bluuebunny/crossref_metadata_2025 huggingface dataset:
Sensitivity of airborne geophysical data to sublacustrine permafrost thaw
Authors: Minsley B. J. , Wellman T. P. , Walvoord M. A. , Revil A.
Published: December 2014

Abstract. A coupled hydrogeophysical forward and inverse modeling approach is developed to illustrate the ability of frequency-domain airborne electromagnetic (AEM) data to characterize subsurface physical properties associated with sublacustrine permafrost thaw during lake talik formation. Several scenarios are evaluated that consider the response to variable hydrologic forcing from different lake depths and hydrologic gradients. The model includes a physical property relationship that connects the dynamic distribution of subsurface electrical resistivity based on lithology as well as ice-saturation and temperature outputs from the SUTRA groundwater simulator with freeze/thaw physics. Electrical resistivity models are used to simulate AEM data in order to explore the sensitivity of geophysical observations to permafrost thaw. Simulations of sublacustrine talik formation over a 1000 year period modeled after conditions found in the Yukon Flats, Alaska, are evaluated. Synthetic geophysical data are analyzed with a Bayesian Markov chain Monte Carlo algorithm that provides a probabilistic assessment of geophysical model uncertainty and resolution. Major lithological and permafrost features are well resolved in the examples considered. The subtle geometry of partial ice-saturation beneath lakes during talik formation cannot be resolved using AEM data, but the gross characteristics of sub-lake resistivity models reflect bulk changes in ice content and can be used to determine the presence of a talik. A final example compares AEM and ground-based electromagnetic responses for their ability to resolve shallow permafrost and thaw features in the upper 1–2 m below ground.
Emergency Department Utilization by Older Adults: a Descriptive Study
Authors: Latham Lesley P. , Ackroyd-Stolarz Stacy
Published: December 2014

BackgroundEmergency Departments (EDs) are playing an increasingly important role in the care of older adults. Characterizing ED usage will facilitate the planning for care delivery more suited to the complex health needs of this population.MethodsIn this retrospective cross-sectional study, administrative and clinical data were extracted from four study sites. Visits for patients aged 65 years or older were characterized using standard descriptive statistics.ResultsWe analyzed 34,454 ED visits by older adults, accounting for 21.8% of the total ED visits for our study time period. Overall, 74.2% of patient visits were triaged as urgent or emergent. Almost half (49.8%) of visits involved diagnostic imaging, 62.1% involved lab work, and 30.8% involved consultation with hospital services. The most common ED diagnoses were symptom- or injury-related (25.0%, 17.1%. respectively). Length of stay increased with age group (Mann-Whitney U;p < .0001), as did the proportion of visits involving diagnostic testing and consultation (χ2; p < .0001). Approximately 20% of older adults in our study population were admitted to hospital following their ED visit.ConclusionsOlder adults have distinct patterns of ED use. ED resource use intensity increases with age. These patterns may be used to target future interventions involving alternative care for older adults.
The Canadian Coalition for Seniors’ Mental Health (CCSMH) and Canadian Academy of Geriatric Psychiatry (CAGP) Joint Scientific Meeting
Authors: Authors Various
Published: December 2014

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The Future of Medical Care for Older Adults in Canada
Authors: Madden Kenneth M.
Published: December 2014

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Produtos metamórficos de sistemas high-sulfidation oceânicos mesoproterozoicos, grupo Serra do Itaberaba, SP
Authors: Pérez-Aguilar Annabel , Moreira Izabella Vicentin , Silles Jacqueline Silva , Juliani Caetano , Carvalho Flávio Machado de Souza
Published: December 2014

O Grupo Serra do Itaberaba, no segmento central da Faixa de Dobramentos Ribeira (sudeste do Brasil), corresponde a uma sucessão meta-vulcanossedimentar do Mesoproterozoico. As rochas deste grupo foram afetadas por dois eventos metamórficos regionais na fácies anfibolito e um terceiro evento retrometamórfico na fácies dos xistos verdes. Esta sucessão depositou-se, inicialmente, em um ambiente oceânico contendo basaltos com assinaturas do tipo N-MORB, que, posteriormente, evoluiu para um ambiente de retro-arco. Neste grupo são conhecidas quatro ocorrências de rochas ricas em alumina (Guavirituba, Pedra Branca, Itaberaba e Pico Pelado), que afloram na forma de pequenas lentes intercaladas entre metabasitos, rochas metavulcanoclásticas, metatufos e metapelitos. A gênese destas rochas está associada à atividade magmática-hidrotermal oceânica em ambiente de retro arco, vinculada à colocação de pequenos corpos de rochas riolíticas e processos mineralizantes em ouro do tipo high-sulfidation. Análises por difração de raios X (DRX) de 15 amostras ricas em alumina, de granulação muito fina, permitiram identificar coríndon, topázio, margarita, rutilo e mica indiferenciada (possivelmente sericita). As associações minerais identificadas possibilitaram reconhecer a atuação de dois eventos de alteração argílica avançada e um terceiro evento de carbonatação ou retrometamórfico nas rochas do Grupo Serra do Itaberaba: o primeiro evento gerou o protolito 1, rico em óxidos de alumínio ± alunita, que, metamorfisadas, produziram litotipos azuis escuros formados por coríndon ± sericita; o segundo caracteriza um evento de silicificação que produziu o protolito 2, composto por topázio + zunyita + alunita ± rutilo ou por andalusita + alunita, correspondendo os seus produtos metamórficos a litotipos de cor marrom e esbranquiçada (ocorrência de Pico Pelado); no evento de carbonatação ou retrometamórfico cristalizou-se margarita a partir da andalusita, cianita ou sillimanita. A soma destes três eventos produziram, durante o metamorfismo ou retrometamorfismo, litotipos de cor marrom, esbranquiçada e heterogênea formados por margarita ou por margarita + sericita ± coríndon (ocorrências Guavirituba e Pedra Branca). A identificação desses litotipos em campo representa valiosa ferramenta em trabalhos de exploração mineral, uma vez que constituem rochas-guias para a localização de depósitos de ouro em sucessões meta-vulcanossedimentares metamofisadas em grau médio.
The effect of metastable pyroxene on the slab dynamics
Authors: Agrusta Roberto , van Hunen Jeroen , Goes Saskia
Published: December 2014

Seismic studies show that some subducting slabs penetrate straight into the lower mantle, whereas others seem to flatten near the base of the mantle transition zone. Slab stagnation is often attributed to an increase in viscosity and phase transformations in the olivine system. However, recent mineral physics studies showed that due to extremely low transformational diffusion rates, low‐density metastable pyroxene may persist into the transition zone in cool slabs. Here we use a dynamically fully self‐consistent subduction model to investigate the influence of metastable pyroxene on the dynamics of subducting oceanic lithosphere. Our results show that metastable pyroxene affects slab buoyancy at least as much as olivine metastability. However, unlike metastable olivine, which can inhibit slab penetration in the lower mantle only for cold, old, and fast slabs, metastable pyroxene is likely to also affect sinking of relatively young and slow slabs.
Investigation of EMIC wave scattering as the cause for the BARREL 17 January 2013 relativistic electron precipitation event: A quantitative comparison of simulation with observations
Authors: Li Zan , Millan Robyn M. , Hudson Mary K. , Woodger Leslie A. , Smith David M. , Chen Yue , Friedel Reiner , Rodriguez Juan V. , Engebretson Mark J. , Goldstein Jerry , Fennell Joseph F. , Spence Harlan E.
Published: December 2014

Electromagnetic ion cyclotron (EMIC) waves were observed at multiple observatory locations for several hours on 17 January 2013. During the wave activity period, a duskside relativistic electron precipitation (REP) event was observed by one of the Balloon Array for Radiation belt Relativistic Electron Losses (BARREL) balloons and was magnetically mapped close to Geostationary Operational Environmental Satellite (GOES) 13. We simulate the relativistic electron pitch angle diffusion caused by gyroresonant interactions with EMIC waves using wave and particle data measured by multiple instruments on board GOES 13 and the Van Allen Probes. We show that the count rate, the energy distribution, and the time variation of the simulated precipitation all agree very well with the balloon observations, suggesting that EMIC wave scattering was likely the cause for the precipitation event. The event reported here is the first balloon REP event with closely conjugate EMIC wave observations, and our study employs the most detailed quantitative analysis on the link of EMIC waves with observed REP to date.
A Layered‐Nanospace‐Confinement Strategy for the Synthesis of Two‐Dimensional Porous Carbon Nanosheets for High‐Rate Performance Supercapacitors
Authors: Fan Xiaoming , Yu Chang , Yang Juan , Ling Zheng , Hu Chao , Zhang Mengdi , Qiu Jieshan
Published: December 2014

A general approach is developed for the synthesis of 2D porous carbon nanosheets (PCNS) from bio‐sources derived carbon precursors (gelatin) by an integrated procedure of intercalation, pyrolysis, and activation. Montmorillonite with layered nanospace is used as a nanotemplate or nanoreactor to confine and modulate the transformation of gelatin, further leading to the formation of 2D nanosheet‐shaped carbon materials. The as‐made 2D PCNS exhibits a significantly improved rate performance, with a high specific capacitance of 246 F g−1 and capacitance retention of 82% at 100 A g−1, being nearly twice that of microsized activated carbon particulates directly from gelatin (131 F g−1, 44%). The shortened ion transport distance in the nanoscaled dimension and modulated porous structure is responsible for such an enhanced superior rate capability. More importantly, the present strategy can be extended to other bio‐sources to create 2D PCNS as electrode materials with high‐rate performance. This will also provide a potential strategy for configuring 2D nanostructured carbon electrode materials with a short ion transport distance for supercapacitors and other carbon‐related energy storage and conversion devices.
Nucleophilic Addition Reaction to the Iminium Salts Generated from Pipecolic Acid Derivatives and Application to the Synthesis of Bicyclic Compounds
Authors: Shimizu Makoto , Yato Atsuhiro , Kawamura Takato
Published: December 2014

Nucleophilic addition of Grignard reagents to the iminium salts generated by the oxidation of cyclic amino ketene silyl acetals derived from pipecolic acid gave α‐quaternary amino ester derivatives. Bicyclic compounds were prepared from N‐allylated and homoallylated derivatives with vinylaion, allylation, or homoallylation followed by ring‐closing metathesis. Application of this method to the synthesis of (±)‐S22178, a potent 5‐HT1A agonist, was also described.
Emulsion Ripening through Molecular Exchange at Droplet Contacts
Authors: Roger Kevin , Olsson Ulf , Schweins Ralf , Cabane Bernard
Published: December 2014

Two coarsening mechanisms of emulsions are well established: droplet coalescence (fusion of two droplets) and Ostwald ripening (molecular exchange through the continuous phase). Here a third mechanism is identified, contact ripening, which operates through molecular exchange upon droplets collisions. A contrast manipulated small‐angle neutron scattering experiment was performed to isolate contact ripening from coalescence and Ostwald ripening. A kinetic study was conducted, using dynamic light scattering and monodisperse nanoemulsions, to obtain the exchange key parameters. Decreasing the concentration or adding ionic repulsions between droplets hinders contact ripening by decreasing the collision frequency. Using long surfactant chains and well‐hydrated heads inhibits contact ripening by hindering fluctuations in the film. Contact ripening can be controlled by these parameters, which is essential for both emulsion formulation and delivery of hydrophobic ingredients.
Nuclear Magnetic Resonance Structure Elucidation of Peptide b2 Ions
Authors: Liu Pengyuan , Cooks R. Graham , Chen Hao
Published: December 2014

Tandem mass spectrometry (MS/MS) is powerful for chemical identification but it is still insufficient for explicit ion structure determination. A strategy is introduced to elucidate MS fragment ion structures using NMR spectroscopy for the first time. In our experiments, precursor ions are dissociated at atmospheric pressure and the resulting fragment ions are identified by mass spectrometry but collected outside the mass spectrometer, making the subsequent NMR measurements possible. This new strategy has been applied to determine the chemical structure of the characteristic b2 fragment ion, a subject of longstanding debate in MS‐based proteomics.
Die Kugeligkeit als geometrische Kenngröße für die Kompaktheit von Gebäuden
Authors: Grafe Michael
Published: December 2014

Im Bauwesen werden kompakte Baukörper aus unterschiedlichen Motiven heraus als sinnvoll erachtet. Die Kompaktheit eines Gebäudes wird bisher mit dem A/V‐Verhältnis durch eine Kenngröße abgebildet, die neben der Geometrie auch die Größe des Baukörpers beschreibt. Größere Baukörper gelten danach als kompakter gegenüber kleineren Baukörpern. In diesem Aufsatz wird die Kugeligkeit von Gebäuden als eine Kenngröße vorgeschlagen, die allein die Geometrie des Baukörpers beschreibt. Sie gibt an, um welchen Faktor die Oberfläche des Baukörpers gegenüber der Oberfläche der volumengleichen Kugel vergrößert ist. Für die Kugeligkeit einfacher geometrischer Körper werden Kennzahlen angegeben, die Hinweise zur Bewertung der Kompaktheit realer Baukörper geben. Abschließend wird eine Funktion zur Beschreibung der optimalen Kugeligkeit eines Baukörpers vorgeschlagen.

Sphericity as geometrical caracteristic for the compactness of buildings. In civil engineering compact structures are considered useful due to different reasons. Up to now the compactness of a building is usually caracterized by the surface‐volume ratio, which describes the geometry and the size of the structure. Following this concept larger structures are considered as more compact than smaller ones. In this article the sphericity of buildings is suggested as a characteristic, that sole describes the geometry of the structure. It indicates the factor by which the surface of the structure is increased compared to the surface of the sphere of equal volume. For the sphericity of simple geometrical shapes characteristic numbers are specified which give information and giudance for the evaluation of the compactness of real structures. Finally a function is suggested for the description of the optimal sphericity of a structure.
Grenzen der Dämmung opaker Bauteile
Authors: Jochum Patrick , Mellwig Peter
Published: December 2014

Das Energiekonzept der Bundesregierung sieht vor, den Einsatz fossiler Brennstoffe in Gebäuden bis zum Jahre 2050 um 80 % zu senken. Da bis 2050 voraussichtlich noch rund 80 % der heutigen Gebäude stehen werden, adressiert dieses Ziel vor allem den Gebäudebestand. Die grundsätzlich einsetzbaren Werkzeuge auf dem Weg zu diesem Ziel sind die Verbesserung der thermischen Hülle und der Einsatz erneuerbarer Energien. Beide Werkzeuge stehen jedoch nur in begrenztem Umfang zur Verfügung und somit stellt sich die Frage, mit welchen jeweiligen Anteilen sie zur Zielerreichung beitragen können. Das Niveau des Wärmeschutzes hängt direkt von den erreichbaren Wärmedurchgangskoeffizienten (U‐Werten) der Bauteile ab. Heutige U‐Werte liegen in der Größenordnung von 0,30 bis 0,14 W/(m²K). In diesem Artikel soll gezeigt werden, wie weit die Wärmedurchgangskoeffizienten durch Dämmmaßnahmen künftig noch weiter sinnvoll abgesenkt werden können. Dabei können neue Dämmstoffe, die erst in der Zukunft entwickelt werden und deren Eigenschaften wir noch nicht kennen, natürlich nur begrenzt vorgedacht werden. Es können jedoch Grundprinzipien gezeigt werden, von denen auch künftige Dämmstoffe betroffen sein werden, aus denen sich gewisse Untergrenzen für den U‐Wert ableiten lassen.

The limits of insulation for opaque structural elements. The German Federal government’s Energy Concept pledges an 80 % reduction in the use of fossil fuels in buildings by 2050. Since around 80 % of existing buildings will still be standing in 2050, this target primarily encompasses the current building stock. The main tools available for use in achieving this target are improvements to the thermal envelope and the use of renewable energies. Yet there are limits to the scope for using these tools. This begs the question of the extent to which each tool can help achieve the target. The level of thermal protection depends directly on the heat transfer coefficients (U‐values) that can be achieved in each structural element. Current U‐values are in the order of 0.30 to 0.14 W/(m²K). In the present article, we investigate any significant reduction in heat transfer coefficients that can be achieved in future using insulation measures. The properties of as yet undeveloped insulation materials are of course unknown, and hence for the purposes of our investigation cannot be considered in full. It will however be possible to demonstrate basic principles which will also apply to any future insulation materials, and to derive from these specific lower limits for U‐values.
Einheitliche Schallschutz‐Maße und Schallschutz‐Klassifikationen im Wohnungsbau
Authors: Lang Judith
Published: December 2014

Eine internationale Studiengruppe mit Vertretern aus 30 europäischen Ländern hat zum Thema “Einheitliche Größen zur Beschreibung des Schallschutzes in Wohngebäuden und Klassifizierung des Schallschutzes und Zusammenhang der physikalischen Größen und subjektiver Zufriedenheit mit dem Schallschutz“ gearbeitet und die Ergebnisse in dem Buch “COST Action TU0901 Towards a common framework in building acoustics throughout Europe“ zusammengefasst, ein ausführlicheres e‐Book folgt. Um die Diskussion darüber in Österreich und auch in Deutschland anzuregen, werden hier die wichtigsten Eckpunkte und Empfehlungen dargestellt.
Maternal and Paternal Filicide: Case Studies from the Australian Homicide Project
Authors: Eriksson Li , Mazerolle Paul , Wortley Richard , Johnson Holly
Published: December 2014

Data drawn from the Australian Homicide Project were used to examine whether and how maternal and paternal filicide perpetrators differ in terms of motivations for filicide and childhood and adulthood adversities. In addition, key differences between filicide and non‐filicide perpetrators were examined. Data were collected across a number of states and territories in Australia between 2010 and 2013 through interviews with 231 men and women convicted of murder or manslaughter. Of these participants, 14 had perpetrated filicide. Detailed information on the developmental background of the perpetrators, as well as motives and situational contexts of the homicide incidents, was gathered through the interviews. Findings from the current study reveal some important gender differences among filicide perpetrators. For example, filicidal fathers are more likely to perpetrate accidental filicide, and to report unemployment, alcohol and drug problems and previous engagement in child abuse, while filicidal mothers are more likely to perpetrate altruistic or neglectful filicide, and to report mental health problems. In addition, male filicide perpetrators report a greater number of adversities compared to male non‐filicide perpetrators, while female filicide perpetrators display fewer adversities compared to their non‐filicide counterparts.

‘Findings from the current study reveal some important gender differences among filicide perpetrators’

Key Practitioner Messages

Practitioners are uniquely placed to assist in filicide prevention.

Opportunities for service providers to raise awareness of key risk factors for filicide are crucial.

Health and social service providers are ideally placed to screen parents seeking support to uncover early warning risks.

Mental health service support is crucial, particularly for mothers, as is screening parents for severe depression or suicidal ideations.

Provision of parenting support skills to help parents cope with extreme stress appears salient.

‘Health and social service providers are ideally placed to screen parents seeking support to uncover early warning risks’
Pollen Diversity and Volatile Variability of Honey from Corsican Anthyllis hermanniae L. Habitat
Authors: Yang Yin , Battesti Marie‐José , Paolini Julien , Costa Jean
Published: December 2014

Melissopalynological, physicochemical, and volatile analyses of 29 samples of Corsican ‘summer maquis’ honey were performed. The pollen spectrum was characterized by a wide diversity of nectariferous and/or polleniferous taxa. The most important were Anthyllis hermanniae and Rubus sp., associated with some endemic taxa. Castanea sativa was also determined in these honeys with a great variation. The volatile fraction was characterized by 37 compounds and dominated by phenolic aldehydes and linear acids. The major compounds were phenylacetaldehyde, benzaldehyde, and nonanoic acid. Statistical analysis of pollen and volatile data showed that 18 samples were characterized by a high abundance of phenylacetaldehyde, which might relate to the high amount of A. hermanniae and Rubus sp. Eleven other samples displayed a higher proportion of phenolic ketones and linear acids, which characterized the nectar contribution of C. sativa and Thymus herba‐barona, respectively.
Comprehensive Phenological Description of Essential‐Oil Chemotypes of Salvia lavandulifoliaVahl Grown under the Same Environmental Conditions
Authors: Usano‐Alemany Jaime , Palá‐Paúl Jesús , Herráiz‐Peñalver David
Published: December 2014

A comprehensive description of diverse essential‐oil chemical profiles was conducted with twelve individual plants of Salvia lavandulifolia Vahl (Spanish sage) gathered from wild populations and grown under identical culture conditions. Whereas the chemical polymorphism within species of aromatic plants is well known, both the statistical significance of the differences in the chemical composition and the setting of chemical profiles have been scarcely studied. Remarkably different essential‐oil chemical profiles were described for the wild‐growing plants, which remained different during the three years of cultivation, even when acute situations of water stress occurred. Different patterns of representative compounds throughout the phenological cycle of the species were also reported, with 1,8‐cineole being the main oil compound described (contents of up to 75.2%). The Mahalanobis distance was used as a separation parameter, to assign a significance level to a single‐compound chemotype. The phytochemical heterogeneity of some wild populations of Spanish sage was proved. Furthermore, some concrete genotypes presented high percentages of the following volatile compounds: limonene, 1,8‐cineole, trans‐caryophyllene, spathulenol, and viridiflorol.
Cytotoxic (9βH)‐Pimarane and (9βH)‐17‐Norpimarane Diterpenes from the Tuber of Icacina trichantha
Authors: Monday Onakpa Michael , Zhao Ming , Gödecke Tanja , Chen Wei‐Lun , Che Chun‐Tao , Santarsiero Bernard D. , Swanson Steven M. , Uzoma Asuzu Isaac
Published: December 2014

Three (9βH)‐pimaranes, 1, 2, and 3, and two (9βH)‐17‐norpimaranes, 4 and 5, belonging to a rare compound class in nature, were obtained from the tubers of Icacina trichantha for the first time. Compound 1 is a new natural product, and 2–5 have been previously reported. The structures were elucidated based on NMR and MS data, and optical rotation values. The absolute configurations of (9βH)‐pimaranes were unambiguously established based on X‐ray crystallographic analysis. Full NMR signal assignments for the known compounds 2, 4, and 5, which were not available in previous publications, are also reported. All five isolates displayed cytotoxic activities on MDA‐MB‐435 cells (IC50 0.66–6.44 μM), while 2, 3, and 4 also exhibited cytotoxicities on HT‐29 cells (IC50 3.00–4.94 μM).
Mathematical and Artificial Neural Network Models to Predict the Membrane Fouling Behavior of an Intermittently‐Aerated Membrane Bioreactor Under Sub‐Critical Flux
Authors: Wang Zuowei , Wu Xiaohui
Published: December 2014

This study established a mathematical model and an artificial neural network (ANN) model based on the theory of critical flux filtration to predict the membrane module fouling performance of an intermittently aerated membrane bioreactor (IAMBR) while simultaneously conducting a prediction performance evaluation of the two models. The key parameters of the mathematical model, such as constant rate, fouling propensity, and others, were determined by a short‐term step‐flux experiment and a long‐term filtration experiment. The transmembrane pressure jump point (tsus) of the long‐term filtration under sub‐critical flux was calculated using the key parameters. An ANN model was also established based on the critical flux theory and the initial weights of the network model were optimized using a genetic algorithm, which accelerated the convergence of the model. The evaluation results indicated that the ANN model had a better simulation performance under the intermittently aerated mode, but the mathematical model predicted tsus more steadily. Therefore, a more in‐depth investigation is required to obtain an elaborate evaluation of those two models.
π‐Expanded α,β‐Unsaturated Ketones: Synthesis, Optical Properties, and Two‐Photon‐Induced Polymerization
Authors: Nazir Rashid , Bourquard Florent , Balčiūnas Evaldas , Smoleń Sabina , Gray David , Tkachenko Nikolai V. , Farsari Maria , Gryko Daniel T.
Published: December 2014

A library of π‐expanded α,β‐unsaturated ketones was designed and synthesized. They were prepared by a combination of Wittig reaction, Sonogashira reaction, and aldol condensation. It was further demonstrated that the double aldol condensation can be performed effectively for highly polarized styrene‐ and diphenylacetylene‐derived aldehydes. The strategic placement of two dialkylamino groups at the periphery of D‐π‐A‐π‐D molecules resulted in dyes with excellent solubility. These ketones absorb light in the region 400–550 nm. Many of them display strong solvatochromism so that the emission ranges from 530–580 nm in toluene to the near‐IR region in benzonitrile. Ketones based on cyclobutanone as central moieties display very high fluorescence quantum yields in nonpolar solvents, which decrease drastically in polar media. Photophysical studies of these new functional dyes revealed that they possess an enhanced two‐photon absorption cross section when compared with simpler ketone derivatives. Due to strong polarization of the resulting dyes, values of two‐photon absorption cross sections on the level of 200–300 GM at 800 nm were achieved, and thanks to that as well as the presence of the keto group, these new two‐photon initiators display excellent performance so that the operating region is 5–75 mW in some cases.
Influence of Excited‐State Absorption on Time‐Resolved Luminescence: General Formalism and Application to the Phosphorescence of Polycyclic Aromatic Hydrocarbons
Authors: Palmeira Tiago , Fedorov Alexander , Berberan‐Santos Mário N.
Published: December 2014

The luminescence decay of a species in an absorbing medium whose optical thickness changes with time, as occurs with triplet–triplet absorption following excitation cut‐off, is studied theoretically and experimentally. A general luminescence decay function based on a distribution of optical thicknesses is presented. A simple decay function previously used empirically is shown to result from an exponential distribution of optical thicknesses. The general approach introduced allows the adequate description of the phosphorescence decays of two polycyclic aromatic hydrocarbons, coronene and triphenylene (normal and perdeuterated forms for both molecules), in polymer films in the presence of excited‐state absorption.
On the Chemistry of Ethanol on Basic Oxides: Revising Mechanisms and Intermediates in the Lebedev and Guerbet reactions
Authors: Chieregato Alessandro , Velasquez Ochoa Juliana , Bandinelli Claudia , Fornasari Giuseppe , Cavani Fabrizio , Mella Massimo
Published: December 2014

A common way to convert ethanol into chemicals is by upgrading it over oxide catalysts with basic features; this method makes it possible to obtain important chemicals such as 1‐butanol (Guerbet reaction) and 1,3‐butadiene (Lebedev reaction). Despite their long history in chemistry, the details of the close inter‐relationship of these reactions have yet to be discussed properly. Our present study focuses on reactivity tests, in situ diffuse reflectance infrared Fourier transform spectroscopy, MS analysis, and theoretical modeling. We used MgO as a reference catalyst with pure basic features to explore ethanol conversion from its very early stages. Based on the obtained results, we formulate a new mechanistic theory able to explain not only our results but also most of the scientific literature on Lebedev and Guerbet chemistry. This provides a rational description of the intermediates shared by the two reaction pathways as well as an innovative perspective on the catalyst requirements to direct the reaction pathway toward 1‐butanol or butadiene.
Catalytic Hydrodechlorination of Benzyl Chloride Promoted by Rh–N‐heterocyclic Carbene Catalysts
Authors: Lázaro Guillermo , Polo Víctor , Fernández‐Alvarez Francisco J. , García‐Orduña Pilar , Lahoz Fernando J. , Iglesias Manuel , Pérez‐Torrente Jesús J. , Oro Luis A.
Published: December 2014

The rhodium(I) complexes [Rh(Cl)(COD)(R‐NHC‐(CH2)3Si(OiPr)3)] [COD=cyclooctadiene; R=2,6‐diisopropylphenyl (1 a); n‐butyl (1 b)] are effective catalyst precursors for the homogeneous hydrodechlorination of benzyl chloride using HSiEt3 as hydrogen source. This reaction is selective to the formation of toluene. However, in presence of a stoichiometric amount of potassium tert‐butoxide (KtBuO) the formation of mixtures containing toluene together with 17–19 mol % of the CC homocoupling product, namely PhCH2CH2Ph, is observed. A mechanism proposal based on experimental insights and theoretical calculations at the DFT level that allows explanation of the experimental findings is included. Moreover, the heterogeneous catalytic system based on catalyst 1 a supported on MCM‐41 has been demonstrated to be effective for the solvent‐free hydrodechlorination of benzyl chloride using HSiEt3 and HSiMe(OSiMe3)2.
Influence of Ligand Substitution Pattern on Structure in Cobalt(II) Complexes of Bulky N,N′‐Diarylformamidinate N‐Oxides
Authors: Cibian Mihaela , Langis‐Barsetti Sophie , De Mendonça Fernanda Gomes , Touaibia Sammy , Derossi Sofia , Spasyuk Denis , Hanan Garry S.
Published: December 2014

Cobalt(II) complexes of bulky N,N′‐diarylformamidinate N‐oxide ligands were synthesized and structurally characterized. The cobalt(II) bis(chelates) are square‐planar (low spin) in the solid state, according to XRD and magnetic measurements (μeff = 1.8 to 2.1 μB), but show square‐planar (low spin) to tetrahedral (high spin: μeff = 3.5 to 4.7 μB) isomerization in solutions of noncoordinating solvents, as demonstrated by different spectroscopic techniques. The isomerization equilibrium is highly sensitive to the substitution pattern on the ligand due to a combination of steric and electronic influences.
Engineering evaluation of direct methane to methanol conversion
Authors: de Klerk Arno
Published: December 2014

Investigations into direct methane to methanol conversion are justified based on the avoidance of synthesis gas generation, which accounts for around 60% of the capital cost of synthesis gas to methanol conversion. A significant body of information already exists on the process chemistry, but little has been reported on the engineering of such a process. An engineering evaluation of the process was performed and the potential of this process as a platform technology for small‐scale gas‐to‐liquids (GTL) applications was evaluated. It was found that direct methane to methanol conversion had 35% carbon efficiency and 28% thermal efficiency, which were about half of the process efficiencies of indirect methanol synthesis using synthesis gas. The poor process efficiency was mainly a consequence of the irreversible loss of carbon to COx during conversion. The direct methane to methanol process also required an air separation unit, which eroded the stated benefit of avoiding a synthesis gas generation step in the process. The utility footprint was typical of GTL processes, with large gas compression duties and cooling duties. Overall, the engineering evaluation indicated there was no benefit to employ direct methane to methanol conversion instead of indirect methanol synthesis (the industry standard), and there was no specific benefit of direct methane to methanol conversion, irrespective of scale, for GTL applications.
Subcortical intelligence: Caudate volume predicts IQ in healthy adults
Authors: Grazioplene Rachael G. , G. Ryman Sephira , Gray Jeremy R. , Rustichini Aldo , Jung Rex E. , DeYoung Colin G.
Published: December 2014

This study examined the association between size of the caudate nuclei and intelligence. Based on the central role of the caudate in learning, as well as neuroimaging studies linking greater caudate volume to better attentional function, verbal ability, and dopamine receptor availability, we hypothesized the existence of a positive association between intelligence and caudate volume in three large independent samples of healthy adults (total N = 517). Regression of IQ onto bilateral caudate volume controlling for age, sex, and total brain volume indicated a significant positive correlation between caudate volume and intelligence, with a comparable magnitude of effect across each of the three samples. No other subcortical structures were independently associated with IQ, suggesting a specific biological link between caudate morphology and intelligence. Hum Brain Mapp 36:1407–1416, 2015. © 2014 Wiley Periodicals, Inc.
Two New Lycodine Alkaloids from Lycopodiastrum casuarinoides
Authors: Wu Ji‐Chun , Wang Qiu‐Yue , Tao Ying‐Jiang , Jiang Jin‐He , Liu Ying , Huang Guo‐Li , Zhan Rui , Liu Bo , Chen Ye‐Gao
Published: December 2014

Two new lycodine alkaloids, 11β‐methoxyhuperzine B (1) and 16‐oxohuperzinine (2), together with seven known ones, huperzinine N‐oxide, huperzine D, casuarinine A, huperzine B, casuarinine B, huperzinine, and N‐methyllycodine, were isolated from whole plants of Lycopodiastrum casuarinoides. Their structures were elucidated by spectroscopic methods, including NMR and MS experiments.
On the Use of a Supramolecular Coarse‐Grained Model for the Solvent in Simulations of the Folding Equilibrium of an Octa‐β‐peptide in MeOH and H2O
Authors: Huang Wei , Hansen Niels , van Gunsteren Wilfred F.
Published: December 2014

Molecular dynamics (MD) simulation can give a detailed picture of conformational equilibria of biomolecules, but it is only reliable if the force field used in the simulation is accurate, and the sampling of the conformational space accessible to the biomolecule shows many (un)folding transitions to allow for precise averages of observable quantities. Here, the use of coarse‐grained (CG) solvent MeOH and H2O models to speed up the sampling of the conformational equilibria of an octa‐β‐peptide is investigated. This peptide is thought to predominantly adopt a 314‐helical fold when solvated in MeOH, and a hairpin fold when solvated in H2O on the basis of the NMR data. Various factors such as the chirality of a residue, a force‐field modification for the solute, coarse‐graining of the solvent model, and an extension of the nonbonded interaction cut‐off radius are shown to influence the simulated conformational equilibria and the agreement with the experimental NMR data for the octa‐β‐peptide.
Synthesis of 2‐Substituted 3‐Alkylidene‐2,3‐dihydro‐1H‐isoindol‐1‐imines through Cyclization of [1‐(2‐Cyanophenyl)alkylidene]aminide Intermediates Generated from the Reaction of 2‐(1‐Azidoalkyl)benzonitriles with NaH
Authors: Kobayashi Kazuhiro , Ezaki Kosuke , Nozawa Ippei
Published: December 2014

A convenient sequence for the preparation of 3‐alkylidene‐2,3‐dihydro‐1H‐isoindol‐1‐imine derivatives 6 has been developed. Thus, 2‐(1‐azidoalkyl)benzonitriles 2, readily accessible from 2‐alkylbenzonitriles, are allowed to react with NaH in DMF at 0° to room temperature to generate [1‐(2‐cyanophenyl)alkylidene]aminide intermediates 3, of which cyclization and the subsequent rearrangement, followed by alkylation with alkyl halides, affords 2‐substituted 1‐alkylidene‐2,3‐dihydro‐1H‐isoindol‐2‐imines 6 in generally moderate yields.
Increased corrosion resistance of the AZ80 magnesium alloy by rapid solidification
Authors: Aghion E. , Jan L. , Meshi L. , Goldman J.
Published: December 2014

Magnesium (Mg) and Mg‐alloys are being considered as implantable biometals. Despite their excellent biocompatibility and good mechanical properties, their rapid corrosion is a major impediment precluding their widespread acceptance as implantable biomaterials. Here, we investigate the potential for rapid solidification to increase the corrosion resistance of Mg alloys. To this end, the effect of rapid solidification on the environmental and stress corrosion behavior of the AZ80 Mg alloy vs. its conventionally cast counterpart was evaluated in simulated physiological electrolytes. The microstructural characteristics were examined by optical microscopy, SEM, TEM, and X‐ray diffraction analysis. The corrosion behavior was evaluated by immersion, salt spraying, and potentiodynamic polarization. Stress corrosion resistance was assessed by Slow Strain Rate Testing. The results indicate that the corrosion resistance of rapidly solidified ribbons is significantly improved relative to the conventional cast alloy due to the increased Al content dissolved in the α‐Mg matrix and the correspondingly reduced presence of the β‐phase (Mg17Al12). Unfortunately, extrusion consolidated solidified ribbons exhibited a substantial reduction in the environmental performance and stress corrosion resistance. This was mainly attributed to the detrimental effect of the extrusion process, which enriched the iron impurities and increased the internal stresses by imposing a higher dislocation density. In terms of immersion tests, the average corrosion rate of the rapidly solidified ribbons was <0.4 mm/year compared with ∼2 mm/year for the conventionally cast alloy and 26 mm/year for the rapidly solidified extruded ribbons. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1541–1548, 2015.
Stem Cells for Reutilization in Bone Regeneration
Authors: Im Gun‐Il
Published: December 2014

Bone is one of the most transplanted tissues. While most bone defects heal spontaneously, critical size defects caused by major trauma/malignant tumor and osteonecrosis of femoral head in young adults pose a great challenge in treatment. While the golden standard in treating bone defects is autologous bone grafting, available bone for grafting is quite limited in an individual. To solve the dilemma, stem cell therapy has been tried as a new modality of treatment in lesions not amenable to autologous bone grafting. While successful results were reported from individual studies, the stem cell therapy is still not an established treatment modality for bone regeneration and needs further assessment. Our focus herein is to introduce stem cell sources that have been investigated so far and review the current status of stem cell reutilization for bone regeneration as well as suggesting future perspectives. J. Cell. Biochem. 116: 487–493, 2015. © 2014 Wiley Periodicals, Inc.
Cardiovascular Complications of Calcium Supplements
Authors: Reid Ian R. , Bristow Sarah M. , Bolland Mark J.
Published: December 2014

There is longstanding concern that calcium supplements might increase cardiovascular risk in patients with renal impairment. The Auckland Calcium Study suggested that the same problem occurs in older people taking these supplements for prevention of osteoporosis. Our subsequent meta‐analyses, (which followed protocols finalized before the data was available) confirmed that calcium supplements, with or without vitamin D, adversely affected risk of myocardial infarction and, possibly, stroke. Several groups have re‐visited these data, consistently finding an adverse effect of calcium on myocardial infarction, not always statistically significant because some meta‐analyses have been under‐powered. Whether or not an adverse effect of calcium plus vitamin D on myocardial infarction is found depends on whether two specific groups of subjects are included—those in the Women's Health Initiative who were already taking calcium at the time of randomization, and subjects from an open, cluster‐randomized study in which baseline cardiovascular risk was different between groups. Vitamin D alone does not affect vascular risk, so it is unlikely that differences between calcium alone and calcium plus vitamin D are real, and they are more likely to result from the inclusion of studies at high risk of bias. The mechanisms of the adverse cardiovascular effects are uncertain but may be mediated by the increase in serum calcium following supplement ingestion, and the effects of this on vascular function and coagulation. Available evidence suggests the risks of calcium supplements outweigh any small benefits on fracture incidence, so the case for their use is weak. J. Cell. Biochem. 116: 494–501, 2015. © 2014 Wiley Periodicals, Inc.
Permeability of canine vocal fold lamina propria
Authors: Meyer Jacob P. , Kvit Anton A. , Devine Erin E. , Jiang Jack
Published: December 2014

Objectives/Hypothesis

Determine the permeability of excised canine vocal fold lamina propria.

Study Design

Basic science.

Methods

Vocal folds were excised from canine larynges and mounted within a device to measure the flow of 0.9% saline through the tissue over time. The resultant fluid volume displaced over time was then used in a variation of Darcy's law to calculate the permeability of the tissue. Permeability was found through each anatomical plane of the vocal fold, with five samples per plane. Permeability was also found for lamina propria stretched to 10%, 20%, and 30% of its initial length to determine the effects of tensile strain on permeability, with five samples per level of strain.

Results

Permeability was found to be 1.40 × 10−13 m3s/kg through the sagittal plane, 1.00 × 10−13 m3s/kg through the coronal plane, and 4.02 × 10−13 m3s/kg through the axial plane. It was significantly greater through the axial plane than both the sagittal (P = .025) and coronal (P = .009) planes. Permeability under strain through the sagittal plane was found to be 1.94 × 10−13 m3s/kg under 10% strain, 3.35 × 10−13 m3s/kg under 20% strain, and 4.80 × 10−13 m3s/kg under 30% strain. The permeability significantly increased after 20% strain (P < .05).

Conclusions

Permeability in canine vocal fold lamina propria was found to be increased along the anterior‐posterior axis, following the length of the vocal folds. This may influence fluid distribution within the lamina propria during and after vibration. Similarly, permeability increased after 20% strain was imposed on the lamina propria, and may influence vocal fold dynamics during certain phonation tasks.

Level of Evidence

NA Laryngoscope, 125:941–945, 2015
Formula Pricing and Profit Sharing in Inter‐Firm Contracts
Authors: Blair Roger D. , Lafontaine Francine
Published: December 2014

Ronald Coase viewed transaction cost minimization as a central goal of contracting and organizational decisions. We discuss how a solution to the traditional successive monopoly problem that has not been discussed in the literature can economize on such costs. Specifically, we show that when we allow for profit sharing between upstream and downstream firms, a simple formula pricing contract can be used to generate the vertically integrated level of profits. This simple contract, empirically, would take the form of the standard linear wholesale price contracts that are ubiquitous in vertical contexts, even those where we might expect successive monopoly to be an issue. We discuss the advantages of the proposed contract from a transaction cost perspective. We also discuss some of its limitations, in particular the likelihood of misrepresentation of costs, and ways in which such misrepresentation might be addressed in the contract. Copyright © 2014 John Wiley & Sons, Ltd.
Coase and International Business: The Origin and Development of Internalisation Theory
Authors: Casson Mark
Published: December 2014

The internalisation theory of the multinational enterprise (MNE) is a significant intellectual legacy of Ronald Coase. US direct investment in Europe became highly political in the 1960s, and neoclassical trade theory had no explanation. A theory of the multiplant enterprise was required, and internalisation theory filled this gap. Using Coasian economics to explain the ownership of production plants and the geography of trade to explain their location, internalisation theory offered a comprehensive account of MNEs and their role in the international economy. This paper outlines the development of the theory, explains the Coasian contribution, and examines in detail the early work of Hymer, McManus and Buckley and Casson. It then reviews the current state of internalisation theory and suggests some future developments. Copyright © 2014 John Wiley & Sons, Ltd.
Aquatic Exercises were Associated with an Acceptable State of Symptoms in Patients with Inflammatory Rheumatic Diseases: Results from a Study with Interrupted Time‐Series Design
Authors: Christie Anne , Hagen Kåre Birger , Mowinckel Petter , Dagfinrud Hanne
Published: December 2014

Aim of study

The aim of this study was two‐fold: to compare symptoms and daily activity in patients with inflammatory rheumatic diseases across periods with and without aquatic exercises, and to examine whether the patients reached an acceptable state of symptoms during the periods with aquatic exercises.

Methods

Thirty‐six patients reported pain, fatigue, stiffness and ability to carry out daily activities across periods with and without aquatic exercises. The study has an interrupted time‐series design and variables were collected with text messages on mobile phones twice a week over a period of 35 weeks.

Results

There was a significant reduction in pain, fatigue, stiffness and enhanced level of daily activity (p > 0.05) during periods of aquatic exercises compared to periods without. Further, a significantly higher proportion of patients reached an acceptable state for both pain and fatigue during periods with aquatic exercises.

Conclusions

Living with an inflammatory rheumatic disease is a lifelong challenge. Pain and fatigue are considered major obstacles for daily functioning and adequate self‐management strategies are requested. Based on the high proportion of patients reporting to be in an acceptable state of both pain and fatigue during periods with aquatic exercises, the intervention should be regarded as an important self‐management tool rather than a treatment option assuming long‐lasting effects. Copyright © 2014 John Wiley & Sons, Ltd.