bluuebunny/crossref_metadata_2025 huggingface dataset:
DO VERNACULAR AO ERUDITO: A (RE) CONSTRUÇÃO DA IGREJA MATRIZ DE BATATAIS-SP
Authors: Piccinato Junior Dirceu , Salgado Ivone
Published: June 2018

O presente trabalho procura traçar um diálogo por meio de questões pertinentes à cultura e à sociedade dos entrantes mineiros, em um primeiro momento, e, depois, dos imigrantes italianos quanto ao processo histórico-construtivo da Igreja Matriz da cidade de Batatais, localizada no nordeste do interior do estado paulista. O edifício religioso foi e ainda permanece, na maior parte das cidades paulistas, como o ponto inicial de formação, ordenamento e expansão urbana. Desse modo, essa edificação reserva em si vestígios, aspectos e contextos singulares para a compreensão do modus faciendi da construção. O edifício em destaque se configura como representativo de técnicas, cultura e sociedade local, revelando-se como um “palimpsesto construtivo”, ou seja, camadas que revelam momentos e aspectos de um tempo, de um saber, de um lugar. Destarte, objetiva-se elucidar as técnicas construtivas e os estilos arquitetônicos adotados no decorrer de sua construção e reconstrução, assim como relacioná-los com o desenvolvimento sociocultural da região, marcado por dois momentos históricos significativos: o primeiro, quando os migrantes das Minas Gerais ocuparam a região, e o segundo marcado pela colonização italiana no município.
Epidemiology of Dengue Fever among clinically Suspected Febrile Patients at A Tertiary Care Center in Punjab
Authors: CHİTKARA Shweta , CHHİNA Deepinder , GUPTA Veenu , MAHAJAN Rajesh , SHARMA Daaman
Published: June 2018

ABSTRACT

Objective: Dengue has emerged as a major public health concern
across the globe in terms of mortality and morbidity. The clinical and
epidemiological profile of dengue infection changes from time to time. The
study was conducted to determine the prevalence of dengue infection, to study
the seasonal variation and the clinical profile in these cases.

Methods: A
prospective, observational study conducted over a period from April 2015 to
March 2016. Patients with acute febrile illness with clinical suspicion of
dengue fever admitted in the hospital were included in the study. Serological
tests like Dengue IgM and NS1 antigen ELISA were performed to confirm the
diagnosis. Serologically confirmed patients of dengue fever were studied for
their clinical presentation and lab parameters.

Results: From
a total 4732 patients tested for dengue viral infection, 1165 (24.6%) tested
positive for dengue. The most affected age group was 26-35 years (25.7%) with
male predominance. Most dengue cases were seen in the months of August to December
2015. Commonly clinical symptoms and signs were myalgia (72.4%), arthralgia
(34.4%), vomiting (50%), abdominal pain (38.6%), hepatomegaly (27.4%) and
ascites (10.8%). Lab parameters revealed leukopenia (43%) and thrombocytopenia
(93.1%) in most cases. Transaminitis was seen in 84.1% cases. Common
complications were shock (4.8%) and encephalopathy (4.8%). Hepatic failure was
seen in 3.7% of patients and renal failure in 1.8% of patients.

Conclusion: Dengue fever has a very non-specific and variable presentation.
Knowledge of local prevalence and recent outbreaks can be very helpful in
recognizing the clinical entity. J
Microbiol Infect Dis 2018; 8(2):43-48
Sistema de controle interno na gestão pública de um município de pequeno porte
Authors:   Universidade Federal de Santa Maria, Marschner Paulo Fernando , Sommer Analisa Tiburski , Welter Larissa Marx ,   Universidade Estadual do Rio Grande do Sul,   Universidade Federal do Rio Grande do Sul
Published: June 2018

O objetivo deste trabalho é analisar o controle interno na gestão pública de um município de pequeno porte a partir de três perspectivas: (i) perfil do controller, (ii) situação do controle interno, e (iii) planejamento e execução das atividades, e verificar, se o conjunto destes estão aderentes ao regimento legal e se aproximam-se da realidade de outros municípios já estudados. O potencial problema do controle interno na gestão pública de municípios de pequeno porte, destacado por Castro (2013) é que nestas prefeituras, existe a tendência da centralização de tarefas em uma mesma pessoa, o que é corroborado por trabalhos anteriores. Entretanto poucos destes trabalhos analisam a dinâmica do controle interno em municípios de pequeno porte. Em termos metodológicos, a pesquisa teve natureza qualitativa, abordagem descritiva. Para coleta de dados, por sua vez, aplicou-se um questionário ao responsável pelo controle interno da prefeitura estudada, com 19 questões, elaborado a partir do trabalho de Roza, Lunkes e Alberton (2012) e Vieira (2009).Os principais resultados indicam que o sistema de controle interno do município estudado está bastante alinhado com o perfil de outras prefeituras evidenciados pelos trabalhos desenvolvidos anteriormente. Os principais resultados sugerem que o controle interno atua em diversas áreas, auxilia no planejamento e desenvolvimento da gestão pública municipal, entretanto, há pontos a serem melhorados. Sugere-se a contratação de servidores de carreira, bem como treinamentos periódicos e pontuais.
Produção de alimentos por agricultores familiares em Vila Bela da Santíssima Trindade (MT), Amazônia Legal
Authors: Soares Keller Regina , Da Silva Ferreira Esvanio Edipo , Junior Santino Seabra , Alves da Silva Neves Sandra Mara , Da Silva Leandro Batista da
Published: June 2018

As produções familiares têm possibilitado a geração de segurança e soberania alimentar para as comunidades rurais, ao proporcionarem eficiência produtiva, energética e ecológica, por meio do adequado manejo do ambiente. Objetivou-se investigar os produtos agrícolas alimentícios que fazem parte do sistema produtivo dos agricultores familiares do Assentamento Seringal e suas respectivas formas de comercialização. Foram entrevistados 86 agricultores familiares vinculados a Associação de Produtores de Látex de Vila Bela da Santíssima Trindade/MT. Os dados foram tabulados em planilha eletrônica e sistematizados por meio das estatísticas de frequência absoluta e relativa. Dos entrevistados 69,01% é do gênero masculino, sendo o cargo de chefia assumido pelas mulheres apenas quando são as únicas responsáveis pela reprodução familiar. Dentre as diversas culturas produzidas a mandioca é a que aparece com maior frequência (26,76%). Quanto a produção pecuária, a criação de frango caipira é a atividade de maior relevância, seguida pela de suínos e gado leiteiro. Os produtos são destinados ao autoconsumo familiar e há comercialização do excedente. Geralmente a comercialização é realizada diretamente com o consumidor, entretanto há frequência relativamente alta com atravessadores, com redução de até 40% no valor pago, se comparado com a venda direta ao consumidor. Com exceção do extrativismo de látex, as demais atividades agrícolas são desenvolvidas na informalidade. Concluiu-se que as principais atividades agropecuárias desenvolvidas nas unidades produtivas do Assentamento Seringal estão ligadas a produção para autoconsumo, com exceção da seringueira, cujo látex é vendido formalmente por uma associação específica, enquanto que para os demais produtos, quando ocorre, é realizado diretamente ao consumidor, cujo produto possui valor agregado ou por intermediários (atravessadores), havendo redução no valor de comercialização.
PHYSICAL AND CHEMICAL PROPERTIES OF SORBENTS USED FOR WASTEWATER PURIFICATION FROM OIL PRODUCTS
Authors: Gusev Grigoriy I. , Gushchin Andrey A. , Grinevich Vladimir I. , Izvekova Tatyana V. , Fillipov Dmitriy V.
Published: June 2018

The work is devoted to the study of the physico-chemical and adsorption properties of synthetic and natural sorbents contaminated with oil products. The parameters such as sorption capacity for petroleum products, water adsorption and moisture content, bulk density, as well as parameters characterizing the sorption equilibrium in the surface layers (distribution coefficients, maximum adsorption values, Henry constants, Gibbs energy changes, adsorption coefficients and filling degrees) were determined. Adsorption isotherms for all sorbents are almost identical in character with a pronounced linear region in the region of low concentrations of oil products and correspond to isotherms of monomolecular adsorption. The sorption capacity of the sorbents under study varies from 10 to 50 mg of oil products per 1 g of sorbent. The maximum sorption capacity among the sorbents studied the Ol-Ex Hard possesses. This sorbent belongs to sorbents of the silicate group and Ol-Ex 82, based on polyurethane. The lowest moisture content is also characteristic for silicate sorbents and does not exceed 0.5 % of their mass. The maximum moisture adsorption is typical for sorbents of SONET Sorb and MGS Sorb. It was revealed that the surface of Ol-Ex Hard is almost completely filled with oil (q → 1), while for shungite the surface will be filled only by 13%. The most effective for trapping oil products should be considered the sorbent Ol-Ex Hard, for which the highest values of adsorption parameters are characteristic.Forcitation:Gusev G.I., Gushchin A.A., Filippov D.V., Grinevich V.I., Izvekova T.V. Physical and chemical properties of sorbents used for wastewater purification from oil products. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2018. V. 61. N 7. P. 136-142
MODELING OF QUASIBINARIES OF Na+, Сa2+ // O2-, F- SYSTEM
Authors: Pratskova S.E. , Tyurin A.G.
Published: June 2018

Thermodynamic modeling of phase equilibria of the Na +, Ca2 + // O2-, F- system in the frame of the generalized theory of "regular" ionic solutions was carried out. The equations for the activities of the system components were derived. The standard Gibbs energy of the exchange reaction was calculated. The values of the energy parameters of the model were determined and the phase diagrams of the binary systems were constructed.
EVALUATION OF PRODUCTIVETY AND POWER OF SCREW FEEDER OF DISPERSE MEDIA
Authors: Kapranova A.B. , Ganin A.V. , Lebedev A.E.
Published: June 2018

On the basis of performed mathematical modeling of process of movement and compaction of dispersed material in a horizontal screw the method was proposed of assessing productivity and power of the screw feeder of roller device taking into account the physical and mechanical characteristics deaerated environment and the apparatus parameters.
Scanning electron microscopic observation of the infection process of a Metarhizium strain Ma6 highly pathogenic to Phyllotreta striolata
Authors: Li Jianyu , Shi Mengzhu , He Yuechao , Fu Jianwei , Zheng Lizhen
Published: June 2018

Background. Phyllotreta striolata is a worldwide pest that harms cruciferous vegetables. The use of pathogenic microorganisms to control pests is an important means of biological control. Using pathogenic microorganisms to prevent and control P. striolata has rarely been reported. Methods. In this study, the infection process of a Metarhizium strain highly pathogenic to P. striolata was observed by stereomicroscopyand scanning electron microscopy (SEM). Results.The results showed that the attachment of Metarhizium strain Ma6 to the body surface varied; the conidia distribution was greatest in the tibia of the posterior leg with thick bristles and in the intersegmental abdominal membrane, and the spore distribution occurred least in the smooth and hard portions of the insect’s body. At the start of the infection, Metarhizium strain Ma6 generally grew from the body parts with gaps or connecting spaces such as mouthparts and the thoracic leg base and joints, then the spores germinated with germ tubes and penetration peg, and the penetration peg penetrated the body surface. Ten days after inoculation, the mycelia divided into conidia, and many mycelia and spores covered the entire adult insect’s body. Discussion. Spore germination occurred on the 5th day after inoculation, and many hyphae and spores covered the entire adult insect body within 10 days after inoculation. And the invasion into tissue gaps from the weaker areas is more efficient than intruding from the body hard surface. This may be the reason for the Metarhizium strain Ma6’s high virulence. This study preliminarily clarified the infection ability and invasion approach of a Metarhizium strain against P. striolata, providing evidence for evaluating the strain’s insecticidal effect and application prospect.
Sensory cortex is optimized for prediction of future input
Authors: Singer Yosef , Teramoto Yayoi , Willmore Ben DB , Schnupp Jan WH , King Andrew J , Harper Nicol S
Published: June 2018

Neurons in sensory cortex are tuned to diverse features in natural scenes. But what determines which features neurons become selective to? Here we explore the idea that neuronal selectivity is optimized to represent features in the recent sensory past that best predict immediate future inputs. We tested this hypothesis using simple feedforward neural networks, which were trained to predict the next few moments of video or audio in clips of natural scenes. The networks developed receptive fields that closely matched those of real cortical neurons in different mammalian species, including the oriented spatial tuning of primary visual cortex, the frequency selectivity of primary auditory cortex and, most notably, their temporal tuning properties. Furthermore, the better a network predicted future inputs the more closely its receptive fields resembled those in the brain. This suggests that sensory processing is optimized to extract those features with the most capacity to predict future input.
Comparison of cryptobenthic reef fish communities among microhabitats in the Red Sea
Authors: Troyer Emily M. , Coker Darren J. , Berumen Michael L.
Published: June 2018

Knowledge of community structure within an ecosystem is essential when trying to understand the function and importance of the system and when making related management decisions. Within the larger ecosystem, microhabitats play an important role by providing inhabitants with a subset of available resources. On coral reefs, cryptobenthic fishes encompass many groups and make up an important proportion of the biodiversity. However, these fishes are relatively small, exhibit extreme visual or behavioral camouflage, and, therefore, are often overlooked. We examined the differences in fish community structure between three common reef microhabitats (live hard coral, dead coral rubble, and sand) using ichthyocide stations in the central Red Sea. Using a combination of morphological and genetic (cytochrome oxidase I (COI) barcoding) techniques, we identified 326 individuals representing 73 species spread across 17 families, from fifteen 1 m2 quadrats. Fish assemblages in the three microhabitats were significantly different from each other. Rubble microhabitats yielded the highest levels of fish abundance, richness, and diversity, followed by hard coral, and then sand. The results show that benthic composition, even at a small scale, influences cryptobenthic communities. This study also provides new COI sequence data to public databases, in order to further the research of cryptobenthic fishes in the Red Sea region.
Hyperbranched Polymers as Nanocarriers
Authors: Houston Zachary H. , Bell Craig A. , Thurecht Kristofer J.
Published: June 2018

Hyperbranched polymers (HBPs) have shown widespread academic and commercial success in the preparation of films and novel materials, and now are emerging into the biomedical research space as nanocarriers for use in drug delivery and diagnostics. HBPs exhibit ideal sizes for delivery
in vivo
, have well‐established chemistries for their synthesis, as well as offering multiple methods of incorporation of a variety of targeting, therapeutic, and diagnostic moieties. By choice of material and functionality, their biostability or biodegradability can be fine‐tuned for multistaged or time‐delayed release of therapeutics. With significant advances in the development of nanomedicines, in particular chemistries surrounding biomolecule conjugation and the evolution of imaging techniques, the multimodal capabilities of HBPs combined with facile and controlled synthetic engineering of HBPs have resulted in properties that are ideal for their application as nanocarriers. While HBP nanocarriers offer limitless synthetic opportunity, to address the many biological challenges that are now well‐established in nanotherapeutics, new approaches to how HBPs are designed are required. This overview aims to address the points that must be considered in the biologically driven nanomaterial design of HBP nanocarriers.
Thermotropic Liquid Crystalline Polymers
Authors: Jaffe Michael , Cheng Si‐Xue , Chung Tai‐Shung , Freidzon Yakov , East Anthony J.
Published: June 2018

Herein we present recent studies on the nature of thermotropic liquid crystalline polymers (LCPs) and their progress. Side‐chain liquid crystals are also discussed briefly, showing the similarities and differences between these closely related molecules. We summarize and review the newly developed thin‐film polymerization technique for the investigation of liquid crystalline formation as a function of monomer moieties, and for the study of reaction kinetics, evolution of liquid crystal texture, and surface energy during polycondensation reactions. We also highlight various modification approaches to yield main‐chain LCPs suitable for conventional processing equipment, without compromising the unique liquid crystalline characteristics and superior mechanical properties. The thermal stability, degradation behavior, and crystallization kinetics of commercially available main‐chain LCPs are recapitulated. Attention is also given to the rheology, polymer blends, micro‐ and nanostructures, processing of LCPs, and their applications. In the past decade, investigations of thermotropic LCPs have decreased from the high interest and publication rate of the latter part of the twentieth century. However, the number of monomer combinations giving rise to main‐chain thermotropic polymers has increased and the origin of LCP rheology and morphology have been elucidated. The most important new work is the invention and description of thermotropic thermosets.
Aromatic Polyamides
Authors: Trigo‐López Miriam , García José M. , Ruiz José A. Reglero , García Félix C. , Ferrer Ramón
Published: June 2018

This article presents the preparation and properties of aromatic polyamides as well as the fibers and films made from these polymers. Particular focus is placed on the polymers that have achieved commercial status, namely, poly(m‐phenylene isophthalamide), poly(p‐phenylene terephthalamide), and copoly(p‐phenylene/3,4′‐diphenyl ether terephthalamide). The production processes of the corresponding monomers for these three polymers are described in detail, analyzing both laboratory and commercial‐scale processes for the preparation of the polymers in the form of fibers and films. A brief review of new developments in the synthesis and applications of functional aromatic polyamides is also given, analyzing new applications in which polyamides are being employed, such as electronics, sensors, and biomaterials. Finally, a brief analysis of the economic impact of the polyamide market is described, including also environmental aspects.
Ziegler–Natta Catalysts
Authors: Fan Zhiqiang , Yu Yue
Published: June 2018

First invented in 1953, Ziegler–Natta catalysts have been used widely in the industrial production of polyolefins and other important polymers since the 1960s. In recent years, polymers synthesized with these catalysts account for more than 30% of the total production of polymers. This article briefly introduces the history and main developments of Ziegler–Natta catalysts and explains their preparation, composition, and mechanism of the catalysis process. Particular emphasis is put on the currently more important MgCl2‐supported Ziegler–Natta catalysts. Main features of the olefin polymerization with MgCl2‐supported Ziegler–Natta catalysts are presented, including the formation and structure of active sites, main reactions with the active sites, origin of stereospecificity, reaction kinetics, and morphology of the nascent polymer particles. The main olefin polymerization processes with these catalysts are also briefly discussed.
Anti‐Obesity Drugs (A08)
Authors: Ritter Kurt
Published: June 2018

The article contains sections titled:1.Introduction2.A08AA Centrally Acting Anti‐Obesity Products3.A08AB Peripherally Acting Anti‐Obesity Products4.A08AX and A10BJ Other Anti‐Obesity Drugs
Drawing what lies ahead: False intentions are more abstractly depicted than true intentions
Authors: Calderon Sofia , Mac Giolla Erik , Ask Karl , Granhag Pär Anders
Published: June 2018

The aim of this study was to examine how people mentally represent and depict true and false statements about claimed future actions—so‐called true and false intentions. On the basis of construal level theory, which proposes that subjectively unlikely events are more abstractly represented than likely ones, we hypothesized that false intentions should be represented at a more abstract level than true intentions. Fifty‐six hand drawings, produced by participants to describe mental images accompanying either true or false intentions, were rated on level of abstractness by a second set of participants (N = 117) blind to the veracity of the intentions. As predicted, drawings of false intentions were rated as more abstract than drawings of true intentions. This result advances the use of drawing‐based deception detection techniques to the field of true and false intentions and highlights the potential for abstractness as a novel cue to deceit.
A Facet‐Dependent Schottky‐Junction Electron Shuttle in a BiVO4{010}–Au–Cu2O Z‐Scheme Photocatalyst for Efficient Charge Separation
Authors: Zhou Chenguang , Wang Shaomang , Zhao Zongyan , Shi Zhan , Yan Shicheng , Zou Zhigang
Published: June 2018

Interfacial charge separation and transfer are the main challenges of efficient semiconductor‐based Z‐scheme photocatalytic systems. Here, it is discovered that a Schottky junction at the interface between the BiVO4 {010} facet and Au is an efficient electron‐transfer route useful for constructing a high‐performance BiVO4{010}–Au–Cu2O Z‐scheme photocatalyst. Spectroscopic and computational studies reveal that hot electrons in BiVO4 {010} more easily cross the Schottky barrier to expedite the migration from BiVO4 {010} to Au and are subsequently captured by the excited holes in Cu2O. This crystal‐facet‐dependent electron shuttle allows the long‐lived holes and electrons to stay in the valence band of BiVO4 and conduction band of Cu2O, respectively, contributing to improved light‐driven CO2 reduction. This unique semiconductor crystal‐facet sandwich structure will provide an innovative strategy for rational design of advanced Z‐scheme photocatalysts.
Stable 2D Conductive Ga/Ga(OxHy) Multilayers with Controlled Nanoscale Thickness Prepared from Gallium Droplets with Oxide Skin
Authors: Runde Sebastian , Ahrens Heiko , Lawrenz Frank , Sebastian Amal , Block Stephan , Helm Christiane A.
Published: June 2018

The practical applicability of ultrathin films, which offer interesting and novel functionalities, is often limited by difficulties in achieving large area deposition while maintaining homogenous layer properties. Herein, a new deposition method allowing ultrathin, conductive gallium‐containing layers to be prepared at ambient conditions on wafer‐scaled areas is presented. Multilayers are formed by repetition of the deposition procedure. High‐resolution structural analysis using X‐ray reflectometry shows that the multilayer thickness is proportional to the number of deposition cycles, yielding a highly reproducible single layer thickness of 2.9 ± 0.2 nm. Furthermore, it is shown that single layers consist of a complex heterostructure composed of a nanometer‐thin metallic Ga core, which is surrounded by stabilizing gallium (hydr)oxide skin layers. The macroscopic electric conductivity of these multilayers increases with increasing number of deposited layers, approaching the value of bulk gallium after six deposition cycles, thereby showing that functional properties such as the multilayer's electrical conductivity can be fine‐tuned based on the chosen number of deposition cycles.
Janus Membranes via Diffusion‐Controlled Atomic Layer Deposition
Authors: Waldman Ruben Z. , Yang Hao‐Cheng , Mandia David J. , Nealey Paul F. , Elam Jeffrey W. , Darling Seth B.
Published: June 2018

The first use of atomic layer deposition (ALD) to produce Janus membranes is reported, with an example system consisting of a compositional gradient ranging from hydrophilic Al2O3 on one face to hydrophobic poly(propylene) on the opposite face. Alternating pulses of trimethyl aluminum and water vapor lead to the growth of covalently bonded Al2O3 conforming to the membrane pore surfaces. Precise control of ALD parameters significantly affects the surface wetting of the modified membrane face and the depth of Al2O3 infiltration into the porosity. This depth control derives from slow precursor diffusion through the 200 nm membrane pores compared to much faster ALD surface reactions. For a given precursor exposure and purge time, increasing the number of ALD cycles decreases the water contact angle at the modified surface from hydrophobic to hydrophilic, until the water droplet is completely imbibed by the membrane. To demonstrate the utility of these Janus membranes, a hydrophilic/superaerophobic Janus treatment is shown to greatly reduce the size of air bubbles generated through the membrane, enabling faster mixing. This technique represents the first application of vapor‐deposited covalently bonded metal oxides to form Janus membranes. Further opportunities are afforded by the ability to laterally pattern Al2O3 across the membrane surface via physical masking.
Copper‐Catalysed (Diacetoxyiodo)benzene‐Promoted Aerobic Esterification Reaction: Synthesis of Oxamates from Acetoacetamides
Authors: Zhang Zhiguo , Gao Xiaolong , Yu Haifeng , Zhang Guisheng , Liu Jianming
Published: June 2018

A copper‐catalysed (diacetoxyiodo)benzene‐promoted aerobic esterification reaction of acetoacetamides was developed for the synthesis of oxamates, which are useful precursors in synthetic organic chemistry. This practical and mild synthetic approach proceeded at 25 °C under open‐air conditions and afforded methyl 2‐oxo‐2‐(phenylamino)acetates in good to excellent yields combined with C−C σ‐bond cleavage and formal oxidative C−H bond functionalization. A mechanism is proposed.

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Promoting Diversity in Mediation
Authors: Lewis Timothy K.
Published: June 2018

This article is adapted and expanded from a keynote presentation the author delivered at the CPR Institute's Regional Meeting in Philadelphia on April 10. See credit below.
Grüne und rasche hydrothermale Kristallisation und Synthese vollständig konjugierter aromatischer Verbindungen
Authors: Taublaender M. Josef , Glöcklhofer Florian , Marchetti‐Deschmann Martina , Unterlass Miriam M.
Published: June 2018

Hochkondensierte, vollständig konjugierte aromatische Verbindungen sind interessante Kandidaten zur Anwendung in organischer Elektronik. Mit steigender Kristallinität verbessern sich ihre elektronischen Eigenschaften. Hier wird gezeigt, dass die Kristallisation von drei Archetypen solcher Moleküle – Pentacentetron, Indigo und Perinon – hydrothermal erreicht werden kann. Dieser Befund ist angesichts der Strukturen dieser Verbindungen höchst erstaunlich. Darüber hinaus wird gezeigt, dass Perinon ausgehend von Naphthalinbisanhydrid und o‐Phenylendiamin in ausschließlich hochtemperiertem Wasser und ohne Zusatz von Cosolventien oder Katalysatoren hergestellt werden kann. Weiterhin kann die Transformation durch den Einsatz von Mikrowellen‐Strahlung drastisch beschleunigt werden. Dies ist der erste Bericht über die hydrothermale Herstellung von zwei kondensierten Heterocyclen.
Ein hundert Jahre altes Experiment auf dem Prüfstand: hochgenaue Ab‐Initio‐Monte‐Carlo‐Schmelzsimulationen von Radon
Authors: Smits Odile R. , Jerabek Paul , Pahl Elke , Schwerdtfeger Peter
Published: June 2018

Moderne, relativistische Coupled‐Cluster‐Methoden wurden verwendet, um Mehrkörperpotentiale des Edelgaselements Radon zu konstruieren und mit Parallel‐Tempering‐Monte‐Carlo‐Simulationen seine Festkörpereigenschaften, darunter den Phasenübergang von fest zu flüssig, zu studieren. Als Schmelztemperaturen wurden in Simulationen des ganzen Festkörpers und durch Extrapolation von finiten Clustern 200(3) K bzw. 200(6) K bestimmt. Dies ist in hervorragender Übereinstimmung mit dem oft angezweifelten (aber weitläufig zitierten) und einzigen experimentellen Wert von 202 K, der auf Messungen von Gray und Ramsay aus dem Jahre 1909 zurückgeht.
Getriggerte Freisetzung und Oxidation von Metallionen: Ferrocen als neuer Mechanophor in Polymeren
Authors: Di Giannantonio Michela , Ayer Mathieu A. , Verde‐Sesto Ester , Lattuada Marco , Weder Christoph , Fromm Katharina M.
Published: June 2018

Die Einführung von Mechanophoren in Polymere erlaubt es, mechanische Kräfte in chemische Reaktionen umzuwandeln, was wiederum zu neuen Funktionalitäten führen kann, wie beispielsweise Selbstheilung, katalytischer Aktivität oder mechanochromen Eigenschaften. Diese Zuschrift beschreibt die mechanisch induzierte Freisetzung von Metallionen aus in Polymerketten (z. B. Poly(methylacrylat) und Polyurethan) eingebetteten Ferrocen‐Einheiten (Fc). Durch die Bestrahlung mit Ultraschall werden diese Sollbruchstellen bevorzugt gespalten, wie anhand kinetischer Molmassenbestimmungen von Fc‐haltigen und Fc‐freien Polymeren gezeigt werden konnte. Die freigesetzten und oxidierten Eisenionen konnten durch die Umsetzung mit KSCN oder K4[Fe(CN)6] als typisch roter [Fe(SCN)n(H2O)6−n)](3−n)+ Komplex, bzw. als Preußischblau nachgewiesen werden.
Three‐Component Gallium(III)‐Promoted Addition of Halide Anions and Acetylenes to Donor–Acceptor Cyclopropanes
Authors: Novikov Roman A. , Borisov Denis D. , Tarasova Anna V. , Tkachev Yaroslav V. , Tomilov Yury V.
Published: June 2018

A new strategy for the three‐component addition of halide anions and acetylenes to donor–acceptor cyclopropanes (DACs) is presented. This reaction, which occurs with high E selectivity, is promoted by gallium(III) salts and based on the 1,2‐zwitterionic reactivity of DACs. It opens up a new group of processes involving DACs. The reaction occurs readily with a broad range of substrates and is tolerant of various functional groups. This methodology makes it possible to assemble highly functionalized vinyl halides, which are very convenient building blocks in organic synthesis. A possible mechanism of this reaction and its stereochemical aspects are discussed in detail.
On‐Line Polyketide Cyclization into Diverse Medium‐Sized Lactones by a Specialized Ketosynthase Domain
Authors: Sundaram Srividhya , Kim Hak Joong , Bauer Ruth , Thongkongkaew Tawatchai , Heine Daniel , Hertweck Christian
Published: June 2018

Ketosynthase (KS) domains of modular type I polyketide synthases (PKSs) typically catalyze the Claisen condensation of acyl and malonyl units to form linear chains. In stark contrast, the KS of the rhizoxin PKS branching module mediates a Michael addition, which sets the basis for a pharmacophoric δ‐lactone moiety. The precise role of the KS was evaluated by site‐directed mutagenesis, chemical probes, and biotransformations. Biochemical and kinetic analyses helped to dissect branching and lactonization reactions and unequivocally assign the entire sequence to the KS. Probing the range of accepted substrates with diverse synthetic surrogates in vitro, we found that the KS tolerates defined acyl chain lengths to produce five‐ to seven‐membered lactones. These results show that the KS is multifunctional, as it catalyzes β‐branching and lactonization. Information on the increased product portfolio of the unusual, TE‐independent on‐line cyclization is relevant for synthetic biology approaches.
Sensing Uranyl(VI) Ions by Coordination and Energy Transfer to a Luminescent Europium(III) Complex
Authors: Harvey Peter , Nonat Aline , Platas‐Iglesias Carlos , Natrajan Louise S. , Charbonnière Loïc J.
Published: June 2018

The release of uranyl(VI) is a hazardous environmental issue, with limited ways to monitor accumulation in situ. Here, we present a method for the detection of uranyl(VI) ions through the utilization of a unique fluorescence energy transfer process to europium(III). Our system displays the first example of a “turn‐on” europium(III) emission process with a small, water‐soluble lanthanide complex triggered by uranyl(VI) ions.
Diboryldiborene: π‐konjugierte B4‐Ketten isoelektronisch zum Butadien‐Dikation
Authors: Hermann Alexander , Cid Jessica , Mattock James D. , Dewhurst Rian D. , Krummenacher Ivo , Vargas Alfredo , Ingleson Michael J. , Braunschweig Holger
Published: June 2018

Die Umsetzung von Bis(catecholato)diboran mit N‐heterocyclischen Carbenen (NHCs) lieferte sp2‐sp3‐Diborane, die hochselektiv einen Catechol/Bromid‐Austausch am sp3‐Boratom eingehen. Die Reduktion der erhaltenen 1,1‐Dibromdiboran‐Addukte führte zur reduktiven Kupplung und Isolierung von zweifach NHC‐stabilisierten 1,2‐Diboryldiborenen. Mit diesen Molekülen konnte erstmals eine Delokalisierung von π‐Elektronen über eine nur aus Boratomen bestehende Kette realisiert werden.
Green and Rapid Hydrothermal Crystallization and Synthesis of Fully Conjugated Aromatic Compounds
Authors: Taublaender M. Josef , Glöcklhofer Florian , Marchetti‐Deschmann Martina , Unterlass Miriam M.
Published: June 2018

Highly fused, fully conjugated aromatic compounds are interesting candidates for organic electronics. With higher crystallinity their electronic properties improve. It is shown here that the crystallization of three archetypes of such molecules—pentacenetetrone, indigo, and perinone—can be achieved hydrothermally. Given their molecular structure, this is a truly startling finding. In addition, it is demonstrated that perinone can also be synthesized in solely high‐temperature water from the starting compounds naphthalene bisanhydride and o‐phenylene diamine without the need for co‐solvents or catalysts. The transformation can be drastically accelerated by the application of microwave irradiation. This is the first report on the hydrothermal generation of two fused heterocycles.
Ca12[Mn19N23] and Ca133[Mn216N260]: Structural Complexity by 2D Intergrowth
Authors: Ovchinnikov Alexander , Bobnar Matej , Prots Yurii , Borrmann Horst , Sichelschmidt Jörg , Grin Yuri , Höhn Peter
Published: June 2018

Two new calcium nitridomanganates, Ca12[Mn19N23] (P3, a=11.81341(3) Å, c=5.58975(2) Å, Z=1) and Ca133[Mn216N260] (
, a=39.477(1) Å, c=5.5974(2) Å, Z=1), were obtained by a gas–solid reaction of Ca3N2 and Mn with N2 at 1273 K and 1223 K, respectively. The crystal structure of Ca12[Mn19N23] was determined from high‐resolution X‐ray synchrotron powder diffraction data, whereas single‐crystal X‐ray diffraction was employed to establish the crystal structure of the Ca133[Mn216N260] phase, which classifies as a complex metallic alloy (CMA). Both crystal structures have 2D nitridomanganate layers containing similar building blocks but of different levels of structural complexity. Bonding analysis as well as magnetic susceptibility and electron spin resonance measurements revealed that only a fraction of the Mn atoms in both structures carries a localized magnetic moment, while for most Mn species the magnetism is quenched as a result of metal–metal bond formation.
Efficient and Robust Hydrogen Evolution: Phosphorus Nitride Imide Nanotubes as Supports for Anchoring Single Ruthenium Sites
Authors: Yang Jian , Chen Bingxu , Liu Xiaokang , Liu Wei , Li Zhijun , Dong Juncai , Chen Wenxing , Yan Wensheng , Yao Tao , Duan Xuezhi , Wu Yuen , Li Yadong
Published: June 2018

Amorphous phosphorus nitride imide nanotubes (HPN) are reported as a novel substrate to stabilize materials containing single‐metal sites. Abundant dangling unsaturated P vacancies play a role in stabilization. Ruthenium single atoms (SAs) are successfully anchored by strong coordination interactions between the d orbitals of Ru and the lone pair electrons of N located in the HPN matrix. The atomic dispersion of Ru atoms can be distinguished by X‐ray absorption fine structure measurements and spherical aberration correction electron microscopy. Importantly, Ru SAs@PN is an excellent electrocatalyst for the hydrogen evolution reaction (HER) in 0.5 m H2SO4, delivering a low overpotential of 24 mV at 10 mA cm−2 and a Tafel slope of 38 mV dec−1. The catalyst exhibits robust stability in a constant current test at a large current density of 162 mA cm−2 for more than 24 hours, and is operative for 5000 cycles in a cyclic voltammetry test. Additionally, Ru SAs@PN presents a turnover frequency (TOF) of 1.67 H2 s−1 at 25 mV, and 4.29 H2 s−1 at 50 mV, in 0.5 m H2SO4 solution, outperforming most of the reported hydrogen evolution catalysts. Density functional theory (DFT) calculations further demonstrate that the Gibbs free energy of adsorbed H* over the Ru SAs on PN is much closer to zero compared with the Ru/C and Ru SAs supported on carbon and C3N4, thus considerably facilitating the overall HER performance.
Diboryldiborenes: π‐Conjugated B4 Chains Isoelectronic to the Butadiene Dication
Authors: Hermann Alexander , Cid Jessica , Mattock James D. , Dewhurst Rian D. , Krummenacher Ivo , Vargas Alfredo , Ingleson Michael J. , Braunschweig Holger
Published: June 2018

B(sp2)–B(sp3) diborane species based on bis(catecholato)diboron and N‐heterocyclic carbenes (NHCs) underwent catechol/bromide exchange selectively at the sp3‐hybridized boron atom. The reduction of the resulting 1,1‐dibromodiborane adducts led to reductive coupling and isolation of doubly NHC‐stabilized 1,2‐diboryldiborenes. These compounds are the first examples of molecules exhibiting π‐electron delocalization over an all‐boron chain.
Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of Alkenes
Authors: Zhang Ji‐Shu , Liu Long , Chen Tieqiao , Han Li‐Biao
Published: June 2018

Three‐component reactions can directly convert three reactants into the desired products in one pot and thus greatly shorten the synthetic path. Recently, transition‐metal catalysis has been applied in the difunctionalization of alkenes and remarkable progress has been achieved to facilitate the construction of a wide range of functional molecules with high atom‐ and step‐economic efficiency. This Focus Review highlights recent advances in this field.
Down‐regulating Proteolysis to Enhance Anticancer Activity of Peptide Nanofibers
Authors: Li Jie , Du Xuewen , Powell Devon J. , Zhou Rong , Shi Junfeng , He Hongjian , Feng Zhaoqianqi , Xu Bing
Published: June 2018

Nanofibers of short peptides are emerging as a promising type of agents for inhibiting cancer cells. But the proteolysis of peptides decreases the anticancer efficacy of the peptide nanofibers. Here we show that decreasing the activity of proteasomes enhance the activity of peptide nanofibers for inhibiting cancer cells. Based on the structure of galactin‐3, we designed a heptapeptide, which self‐assembles to form nanofibers. The nanofibers of the heptapeptide exhibit moderate cytotoxicity to three representative cancer cell lines (HeLa, MCF‐7, and HepG2), largely due to the proteolysis of the peptides. Using a clinically approved proteasome inhibitor, bortezomib, to treat the cancer cells significantly decreases the proteolysis of the peptides and enhances the activity of the peptide nanofibers for inhibiting the cancer cells. This work illustrates a promising approach for enhancing the anticancer efficacy of peptide nanofibers by modulating intracellular protein degradation machinery, as well as provides insights for understanding the cytotoxicity of aberrant protein or peptide aggregates in complicated cellular environment.
Generalized Nonlinear Stiffness Identification on Controlled Mechanical Vibrating Systems
Authors: Beltran‐Carbajal Francisco , Silva‐Navarro Gerardo
Published: June 2018

A new algebraic parametric identification method in time domain for multiple degrees‐of‐freedom mechanical vibrating systems with high‐order nonlinear stiffness is proposed. Parameters of mass, damping and linear and nonlinear stiffness are estimated on‐line and, simultaneously, using transient real‐time position measurements and active control force signals. Parametric identification can be applied for real‐time estimation of both symmetrical and non‐symmetrical stiffness. Parametric identification is combined with adaptive planned motion control on Multiple‐Input‐Multiple‐Output nonlinear mechanical vibrating systems. Analytical and numerical results prove the effectiveness and efficiency of the proposed on‐line algebraic parametric identification approach.
Transformation of Nonlinear MIMO Discrete‐Time Systems into the Extended Observer Form
Authors: Kaparin Vadim , Kotta Ülle
Published: June 2018

The paper addresses the problem of transforming discrete‐time multi‐input multi‐output nonlinear state equations into the extended observer form, which, besides the inputs and outputs, also depends on a finite number of their past values. Necessary and sufficient conditions for the existence of the extended coordinate transformation are formulated in terms of differential one‐forms, associated with the input‐output equations, corresponding to the state equations. The difference between the single‐input single‐output and multi‐input multi‐output cases is described. The applicability of the conditions is illustrated by an example.
Extreme malleability of preferences: Absolute preference sign changes under uncertainty
Authors: Vosgerau Joachim , Peer Eyal
Published: June 2018

Malleability of preferences is a central tenet of behavioral decision theory. How malleable preferences really are, however, is a topic of debate. Do preference reversals imply preference construction? We argue that to claim preferences are construed, a demonstration of more extreme preference malleability than simple preference reversals is required: absolute preference sign changes within participants. If respondents value a prospect positively in 1 condition but negatively in a different condition, preferences cannot be considered stable. Such absolute preference sign changes are possible under uncertainty. In 2 incentive‐compatible experiments, we found participants were willing to pay to take part in a gamble and also demanded to be compensated to take part in a subsequent gamble with identical outcomes and probabilities. Such absolute preference sign changes within participants led to simultaneous risk aversion and risk seeking for the same risky prospect, suggesting that, at least in the domain of risky decisions, consumers' preferences are indeed malleable and construed.
Enhancing efficiency, reliability, and rigor in competency model analysis using natural language processing
Authors: Garman Andrew N. , Standish Melanie P. , Kim Dae Hyun
Published: June 2018

Background

Competency modeling is frequently used in higher education and workplace settings to inform a variety of learning and performance improvement programs. However, approaches commonly taken to modeling tasks can be very labor‐intensive, and are vulnerable to perceptual and experience biases of raters.

Aims

The present study assesses the potential for natural language processing (NLP) to support competency‐related tasks, by developing a baseline comparison of results generated by NLP to results generated by human raters.

Methods

Two raters separately conducted cross‐walks for leadership competency models of graduate healthcare management programs from eight universities against a newly validated competency model from the National Center for Healthcare Leadership containing 28 competencies, to create 224 cross‐walked pairs of “best matches”.

Results

Results indicated that the NLP model performed at least as accurately as human raters, who required a total of 16 work hours to complete, versus the NLP calculations which were nearly instantaneous.

Conclusion

Based on these findings, we conclude that NLP has substantial promise as a high‐efficiency adjunct to human evaluations in competency cross‐walks.
Behavior of Alkaline‐Metal Catalysts in Supercritical Water Gasification of Lignite
Authors: Qu Xuan , Zhou Xianxian , Yan Xiaoqiang , Zhang Rong , Bi Jicheng
Published: June 2018

The efficient utilization of abundant low‐rank coals, which show high moisture and ash content, is significant for coal‐based energy systems. The gasification of Zhaotong lignite was performed with different alkaline‐metal catalysts, such as KOH, NaOH, K2CO3, and Na2CO3, in supercritical water. The behavior of the alkaline metal was also investigated. Potassium shows better catalytic activity than sodium. KOH not only promotes breakage of chemical bonds in the coal matrix to generate low‐molecular‐weight gases, but also alters the pore structure of the char to improve the gasification of carbon in the residue. However, potassium is partly inactivated upon reaction with minerals in coal in supercritical water gasification. In situ protection of potassium is realized by adding Ca(OH)2 under supercritical conditions.
Binding Studies of Metal–Salphen and Metal–Bipyridine Complexes towards G‐Quadruplex DNA
Authors: Łęczkowska Anna , Gonzalez‐Garcia Jorge , Perez‐Arnaiz Cristina , Garcia Begoña , White Andrew J. P. , Vilar Ramon
Published: June 2018

The proposed in vivo formation of G‐quadruplex DNA (G4 DNA) in promoter regions of oncogenes and in telomeres has prompted the development of small molecules with high affinity and selectivity for these structures. Herein we report the synthesis of a new di‐substituted bipyridine ligand and the corresponding complexes with Ni2+ and VO2+. Both these new complexes have been characterized spectroscopically and by X‐ray crystallography. Detailed DNA binding studies of these two complexes, together with three previously reported metal salphen complexes, are presented. Using FRET melting assays, the binding affinity and selectivity of the five metal complexes against six different G4 DNA structures as well as a duplex DNA have been determined. In addition, we present detailed ITC and UV/Vis studies to characterize the interaction of the complexes with human telomeric G4 DNA. Finally, we show via a polymerase stop assay that these complexes are able to stabilize a G4 DNA structure (from the c‐Myc oncogene promoter) and halt the activity of Taq polymerase.
Concomitant Site‐Specific Incorporation of Silver(I) and Mercury(II) Ions into a DNA Duplex
Authors: Jash Biswarup , Müller Jens
Published: June 2018

A GNA (glycol nucleic acid)‐based nucleoside analogue containing 1 H‐imidazo[4,5‐f][1,10]phenanthroline (P) as an artificial nucleobase was used to form a stable mercury(II)‐mediated P‐HgII‐T‐H base pair within a parallel‐stranded DNA duplex. The nucleobase P shows an affinity towards silver(I) and mercury(II), tuneable through the acidity of the medium when the canonical nucleobase thymine is located in its complementary position. This extraordinary behavior was exploited to enable the concomitant site‐specific incorporation of silver(I) and mercury(II) into a DNA scaffold for the first time. This achievement is all the more remarkable because it was made possible by the involvement of only one type of artificial nucleobase. The simultaneous incorporation of two different soft metal ions with a precise control of their respective positions within the nucleic acid scaffold significantly reduces the complexity in the formation of a heterometallic array of metal ions in DNA and thereby facilitates new applications of metal‐functionalized nucleic acids.