bluuebunny/crossref_metadata_2025 huggingface dataset:
The Impact of Diet on Common Skin Disorders
Authors: Rezakovic Saida , Pavlic Mirjana , Navratil Marta , Pocanic Lidija , Žužul Kristina , Kostovic Krešimir
Published: October 2014

The role of nutrition in the treatment of common dermatoses is often overlooked. Nevertheless, there is a large amount of evidence suggesting that diet may have an important role in the pathogenesis, as well as in determining the clinical course of common skin disorders; including acne, psoriasis, atopic dermatitis and allergic contact dermatitis. Consequently, diet could have significant preventive or therapeutic impact in these skin conditions. Psoriasis, atopic dermatitis and allergic contact dermatitis are chronic relapsing skin disorders characterised by remissions and flare-ups, requiring long-term maintenance therapy. Although acne occurs most commonly during adolescence, and rarely continues into adulthood, it has a large impact on patients' self-confidence and self-image. For each of these skin conditions, a variety of foods may lead to exacerbation of the disease and may have a significant role in increasing the risk of other comorbidities. The aim of this review is to present current knowledge on the relationship between high-fat and high glycemic index diet and acne and psoriasis. Additionally, possible role of nutritional supplementation in such will also be reviewed. And finally, the role of dietary restriction in patients with atopic dermatitis and low nickel diet, in those who are sensitive to nickel, will be discussed. Although future studies are necessary in order to evaluate the effect of diet in these skin disorders, identifying certain foods as a potential factor that could contribute to exacerbation of the disease or to development of further complications can provide important preventive measure.
Exploitation et obligation de travailler
Authors: Vandamme Pierre-Étienne
Published: October 2014

Cet article défend une définition de l’exploitation, restreinte aux relations de travail, en tentant d’une part d’expliciter une certaine compréhension de sens commun du concept (rémunération inéquitable en fonction du travail presté), et d’autre part d’échapper aux difficultés qui ont affecté la définition marxiste traditionnelle de l’exploitation comme extorsion de la plus-value (dans ses diverses variantes). Il explore ainsi le lien entre l’exploitation et l’obligation matérielle de travailler pour subvenir à ses besoins fondamentaux. Après avoir mis en garde contre les politiques d’activation des chômeurs, il conclut que l’exploitation est un phénomène contre lequel on peut lutter à l’aide de mécanismes relativement simples, même dans les sociétés capitalistes. Il rappelle toutefois que cela ne suffit pas à réaliser la justice sociale, resituant l’exploitation parmi d’autres enjeux fondamentaux pour une philosophie politique égalitariste
Fitting-Attitude Analyses and the Relation Between Final and Intrinsic Value
Authors: C. Dussault Antoine
Published: October 2014

This paper examines the debate as to whether something can have final value in virtue of its relational (i.e., non-intrinsic) properties, or, more briefly put, whether final value must be intrinsic. The paper adopts the perspective of the fitting-attitude analysis (FA analysis) of value, and argues that from this perspective, there is no ground for the requirement that things may have final value only in virtue of their intrinsic properties, but that there might be some grounds for the alternate requirement that final value be grounded only in the essential properties of their bearers. First, the paper introduces the key elements of the FA analysis, and sets aside an obvious but unimportant way in which this analysis makes all final values relational. Second, it discusses some classical counterexamples to the view that final value must be intrinsic. Third, it discusses the relation between final, contributive, and signatory value. Fourth, it examines Zimmerman’s defense of the requirement that final value must be intrinsic on the grounds that final value cannot be derivative. And finally, it explores the alternative requirement that something may have final value in virtue of its essential properties.
Estado da Arte e o Rumo do Conhecimento Científico em Secretariado Executivo: Mapeamento e Análise de Áreas de Pesquisa
Authors: Maçaneiro Marlete Beatriz , Kuhl Marcos Roberto
Published: October 2014

O objetivo deste estudo é realizar um mapeamento da produção científica dos formados em Secretariado Executivo, no sentido de verificar as áreas e a quantificação pertinentes a essa publicação, bem como analisar a relação entre essa publicação e a titulação dos pesquisados. Este estudo é do tipo exploratório e descritivo, sendo que a metodologia foi ancorada na abordagem quantitativa, por meio da estratégia de levantamento de dados em bases secundárias de acesso público, tais como a Plataforma Lattes e o WebQualis, dentre outras. O tratamento, análise e interpretação das evidências foram realizados através de técnicas estatísticas descritivas. Foram analisados os currículos Lattes de profissionais formados em Secretariado Executivo e que possuíam algum tipo de produção científica, totalizando uma amostra de 219 profissionais, vinculados a instituições/empresas de todas as regiões do Brasil. Dentre os principais resultados, verificamos que apenas 33,7% da produção estão na área de Secretariado ou fazem relação com ela e que os que possuem somente graduação e especialização publicam em maior número na área, enquanto que os do nível de mestrado e de doutorado publicam bem menos na área de Secretariado. Esse resultado confirma a hipótese do estudo, de que as publicações realizadas por profissionais com nível de mestrado e doutorado são realizadas, em sua maioria, em outras áreas que não no contexto do Secretariado Executivo.DOI: 10.7769/gesec.v4i3.274
As Competências do Profissional de Secretariado na Implantação de Projetos Sustentáveis
Authors: Todorov Maria do Carmo Assis , Kniess Claudia Terezinha , Chaves Marcírio Silveira
Published: October 2014

Desde a década de 1990, o tema da Sustentabilidade passou a incorporar com mais intensidade o mundo dos negócios (Barbieri, Vasconcelos, Andreassi, & Vasconcelos, 2010). Neste sentido, o gerenciamento de projetos precisou levar em conta a sustentabilidade, em suas três dimensões: econômica, ambiental e social (Carvalho & Rabechini Jr, 2011). O gerenciamento de projetos sustentáveis também cresceu nas últimas décadas, exigindo profissionais que contribuam para o sucesso destes projetos (Souza, 1993). Diante deste cenário, este trabalho busca responder a seguinte questão: Quais as competências do profissional de secretariado na implantação de projetos sustentáveis? O objetivo do trabalho é identificar as competências do profissional de secretariado na implantação de projetos sustentáveis, por meio de uma pesquisa qualitativa e exploratória. As competências apresentadas pelos 206 respondentes compatíveis com as competências da sustentabilidade são: gerenciamento de informações, assegurando uniformidade e referencial para diferentes usuários; habilidade de lidar com modelos inovadores de gestão; adoção de meios alternativos relacionados com a melhoria da qualidade e da produtividade dos serviços; abertura às mudanças, iniciativa, criatividade, determinação, vontade de aprender; consciência das implicações e responsabilidades éticas e utilização do raciocínio lógico, crítico e analítico; domínio dos recursos de expressão e de comunicação, inclusive nos processos de negociação e nas comunicações interpessoais ou inter-grupais.DOI: 10.7769/gesec.v4i3.275
Secretariar ou não Secretariar? Eis a Questão: Um Estudo sobre a Evasão no Curso de Secretariado Executivo
Authors: Schuarcz Luana Dias , Sá Mariana Pereira Cardoso de , Warmuth Déris , Maçaneiro Marlete Beatriz
Published: October 2014

Esta pesquisa tem por objetivo analisar as causas da evasão entre os ingressantes do curso de Secretariado Executivo em duas Universidades Públicas do Paraná, entre o período de 2009 a 2012. O estudo se caracteriza por ser um levantamento (survey) e a metodologia utilizada considerou os dados coletados por meio da aplicação de um questionário envolvendo uma amostra do universo dos evadidos do curso de Secretariado Executivo de ambas as Universidades. Os resultados encontrados, mediante uma análise quantitativa e o diálogo com o referencial teórico pesquisado sobre o tema, elencaram os principais fatores que levaram os alunos a desistirem do curso de Secretariado Executivo. As causas da evasão podem ser externas à instituição, ligadas a características individuais do evadido, como habilidades de estudo, incompatibilidade de horários e desencanto com o curso, escolha precoce da profissão e descoberta de novos interesses. Mas também podem ser internas relacionadas à estrutura do curso e ou da Universidade, o desinteresse do docente, critérios impróprios de avaliação e a falta de programas institucionais para o aluno. Não está ao alcance dos envolvidos com o curso de Secretariado Executivo interferir nas causas externas da evasão relacionadas à personalidade do aluno, mas em relação aos déficits institucionais internos mencionados pelos evadidos.DOI: 10.7769/gesec.v5i1.167
A Atuação do Secretário Executivo no Terceiro Setor na Cidade de Aracaju
Authors: Pereira Karen Almeida , Silva Manuela Ramos da
Published: October 2014

A atuação dosecretário executivo é indispensável para a gestão das organizações modernas.Essa afirmativa advém da atuação deste profissional diretamente com os gestorese executivos, por meio da multiplicidade de competências e da polivalência queele possui, uma vez que este ator está apto a trabalhar em qualquer tipologiaorganizacional. Com o crescimento das organizações do terceiro setor no Brasile também na cidade de Aracaju, o objetivo da pesquisa foi de identificar quaisas formas de atuação do secretário e quais as competências pertinentes desseprofissional para trabalhar nessas instituições que possuem característicaspeculiares na sua gestão. Para subsídio da pesquisa discutiu-se sobre terceirosetor e as características das organizações inseridas neste campo, a evoluçãoda carreira do secretário, considerando a sua atuação no mercado de trabalho; eas competências a serem desenvolvidas. Dessa forma, identificaram-se, na cidadede Aracaju, organizações do terceiro setor que possuem uma gestão fragilizadadevido, principalmente, à falta de recursos, à dependência financeira de outrosórgãos e à ausência de mão de obra qualificada. No que se refere ao perfil dossecretários, a maioria não possui formação específica, são polivalentes, porémnão são inovadores. Quanto à rotina de trabalho dos mesmos, ela está divididaem atividades operacionais e estratégicas, tendo como principal atribuição oassessoramento.DOI: 10.7769/gesec.v5i1.257
Pesquisa Quantitativa: Elementos, Paradigmas e Definições
Authors: Da Silva Dirceu , Lopes Evandro Luiz , Junior Sérgio Silva Braga
Published: October 2014

O presente artigo tem por finalidade a apresentação de aspectos essenciais da pesquisa quantitativa na área de gestão. Assim, buscaram-se apresentar alguns aspectos sobre a natureza dos dados e sua exploração inicial, os testes de hipóteses mais usados e os critérios para sua escolha; além disso, quatro métodos multivariados foram apresentados. Tentou-se utilizar como exemplos referências que podem ser obtidas, na maioria, na internet, sobretudo, aquelas que são artigos científicos já publicados.Palavras-chave: Pesquisa quantitativa. Pesquisa em gestão. Técnicas estatísticas.DOI: 10.7769/gesec.v5i1.297
Interacting components of the top‐of‐atmosphere energy balance affect changes in regional surface temperature
Authors: Merlis Timothy M.
Published: October 2014

The role of interactions between components of the top‐of‐atmosphere (TOA) energy balance in determining regional surface temperature changes, such as polar amplification, is examined in diffusive energy balance model (EBM) simulations. These interactions have implications for the interpretation of local feedback analyses when they are applied to regional surface temperature changes. Local feedback analysis succeeds at accounting for the EBM‐simulated temperature change given the changes in the radiative forcing, atmospheric energy transport, and radiative feedbacks. However, the inferences about the effect of individual components of the TOA energy balance on regional temperature changes do not account for EBM simulations in which individual components are prescribed or “locked.” As changes in one component of the TOA energy balance affect others, unambiguous attribution statements relating changes in regional temperature or its intermodel spread to individual terms in the TOA energy balance cannot be made.
Effects of trans‐Eurasian transport of air pollutants on surface ozone concentrations over Western China
Authors: Li Xiaoyuan , Liu Junfeng , Mauzerall Denise L. , Emmons Louisa K. , Walters Stacy , Horowitz Larry W. , Tao Shu
Published: October 2014

Due to a lack of industrialization in Western China, surface air there was, until recently, believed to be relatively unpolluted. However, recent measurements and modeling studies have found high levels of ozone (O3) there. Based on the state‐of‐the‐science global chemical transport model MOZART‐4, we identify the origin, pathway, and mechanism of trans‐Eurasian transport of air pollutants to Western China in 2000. MOZART‐4 generally simulates well the observed surface O3 over inland areas of China. Simulations find surface ozone concentrations over Western China on average to be about 10 ppbv higher than Eastern China. Using sensitivity studies, we find that anthropogenic emissions from all Eurasian regions except China contribute 10–15 ppbv surface O3 over Western China, superimposed upon a 35–40 ppbv natural background. Transport from European anthropogenic sources to Northwestern China results in 2–6 ppbv O3 enhancements in spring and summer. Indian anthropogenic sources strongly influence O3 over the Tibetan Plateau during the summer monsoon. Transport of O3 originating from emissions in the Middle East occasionally reach Western China and increase surface ozone there by about 1–4 ppbv. These influences are of similar magnitude as trans‐Pacific and transatlantic transport of O3 and its precursors, indicating the significance of trans‐Eurasian ozone transport in hemispheric transport of air pollution. Our study further indicates that mitigation of anthropogenic emissions from Europe, the Indian subcontinent, and the Middle East could benefit public health and agricultural productivity in Western China.
Modeled aerosol nitrate formation pathways during wintertime in the Great Lakes region of North America
Authors: Kim Yoo Jung , Spak Scott N. , Carmichael Gregory R. , Riemer Nicole , Stanier Charles O.
Published: October 2014

Episodic wintertime particle pollution by ammonium nitrate is an important air quality concern across the Midwest U.S. Understanding and accurately forecasting PM2.5 episodes are complicated by multiple pathways for aerosol nitrate formation, each with uncertain rate parameters. Here, the Community Multiscale Air Quality model (CMAQ) simulated regional atmospheric nitrate budgets during the 2009 LADCO Winter Nitrate Study, using integrated process rate (IPR) and integrated reaction rate (IRR) tools to quantify relevant processes. Total nitrate production contributing to PM2.5 episodes is a regional phenomenon, with peak production over the Ohio River Valley and southern Great Lakes. Total nitrate production in the lower troposphere is attributed to three pathways, with 57% from heterogeneous conversion of N2O5, 28% from the reaction of OH and NO2, and 15% from homogeneous conversion of N2O5. TNO3 formation rates varied day‐to‐day and on synoptic timescales. Rate‐limited production does not follow urban‐rural gradients and NOx emissions due, to counterbalancing of urban enhancement in daytime HNO3 production with nocturnal reductions. Concentrations of HNO3 and N2O5 and nighttime TNO3 formation rates have maxima aloft (100–500 m), leading to net total nitrate vertical flux during episodes, with substantial vertical gradients in nitrate partitioning. Uncertainties in all three pathways are relevant to wintertime aerosol modeling and highlight the importance of interacting transport and chemistry processes during ammonium nitrate episodes, as well as the need for additional constraint on the system through field and laboratory experiments.
Percentiles and regional distribution of skinfold thickness among children and adolescents in Shandong, China
Authors: Zhang Ying‐Xiu , Zhao Jin‐Shan , Chu Zun‐Hua
Published: October 2014

Objective

Skinfold thicknesses (SFT) have long been considered important and valid measurements of subcutaneous fat. The present study reported the percentiles and regional distribution of SFT among children and adolescents in Shandong, China.

Methods

Data for this study were obtained from a large cross‐sectional survey of schoolchildren. A total of 42,268 students (21,200 boys and 21,068 girls) aged 7–18 years from 16 districts participated in this study. Triceps, subscapular, and abdomen SFT of all subjects were measured.

Results

Shandong children and adolescents had a high SFT level and substantial regional disparities in SFT were observed. Boys and girls resident in high socioeconomic status (SES) districts had higher SFT level than those living in moderate and low SES districts.

Conclusion

The SFT level of children and adolescents is associated with regional SES in Shandong, China. This may be interpreted as a result of geographic variation between the districts in the process of urbanization, living standards, nutritional conditions, dietary patterns, and public health. Am. J. Hum. Biol. 27:417–420, 2015. © 2014 Wiley Periodicals, Inc.
Charakterisierung eines Mehrkomponenten‐Lithiumlithats durch eine Kombination von Röntgenstrukturanalyse, NMR‐Spektroskopie und theoretischen Studien
Authors: Pöppler Ann‐Christin , Granitzka Markus , Herbst‐Irmer Regine , Chen Yu‐Sheng , Iversen Bo B. , John Michael , Mata Ricardo A. , Stalke Dietmar
Published: October 2014

Untersuchungen mithilfe von Röntgenstrukturanalyse, NMR‐Spektroskopie und Rechnungen ermöglichen die vollständige Charakterisierung des ungewöhnlichen Lithiumlithats [Li(diglyme)2][(diglyme)Li2(C4H3S)3] im Festkörper und in Lösung. Es setzt sich zusammen aus einem komplexen Anion, bestehend aus drei Carbanionen, zwei Lithiumkationen sowie einer Lewis‐Base, und einem separierten Lithiumkation, das von zwei Lewis‐Basen koordiniert wird. Während das Mehrkomponenten‐Lithat die einzige Spezies im Festkörper ist, konnten NMR‐Spektroskopie und theoretische Ansätze zeigen, dass in Lösung eine weitere Spezies, das Dimer [(diglyme)Li(C4H3S)]2 neben dem Lithat in einem von der Polarität des Lösungsmittels abhängigen Verhältnis vorliegt. Nur durch die Kombination der genannten Methoden gelingt eine zuverlässige Gesamtbeschreibung.
Functional Dynamics of Deuterated β2‐Adrenergic Receptor in Lipid Bilayers Revealed by NMR Spectroscopy
Authors: Kofuku Yutaka , Ueda Takumi , Okude Junya , Shiraishi Yutaro , Kondo Keita , Mizumura Takuya , Suzuki Shiho , Shimada Ichio
Published: October 2014

G‐protein‐coupled receptors (GPCRs) exist in conformational equilibrium between active and inactive states, and the former population determines the efficacy of signaling. However, the conformational equilibrium of GPCRs in lipid bilayers is unknown owing to the low sensitivities of their NMR signals. To increase the signal intensities, a deuteration method was developed for GPCRs expressed in an insect cell/baculovirus expression system. The NMR sensitivities of the methionine methyl resonances from the β2‐adrenergic receptor (β2AR) in lipid bilayers of reconstituted high‐density lipoprotein (rHDL) increased by approximately 5‐fold upon deuteration. NMR analyses revealed that the exchange rates for the conformational equilibrium of β2AR in rHDLs were remarkably different from those measured in detergents. The timescales of GPCR signaling, calculated from the exchange rates, are faster than those of receptor tyrosine kinases and thus enable rapid neurotransmission and sensory perception.
Characterization of a Multicomponent Lithium Lithiate from a Combined X‐Ray Diffraction, NMR Spectroscopy, and Computational Approach
Authors: Pöppler Ann‐Christin , Granitzka Markus , Herbst‐Irmer Regine , Chen Yu‐Sheng , Iversen Bo B. , John Michael , Mata Ricardo A. , Stalke Dietmar
Published: October 2014

An unusual lithium lithiate [Li(diglyme)2][(diglyme)Li2(C4H3S)3], made up from three carbanions, two lithium cations, and a single donor base molecule in the anion and a single lithium cation, coordinated by two donor base molecules, is investigated in a combined study including X‐ray diffraction, NMR spectroscopy and computational approaches in solution and the solid state. While the multicomponent lithiate is the only species present in the solid state, solution NMR spectroscopy and computational methods were employed to identify a second species in solution. The dimer [(diglyme)Li(C4H3S)]2 coexists with the lithiate in solution in a 1:1 ratio, the more the higher the polarity of the solvent is. Only the combination of this multitude of methods provides a firm picture of the whole.
Reading Polymers: Sequencing of Natural and Synthetic Macromolecules
Authors: Mutlu Hatice , Lutz Jean‐François
Published: October 2014

The sequencing of biopolymers such as proteins and DNA is among the most significant scientific achievements of the 20th century. Indeed, modern chemical methods for sequence analysis allow reading and understanding the codes of life. Thus, sequencing methods currently play a major role in applications as diverse as genomics, gene therapy, biotechnology, and data storage. However, in terms of fundamental science, sequencing is not really a question of molecular biology but rather a more general topic in macromolecular chemistry. Broadly speaking, it can be defined as the analysis of comonomer sequences in copolymers. However, relatively different approaches have been used in the past to study monomer sequences in biological and manmade polymers. Yet, these “cultural” differences are slowly fading away with the recent development of synthetic sequence‐controlled polymers. In this context, the aim of this Minireview is to present an overview of the tools that are currently available for sequence analysis in macromolecular science.
“Kronecker Basis” Based Average Consensus Analyses for High‐Order Linear Multi‐Agent Systems with Multiple Time Delays
Authors: Zhu Huangyong , Cong Yirui , Wang Xiangke , Zhang Daibing , Zhang Qingjie
Published: October 2014

This paper investigates the average consensus for multi‐agent systems governed by high‐order linear dynamics with multiple time delays. Necessary and sufficient conditions for high‐order average consensus under balanced communication topology are provided by using a newly defined mathematical concept – the Kronecker basis. Furthermore, previous studies for average consensus governed by first‐order, or high‐order integrator can be regarded as special cases of our results. Simulation results are employed to demonstrate the effectiveness of our results for high‐order average consensus.
Deadlock Control for a Class of Generalized Petri Nets Based on Proper Resource Allocation
Authors: Hou YiFan , Zhao Mi , Liu Ding
Published: October 2014

This article develops a deadlock prevention policy for a class of generalized Petri nets, namely G‐systems, which can model flexible manufacturing systems with machining, assembly, and disassembly operations. In this research, a polynomial complexity control policy for non‐blocking supervisors is established by properly adjusting resource allocation. First, a set of linear inequality constraints is derived with respect to different resource requirements such that the allocation of the system resources to various requesting processes can be appropriately restricted, that is, the resulting system has no deadlock state by imposing monitors on operation places. Moreover, an algorithm is proposed to identify the redundant constraints such that structurally simple liveness‐enforcing net supervisors can be obtained. Compared with existing polices, the proposed method can usually lead to a suboptimal supervisor with high computational efficiency. Finally, a flexible manufacturing system example is utilized to demonstrate the proposed method.
Absorption, distribution, metabolism and excretion of novel phosphodiesterase type 4 inhibitor ASP3258 in rats
Authors: Ohtsu Yoshiaki , Sonoda Takuya , Susaki Yoko , Tohda Toshifumi , Fukunaga Yasuhisa , Iwatsubo Takafumi , Noguchi Kiyoshi
Published: October 2014

The potent and selective phosphodiesterase 4 inhibitor ASP3258 is a novel therapeutic agent for asthma and chronic obstructive pulmonary disease (COPD). After a single oral administration to rats, ASP3258 is rapidly absorbed with a bioavailability of 106%. In situ absorption data indicated that ASP3258 is mainly absorbed in the small intestine. Tissue distribution data after oral administration of 14C‐ASP3258 showed rapid and extensive distribution to various tissues. Excluding the gastrointestinal tract, the tissues with the highest concentrations were liver, heart and plasma. Liquid chromatography‐nuclear magnetic resonance spectroscopy data revealed that O‐glucuronidation of the carboxylic acid moiety of ASP3258 (formation of an acyl glucuronide) plays a key role in metabolism. No indication was found that the acyl glucuronide reacted with proteins in plasma or tissues. When 14C‐ASP3258 was orally administered to intact rats, urinary and fecal excretion accounted for 1.3% and 100.6% of the administered radioactivity, respectively. After a single oral administration of 14C‐ASP3258 to bile‐cannulated rats, urinary and biliary excretion accounted for 0.7% and 93.8% of the administered radioactivity, respectively. These findings suggest that fecal excretion via bile plays an important role in the elimination of ASP3258‐derived radioactivity. In vitro metabolic profiles were relatively similar among the species examined, suggesting that our findings in rats may help us to understand pharmacokinetics, efficacy and safety profiles in humans and other species. Copyright © 2014 John Wiley & Sons, Ltd.
Silver Corrole Complexes: Unusual Oxidation States and Near‐IR‐Absorbing Dyes
Authors: Sinha Woormileela , Sommer Michael G. , Deibel Naina , Ehret Fabien , Sarkar Biprajit , Kar Sanjib
Published: October 2014

Macrocycles such as porphyrins and corroles have important functions in chemistry and biology, including light absorption for photosynthesis. Generation of near‐IR (NIR)‐absorbing dyes based on metal complexes of these macrocycles for mimicking natural photosynthesis still remains a challenging task. Herein, the syntheses of four new AgIII corrolato complexes with differently substituted corrolato ligands are presented. A combination of structural, electrochemical, UV/Vis/NIR‐EPR spectroelectrochemical, and DFT studies was used to decipher the geometric and electronic properties of these complexes in their various redox states. This combined approach established the neutral compounds as stable AgIII complexes, and the one‐electron reduced species of all the compounds as unusual, stable AgII complexes. The one‐electron oxidized forms of two of the complexes display absorptions in the NIR region, and thus they are rare examples of mononuclear complexes of corroles that absorb in the NIR region. The appearance of this NIR band, which has mixed intraligand charge transfer/intraligand character, is strongly dependent on the substituents of the corrole rings. Hence, the present work revolves round the design principles for the generation of corrole‐based NIR‐absorbing dyes and shows the potential of corroles for stabilizing unusual metal oxidation states. These findings thus further contribute to the generation of functional metal complexes based on such macrocyclic ligands.
Mapping of the Modular Closthioamide Architecture Reveals Crucial Motifs of Polythioamide Antibiotics
Authors: Kloss Florian , Chiriac Alina Iulia , Hertweck Christian
Published: October 2014

Closthioamide, the first known secondary metabolite from an anaerobic microorganism (Clostridium cellulolyticum), represents a highly potent antibiotic that is active against methicillin‐resistant Staphylococcus aureus (MRSA) and vancomycin‐resistant Enterococcus faecalis (VRE) at nanomolar concentrations. To unveil structure–activity relationships of the unusual polythioamide natural product we have designed a synthetic grid to access analogues with altered terminal aromatic moieties, diverse p‐phenyl substituents, different types and sizes of aliphatic spacers, varying numbers of thioamide residues, and diverse sizes and symmetries of the poly‐β‐thioalanyl backbone. A library of 28 closthioamide analogues was tested against a panel of human pathogenic bacteria. We found that aromatic terminal groups, the defined length of the spacer groups, the presence of all six thioamide residues and the modular arrangement of the β‐thioalanyl units play essential roles for the antibiotic activity of closthioamide, yet there is a degree of freedom in the symmetry of the molecule. This study yields the first insights into pivotal structural motifs and the structural space of this new family of antibiotics, a prerequisite for the development of these promising antibiotics.
A Direct Hybridization between Isocharged Nanosheets of Layered Metal Oxide and Graphene through a Surface‐Modification Assembly Process
Authors: Adpakpang Kanyaporn , Oh Seung Mi , Jin Xiaoyan , Hwang Seong‐Ju
Published: October 2014

An efficient and universal method to directly hybridize isocharged nanosheets of layered metal oxide and reduced graphene oxide (rGO) is developed on the basis of the surface modification and an electrostatically driven assembly process. On the basis of this synthetic method, the CoO2–rGO nanocomposite can be synthesized with exfoliated CoO2 and rGO nanosheets, and transformed into CoO–CoO2–rGO nanocomposites with excellent electrode performance for lithium‐ion batteries. Also, this surface‐modification assembly route is successfully applied for the synthesis of another mesoporous TiO2–rGO nanocomposite. This result provides clear evidence for the usefulness of the present method as a universal way of hybridizing isocharged anionic nanosheets of inorganic solids and graphene.
Binding of Scandium Ions to Metalloporphyrin–Flavin Complexes for Long‐Lived Charge Separation
Authors: Kojima Takahiko , Kobayashi Ryosuke , Ishizuka Tomoya , Yamakawa Shinya , Kotani Hiroaki , Nakanishi Tatsuaki , Ohkubo Kei , Shiota Yoshihito , Yoshizawa Kazunari , Fukuzumi Shunichi
Published: October 2014

A porphyrin–flavin‐linked dyad and its zinc and palladium complexes (MPorFl: 2M, M=2 H, Zn, and Pd) were newly synthesized and the X‐ray crystal structure of 2Pd was determined. The photodynamics of 2M were examined by femto‐ and nanosecond laser flash photolysis measurements. Photoinduced electron transfer (ET) in 2H2 occurred from the singlet excited state of the porphyrin moiety (H2Por) to the flavin (Fl) moiety to produce the singlet charge‐separated (CS) state 1(H2Por.+Fl.−), which decayed through back ET (BET) to form 3[H2Por]*Fl with rate constants of 1.2×1010 and 1.2×109 s−1, respectively. Similarly, photoinduced ET in 2Pd afforded the singlet CS state, which decayed through BET to form 3[PdPor]*Fl with rate constants of 2.1×1011 and 6.0×1010 s−1, respectively. The rate constant of photoinduced ET and BET of 2M were related to the ET and BET driving forces by using the Marcus theory of ET. One and two Sc3+ ions bind to the flavin moiety to form the FlSc3+ and Fl(Sc3+)2 complexes with binding constants of K1=2.2×105 M−1 and K2=1.8×103 M−1, respectively. Other metal ions, such as Y3+, Zn2+, and Mg2+, form only 1:1 complexes with flavin. In contrast to 2M and the 1:1 complexes with metal ions, which afforded the short‐lived singlet CS state, photoinduced ET in 2Pd⋅⋅⋅Sc3+ complexes afforded the triplet CS state (3[PdPor.+Fl.−(Sc3+)2]), which exhibited a remarkably long lifetime of τ=110 ms (kBET=9.1 s−1).
Breaking the Odd–Even Effect in the Self‐Assembly of Linear Bis(benzamides)
Authors: Aparicio Fátima , Matesanz Emilio , Sánchez Luis
Published: October 2014

The twisting of supramolecular aggregates formed from simple linear bis(benzamides) has been investigated. The antiparallel arrangement of the amide functional groups controls the generation of twisted supramolecular structures. The results presented herein could contribute to elaborate predictive tools applicable in the generation of chiral supramolecular structures.
Regarding Initial Ring Opening of Propylene Oxide in its Copolymerization with CO2 Catalyzed by a Cobalt(III) Porphyrin Complex
Authors: Xia Wei , Vagin Sergei I. , Rieger Bernhard
Published: October 2014

Cobalt(III) tetraphenylporphyrin chloride (TPPCoCl) was experimentally proved to be an active catalyst for poly(propylene carbonate) production. It was chosen as a model catalyst in the present work to investigate the initiation step of propylene oxide (PO)/CO2 copolymerization, which is supposed to be the ring opening of the epoxide. Ring‐opening intermediates (1–7) were detected by using 1H NMR spectroscopy. A first‐order reaction in TPPCoCl was determined. A combination of monometallic and bimetallic ring‐opening pathways is proposed according to kinetics experiments. Addition of onium salts (e.g., bis(triphenylphosphine)iminium chloride, PPNCl) efficiently promoted the PO ring‐opening rate. The existence of axial ligand exchange in the cobalt porphyrin complex in the presence of onium salts was suggested by analyzing collected 1H NMR spectra.
A Universal Approach for the Reversible Phase Transfer of Hydrophilic Nanoparticles
Authors: Ma Shenghua , Yong Daming , Zhang Ying , Wang Xuejing , Han Xiaojun
Published: October 2014

The ability to engineer the surface properties of magnetic nanoparticles is important for their various applications, as numerous physical and chemical properties of nanoscale materials are seriously affected by the chemical constitution of their surfaces. For some specific applications, nanoparticles need to be transferred from a polar to a nonpolar environment (or vice versa) after synthesis. In this work we have developed a universal method for the phase transfer of magnetic nanoparticles that preserves their shape and size. Octadecyltrimethoxysilane was used to cap the surfaces of the aqueous magnetic nanoparticles, thereby allowing their transfer into nonpolar solution. The resulting hydrophobic magnetic nanoparticles were transferred back into aqueous solution by subsequently covering them with an egg‐PC lipid monolayer. The superparamagnetic properties of the particles were retained after the phase transfer. The maximum transfer yields are dependent on their particle size with a maximum value of 93.16±4.75 % for magnetic nanoparticles with a diameter of 100 nm. The lipid‐modified magnetic particles were stable over 1 week, and thus they have potential applications in the field of biomedicine. This work also provides a facile strategy for the controllable engineering of the surface properties of nanoparticles.
Selective Catalytic Behavior of a Phosphine‐Tagged Metal‐Organic Framework Organocatalyst
Authors: Xu Xiaoying , Rummelt Stephan M. , Morel Flavien L. , Ranocchiari Marco , van Bokhoven Jeroen A.
Published: October 2014

Steric hindrance by a metal–organic framework (MOF) is shown to influence the outcome of a catalytic reaction by controlling the orientation of its intermediates. This is demonstrated using an organocatalyst, phosphine MOF LSK‐3, which is evaluated with the aid of molecular modeling and NMR spectroscopy techniques. This report is the first application of phosphine MOFs in organocatalysis and explores the potential of a framework steric hindrance to impose selectivity on a catalytic reaction. These findings expand the opportunities for control and design of the active site in the pocket of heterogeneous catalysts.
Ligand‐Controlled Regiodivergent Pathways of Rhodium(III)‐Catalyzed Dihydroisoquinolone Synthesis: Experimental and Computational Studies of Different Cyclopentadienyl Ligands
Authors: Wodrich Matthew D. , Ye Baihua , Gonthier Jérôme F. , Corminboeuf Clémence , Cramer Nicolai
Published: October 2014

RhIII‐catalyzed directed CH functionalizations of arylhydroxamates have become a valuable synthetic tool. To date, the regioselectivity of the insertion of the unsaturated acceptor into the common cyclometalated intermediate was dependent solely on intrinsic substrate control. Herein, we report two different catalytic systems that allow the selective formation of regioisomeric 3‐aryl dihydroisoquinolones and previously inaccessible 4‐aryl dihydroisoquinolones under full catalyst control. The differences in the catalysts are computationally examined using density functional theory and transition state theory of different possible pathways to elucidate key contributing factors leading to the regioisomeric products. The stabilities of the initially formed rhodium complex styrene adducts, as well as activation barrier differences for the migratory insertion, were identified as key contributing factors for the regiodivergent pathways.
Carbon‐Centered Radical Addition to OC of Amides or Esters as a Route to CO Bond Formations
Authors: Liu Dong , Tang Shan , Yi Hong , Liu Chao , Qi Xiaotian , Lan Yu , Lei Aiwen
Published: October 2014

Among various types of radical reactions, the addition of carbon radicals to unsaturated bonds is a powerful tool for constructing new chemical bonds, in which the typical applied unsaturated substrates include alkenes, alkynes and imines. Carbonyl is perhaps the most common unsaturated group in nature. This work demonstrates a novel CO bond formation through carbon‐centered radical addition to the carbonyl oxygen of amide or ester, in which amide and ester groups are easily activated through the radical process. EPR spectroscopy and radical clock experiments support the radical process for this transformation, and density functional theory (DFT) calculations support the possibility of carbon‐centered radical addition to the carbonyl oxygen of amides or esters.
Rapid Synthesis of Hollow Ag–Au Nanodendrites in 15 Seconds by Combining Galvanic Replacement and Precursor Reduction Reactions
Authors: da Silva Anderson G. M. , de Souza Michele L. , Rodrigues Thenner S. , Alves Rafael S. , Temperini Marcia L. A. , Camargo Pedro H. C.
Published: October 2014

Metallic nanomaterials displaying hollow interiors as well as sharp tips/branches at their surface (such as hollow nanodendrites) are attractive, because these features enable higher surface‐to‐volume ratios than their solid and/or rounded counterparts. This paper describes a simple strategy for the synthesis of Ag–Au nanodendrites in 15 s using Ag nanospheres prepared in a previous synthetic step as seeds. Our approach was based on the utilization of Ag nanospheres as seeds for Au deposition by a combination of galvanic replacement reaction between Ag and AuCl4−(aq) and AuCl4−(aq) reduction using hydroquinone in the presence of polyvinylpyrrolidone (PVP) as a stabilizer and water as the solvent. The produced Ag–Au nanodendrites presented monodisperse sizes, and their surface morphologies could be tuned as a function of growth time. Owing to their hollow interiors and sharp tips, the Ag–Au nanodendrites performed as effective substrates for surface‐enhanced Raman scattering (SERS) detection of 4‐MPy (4‐mercaptopyridine) and R6G (rhodamine 6G) as probe molecules. We believe that the approach described herein can serve as a protocol for the fast and one‐step synthesis of Ag–Au hollow nanondendrites with a wide range of sizes, compositions, and surface morphologies for applications in SERS and catalysis.
Polyimido Sulfur(VI) Phosphanyl Ligand in Metal Complexation
Authors: Carl Elena , Stalke Dietmar
Published: October 2014

Herein, new complexes containing the [Ph2PCH2S(NtBu)3]− anion are presented, supplying three imido nitrogen atoms and a remote phosphorus atom as potential donor sites to main group and transition‐metal cations. The lithiated complex [(tmeda)Li{(NtBu)3SCH2PPh2}] (1) is an excellent starting material in transmetalation reactions. Herein, the transition‐metal complexes [M{(NtBu)3SCH2PPh2}2] (M=Mn (2), Ni (3), Zn (4)) were synthesized and structurally characterized. Their isotypical molecules show SN2 chelation and no employment of the adjacent phosphorus atom in coordination. The third pendent imido group is always twisted toward the vacant face of the tetrahedrally coordinated sulfur atom.
Performance of optimized link state routing protocol for video streaming application in vehicular ad‐hoc networks cloud computing
Authors: Ikeda Makoto , Honda Taiki , Barolli Leonard
Published: October 2014

In recent years, vehicular ad‐hoc networks (VANETs) have emerged as a unique type of mobile ad‐hoc networks. VANETs are an important component of the intelligent transportation systems. They can been utilized to guarantee road safety, avoid potential accidents and create new forms of inter‐vehicle communications. In this paper, we consider a network‐as‐a‐service architecture for VANET cloud computing. We investigate the performance of optimized link state routing protocol for video streaming application. The simulations are conducted in urban environment in three scenarios, where roadside access points (AP) are present and not present, with and without buildings. We consider 802.11p standard and send multiple video streaming flows over user diagram protocol. We use throughput, delay and jitter as evaluation metrics. Based on simulation results, we noticed that transmission for streaming is improved when roadside AP are used. Copyright © 2014 John Wiley & Sons, Ltd.
Reduced Graphene Oxide Nanosheets Decorated with Au Nanoparticles as an Effective Bactericide: Investigation of Biocompatibility and Leakage of Sugars and Proteins
Authors: Hussain Najrul , Gogoi Animesh , Sarma Rupak K. , Sharma Ponchami , Barras Alexandre , Boukherroub Rabah , Saikia Ratul , Sengupta Pinaki , Das Manash R.
Published: October 2014

This article reports the synthesis of a composite of reduced graphene oxide nanosheets decorated with gold nanoparticles (AuNPs‐rGO) through an ecofriendly route, and the investigation of its biocompatibility to HeLa cells and its antibacterial activity against Gram‐positive and Gram‐negative bacteria. The composite material is synthesized by using an environmentally friendly reducing agent, ascorbic acid, under ultrasonication. The composite material is characterized by UV/Vis spectroscopy, X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), small‐angle X‐ray scattering (SAXS), high‐resolution transmission electron microscopy (HRTEM), and thermogravimetric analysis (TGA). HRTEM analysis reveals the formation of spherical Au NPs of 8–45 nm in size on the folded rGO nanosheets, which is further confirmed by XRD and SAXS analyses. The AuNPs‐rGO shows good biocompatibility with cervix carcinoma, human (HeLa) cells, and possesses high antibacterial activity against two Gram‐positive bacteria (Staphylococcus aureus and Bacillus subtilis) and two Gram‐negative bacteria (Escherichia coli and Pseudomonous aeruginosa). The bacterial cell death is caused by the leakage of sugars and proteins from the cell membrane in contact with the AuNPs‐rGO composite material.
Characteristics of traps in Tl2Ga2Se3S single crystals by low‐temperature thermoluminescence measurements
Authors: Delice S. , Gasanly N.M.
Published: October 2014

Defect characterization of Tl2Ga2Se3S single crystals has been performed by thermoluminescence (TL) measurements at low temperatures between 10 and 70 K with various heating rate ranging from 0.6 to 1.0 K/s. The TL signal due to the luminescence from trap centers revealed one glow peak having maximum temperature of 36 K. Curve fitting and various heating rate methods were used for the analysis of the glow curve. The activation energy of 13 meV was found by the application of curve fitting method. This practical method also established that the trap center exhibits the characteristics of mixed (general) kinetic order. In addition, various heating rate analysis gave a compatible result (13 meV) with curve fitting as the temperature lag effect was taken into consideration. Distribution of traps was also investigated using an experimental method. A quasi‐continuous distribution was attributed to the determined trap centers.
The epigenetic factor Kmt2a/Mll1 regulates neural progenitor proliferation and neuronal and glial differentiation
Authors: Huang Yin‐Cheng , Shih Hung‐Yu , Lin Sheng‐Jia , Chiu Ching‐Chi , Ma Tsu‐Lin , Yeh Tu‐Hsueh , Cheng Yi‐Chuan
Published: October 2014

Multiple epigenetic factors play a critical role in cell proliferation and differentiation. However, their function in embryogenesis, especially in neural development, is currently unclear. The Trithorax group (TrxG) homolog KMT2A (MLL1) is an important epigenetic regulator during development and has an especially well‐defined role in hematopoiesis. Translocation and aberrant expression of KMT2A is often observed in many tumors, indicating its proto‐oncogenic character. Here, we show that Kmt2a was essential for neural development in zebrafish embryos. Disrupting the expression of Kmt2a using morpholino antisense oligonucleotides and a dominant‐negative variant resulted in neurogenic phenotypes, including downregulated proliferation of neural progenitors, premature differentiation of neurons, and impaired gliogenesis. This study therefore revealed a novel function of Kmt2a in cell proliferation and differentiation, providing further insight into the function of TrxG proteins in neural development and brain tumors. © 2014 Wiley Periodicals, Inc. Develop Neurobiol 75: 452–462, 2015
Community assembly rules affect the diversity of expanding communities
Authors: Peng Zechen , Zhou Shurong
Published: October 2014

Despite centuries of interest in species range limits, few studies have taken a whole community into consideration. Actually, multiple species may simultaneously respond to environmental changes, for example, global warming, leading a series of dynamical communities toward the advancing front. We investigated multiple species range expansions through the analysis of a two‐species dispersion model and simulations of multiple species assemblages regulated by neutral and fecundity–survival trade‐offs (FSTs), respectively, and found that species assemblages regulated by different mechanisms would initiate different expanding patterns in geographic ranges in response to environmental changes. The neutral model generally predicts a higher biodiversity near the core of an expanding range, and a lower community similarity compared with a FST model. Without considering the evolution of life history traits, an assortment of the reproduction ability happens at the advancing front under FSTs at the expense of a higher death rate or lower competitive ability. These results emphasize the importance of community assembly rules to the biodiversity maintenance of range expanding communities.