bluuebunny/crossref_metadata_2025 huggingface dataset:
A VIOLAÇÃO DOS DIREITOS FUNDAMENTAIS NO SISTEMA PRISIONAL BRASILEIRO À LUZ DA TEORIA DO GARANTISMO PENAL
Authors: Casari Camila Maria Rosa , Giacóia Gilberto
Published: June 2016

O indivíduo que comete uma infração penal em um Estado Democrático de Direito, após ser devidamente processado e condenado a cumprir pena privativa de liberdade, respeitando-se os princípios constitucionais, somente será destituído do bem jurídico liberdade. Não há qualquer legitimidade e fere a finalidade da aplicação da pena, qualquer espécie de desrespeito aos direitos fundamentais do preso. Contudo, de forma reiterada o sistema prisional brasileiro viola direitos fundamentais, muito além da privação da liberdade. Este trabalho propõe-se a analisar a ocorrência e quais as consequências das violações dos direitos fundamentais dos presos à luz da teoria do garantismo penal, na perspectiva desenvolvida pelo doutrinador Luigi Ferrajoli, propondo que o Estado desenvolva políticas criminais garantistas, tais como aplicação de penas alternativas à prisão, medidas educacionais e profissionalizantes além do fortalecimento da Justiça Restaurativa, bem como medidas destinadas a reinserção do egresso ao convívio social.
HERMENÊUTICA FLEXÍVEL E DISCRICIONARIEDADE JUDICIAL
Authors: Cambi Eduardo Augusto Salomão , Stipp Luna
Published: June 2016

O artigo tem como propósito discutir a discricionariedade judicial na aplicação dos princípios jurídicos, no contexto da modernidade líquida. O artigo procura, por meio do método de revisão bibliográfica, demonstrar as consequências e perigos na utilização de métodos interpretativos desvinculados do sistema normativo preestabelecido
ASSÉDIO MORAL NA ADMINISTRAÇÃO PÚBLICA: UMA VISÃO CRÍTICA DA JURISPRUDÊNCIA BRASILEIRA
Authors: Cardoso Guilherme Augusto , Almeida Victor Hugo de
Published: June 2016

O presente estudo visou à analise de decisões proferidas pelo Tribunal Regional do Trabalho da 15ª Região (TRT-15) e pelo Tribunal de Justiça do Estado de São Paulo (TJSP), a fim de se verificar a existência ou não de uniformidade de entendimento a respeito da definição e dos elementos caracterizadores do assédio moral vertical descendente na administração pública. Para tanto, a partir do método de análise de decisões, delinearam-se os conceitos básicos para a melhor intelecção dos acórdãos coletados, além da divisão de competência dos órgãos do Poder Judiciário escolhidos para o desenvolvimento do estudo. Buscando entender o sentido aplicado ao fenômeno na seara jurisprudencial, foram estabelecidos parâmetros de pesquisa para a coleta de dados em recorte temporal semestral, concluindo-se pelo escasso enfrentamento ao tema no conteúdo decisório verificado. As lacunas constatadas nos conteúdos dos acórdãos de ambos os tribunais permitiram a constatação da necessidade de melhor exploração do assédio moral por parte das decisões, principalmente na seara da administração pública, pois que o fenômeno se mostrou ferramenta de relativização de direitos já legitimados aos agentes públicos.
Contrastive analysis of Turkish and English in Turkish EFL learners’ spoken discourse
Authors: Yildiz Mustafa
Published: June 2016

The present study aimed at finding whether L1 Turkish caused interference errors on Turkish EFL learners’ spoken English discourse. Whether English proficiency level had any effect on the number of errors learners made was further investigated. The participants were given the chance to choose one of the two alternative topics to speak about. The entire videotaped speaking session was further transcribed to analyze the spoken errors. The results indicated that prepositional, lexical, and grammatical errors were the most frequently encountered errors, in descending order. Also, independent samples t-test was applied to the data to determine whether English proficiency level had any effect on the number of errors made by two different English proficiency groups. It was found that there was no significant difference between two different English proficiency groups with regard to the number of errors they made.
Anglicisms and calques in upper social class in pre-revolutionary Cuba (1930–1959): A sociolinguistic analysis
Authors: Sánchez Jose Antonio
Published: June 2016

The geographical proximity and socioeconomic dependence on the United States brought about a deep rooted anglicization of the Cuban Spanish lexis and social strata, especially throughout the Neocolonial period (1902–1959). This study is based on the revision of a renowned newspaper of that time, Diario de la Marina, and the corresponding elaboration of a corpus of English-induced loanwords. Diario de la Marina particularly targeted upper social class, and only crónicas sociales (society pages’ columns) and print advertising were revised because of their fully descriptive texts, which encoded the ruling class ideology and consumerism. The findings show that there existed a high number of lexical and cultural anglicisms in the sociolect in question, and that the sociolinguistic anglicization was openly embraced by the upper socioeconomic stratum, entailing a differentiating sign of sophistication and social stratification. Likewise, a number of the anglicisms collected, particularly those related with social events, are unused in contemporary Cuban Spanish, which suggests a major semantic shifting in this sociolect after 1959.
Valoración económica de los beneficios ambientales de no mercado derivados de la mejora de la calidad del agua: Una estimación en aplicación de la Directiva Marco del Agua al Guadalquivir
Authors: Martín-Ortega Julia , Berbel Julio , Brouwer Roy
Published: June 2016

This study contributes to the economic assessment of the benefits derived from the implementation of the Water Framework Directive (WFD). A practical definition of environmental benefits and a valuation scenario of the non-market benefits of water quality improvement is proposed. This economic assessment is needed to asses whether the WFD is disproportionately costly. The contingent valuation method is applied to the Guadalquivir River Basin (Southern Spain), using a two-stage Heckman estimation model.
Preferencias hacia el origen de un alimento étnico y la influencia de variables psicográficas
Authors: Camarena-Gómez Dena Mª , Sanjuán-López Ana I.
Published: June 2016

In recent years, knowledge and consumption of ethnic food has spread in Spain, among other factors, enhanced by immigration. Immigrants constitute a new market segment, with specific food demands that respond to the necessity of keeping their culinary traditions. In this research a choice experiment is conducted in order to investigate Latin-American consumers’ preferences toward an essential food in their diets, corn flour. In order to allow preferences to differ across individuals, a mixed logit model is estimated. Three psychographic variables are contemplated as possible sources for preference heterogeneity: the degree of food neo-phobia, ethnocentrism and personal values. Consumers more neo-phobic, and those with personal values than emphasize personal development, are more price-sensitive, while, more ethnocentric consumers favour the patriotic origin of the ethnic food.
Travailleuses, gestionnaires, syndicat. Trois perspectives sur la conciliation travail-famille au sein de marchés d’alimentation et de restaurants au Québec
Authors: Lefrançois Mélanie , Des Rivières-Pigeon Catherine , Fortin Sylvie
Published: June 2016

Non seulement les horaires de travail « non standards » propres aux marchés d’alimentation et aux restaurants posent d’énormes défis à la conciliation travail-famille (CTF), mais ils influent sur la santé physique et mentale des personnes employées. Cette étude qualitative vise la compréhension des pratiques, des difficultés et des stratégies de CTF présentes dans ces deux milieux de travail. Quarante-deux entretiens semi-dirigés ont été menés auprès de travailleuses, de gestionnaires et de représentantes et représentants syndicaux. Une analyse thématique nous a permis de saisir la complexité de l’articulation entre les aspects formels et informels des pratiques de conciliation, ainsi que les différents facteurs qui contribuent à l’invisibilité des enjeux auxquels doivent faire face les travailleuses de ces milieux. Plus particulièrement, l’inégalité entre les postes occupés par les femmes et par les hommes a émergé des données, notamment la précarité importante vécue par les caissières. L’ampleur des difficultés de conciliation rapportées et la faible ouverture des milieux de travail aux enjeux de CTF pourraient expliquer la résignation des travailleuses et l’impression partagée par tous les acteurs que les conditions de ces milieux ne peuvent être changées.
The Argument for Teaching Financial Literacy at Higher-Education Institutions
Authors: GEDDES SHERI , STEEN TODD
Published: June 2016

Evidence suggests that financial decisions have a substantial impact on human flourishing. This paper examines the arguments for higher-education institutions to take a role in the provision of financial education for their students, families and alumni, who often incur substantial debt and make other sacrifices to obtain a postsecondary education. It also analyzes the current state of financial education at 322 higher-education institutions. While many postsecondary institutions have embraced some aspects of financial education, other higher-education institutions appear reluctant to infuse this multidisciplinary topic into their academic programs. Colleges and universities should consider developing robust programs that boost financial literacy and improve lifelong economic well-being.
Johan Huizinga, The Waning of the Middle Ages, and the Writing of History
Authors: MORAN SEÁN FARRELL
Published: June 2016

Contemporary professional history does not train its practitioners to write works of genuine innovation. The commitment to archive-driven research and the need to establish a niche for one's research discourages originality. It also denies the validity of history which reveals the emotional engagement of the writer or appeals beyond the narrow confines of the professional historian. Johann Huizinga's work, especially his magnum opus The Waning of the Middle Ages, serves to remind us of how breathtaking and bold history can be. In print for eight decades, Huizinga's great book is loved outside of the halls of academe despite its inadequacies and stands as one of the most influential works of the past century.
First-principles study of crystalline silicon hyperdoped with cobalt at a concentration exceeding the Mott limit
Authors: Dong Xiao , Wang Yongyong , Song Xiaohui , Wang Jinfeng , Li Xueping
Published: June 2016

We systematically studied the properties of Co-hyperdoped silicon using first-principles calculations based on density-functional theory. A series of more complex configurations, such as quasi-substitutional and paired-Co-doped structures, are considered in our study. Our calculational results indicate that the quasi-substitutional and paired-Co-doped structures can introduce several intermediate bands (IBs) in the band gap and lead to the sub-band gap absorption. The quasi-substitutional and paired-Co-doped structures exhibit red-shift in their sub-band gap absorption spectra when compared to the substitutional structure. The formation energy calculations imply that the material would exhibit thermal stability of absorption in the infrared wavelength.
Spin Hall magnetoresistance in Ta/CoFe2O4 nanostructures
Authors: Hui Ya-Juan , Cheng Wei-Ming , Zhang Zhao-Bing , Ji Hong-Kai , Cheng Xiao-Min , You Long , Miao Xiang-Shui
Published: June 2016

Spin Hall magnetoresistance (SMR) has been investigated in Ta/CoFe2O4 nanostructures grown on different substrates. Spin currents in CoFe2O4 films are electrically detected in adjacent Ta layers owing to inverse spin Hall effects. The sign of the magnetic-field-dependent resistivity signal shows different polarities along different axes, showing different spin-dependent electron transports. A cosinelike curve of the angular dependence signal with opposite polarity is observed in two orthogonal magnetization planes, whereas a basic line is observed in another plane, revealing the spin accumulation phenomenon. The roughness of the CoFe2O4 surface tuned by substrate strains is responsible for the extent of spin accumulations and the strength of the SMR signal in the nanostructures.
Insulator-to-metal transition of WO3 epitaxial films induced by electrochemical Li-ion intercalation
Authors: Yoshimatsu Kohei , Soma Takuto , Ohtomo Akira
Published: June 2016

We investigated the systematic evolution of the structural and electronic properties of Li
x
WO3 films induced by Li-ion electrochemical reactions. Chronoamperometric Li-ion intercalation could control the Li content up to x ∼ 0.5. The resistivity decreased abruptly with increasing x, and the films underwent an insulator-to-metal transition (IMT) within a range of 0.2 < x < 0.24, which was consistent with the IMT of cubic Na
x
WO3. X-ray diffraction analyses revealed the coexistence of tetragonal and cubic phases across the IMT, suggesting that the alkaline ion content was the primary factor in the metallic conductivity of the ReO3-type WO3 system.
Advanced simulation technology for etching process design for CMOS device applications
Authors: Kuboi Nobuyuki , Fukasawa Masanaga , Tatsumi Tetsuya
Published: June 2016

Plasma etching is a critical process for the realization of high performance in the next generation of CMOS devices. To predict and control fluctuations in the etching properties accurately during mass production, it is essential that etching process simulation technology considers fluctuations in the plasma chamber wall conditions, the effects of by-products on the critical dimensions, the Si recess dependence on the wafer open area ratio and local pattern structure, and the time-dependent plasma-induced damage distribution associated with the three-dimensional feature scale profile at the 100 nm level. This consideration can overcome the issues with conventional simulations performed under the assumed ideal conditions, which are not accurate enough for practical process design. In this article, these advanced process simulation technologies are reviewed, and, from the results of suitable process simulations, a new etching system that automatically controls the etching properties is proposed to enable stable CMOS device fabrication with high yields.
Shapes of leaves with parallel venation. Modelling of theEpipactissp. (Orchidaceae) leaves with the help of a system of coupled elastic beams
Authors: Jakubska-Busse Anna , Janowicz Maciej , Ochnio Luiza , Jackowska-Zduniak Beata
Published: June 2016

Static properties of leaves with parallel venation, with particular emphasis on the genusEpipactisZinn, 1757 (Orchidaceae, Neottieae) have been modelled with coupled quasi-parallel elastic “beams.” The non-linear theory of strongly bended beams have been employed. The resulting boundary-value problem has been solved numerically with the help of the finite-difference method. Possible dislocations resulting in additional Dirac-delta like forces have been take into account. Morphological similarity of the model and real leaves has been obtained. In particular, the concentrated forces have been shown to cause undulation in the leaves.
Extreme dry spell detection and climatology over the Mediterranean Basin during the wet season
Authors: Raymond Florian , Ullmann Albin , Camberlin Pierre , Drobinski Philippe , Smith Carmela Chateau
Published: June 2016

The E‐OBS precipitation gridded data set v.10.0 is used to detect very long dry spell (VLDS) events over the entire Mediterranean Basin for the 1957–2013 period, during the wet season (September to April). The main objective is to characterize these events as climatic objects, in terms of location, spatial extent, duration, and temporal variability. In this study, 76 VLDS events were detected in the Mediterranean Basin and grouped into four spatial patterns: scattered localized (with 25 events), northeast Mediterranean (11 events), West Mediterranean (15 events), and southeast Mediterranean (25 events). Each pattern shows seasonality in events. Most of the scattered localized, northeast, and southeast events begin in September, at the beginning of the wet season. In contrast, most of the West Mediterranean events begin in the middle of the wet season. Over time, there is a slight but not significant increase in the cumulative number of days per season affected by VLDS events.
Advancing the Evolution of Sexual Offender Risk Assessment
Authors: Thornton David , D'Orazio Deirdre M.
Published: June 2016

This chapter explores the nature and role of psychological factors in assessing the risk presented by sexual offenders. It is argued that it is incumbent upon those tasked with assessing risk to conduct a comprehensive assessment of psychological factors as an essential aspect of effective sexual offender risk assessment. Not only do instruments that provide comprehensive assessment of psychological risk factors afford a similar level of predictive accuracy compared with that afforded by traditional static actuarial instruments, but the combination of static and psychological risk factors leads to even better prediction than either alone. Moreover, the predictive properties of the static actuarial instruments become unstable if either the density of psychological risk factors or the degree of external control prevailing in the release environment varies. Psychological risk factors have both enduring and more actively dynamic aspects and assessors are cautioned not to overweight recent functioning in rendering risk predictions. The chapter articulates a model of these temporal aspects of risk factors and their interaction. Risk reduction is understood in terms of managing long‐term vulnerabilities through improved self‐regulation and the development of resources supportive of prosocial goals.
3D Networks of Carbon‐Coated Magnesium‐Doped Olivine Nanofiber as Binder‐Free Cathodes for High‐Performance Li‐Ion Battery
Authors: Ma Dingtao , Zhang Peixin , Li Yongliang , Abdelkader Amor M. , Singh Deepak P. , Ren Xiangzhong , Deng Libo
Published: June 2016

3D nanoarchitecture of LiFe0.98Mg0.02PO4/C nanofibers is synthesized by a one‐pot electrospinning method and employed as a binder‐free cathode material for Li‐ion batteries. The novel cathode shows significant improvement in the electrochemical performance, particularly for stability and rate capability due to the unique combination of the interconnected fibrous structure and the high electronic and ionic conductivity induced by Mg‐doping. The LiFe0.98Mg0.02PO4/C nanofiber cathode displays a discharge capacity of 152 mAh g−1 with capacity retention of 98.2% at 0.5 C after 100 cycles. Investigations on the stability and rate capability of the novel porous electrode studied at different rates of 0.05 C to 10 C for 100 cycles also show high capacity values that indicate their potential as cathode materials.
Self‐Assembled BiFeO3‐ε‐Fe2O3 Vertical Heteroepitaxy for Visible Light Photoelectrochemistry
Authors: Quynh Le Thi , Van Chien Nguyen , Bitla Yugandhar , Chen Jhih‐Wei , Do Thi Hien , Tzeng Wen‐Yen , Liao Sheng‐Chieh , Tsai Kai‐An , Chen Yi‐Chun , Wu Chun‐Lin , Lai Chih‐Huang , Luo Chih‐Wei , Hsu Yung‐Jung , Chu Ying‐Hao
Published: June 2016

Self‐assembled vertical heterostructure with a high interface‐to‐volume ratio offers tremendous opportunities to realize intriguing properties and advanced modulation of functionalities. Here, a heterostructure composed of two visible‐light photocatalysts, BiFeO3 (BFO) and ε‐Fe2O3 (ε‐FO), is designed to investigate its photoelectrochemical performance. The structural characterization of the BFO‐FO heterostructures confirms the phase separation with BFO nanopillars embedded in the ε‐FO matrix. The investigation of band structure of the heterojunction suggests the assistance of photoexcited carrier separation, leading to an enhanced photoelectrochemical performance. The insights into the charge separation are further revealed by means of ultrafast dynamics and electrochemical impedance spectroscopies. This work shows a delicate design of the self‐assembled vertical heteroepitaxy by taking advantage of the intimate contact between two phases that can lead to a tunable charge interaction, providing a new configuration for the optimization of photoelectrochemical cell.
Siblings with severe pyruvate kinase deficiency and a complex genotype
Authors: Christensen Robert D. , Yaish Hassan M. , Nussenzveig Roberto H. , Agarwal Archana M.
Published: June 2016

Siblings presented as neonates with severe jaundice and transfusion‐dependent hemolytic anemia. Next‐generation sequencing revealed both to have three heterozygous mutations in the gene encoding erythrocyte pyruvate kinase (PKLR), plus a heterozygous splice mutation in the beta‐spectrin gene (SPTB). In addition, both have a different 5th mutation in a gene encoding other erythrocyte membrane proteins. The asymptomatic parents and all three asymptomatic siblings have different sets of these mutations. © 2016 Wiley Periodicals, Inc.
Monofluoralkenylierung von Dimethylaminoverbindungen durch Radikal‐Radikal‐Kreuzkupplung
Authors: Xie Jin , Yu Jintao , Rudolph Matthias , Rominger Frank , Hashmi A. Stephen K.
Published: June 2016

Eine neuartige und schwierige Radikal‐Radikal‐Kreuzkupplung von α‐Aminoalkylradikalen mit von gem‐Difluoralkenen abgeleiteten Monofluoralkenylradikalen wurde erreicht. Dieses erste Beispiel einer Tandem‐C(sp3)‐H/C(sp2)‐F‐Bindungsfunktionalisierung über Photoredoxkatalyse mit sichtbarem Licht eröffnet einen leichten und flexiblen Zugang zu privilegierten, tetrasubstituierten Monofluoralkenen unter sehr milden Reaktionsbedingungen. Die besonderen Eigenschaften dieses redoxneutralen Verfahrens bezüglich der Anwendungsbreite, der Toleranz gegenüber funktionellen Gruppen und Regioselektivität zeigen sich durch die Fluoralkenylierungen von komplexen molekularen Architekturen wie dem bioaktiven (+)‐Filtiazem, Rosiglitazon, Dihydroartemisinin, Oleanolsäure und einem Androsteron‐Derivat; dies sind wichtige neue α‐Amino‐C‐H‐Monofluoralkenylierungen.
Synthesis of Calcium(II) Amidinate Precursors for Atomic Layer Deposition through a Redox Reaction between Calcium and Amidines
Authors: Kim Sang Bok , Yang Chuanxi , Powers Tamara , Davis Luke M. , Lou Xiabing , Gordon Roy G.
Published: June 2016

We have prepared two new CaII amidinates, which comprise a new class of ALD precursors. The syntheses proceed by a direct reaction between Ca metal and the amidine ligands in the presence of ammonia. Bis(N,N′‐diisopropylformamidinato)calcium(II) (1) and bis(N,N′‐diisopropylacetamidinato)calcium(II) (2) adopt dimeric structures in solution and in the solid state. X‐ray crystallography revealed asymmetry in one of the bridging ligands to afford the structure [(η2‐L)Ca(μ‐η2:η2‐L)(μ‐η2:η1‐L)Ca(η2‐L)]. These amidinate complexes showed unprecedentedly high volatility as compared to the widely employed and commercially available CaII precursor, [Ca3(tmhd)6]. In CaS ALD with 1 and H2S, the ALD window was approximately two times wider and lower in temperature by about 150 °C than previously reported with [Ca3(tmhd)6] and H2S. Complexes 1 and 2, with their excellent volatility and thermal stability (up to at least 350 °C), are the first homoleptic CaII amidinates suitable for use as ALD precursors.
Selective Protein Hyperpolarization in Cell Lysates Using Targeted Dynamic Nuclear Polarization
Authors: Viennet Thibault , Viegas Aldino , Kuepper Arne , Arens Sabine , Gelev Vladimir , Petrov Ognyan , Grossmann Tom N. , Heise Henrike , Etzkorn Manuel
Published: June 2016

Nuclear magnetic resonance (NMR) spectroscopy has the intrinsic capabilities to investigate proteins in native environments. In general, however, NMR relies on non‐natural protein purity and concentration to increase the desired signal over the background. We here report on the efficient and specific hyperpolarization of low amounts of a target protein in a large isotope‐labeled background by combining dynamic nuclear polarization (DNP) and the selectivity of protein interactions. Using a biradical‐labeled ligand, we were able to direct the hyperpolarization to the protein of interest, maintaining comparable signal enhancement with about 400‐fold less radicals than conventionally used. We could selectively filter out our target protein directly from crude cell lysate obtained from only 8 mL of fully isotope‐enriched cell culture. Our approach offers effective means to study proteins with atomic resolution in increasingly native concentrations and environments.
Photo‐induced Substitutive Introduction of the Aldoxime Functional Group to Carbon Chains: A Formal Formylation of Non‐Acidic C(sp3)−H Bonds
Authors: Kamijo Shin , Takao Go , Kamijo Kaori , Hirota Masaki , Tao Keisuke , Murafuji Toshihiro
Published: June 2016

A photo‐induced substitutive introduction of an aldoxime functional group to carbon chains was achieved using photo‐excited 4‐benzoylpyridine as a C(sp3)−H bond cleaving agent and arylsulfonyl oxime as an aldoxime precursor. The non‐acidic C−H bonds in various substances, including cycloalkanes, ethers, azacycles, and cyclic sulfides, were chemoselectively converted at ambient temperature under neutral conditions. The present transformation is a formal formylation of non‐acidic C(sp3)−H bonds in a single step.
Unidirectional Threading into a Bowl‐Shaped Macrocyclic Trimer of Boron–Dipyrrin Complexes through Multipoint Recognition
Authors: Nakamura Takashi , Yamaguchi Gento , Nabeshima Tatsuya
Published: June 2016

Bowl‐shaped macrocycles have the distinctive feature that their two sides are differentiated, and thus can be developed into elaborate hosts that fix a target molecule in a controlled geometry through multipoint interactions. We now report the synthesis of a bowl‐shaped macrocyclic trimer of the boron–dipyrrin (BODIPY) complex and its unidirectional threading of guest molecules. Six polarized Bδ+−Fδ‐ bonds are directed towards the center of the macrocycle, which enables strong recognition of cationic guests. Specifically, the benzylbutylammonium ion is bound in a manner in which the benzyl group is located at the convex face of the bowl and the butyl group at its concave face. Furthermore, adrenaline was strongly captured on the convex side of the bowl by hydrogen bonding, Coulomb forces, and C−H⋅⋅⋅π interactions.
Supramolecular Control over Split‐Luciferase Complementation
Authors: Bosmans Ralph P. G. , Briels Jeroen M. , Milroy Lech‐Gustav , de Greef Tom F. A. , Merkx Maarten , Brunsveld Luc
Published: June 2016

Supramolecular split‐enzyme complementation restores enzymatic activity and allows for on–off switching. Split‐luciferase fragment pairs were provided with an N‐terminal FGG sequence and screened for complementation through host‐guest binding to cucurbit[8]uril (Q8). Split‐luciferase heterocomplex formation was induced in a Q8 concentration dependent manner, resulting in a 20‐fold upregulation of luciferase activity. Supramolecular split‐luciferase complementation was fully reversible, as revealed by using two types of Q8 inhibitors. Competition studies with the weak‐binding FGG peptide revealed a 300‐fold enhanced stability for the formation of the ternary heterocomplex compared to binding of two of the same fragments to Q8. Stochiometric binding by the potent inhibitor memantine could be used for repeated cycling of luciferase activation and deactivation in conjunction with Q8, providing a versatile module for in vitro supramolecular signaling networks.
Synthesis of Diversely Functionalized Oxindoles Enabled by Migratory Insertion of Isocyanide to a Transient σ‐Alkylpalladium(II) Complex
Authors: Kong Wangqing , Wang Qian , Zhu Jieping
Published: June 2016

Palladium‐catalyzed intramolecular carbopalladation of N‐aryl acrylamides followed by migratory insertion of an isocyanide‐coordinated C(sp3)−Pd intermediate afforded an alkylimidoyl−PdII complex, which can be intercepted by a nucleophile, including heteroarenes. In addition to amides, the alkylimidoyl−PdII complex was successfully converted into esters, ketones, and bis‐heterocyclic compounds. An unprecedented palladium‐catalyzed enantioselective domino process involving isocyanide was also documented.
Biomimetic Transmembrane Channels with High Stability and Transporting Efficiency from Helically Folded Macromolecules
Authors: Lang Chao , Li Wenfang , Dong Zeyuan , Zhang Xin , Yang Feihu , Yang Bing , Deng Xiaoli , Zhang Chenyang , Xu Jiayun , Liu Junqiu
Published: June 2016

Membrane channels span the cellular lipid bilayers to transport ions and molecules into cells with sophisticated properties including high efficiency and selectivity. It is of particular biological importance in developing biomimetic transmembrane channels with unique functions by means of chemically synthetic strategies. An artificial unimolecular transmembrane channel using pore‐containing helical macromolecules is reported. The self‐folding, shape‐persistent, pore‐containing helical macromolecules are able to span the lipid bilayer, and thus result in extraordinary channel stability and high transporting efficiency for protons and cations. The lifetime of this artificial unimolecular channel in the lipid bilayer membrane is impressively long, rivaling those of natural protein channels. Natural channel mimics designed by helically folded polymeric scaffolds will display robust and versatile transport‐related properties at single‐molecule level.
Rapid Access to Orthogonally Functionalized Naphthalenes: Application to the Total Synthesis of the Anticancer Agent Chartarin
Authors: Unzner Teresa A. , Grossmann Adriana S. , Magauer Thomas
Published: June 2016

We report the synthesis of orthogonally functionalized naphthalenes from simple, commercially available indanones in four steps. The developed method proceeds through a two‐step process that features a thermally induced fragmentation of a cyclopropane indanone with simultaneous 1,2‐chloride shift. Migration of the chloride substituent occurs in a regioselective manner to preferentially afford the para‐chloronaphthol substitution pattern. The obtained naphthols are versatile building blocks that can be selectively modified and used for the efficient construction of biologically active molecules. This has enabled the total synthesis of the potent anticancer natural product chartarin through a highly convergent retrosynthetic bond disconnection.
Mechanical behavior of palm oil–based composite foam and its sandwich structure with a flax–epoxy composite
Authors: Teo Siew Cheng , Lan Du Ngoc Uy , Teh Pei Leng , Tran Le Quan Ngoc
Published: June 2016

Empty fruit bunch fiber (EFB), an abundant biomass waste from the palm oil industry, is used to reinforce palm oil–based polyurethane foam (POPU), and the mechanical properties of the composite foams are also assessed. The fiber–foam interfacial adhesion is also investigated by SEM images and Fourier transform infrared spectrometry. The results show that the composite foam reinforced by 15–30% EFB volume fractions could be enhanced by up to 10 times in flexural strength and twice in compressive strength compared to neat POPU. The composite foams with 20% and 30% volume fraction of EFB are exploited as a core in a sandwich construction with unidirectional flax fiber–reinforced epoxy composites (as face sheets). Sandwiches using EFB/POPU composite foam cores exhibited better toughness and achieved higher flexural energy at break compared to that using a commercial poly(ethylene terephthalate (PET) foam core. Furthermore, the failure mechanisms occurred under a combination of flexural and shear deformation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43977.
Reinforcement of ethylene‐acrylic elastomer with a dispersion of grafted PA6 droplets
Authors: Oriani S. R.
Published: June 2016

Cured elastomers are commonly dispersed in thermoplastics, but the reverse morphology has received little attention. The present work examines dispersions of 0.5–2 μm PA6 droplets in ethylene‐acrylic elastomer (AEM), created by melt blending. After cooling, the blends are compounded with amine curative and crosslinked. Uncrosslinked blends exhibit high bound rubber levels compared to N990 carbon black filled AEM, but similar viscosity at equal filler volume fraction. Crosslinking the blends produces strong, heat resistant vulcanizates with minimal Payne effect and good compression set resistance. These properties result from extensive AEM‐PA6 grafting, absence of filler‐filler contacts, and beneficial modification of the oxidation profile under diffusion limited conditions. The data show rubber‐filler grafting strongly influences filler reinforcing ability, but does not directly influence the Payne effect. Relative to unfilled AEM, silica and carbon black fillers accelerate oxidative degradation in proportion to their reinforcing ability, whereas PA6 has a stabilizing effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43995.
Structural modeling of tumor necrosis factor: A protein of immunological importance
Authors: Roy Urmi
Published: June 2016

Tumor necrosis factor (TNF) is a multifunctional pro‐inflammatory cytokine responsible for various immunoregulatory activities. Upon binding with its receptor, TNF triggers multiple complex signaling pathways such as the activations of nuclear factor kappa B and caspase cascade, which are the leading determining factors for cell survival or cell death. The present work studies certain modeling aspects of the TNF, with comparative structural analyses of the wild and mutant types of this protein. Additionally, nanoscale molecular dynamics simulations are performed to assess the structure–property relationships of proteins as functions of time.
Peripheral neuropathy via mutant tRNA synthetases: Inhibition of protein translation provides a possible explanation
Authors: Storkebaum Erik
Published: June 2016

Recent evidence indicates that inhibition of protein translation may be a common pathogenic mechanism for peripheral neuropathy associated with mutant tRNA synthetases (aaRSs). aaRSs are enzymes that ligate amino acids to their cognate tRNA, thus catalyzing the first step of translation. Dominant mutations in five distinct aaRSs cause Charcot‐Marie‐Tooth (CMT) peripheral neuropathy, characterized by length‐dependent degeneration of peripheral motor and sensory axons. Surprisingly, loss of aminoacylation activity is not required for mutant aaRSs to cause CMT. Rather, at least for some mutations, a toxic‐gain‐of‐function mechanism underlies CMT‐aaRS. Interestingly, several mutations in two distinct aaRSs were recently shown to inhibit global protein translation in Drosophila models of CMT‐aaRS, by a mechanism independent of aminoacylation, suggesting inhibition of translation as a common pathogenic mechanism. Future research aimed at elucidating the molecular mechanisms underlying the translation defect induced by CMT‐mutant aaRSs should provide novel insight into the molecular pathogenesis of these incurable diseases.
Local influence diagnostics for hierarchical count data models with overdispersion and excess zeros
Authors: Rakhmawati Trias Wahyuni , Molenberghs Geert , Verbeke Geert , Faes Christel
Published: June 2016

We consider models for hierarchical count data, subject to overdispersion and/or excess zeros. Molenberghs et al. () and Molenberghs et al. () extend the Poisson‐normal generalized linear‐mixed model by including gamma random effects to accommodate overdispersion. Excess zeros are handled using either a zero‐inflation or a hurdle component. These models were studied by Kassahun et al. (). While flexible, they are quite elaborate in parametric specification and therefore model assessment is imperative. We derive local influence measures to detect and examine influential subjects, that is subjects who have undue influence on either the fit of the model as a whole, or on specific important sub‐vectors of the parameter vector. The latter include the fixed effects for the Poisson and for the excess‐zeros components, the variance components for the normal random effects, and the parameters describing gamma random effects, included to accommodate overdispersion. Interpretable influence components are derived. The method is applied to data from a longitudinal clinical trial involving patients with epileptic seizures. Even though the data were extensively analyzed in earlier work, the insight gained from the proposed diagnostics, statistically and clinically, is considerable. Possibly, a small but important subgroup of patients has been identified.
Identification of subpopulations with distinct treatment benefit rate using the Bayesian tree
Authors: Shen Changyu , Hu Yang , Li Xiaochun , Wang Yadong , Chen Peng‐Sheng , Buxton Alfred E.
Published: June 2016

Characterization of a subpopulation by the difference in marginal means of the outcome under the intervention and control may not be sufficient to provide informative guidance for individual decision and public policy making. Specifically, often we are interested in the treatment benefit rate (TBR), that is, the probability of benefitting an intervention in a meaningful way. For binary outcomes, TBR is the proportion that has “unfavorable” outcome under the control and “favorable” outcome under the intervention. Identification of subpopulations with distinct TBR by baseline characteristics will have significant implications in clinical setting where a medical intervention with potential negative health impact is under consideration for a given patient. In addition, these subpopulations with unique TBR set the basis for guidance in implementing the intervention toward a more personalized scheme of treatment. In this article, we propose a Bayesian tree based latent variable model to seek subpopulations with distinct TBR. Our method offers a nonparametric Bayesian framework that accounts for the uncertainty in estimating potential outcomes and allows more exhaustive search of the partitions of the baseline covariates space. The method is evaluated through a simulation study and applied to a randomized clinical trial of implantable cardioverter defibrillators to reduce mortality.
Endothioxopeptides: A conformational overview
Authors: De Zotti Marta , Peggion Cristina , Biondi Barbara , Crisma Marco , Formaggio Fernando , Toniolo Claudio
Published: June 2016

Although thionamides would have been first prepared two centuries ago and their chemical and spectroscopic properties extensively investigated, only much more recently (since about 1985) a well deserved but still insufficient attention has been paid to their endothioxopeptide subfamily which nonetheless currently represents a rapidly emerging area of great scientific interest in the broader field of foldameric compounds based on biologically relevant building blocks. After two brief sections offering information on the unfortunately still limited number of endothioxopeptides discovered from natural sources but also on the impressive advancements registered in the last few years in their synthetic methods, this review article outlines the results of a detailed literature survey on the ongoing great, but not systematic, progress related to the conformational consequences generated by incorporating one (or more) thionamide group(s) into a polypeptide chain. Finally, a short discussion of the growing, but still in its infancy, class of the endoselenoxopeptide congeners is also presented.
A current perspective on applications of macrocyclic‐peptide‐based high‐affinity ligands
Authors: Leenheer Daniël , ten Dijke Peter , Hipolito Christopher John
Published: June 2016

Monoclonal antibodies can bind with high affinity and high selectivity to their targets. As a tool in therapeutics or diagnostics, however, their large size (∼150 kDa) reduces penetration into tissue and prevents passive cellular uptake. To overcome these and other problems, minimized protein scaffolds have been chosen or engineered, with care taken to not compromise binding affinity or specificity. An alternate approach is to begin with a minimal non‐antibody scaffold and select functional ligands from a de novo library. We will discuss the structure, production, applications, strengths, and weaknesses of several classes of antibody‐derived ligands, that is, antibodies, intrabodies, and nanobodies, and nonantibody‐derived ligands, that is, monobodies, affibodies, and macrocyclic peptides. In particular, this review is focussed on macrocyclic peptides produced by the Random non‐standard Peptides Integrated Discovery (RaPID) system that are small in size (typically ∼2 kDa), but are able to perform tasks typically handled by larger proteinaceous ligands.
Enantioselective Cu‐Catalyzed Functionalizations of Unactivated Alkenes
Authors: Sorádová Zuzana , Šebesta Radovan
Published: June 2016

Copper hydride or copper boranyl species have already been used in reactions with Michael acceptors. Recently, notable advances have been described and the methodology extended to unactivated alkenes as well. In situ generated copper hydride ligated with chiral ligands is able to catalyze enantioselective aminations of alkenes. Furthermore, transient organocopper species formed upon initial hydrocupration of the alkene can be intercepted by other electrophiles such as imines, organohalides, or boranes.
Three‐Dimensional Metal–Organic Framework Graphene Nanocomposite as a Highly Efficient and Stable Electrocatalyst for the Oxygen Reduction Reaction in Acidic Media
Authors: Sohrabi Samaneh , Dehghanpour Saeed , Ghalkhani Masoumeh
Published: June 2016

We report on the design of a bio‐inspired composite as a noble‐metal‐free electrocatalyst for the oxygen reduction reaction (ORR). The composite is made from the assembly of pyridine‐functionalized graphene (G‐py) and a 3 D metal–organic framework (MOF) deposited onto a glassy carbon electrode (GCE). The 3 D heme‐like MOF was synthesized from tetrakis(4‐carboxyphenyl)porphyrin iron(III) chloride and Zr6 clusters for the assembly of the stable porous coordination network. G‐py, which possesses an axial ligand to anchor to the centers of porphyrin in the MOF, results in a significant change in the electronic and geometric structure of centers, which enhances the rate of ORR and durability during cycling in acidic media. The occurrence potential of the ORR by the composite is shifted to the positive potential near 100 mV. Our results introduce a new strategy for the rational design of inexpensive and highly stable oxygen reduction electrocatalysts for fuel cells without the requirement of pyrolysis.
Corrole and Porphyrin Amino Acid Conjugates: Synthesis and Physicochemical Properties
Authors: Karikis Kostas , Georgilis Evangelos , Charalambidis Georgios , Petrou Athanasia , Vakuliuk Olena , Chatziioannou Theodore , Raptaki Iliana , Tsovola Sofia , Papakyriacou Ioanna , Mitraki Anna , Gryko Daniel T. , Coutsolelos Athanassios G.
Published: June 2016

A series of conjugates of amino acids with porphyrins and corroles was synthesized. Their self‐assembling ability under defined conditions was investigated by scanning electron microscopy. The morphology and photophysical properties of these molecules were studied by absorption and fluorescence spectroscopy in solid, liquid, and self‐assembled forms. We observed that both corrole and porphyrin conjugated with the l‐phenylalanine–l‐phenylalanine peptide to form spherical nanostructures with bathochromic shifts in the emission spectra, indicating the formation of aggregates. These aggregates are characterized by the impressive absorption of light over nearly the whole visible range. The broadening of all bands was particularly strong in the case of corroles. The fluorescence lifetimes of self‐assembled species were longer as compared to the solid‐state form.
On the Activation of Methane and Carbon Dioxide by [HTaO]+ and [TaOH]+ in the Gas Phase: A Mechanistic Study
Authors: Firouzbakht Marjan , Rijs Nicole J. , González‐Navarrete Patricio , Schlangen Maria , Kaupp Martin , Schwarz Helmut
Published: June 2016

The thermal reactions of [Ta,O,H]+ with methane and carbon dioxide have been investigated experimentally and theoretically by using electrospray ionization mass spectrometry (ESI MS) and density functional theory calculations. Although the activation of methane proceeds by liberation of H2, the activation of CO2 gives rise to the formation of [OTa(OH)]+ under the elimination of CO. Computational studies of the reactions of methane and carbon dioxide with the two isomers of [Ta,O,H]+, namely, [HTaO]+ and [Ta(OH)]+, have been performed to elucidate mechanistic aspects and to explain characteristic reaction patterns.
Supramolecular Self‐Assembly of Histidine‐Capped‐Dialkoxy‐Anthracene: A Visible‐Light‐Triggered Platform for Facile siRNA Delivery
Authors: Patil Sachin P. , Moosa Basem A. , Alsaiari Shahad , Alamoudi Kholod , Alshamsan Aws , AlMalik Abdulaziz , Adil Karim , Eddaoudi Mohamed , Khashab Niveen M.
Published: June 2016

Supramolecular self‐assembly of histidine‐capped‐dialkoxy‐anthracene (HDA) results in the formation of light‐responsive nanostructures. Single‐crystal X‐ray diffraction analysis of HDA shows two types of hydrogen bonding. The first hydrogen bond is established between the imidazole moieties while the second involves the oxygen atom of one amide group and the hydrogen atom of a second amide group. When protonated in acidic aqueous media, HDA successfully complexes siRNA yielding spherical nanostructures. This biocompatible platform controllably delivers siRNA with high efficacy upon visible‐light irradiation leading up to 90 % of gene silencing in live cells.
Synthesis of 1,2,4‐Triazolo[4,3‐a]pyridines and Related Heterocycles by Sequential Condensation and Iodine‐Mediated Oxidative Cyclization
Authors: Li Ertong , Hu Zhiyuan , Song Lina , Yu Wenquan , Chang Junbiao
Published: June 2016

A facile and efficient approach to access 1,2,4‐triazolo[4,3‐a]pyridines and related heterocycles has been accomplished through condensation of readily available aryl hydrazines with corresponding aldehydes followed by iodine‐mediated oxidative cyclization. This transition‐metal‐free synthetic process is broadly applicable to a variety of aromatic, aliphatic, and α,β‐unsaturated aldehydes, and can be conveniently conducted on the gram scale.
Reductive Coupling of Diynes at Rhodium Gives Fluorescent Rhodacyclopentadienes or Phosphorescent Rhodium 2,2’‐Biphenyl Complexes
Authors: Sieck Carolin , Tay Meng Guan , Thibault Marie‐Hélène , Edkins Robert M. , Costuas Karine , Halet Jean‐François , Batsanov Andrei S. , Haehnel Martin , Edkins Katharina , Lorbach Andreas , Steffen Andreas , Marder Todd B.
Published: June 2016

Reactions of [Rh(κ2‐O,O‐acac)(PMe3)2] (acac=acetylacetonato) and α,ω‐bis(arylbutadiynyl)alkanes afford two isomeric types of MC4 metallacycles with very different photophysical properties. As a result of a [2+2] reductive coupling at Rh, 2,5‐bis(arylethynyl)rhodacyclopentadienes (A) are formed, which display intense fluorescence (Φ=0.07–0.54, τ=0.2–2.5 ns) despite the presence of the heavy metal atom. Rhodium biphenyl complexes (B), which show exceptionally long‐lived (hundreds of μs) phosphorescence (Φ=0.01–0.33) at room temperature in solution, have been isolated as a second isomer originating from an unusual [4+2] cycloaddition reaction and a subsequent β‐H‐shift. We attribute the different photophysical properties of isomers A and B to a higher excited state density and a less stabilized T1 state in the biphenyl complexes B, allowing for more efficient intersystem crossing S1→Tn and T1→S0. Control of the isomer distribution is achieved by modification of the bis‐ (diyne) linker length, providing a fundamentally new route to access photoactive metal biphenyl compounds.