bluuebunny/crossref_metadata_2025 huggingface dataset:
O que leva homens a se tornar cuidadores informais: um estudo qualitativo
Authors: Moherdaui Julia Horita , Fernandes Carmen Luiza Correa , Soares Konrad Gutterres
Published: October 2019

Introdução: O aumento da expectativa de vida tem levado a um aumento do número de pessoas que necessitam de cuidado, sendo a maior parte dele exercido por cuidadores informais e do sexo feminino. Entretanto, diversos estudos têm apontado um aumento no número de cuidadores masculinos. Neste contexto, este estudo pretende elencar motivações que levam homens a serem cuidadores informais. Métodos: Estudo qualitativo com entrevistas semiestruturadas, questionários sociodemográficos e questionários de Zarit em dez cuidadores homens inscritos no programa de atenção domiciliar de duas unidades de saúde de Porto Alegre. Resultados e Discussão: As motivações identificadas na prestação do cuidado foram a obrigação e a reciprocidade. A obrigação foi citada por todos os cuidadores e a falta de rede de apoio pareceu reforçá-la. A reciprocidade foi mencionada em quatro entrevistas e possuía maior correlação com o grau de parentesco “filho”. Estudos apontam que a motivação “obrigação” parece se correlacionar com maiores índices de sobrecarga, depressão e ansiedade quando comparado a um cuidado motivado pela reciprocidade. Na escala de Zarit, nenhum cuidador apresentou índice de sobrecarga severa, o que pode ter relação com uma maior procura por suporte social. Conclusão: Nota-se como é amplo e desconhecido o tema da relação da masculinidade com o papel de cuidador. Contudo, observou-se correlação entre o gênero e as motivações como obrigação e reciprocidade na prestação do cuidado, e insinua-se uma maior sobrecarga quando obrigação é o principal fator motivador.
Cipozeiras e cipozeiros da Mata Atlântica e conflitos ambientais territoriais em Santa Catarina
Authors: Da Silva Grava Diego , Florit Luciano Félix , Ladik Antunes Douglas
Published: October 2019

Cipozeiras e cipozeiros constituem “comunidades tradicionais” que vivem da extração e do artesanato de diferentes espécies de cipós e de outras atividades de subsistência. Nosso objetivo foi identificar e caracterizar as comunidades em Santa Catarina e verificar a existência de situações de conflitos ambientais. Para isso, efetuamos uma revisão bibliográfica e realizamos, à luz da perspectiva da justiça ambiental, uma reflexão crítica sobre a situação dessas populações no estado. Apresentamos as cipozeiras e os cipozeiros como pertencentes à categoria de “povos e comunidades tradicionais” e evidenciamos que estes grupos vivenciam diferentes conflitos ambientais. Esses conflitos se caracterizam como situações de injustiça ambiental, o que parece um fenômeno comum e recorrente entre os povos e comunidades tradicionais em Santa Catarina e em todo o Brasil.
PINTO-COELHO, Ricardo Motta; HAVENS, Karl. Gestão de recursos hídricos em tempos de crise. Porto Alegre: Artmed Editora, 2016. 240 p.
Authors: Morais Bárbara Oliveira de , Lopes Alexandre Ferreira
Published: October 2019

O livro “Gestão de recursos hídricos em tempos de crise” é uma obra que se difere das demais na área, pois traz à tona aspectos pouco encontrados quando se trata de discussões sobre o cenário global dos recursos hídricos no planeta. Uma das questões que se destacaram como foco principal dos autores se referiu ao cuidado de trazer para o leitor informações que permitissem demonstrar a colaboração do homem nos efeitos de transformação nos principais ecossistemas (rios, lagos, reservatórios, estuários e áreas litorâneas, aquíferos, geleiras e capotas polares).Os autores se preocuparam em tecer considerações acerca da importância ecológica e ambiental utilizando-se de estudos de casos que foram apresentados para sustentar os exemplos e discussões que envolveram como citado no tópico anterior, a contribuição da humanidade nos impactos aos ecossistemas, gerando conflitos sociais, econômicos e geopolíticos.O professor Ricardo Motta é Pesquisador no Departamento de Biologia Geral da Universidade Federal de Minas Gerais (UFMG) e no ano de 2009 lançou a obra Reciclagem e Desenvolvimento Sustentável no Brasil. Já o professor Karl Havens atua no Instituto de Agricultura e Cie?ncias Agra?rias da University of Florida (UF/IFAS). Os professores possuem larga experiência e produção científica na área de limnologia (hidrobiologia) cuja ciência trata do estudo da ecologia das águas continentais.
Modelo holístico: respaldo teórico para ensino de L2 e avaliação de materiais didáticos
Authors: Pinto Cândida Martins , Braida Fabrícia Cavichioli
Published: October 2019

The aim of this paper is to present some relevant issues about the elaboration of materials for teaching a second language taking into account the Richter’s Holistic Model. Examples of task-based learning exercises of a class will be showed in order to give theoretical support for evaluation criterions of didactic materials.
Teoria da atividade e modelos de leitura em livros didáticos de Português – L2
Authors: Pinto Cândida Martins , Richter Marcos Gustavo
Published: October 2019

Nowadays, considering the process of a foreign language or second language acquisition, a big importance is given to the previous knowledge of the learner: top-down model. As the same rule, bottom-up model, involving formal and grammatical aspects, has its relevance in a second stage of the learning. A mature learner is that who is able to link these two models during the reading, using, thus, the interactive model. Considering this, this study aims to, in a first stage, discuss relevant questions for the use of the three models in language classes in general and in Portuguese for foreigner classes in particular, as well as the importance of them for a good reading. In a second stage, a Portuguese for foreigners textbook will be analyzed, according to Activity Theory, in order to verify when the models appear in reading tasks.
O material didático no ensino de línguas
Authors: Richter Marcos Gustavo
Published: October 2019

O autor não elaborou um resumo.
Teoria da atividade e mediação tecnológica: exemplar de uma prática desenvolvida no AMEM
Authors: Alberti Taís Fim , Bastos Fábio Da Purificação de
Published: October 2019

Com o surgimento da Internet, os Ambientes Virtuais de Ensino-Aprendizagem (AVEA) representam um recurso didático que pode viabilizar os processos de formação, oportunizando acesso a escolarização. Esses AVEA permitem um trabalho didático-metodológico integrando diversas ferramentas que contribuem na realização de uma prática dialógica e problematizadora. Etnografamos a constru- ção da prática docente mediada por um AVEA (AMEM) em um curso de formação continuada, onde observamos que as atividades de estudo e a educação dialógico-problematizadora integradas ao planejamento dos conceitos a serem aprendidos potencializam o processo de aquisição dos conhecimentos teóricos, promovendo desenvolvimento psicointelectual. Destacamos que a diretividade dos professores foi fundamental nessa experiência mediada por tecnologias.
A Teoria Atribucional: (re)conceituando a motivação na aprendizagem
Authors: Andrade Rogério Alencar Ferraz de
Published: October 2019

Este artigo tem por objetivo propor alguns aspectos referentes às possíveis variáveis intervenientes na formação dos conceitos de motivação para a aprendizagem e suas implicações na práxis educacional. Trata-se de investigar a que ou a quem o sujeito atribui o êxito ou o fracasso de seus empreendimentos e como isso interfere na consecução de novos objetivos. Examina-se ainda como a teoria da atribuição compreende a motivação para a aprendizagem. E, por fim, que caminhos os educadores podem tomar no sentido de re-significar suas compreensões acerca do desempenho positivo ou negativo dos educandos.
Formação de conceitos no ensino de língua materna: o princípio da funcionalidade
Authors: Motta Vaima Regina Alves
Published: October 2019

Este artigo visa a examinar aspectos da perspectiva vygotskiana sobre a formação de conceitos no que tange a sua importância para a ação pedagógica no ensino de línguas. Propõe-se uma releitura do desafio de ensinar português como língua materna a partir de uma experiência vivida em uma escola pública do município de Cruz Alta-RS, no ano de 2004. O problema didático focalizado foi o ensino do emprego adequado dos principais sinais de pontuação. O trabalho busca ainda estabelecer um elo entre a teoria visitada e a experiência pedagógica relatada, ou seja, dar conta das questões suscitadas em nível teórico-prático.
A colaboração fortalecendo a prática
Authors: Cortelini Caroline Machado , Grabauska Claiton José
Published: October 2019

Este artigo propõe-se compartilhar nossas reflexões e experiências referentes à construção de uma prática colaborativa, apontando a colaboração como categoria orientadora das práticas educativas. Norteamo-nos pelos fundamentos da educação dialógico-problematizadora (Freire, 1988) e na investigação-ação educacional (Carr e Kemmis, 1988), a fim de propor uma perspectiva de educação crítica que se alicerce sobre o diálogo, a colaboração e a auto-reflexão. Aponta-se a colaboração como possibilidade de melhora e transformação das práticas educativas e do resgate do poder profissional. Ressalta-se o papel do professor como intelectual transformador, investigador da sua prática, na busca de compreendê-la, melhorá-la e transformá-la. Assinala-se a investigação-ação educacional como processo de investigação que atua transformativamente no âmbito do trabalho individual e coletivo. Ela cria condições que permitem a constituição de comunidades auto-criticas de investigação, composta por pessoas que participam e colaboram em todas as fases do processo de investigação.  Delineamos algumas considerações referentes à prática educativa no sentido de antevermos a possibilidade de através de um processo colaborativo compreendê-las e transformá-las, pensando em transformação social efetiva, a partir da transformação das práticas de grupos organizados.
Conceitos de leitura de professores em formação inicial: um estudo de caso
Authors: Moreira Tânia Maria
Published: October 2019

É sabido que as dificuldades de leitura apresentadas pelos alunos têm sua origem em fatores de diferentes ordens, tais como: social, econômico, político e educacional; e que o caminho para solucionar o problema consiste em desenvolver ações e pesquisas sobre esses fatores. Em um estudo realizado procurou-se centrar a atenção em questões educacionais, mais especificamente sobre a formação de conceitos de leitura de acadêmicos em formação. Neste trabalho, desenvolveu-se uma experiência pedagógica com o objetivo de investigar e descrever os processos cognitivos e eventuais evoluções na formação de conceitos de leitura de acadêmicos-estagiários de língua materna, do Curso de Letras da UFSM, a partir de registros retrospectivos e prospectivos revelados em diários.
O PROCESSO DA LEITURA EM MANCHETES DE JORNAIS
Authors: Albuquerque Maria Eulalia Tomasi
Published: October 2019

O PROCESSO DA LEITURA EM MANCHETES DE JORNAIS
EXPRESSÕES ESTEREOTIPADAS E ESTRUTURA TEXTUAL
Authors: Teixeira Jamir Soriano
Published: October 2019

EXPRESSÕES ESTEREOTIPADAS E ESTRUTURA TEXTUAL
EDUCAÇÃO: MATRIZ DE TODO PROJETO FORMATIVO
Authors: Pontes Beatriz Santos
Published: October 2019

EDUCAÇÃO: MATRIZ DE TODO PROJETO FORMATIVO
AUTONOMIA E EDUCAÇÃO HOJE: ALGUMAS CONSIDERAÇÕES
Authors: Richter Marcos Gustavo , Cechin Marizete Righi
Published: October 2019

AUTONOMIA E EDUCAÇÃO HOJE: ALGUMAS CONSIDERAÇÕES
A DISSERTAÇÃO COMO EXERCÍCIO ESCOLAR
Authors: Albuquerque Maria Eulalia Tomasi
Published: October 2019

A DISSERTAÇÃO COMO EXERCÍCIO ESCOLAR
FORMAÇÃO DE PROFESSORES EM COMUNIDADES DE APRENDIZAGEM
Authors: Grabauska Claiton José
Published: October 2019

FORMAÇÃO DE PROFESSORES EM COMUNIDADES DE APRENDIZAGEM
Rio-Paris: primórdios da publicação da Literatura Brasileira chez Garnier
Authors: Granja Lúcia
Published: October 2019

Este artigo dá notícias de nossas últimas pesquisas sobre as atividades de Baptiste-Louis Garnier, livreiro e editor francês estabelecido no Rio de Janeiro, em suas relações como mundo editorial francês: métodos, procedimentos, livros, autores e editores. As trocasculturais entre esses dois sistemas ajudaram a consolidar o cânone dos autores e obrasda Literatura Brasileira no século XIX e o estudo dessas relações poderá detalhar algumasinformações que, até hoje, forneceu-nos a história da Literatura Brasileira, contribuindo paraum maior conhecimento do processo de produção e circulação de obras literárias no Brasil.
Desenvolvimento da consciência fonológica: uma proposta de trabalho com o gênero trava-língua
Authors: Corbari Clarice Cristina , Niedermayer Luci Piletti , Baumgartner Carmen Teresinha
Published: October 2019

Este artigo apresenta algumas reflexões sobre o trabalho com gêneros textuais e o desenvolvimento da consciência fonológica no processo de aquisição da leitura e escrita, bem como descreve uma proposta de trabalho com o gênero trava-língua para alunos em fase de alfabetização. Trata-se de pesquisa-ação pautada na perspectiva da relação necessária entre alfabetização e letramento, em que se busca desenvolver as habilidades de leitura e escrita voltadas aos usos sociais da linguagem ao mesmo tempo em que promove a apropriação do sistema de escrita alfabética.
Modeling Bubble Entrainment and Transport for Ship Wakes: Progress Using Hybrid RANS/LES Methods
Authors: Li Jiajia , Yuan Ben , Carrica Pablo M.
Published: October 2019

This article presents progress on modeling bubble entrainment and transport around ships using hybrid Reynolds-averaged Navier-Stokes/large eddy simulation (RANS/ LES) methods. Previous results using a Boltzmann-based polydisperse bubbly flow model show that LES perform better than RANS in predicting transport of bubbles to depth, a very important process to predict bubbly wakes. However, standard DES-type models fail to predict proper turbulent kinetic energy (TKE) and dissipation, needed by bubble entrainment, breakup, and coalescence models. We propose different approaches to obtain TKE and dissipation in LES regions and evaluate them for cases of increasing complexity, including decay of isotropic turbulence, a flat plate boundary layer, and the flow in the wake of the research vessel Athena. An exponential weighted average is used to estimate statistics and obtain the averaged quantities in regions with resolved turbulence. The TKE is satisfactorily predicted in the cases tested. A modified ω equation in the SST model is proposed to implicitly compute the dissipation, showing superior results than the standard DES models, although further improvements are necessary. A hybrid RANS/LES approach is proposed, which focused at conserving total TKE as the flow crosses RANS/LES interfaces, as previously performed for zonal approaches but attempting a DES-like detection of regions suitable for LES, critical for large-scale computations of bubbly flows involving complex geometries. A general form of a dynamic forcing term is derived to transfer the modeled TKE to resolved TKE with a controller to guarantee proper conservation of the energy transferred. It was verified that the model is not sensitive to grid size or time step. Improvements to DDES and the proposed TKE-conserving hybrid RANS/ LES method show encouraging results, although remaining challenges are discussed.
Comunicación Política en tiempos de Nueva Cultura Política
Authors: Barandiaran Xabier , Unceta Alfonso , Peña Simon
Published: October 2019

El proceso de globalización y sus manifiestos efectos comunicativos, culturales y políticos están afectando crucialmente a dos conceptos relativamente jóvenes en la investigación académica, en concreto, la Comunicación Política y la Cultura Política. La relación entre estos conceptos es cada vez más interdependiente pues las herramientas y los lenguajes de la Comunicación Política influyen decisivamente en la conformación de la Nueva Cultura Política y, a su vez, la actividad de la ciudadanía a través de las herramientas comunicativas digitales está condicionando la generación de contenidos y la creación de los discursos que toman cuerpo en forma de Comunicación Política.

Creemos que para entender las razones de esta relación es necesario establecer, por un lado, las características de la Nueva Cultura Política y, por la otra, la manera en que las posibilidades que ofrece la tecnología transforman la generación y la transmisión de la Comunicación Política. Posiblemente lo más novedoso de esta relación es que tiene carácter bidireccional, alterando los roles clásicos del proceso comunicativo que distinguía nítidamente entre emisores y receptores. Novedad que constituye una evidencia global y se deja sentir de manera muy similar en el conjunto de las democracias representativas occidentales.

Este trabajo se esfuerza en describir y analizar este escenario emergente que ha tomado cuerpo como otra de las transformaciones que están aconteciendo en las sociedades avanzadas, y en identificar algunas tendencias que, en todo caso, están sometidas al cambio vertiginoso propio de nuestro tiempo.

 

Palabras Clave: Cultura Política, Desafección, Participación, Comunicación Política, Tecnologías Digitales, Lenguajes Comunicativos.
Automated, phylogeny-based genotype delimitation of the Hepatitis Viruses HBV and HCV
Authors: Serdari Dora , Kostaki Evangelia-Georgia , Paraskevis Dimitrios , Stamatakis Alexandros , Kapli Paschalia
Published: October 2019

Background

The classification of hepatitis viruses still predominantly relies on ad hoc criteria, i.e., phenotypic traits and arbitrary genetic distance thresholds. Given the subjectivity of such practices coupled with the constant sequencing of samples and discovery of new strains, this manual approach to virus classification becomes cumbersome and impossible to generalize.

Methods

Using two well-studied hepatitis virus datasets, HBV and HCV, we assess if computational methods for molecular species delimitation that are typically applied to barcoding biodiversity studies can also be successfully deployed for hepatitis virus classification. For comparison, we also used ABGD, a tool that in contrast to other distance methods attempts to automatically identify the barcoding gap using pairwise genetic distances for a set of aligned input sequences.

Results—Discussion

We found that the mPTP species delimitation tool identified even without adapting its default parameters taxonomic clusters that either correspond to the currently acknowledged genotypes or to known subdivision of genotypes (subtypes or subgenotypes). In the cases where the delimited cluster corresponded to subtype or subgenotype, there were previous concerns that their status may be underestimated. The clusters obtained from the ABGD analysis differed depending on the parameters used. However, under certain values the results were very similar to the taxonomy and mPTP which indicates the usefulness of distance based methods in virus taxonomy under appropriate parameter settings. The overlap of predicted clusters with taxonomically acknowledged genotypes implies that virus classification can be successfully automated.
Combined effect of the entomopathogenic fungusMetarhizium robertsiiand avermectins on the survival and immune response ofAedes aegyptilarvae
Authors: Noskov Yuriy A. , Polenogova Olga V. , Yaroslavtseva Olga N. , Belevich Olga E. , Yurchenko Yuriy A. , Chertkova Ekaterina A. , Kryukova Natalya A. , Kryukov Vadim Yu , Glupov Viktor V.
Published: October 2019

Combination of insect pathogenic fungi and microbial metabolites is a prospective method for mosquito control. The effect of the entomopathogenic fungusMetarhizium robertsiiJ.F. Bischoff, S.A. Rehner & Humber and avermectins on the survival and physiological parameters ofAedes aegypti(Linnaeus, 1762) larvae (dopamine concentration, glutathione S-transferase (GST), nonspecific esterases (EST), acid proteases, lysozyme-like, phenoloxidase (PO) activities) was studied. It is shown that the combination of these agents leads to a synergistic effect on mosquito mortality. Colonization ofAe. aegyptilarvae by hyphal bodies following water inoculation with conidia is shown for the first time. The larvae affected by fungi are characterized by a decrease in PO and dopamine levels. In the initial stages of toxicosis and/or fungal infection (12 h posttreatment), increases in the activity of insect detoxifying enzymes (GST and EST) and acid proteases are observed after monotreatments, and these increases are suppressed after combined treatment with the fungus and avermectins. Lysozyme-like activity is also most strongly suppressed under combined treatment with the fungus and avermectins in the early stages posttreatment (12 h). Forty-eight hours posttreatment, we observe increases in GST, EST, acid proteases, and lysozyme-like activities under the influence of the fungus and/or avermectins. The larvae affected by avermectins accumulate lower levels of conidia than avermectin-free larvae. On the other hand, a burst of bacterial CFUs is observed under treatment with both the fungus and avermectins. We suggest that disturbance of the responses of the immune and detoxifying systems under the combined treatment and the development of opportunistic bacteria may be among the causes of the synergistic effect.
THE SPIRIT OF ENTREPRENEURSHIP IN BUSINESS STUDENTS, NON-BUSINESS STUDENTS, AND SMALL AND MEDIUM ENTREPRENEUR
Authors: Narsa Niluh Made Dian Novita Handayani , Narsa I Made , Narsa Niluh Putu Dian Rosalina Handayani
Published: October 2019

There is debate as to whether entrepreneurs are born or can be created through education. Many business schools were established to produce entrepreneurs, but the fact is that many suc­cesful entrepreneurs are not graduates of business schools. This study aims to examine empi­ri­cally the entrepreneurial spirit of three different sample groups students who undertook a business course (accounting students), non-business students (engineering students), businessmen who are already involved in business activities (entrepreneurs). This study used a survey method. Data were analyzed using ANOVA. The total sample of this research were 254 respondents. The result showed that there was no empirical evidence regarding the entrepreneurial differences in the three groups. It was concluded that entrepreneurial skills are either there or not from birth. Business courses are not (or not yet) capable of triggering the entrepreneurial skills in a person
The
N
egishi Cross‐Coupling Reaction
Authors: Diner Colin , Organ Michael G.
Published: October 2019

The Negishi cross‐coupling reaction is a carbon‐carbon bond forming reaction between an organozinc reagent and an organo(pseudo)halide. The reaction has an extremely broad scope and can form bonds between all hybridizations of the reactive carbon atoms in both coupling partners. The reaction tolerates many protic or electrophilic functionalities and is celebrated for its relative ease in forging linkages to heteroarenes. The reaction is generally palladium‐catalyzed but other first‐row metal catalysts can be used effectively in certain cases. Many organozinc reagents are commercially available while others can be made from more reactive organometallics, aryl halides, or by direct zincation of (hetero)arenes.

This chapter covers some of the major breakthroughs since the reaction's inception but mainly focuses on the current state‐of‐the‐art (up to mid‐2017) in cross‐coupling as well as organozinc reagent formation. An overview of the mechanistic features of the reaction for both palladium‐ and nickel‐catalyzed reactions is provided as well as an analysis of the resulting regio‐ and stereoselectivity issues. A summary of the scope of the reaction partners is provided as well as a Tabular Survey providing examples covering the gambit of potential nucleophile/electrophile combinations. A thoughtful selection of examples from the literature along with their experimental procedures, and a comparison of the Negsihi reaction with other cross‐coupling methodologies are also included.
Enantioselective Lithiation–Substitution of Nitrogen‐Containing Heterocycles
Authors: Kasten Kevin , Seling Nico , O'Brien Peter
Published: October 2019

This review covers the enantioselective lithiation–substitution at the α‐position of nitrogen‐containing heterocycles mediated by strong organolithium bases and chiral ligands. The reactions occur by two main mechanistic pathways: asymmetric deprotonation and asymmetric substitution. For
N
‐Boc heterocycles, asymmetric deprotonation is the predominant pathway, and
s
‐BuLi, in combination with chiral diamines, such as (–)‐sparteine and the (+)‐sparteine surrogate, are used. This approach is highly successful with
N
‐Boc pyrrolidines, piperidines, and piperazines. Substrates for asymmetric‐substitution‐mediated reactions include some
N
‐Boc heterocycles, but other
N
‐substituents, such as
N
‐alkyl groups,
N
‐alkyl‐BY
3
salts (Y = H, F) and
N
‐thioamide groups are also used. With both mechanistic pathways, the lithiated heterocycle can be transmetalated to form an organocopper or organozinc species to widen the scope of the electrophile. The full scope and limitations of this approach to synthesize enantioenriched α‐substituted aziridines, azetidines, pyrrolidines, piperidines, piperazines, azepanes and other five‐/six‐membered‐ring heterocyles are summarized.
Hydrofunctionalization of Alkenes by Hydrogen‐Atom Transfer
Authors: Shenvi Ryan A. , Matos Jeishla L. M. , Green Samantha A.
Published: October 2019

This chapter reviews a series of general reactions that hydrofunctionalize electron‐neutral alkenes with Markovnikov selectivity through the intermediacy of carbon‐centered radicals. This process represents the radical equivalent of Brønsted acid proton transfer. All reactions discussed here involve catalysis by manganese, iron, or cobalt complexes. The scope and limitations of these transformations, along with our current understanding of the mechanism are discussed. The literature is covered up to the end of 2017.
Carbon–Carbon Bond Formation by Metallaphotoredox Catalysis
Authors: Nacsa Eric D. , MacMillan David W. C.
Published: October 2019

The merger of photoredox catalysis with transition‐metal catalysis, termed metallaphotoredox catalysis, has enabled the development of a broad range of novel organic reactions. Photoredox catalysis is the activation of an organic molecule by single‐electron transfer with an excited‐state catalyst, typically generating a radical intermediate. The selective delivery of chemical energy to the catalyst by visible light allows for the generation of these reactive species under mild conditions. The union of this platform with transition‐metal catalysis enables cross‐coupling reactions of several bench‐stable and widely available classes of sp
3
‐hybridized starting materials that have historically been challenging or impossible to activate with transition metals alone. The photoredox catalyst can also modulate the oxidation state of the transition‐metal catalyst, leading to new reactivity profiles. This chapter covers the types of carbon–carbon bonds that may be formed using this technology.
Suzuki–Miyaura Cross‐Coupling
Authors: Pagett Alexander B. , Lloyd‐Jones Guy C.
Published: October 2019

The Suzuki–Miyaura cross coupling reaction uses a metal catalyst to create carbon–carbon bonds from organoboron reagents and organo(pseudo)halides. By careful adjustment of the ligand system, solvents, and other additives, this reaction can couple a diverse range of sp‐, sp
2
‐, and sp
3
‐hybridized organoboron and organo(pseudo)halide reactants. The Suzuki–Miyaura cross coupling reaction has become preeminent in both small‐ and large‐scale synthesis owing to its mild reaction conditions, predictable stereochemical outcomes, chemoselectivity, functional‐group compatibility, and use of relatively non‐toxic and air‐stable starting materials.

This chapter describes the theoretical and practical aspects of the palladium‐catalyzed Suzuki–Miyaura cross‐coupling reaction. A broad overview of the reaction mechanism and scope is described, with selected examples of how mechanistic insights have enabled progress in the development of this coupling reaction. Examples include early reaction discovery as well as modern applications in synthesis using a diverse array of organoboron and organo(pseudo)halide reactants, and on scales that range from milligram to multi‐kilogram. Tabular surveys are organized by the structure of the transferable group attached to boron as the primary rubric (alkyl, alkenyl, aryl, alkynyl, then heterocyclic), with the structure of the electrophile as the secondary rubric. Selected literature is covered from the seminal paper in 1979 to mid‐2018.
Catalytic, Enantioselective, Copper–Boryl Additions to Alkenes
Authors: Hoveyda* Amir H. , Koh Ming Joo , Lee Kyunga , Lee Jaehee
Published: October 2019

Enantiomerically enriched organoboron compounds are of considerable utility in organic synthesis. Unlike other organometallic reagents (e.g., RM, M = Li, Al, Mg, or Zn), boron‐containing hydrocarbons possess a number of desirable properties that include air, moisture, and configurational stability in addition to ease of preparation and exceptional functional group tolerance. Multicomponent, CB bond forming reactions, catalyzed by readily accessible, copper‐based complexes, have recently emerged as an attractive option for efficient, chemo‐, regio‐, diastereo‐ and enantioselective generation of multifunctional organoboron compounds. These processes typically begin with the addition of a copper–boryl complex to an alkenyl site, generating a copper–alkyl intermediate that then reacts with an electrophile. The focus of this chapter will be these transformations. A brief analysis of the key mechanistic nuances that impact the observed selectivity will be followed by an overview of the scope and limitations of the various strategies and their applications to the synthesis of bioactive molecules.
IL‐8 induces transdifferentiation of mature hepatocytes toward the cholangiocyte phenotype
Authors: Sasaki Tokio , Suzuki Yuji , Kakisaka Keisuke , Wang Ting , Ishida Kazuyuki , Suzuki Akiko , Abe Hiroaki , Sugai Tamotsu , Takikawa Yasuhiro
Published: October 2019

The adult mammalian liver exhibits a remarkable regenerative capacity, with different modes of regeneration according to the type and extent of injury. Hepatocyte–cholangiocyte biphenotypic liver progenitor cell populations appear under conditions of excessive injury. It has been reported that mature hepatocytes can transdifferentiate toward a cholangiocyte phenotype and be a cellular source of progenitor cell populations. Here, we determined that among various plasma cytokines, interleukin (IL)‐8 levels were significantly elevated in acute liver failure and severe acute liver injury patients. In vitro assays revealed that administration of IL‐8 homologues increases the expression of Sry HMG box protein 9 (SOX9). In liver biopsies of acute liver injury patients, we observed the appearance of SOX9‐positive biphenotypic hepatocytes accompanied by elevation of plasma IL‐8 levels. Our results suggest that IL‐8 regulates the phenotypic conversion of mature hepatocytes toward a cholangiocyte phenotype.
The Impact of Exercise, Lifestyle, and Clinical Factors on Perceived Cognitive Function in Patients with Rheumatoid Arthritis: Results from a Prospective Cohort Study
Authors: Shadick Nancy A. , Katz Patricia , Iannaccone Christine I. , Maica Gabriela , Coblyn Jonathan , Weinblatt Michael E. , Cui Jing
Published: October 2019

Objective

Lifestyle factors, such as inactivity and obesity, contribute to cognitive decline in the general population, but little is known about how these factors may affect individuals with a chronic inflammatory condition such as rheumatoid arthritis (RA). We studied the clinical and functional risk factors related to a worsening of perceived cognitive function in patients with RA.

Methods

We collected clinical and functional questionnaire data over 10 years in a prospective RA cohort including yearly self‐reported memory, concentration, and word‐finding difficulties graded from “never” to “often.” Generalized estimating equation models examined the role of exercise (defined as those meeting the Department of Health and Human Services physical activity guidelines of 75 minutes of vigorous or 150 minutes of moderate aerobic activity per week), body mass index (BMI), sleep, depression (Mental Health Index‐Depression), Disease Activity Score (DAS)28–c‐reactive protein (CRP)3 score, disease‐modifying antirheumatic drug, and corticosteroid use from the previous year as predictors of cognitive complaints that progressed to “often” compared with the previous year (the first year (Ti) progressed to “often” 1 year later (Ti+1)).

Results

Of 1219 RA subjects, 127 (10.4%) described either poor memory, concentration, or word‐finding difficulties as affecting them “often” at study entry. RA patients (n = 1092, mean age = 56.5 years, 82% female, 58% college educated) were less likely to report word‐finding difficulties, poor memory, and concentration as “often” if they were physically active (p = 0.0001, P = 0.01, P < 0.0001, respectively). Female RA patients developed more concentration complaints compared with males (P = 0.03); patients taking an anti–tumor necrosis factor therapy were less likely to complain of poor memory (P = 0.01). Sleep, BMI, fatigue, depression, DAS28‐CRP3, methotrexate, and corticosteroid use were not independently associated with a worsening of any cognitive complaints.

Conclusion

RA patients who are physically active are less likely to report cognitive difficulties. Our study suggests potential modifiable risk factors for the prevention of cognitive dysfunction in RA.
Deep‐Subwavelength Holey Acoustic Second‐Order Topological Insulators
Authors: Zhang Zhiwang , Long Houyou , Liu Chen , Shao Chen , Cheng Ying , Liu Xiaojun , Christensen Johan
Published: October 2019

Higher‐order topological insulators (HOTIs) belong to a new class of materials with unusual topological phases. They have garnered considerable attention due to their capabilities in confining energy at the hinges and corners, which is entirely protected by the topology, and have thus become attractive structures for acoustic wave studies and control. However, for most practical applications at audible and low frequencies, compact and subwavelength implementations are desirable in addition to providing robust guiding of sound beyond a single‐frequency operation. Here, a holey HOTI capable of sustaining deeply confined corner states 50 times smaller than the wavelength is proposed. A remarkable resilience of these surface‐confined acoustic states against defects is experimentally observed, and topologically protected sound is demonstrated in three different frequency regimes. Concerning this matter, the findings will thus have the capability to push forward exciting applications for robust acoustic imaging way beyond the diffraction limit.
Stability of PEDOT:PSS‐Coated Gold Electrodes in Cell Culture Conditions
Authors: Dijk Gerwin , Rutz Alexandra L. , Malliaras George G.
Published: October 2019

Poly(3,4‐ethylenedioxythiophene) doped with polystyrene sulfonate (PEDOT:PSS) is widely used as a coating on microelectrode arrays in order to reduce impedance for both in vitro and in vivo electrophysiology. In many applications, electrode performance of months to years is desired; yet, there are few studies to date that examine the long‐term stability of conducting polymers and their devices. Here, the stability of PEDOT:PSS microelectrodes is examined over a period of four months in cell culture media enriched with fetal bovine serum. The electrochemical impedance remains constant for most electrodes throughout the study, and only small changes in the structure of functional electrodes are observed. The results demonstrate that PEDOT:PSS electrodes show adequate stability for a variety of in vitro electrophysiology applications in toxicology, drug development, tissue engineering, and fundamental studies of electrically active cells and tissues.
Mild C−F Activation in Perfluorinated Arenes through Photosensitized Insertion of Isonitriles at 350 nm
Authors: Weidlich Frauke , Esumi Naoto , Chen Dongyang , Mück‐Lichtenfeld Christian , Zysman‐Colman Eli , Studer Armido
Published: October 2019

Fluorinated compounds have become important in the fields of agrochemical industry, pharmaceutical chemistry and materials sciences. Accordingly, various methods for their preparation have been developed in the past. Fluorinated compounds can be accessed via conjugation with fluorinated building blocks, via C−H fluorination or via selective activation of perfluorinated compounds to give the partially fluorinated congeners. Especially the direct activation of C−F bonds, one of the strongest σ‐bonds, still remains challenging and new strategies for C−F activation are desirable. Herein a method for the photochemical activation of aromatic C−F bonds is presented. It is shown that isonitriles selectively insert into aromatic C−F bonds while aliphatic C−F bonds remain unaffected. Mechanistic studies reveal the reaction to proceed via the indirect excitation of the isonitrile to its triplet state by photoexcited acetophenone at 350 nm. Due to the relatively mild light used, the process shows high functional group tolerance and various compounds of the class of benzimidoyl fluorides are accessible from aryl isonitriles and commercially available perfluorinated arenes.

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An Aptamer‐Nanotrain Assembled from Six‐Letter DNA Delivers Doxorubicin Selectively to Liver Cancer Cells
Authors: Zhang Liqin , Wang Sai , Yang Zunyi , Hoshika Shuichi , Xie Sitao , Li Jin , Chen Xigao , Wan Shuo , Li Long , Benner Steven A. , Tan Weihong
Published: October 2019

Expanding the number of nucleotides in DNA increases the information density of functional DNA molecules, creating nanoassemblies that cannot be invaded by natural DNA/RNA in complex biological systems. Here, we show how six‐letter GACTZP DNA contributes this property in two parts of a nanoassembly: 1) in an aptamer evolved from a six‐letter DNA library to selectively bind liver cancer cells; and 2) in a six‐letter self‐assembling GACTZP nanotrain that carries the drug doxorubicin. The aptamer‐nanotrain assembly, charged with doxorubicin, selectively kills liver cancer cells in culture, as the selectivity of the aptamer binding directs doxorubicin into the aptamer‐targeted cells. The assembly does not kill untransformed cells that the aptamer does not bind. This architecture, built with an expanded genetic alphabet, is reminiscent of antibodies conjugated to drugs, which presumably act by this mechanism as well, but with the antibody replaced by an aptamer.
Effect of triphenyl phosphite as a reactive compatibilizer on the properties of poly(L‐lactic acid)/poly(butylene succinate) blends
Authors: Ma Meng , Xu Lin , Liu Kai , Chen Si , He Huiwen , Shi Yanqin , Wang Xu
Published: October 2019

Reactive blending is an innovative method for the improvement of compatibility of polymer blend. In this work, poly (L‐lactic acid) and poly (butylene succinate) (PLLA/PBS) blends were prepared by melt blending to ameliorate the toughness of PLLA. Triphenyl phosphite (TPP) was introduced into the PLLA/PBS blends (80/20 by weight) to enhance their compatibility via reactive blending. The effects of TPP on the morphology and properties of PLLA/PBS blends were studied systematically. The increased torque during melt blending demonstrated that the compatibilizer successfully reacted with PLLA and PBS. The mechanical properties of the blends were exceedingly improved only with 0.5 wt% TPP. A reduction tendency of size of the dispersed phase was observed due to the improvement of compatibility. The DSC and DMA results indicate that theTgof PLLA decreased at a slow rate with the increasing content of TPP. This work provided a simple approach for preparing a kind of high toughed PLLA material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2020,137, 48646.
Surface‐Coated Thermally Expandable Microspheres with a Composite of Polydisperse Graphene Oxide Sheets
Authors: Jiao Shouzheng , Sun Zhicheng , Zhou Yang , Li Furong , Wen Jinyue , Chen Yinjie , Du Xiaoyang , Li Luhai , Liu Yuanyuan
Published: October 2019

Surface‐modified thermally expandable microcapsules (TEMs) hold potential for applications in various fields. In this work, we discussed the possible surface coating mechanism and reported the properties of TEMs coated with polyaniline (PANI) and polydisperse graphene oxide sheets (ionic liquid‐graphene oxide hybrid nanomaterial (ILs‐GO)). The surface coating of PANI/ ILs‐GO increased the corresponding particle size and its distribution range. The morphologies analyzed by scanning electron microscopy indicated that no interfacial gap was observed between the microspheres ink and substrate layer during the substrate application. The thermal properties were determined by thermogravimetric and differential thermal analyses. The addition of ILs‐GO to the polyaniline coating significantly improved the thermal expansion and thermal conductivity of the microcapsules. The evaporation of hexane present in the core of TEMs was not prevented by the coating of PANI/ ILs‐GO. The printing application of TEMs showed excellent adaptability to various flexible substrates with great 3D appearance. By incorporating a flame retardant agent into TEMs coated by PANI/ILs‐GO, finally, these TEMs also demonstrated a great flame retardant ability. We expect that these TEM‐coated PANI/ ILs‐GO are likely to have the potential to improve the functional properties for various applications.
Real‐world health utility scores and toxicities to tyrosine kinase inhibitors in epidermal growth factor receptor mutated advanced non‐small cell lung cancer
Authors: Jiang Shirley Xue , Walton Ryan N. , Hueniken Katrina , Baek Justine , McCartney Alexandra , Labbé Catherine , Smith Elliot , Chan Sze Wah Samuel , Chen RuiQi , Brown Catherine , Patel Devalben , Liang Mindy , Eng Lawson , Sacher Adrian , Bradbury Penelope , Leighl Natasha B. , Shepherd Frances A. , Xu Wei , Liu Geoffrey , Hurry Manjusha , O'Kane Grainne M.
Published: October 2019

Background

As the treatment landscape in patients with non‐small cell lung cancer (NSCLC) harboring mutations in the epidermal growth factor receptor (EGFRm) continues to evolve, real‐world health utility scores (HUS) become increasingly important for economic analyses.

Methods

In an observational cohort study, questionnaires were completed in EGFRm NSCLC outpatients, to include demographics, EQ‐5D‐based HUS and patient‐reported toxicity and symptoms. Clinical and radiologic characteristics together with outcomes were extracted from chart review. The impact of health states, treatment type, toxicities, and clinical variables on HUS were evaluated.

Results

Between 2014 and 2018, a total of 260 patients completed 994 encounters. Across treatment groups, patients with disease progression had lower HUS compared to controlled disease (0.771 vs 0.803; P = .01). Patients predominantly received gefitinib as the first‐line EGFR tyrosine kinase inhibitor (TKI) (n = 157, mean‐HUS = 0.798), whereas osimertinib (n = 62, mean‐HUS = 0.806) and chemotherapy (n = 38, mean‐HUS = 0.721) were more likely used in subsequent treatment lines. In longitudinal analysis, TKIs retained high HUS (>0.78) compared to chemotherapy (HUS < 0.74). There were no differences between the frequency or severity of toxicity scores in patients receiving gefitinib compared to osimertinib; however, TKI therapy resulted in fewer toxicities than chemotherapy (P < .05), with the exception of worse diarrhea and skin rash (P < .001). Severity in toxicities inversely correlated with HUS (P < .001). Clinico‐demographic factors significantly affecting HUS included age, Eastern Cooperative Oncology Group Performance Score (ECOG PS), disease state, treatment group, and metastatic burden.

Conclusions

In a real‐world EGFRm population, patients treated with gefitinib or osimertinib had similar HUS and toxicities, scores which were superior to chemotherapy. Health utility scores inversely correlated with patient‐reported toxicity scores. In the era of targeted therapies, future economic analyses should incorporate real‐world HUS.
Client‐initiated disclosure of psychotherapists' sexual orientation: A narrative inquiry
Authors: McPherson Alan Stuart
Published: October 2019

Intention

This study considers the effect on counsellors and psychotherapists when their sexual orientation is discovered and introduced into the therapeutic relationship by their clients.

Method

Using a narrative inquiry approach, four qualified and experienced counsellors/psychotherapists share their stories by means of unstructured conversations. The findings are presented and analysed through a reconstructed conversation illustrating the similarities and differences between these participants' stories, considered alongside my own.

Findings

Through this reconstituted dialogue, the process of unintended revealing of the participants' sexual orientation and the perceived effect on the client and on the therapeutic relationship are explored, and how these experiences altered the practitioner's view of themselves, clients in general and wider society.

Implications for practice

These stories suggest clients' curiosity into the lives of their counsellor/psychotherapist is inevitable with the growth of the availability of personal information in the public domain, and as such, practitioners are encouraged to take ownership of their narratives of their sexual orientation.
Interstitial duplication of 8q22.1‐q23.1‐ A case report and review of the literature
Authors: Leary Steven , Porterfield Harry S. , Kotlarek Jaclyn R. , Darbro Benjamin W. , Sidhu Alpa
Published: October 2019

This report highlights the clinical features seen in duplication of 8q22.1q23.1 inherited from balanced father. It stresses the importance of obtaining a karyotype to identify the location of a large copy number variant for accurate recurrence risk estimation.
CuSn Alloy Nanoparticles on Nitrogen‐Doped Graphene for Electrocatalytic CO2 Reduction
Authors: Xiong Wei , Yang Jian , Shuai Ling , Hou Yang , Qiu Ming , Li Xinyong , Leung Michael K. H.
Published: October 2019

We report an efficient electrocatalyst utilizing non‐noble metals consisting of Cu and Sn supported on nitrogen‐doped graphene (NG) for reduction of CO2 over a wide potential range. The CuSn alloy nanoparticles (NPs) on NG were prepared through a hydrothermal method followed by pyrolysis under nitrogen atmosphere to achieve a uniform dispersion of the alloy NPs. The CuSn NP (Cu/Sn ratio of 0.175) decorated NG catalyst performed electrocatalytic reduction of CO2 into C1 products at a Faradaic efficiency (FE) of nearly 93 % at an overpotential of −1.0 V vs. RHE, considerably higher than that of the Cu and Sn counterparts, i. e., 32 % and 58 %, respectively. The enhanced catalytic activity could be attributed to the collaboration between the CuSn alloy and Sn metal. The first‐principles density functional theory (DFT) simulation results indicate that the CuSn bimetal alloy nanoparticles enable more H atoms to participate in the electrocatalytic reduction of CO2 and exhibit an improved CO2 capture performance. In addition, the CuSn alloy having a lower barrier than that of Sn metal can accelerate the CO2 reduction process. This study presents the strategy that utilizes low‐cost non‐noble metals as highly efficient electrocatalysts for aqueous reduction of CO2.