolution reaction (OER) discovered via high‐throughput screening of 1771 discrete metal oxide compositions covering the nickel–lanthanum–cobalt–cerium composition space. The catalytic performance of each of these compositions was measured under conditions applicable to distributed solar fuel generation using a three‐electrode scanning‐drop electrochemical cell. These high‐throughput measurements show enhanced activity for catalyst compositions containing 20–65 metal atom % Ce. The catalytic activity and stability of a representative highly active composition (Ni0.1La0.1Co0.3Ce0.5)Ox was verified by standard rotating‐disc electrochemistry. Catalysts of this composition showed stable operational performance at 10 mA cm−2 for 2 h and survived a 100 h endurance test in a testbed electrolyzer.
Total Synthesis of (−)‐Platensimycin by Advancing Oxocarbenium‐ and Iminium‐Mediated Catalytic Methods
Authors: Eey Stanley T.‐C. , Lear Martin J.
Published: July 2014

(−)‐Platensimycin is a potent inhibitor of fatty acid synthase that holds promise in the treatment of metabolic disorders (e.g., diabetes and “fatty liver”) and pathogenic infections (e.g., those caused by drug‐resistant bacteria). Herein, we describe its total synthesis through a four‐step preparation of the aromatic amine fragment and an improved stereocontrolled assembly of the ketolide fragment, (−)‐platensic acid. Key synthetic advances include 1) a modified Lieben haloform reaction to directly convert an aryl methyl ketone into its methyl ester within 30 seconds, 2) an experimentally improved dialkylation protocol to form platensic acid, 3) a sterically controlled chemo‐ and diastereoselective organocatalytic conjugate reduction of a spiro‐cyclized cyclohexadienone by using the trifluoroacetic acid salt of α‐amino di‐tert‐butyl malonate, 4) a tetrabutylammonium fluoride promoted spiro‐alkylative para dearomatization of a free phenol to assemble the cagelike ketolide core with the moderate leaving‐group ability of an early tosylate intermediate, and 5) a bismuth(III)‐catalyzed Friedel–Crafts cyclization of a free lactol, with LiClO4 as an additive to liberate a more active oxocarbenium perchlorate species and suppress the Lewis basicity of the sulfonyloxy group. The longest linear sequence is 21 steps with an overall yield of 3.8 % from commercially available eugenol.
Quantum Mechanics/Molecular Mechanics Studies on the Mechanism of Action of Cofactor Pyridoxal 5′‐Phosphate in Ornithine 4,5‐Aminomutase
Authors: Pang Jiayun , Scrutton Nigel S. , Sutcliffe Michael J.
Published: July 2014

A computational study was performed on the experimentally elusive cyclisation step in the cofactor pyridoxal 5′‐phosphate (PLP)‐dependent D‐ornithine 4,5‐aminomutase (OAM)‐catalysed reaction. Calculations using both model systems and a combined quantum mechanics/molecular mechanics approach suggest that regulation of the cyclic radical intermediate is achieved through the synergy of the intrinsic catalytic power of cofactor PLP and the active site of the enzyme. The captodative effect of PLP is balanced by an enzyme active site that controls the deprotonation of both the pyridine nitrogen atom (N1) and the Schiff‐base nitrogen atom (N2). Furthermore, electrostatic interactions between the terminal carboxylate and amino groups of the substrate and Arg297 and Glu81 impose substantial “strain” energy on the orientation of the cyclic intermediate to control its trajectory. In addition the “strain” energy, which appears to be sensitive to both the number of carbon atoms in the substrate/analogue and the position of the radical intermediates, may play a key role in controlling the transition of the enzyme from the closed to the open state. Our results provide new insights into several aspects of the radical mechanism in aminomutase catalysis and broaden our understanding of cofactor PLP‐dependent reactions.
Regioselective Conversion of Arenes to N‐aryl‐1,2,3‐triazoles Using CH Borylation
Authors: Srinivasan Rajavel , Coyne Anthony G. , Abell Chris
Published: July 2014

A one‐pot protocol for the synthesis of N‐aryl 1,2,3‐triazoles from arenes by an iridium‐catalyzed CH borylation/copper catalyzed azidation/click sequence is described. 1 mol % of Cu(OTf)2 was found to efficiently catalyze both the azidation and the click reaction. The applicability of this method is demonstrated by the late‐stage chemoselective installation of 1,2,3‐triazole moiety into unactivated molecules of pharmaceutical importance.
Methandiide as a Non‐Innocent Ligand in Carbene Complexes: From the Electronic Structure to Bond Activation Reactions and Cooperative Catalysis
Authors: Becker Julia , Modl Tanja , Gessner Viktoria H.
Published: July 2014

The synthesis of a ruthenium carbene complex based on a sulfonyl‐substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal–carbon interaction can be tuned between a RuC single bond with additional electrostatic interactions and a RuC double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non‐polar bonds (OH, HH) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non‐innocent ligand supporting the bond activation as nucleophilic center in the 1,2‐addition across the metal–carbon double bond. This metal–ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis.
Heteroscedastic modelling via the autoregressive conditional variance subspace
Authors: Park Jin‐Hong , Samadi S. Yaser
Published: July 2014

The paper deals with nonparametric estimation of the conditional variance of a time series based on a nonlinear autoregressive model in the squared innovation time series, which does not require specification of a model. We introduce a notion called the autoregressive central variance subspace (ACVS) to obtain the information included in the conditional variance of time series data. We use the squared time series to identify the ACVS by a nonparametric kernel method. In addition, we simultaneously estimate the unknown dimension and lag of the ACVS by a modified information criterion. Finally, we investigate the performance of all the estimators including the ACVS through simulations and a real analysis, which suggests implementing a new dimension reduction approach to modelling time series data that exhibits volatility. The Canadian Journal of Statistics 42: 423–435; 2014 © 2014 Statistical Society of Canada
Amphiphilic Bicyclic Peptides as Cellular Delivery Agents
Authors: Oh Donghoon , Darwish Shaban Anwar , Shirazi Amir Nasrolahi , Tiwari Rakesh Kumar , Parang Keykavous
Published: July 2014

Two bicyclic peptides composed of tryptophan and arginine residues were synthesized from monocyclic peptide building blocks and evaluated as cellular delivery agents. [W5G]‐(triazole)‐[KR5] and [W5E]‐(β‐Ala)‐[KR5] containing triazole and β‐alanine linkers improved the cellular delivery of fluorescein (F′)‐labeled phosphopeptide F′‐GpYEEI (F′‐PP) by 7.6‐ and 19.3‐fold, respectively, in human ovarian adenocarcinoma cells. However, parent monocyclic peptide [R5] and monocyclic peptide [WR]4 only enhanced the cellular uptake of the phosphopeptide by only 1.3‐ and 3.7‐fold, respectively. Confocal microscopy showed that the corresponding fluorescein‐labeled bicyclic peptide F′‐[KW4E]‐(β‐Ala)‐[KR5] was localized in the cytosol and nucleus. Studying the cellular uptake of F′‐[KW4E]‐(β‐Ala)‐[KR5] in the presence of endocytosis inhibitors indicated that the clathrin‐ and caveolin‐dependent endocytosis are the main pathways for cellular uptake. The bicyclic peptide was able to improve antiproliferative activity of doxorubicin by 20 %. These data suggest that this bicyclic peptide can be utilized as a new class of cell‐penetrating peptides and cellular delivery tools.