bluuebunny/crossref_metadata_2025 huggingface dataset:
Nonlinear fluctuation analysis for a set of 41 magnetic clouds measured by the Advanced Composition Explorer (ACE) spacecraft
Authors: Ojeda González A. , Gonzalez W. D. , Mendes O. , Domingues M. O. , Rosa R. R.
Published: October 2014

Abstract. The statistical distribution of values in the signal and the autocorrelations (interpreted as the memory or persistence) between values are attributes of a time series. The autocorrelation function values are positive in a time series with persistence, while they are negative in a time series with anti-persistence. The persistence of values with respect to each other can be strong, weak, or nonexistent. A strong correlation implies a "memory" of previous values in the time series. The long-range persistence in time series could be studied using semivariograms, rescaled range, detrended fluctuation analysis and Fourier spectral analysis, respectively. In this work, persistence analysis is to study interplanetary magnetic field (IMF) time series. We use data from the IMF components with a time resolution of 16 s. Time intervals corresponding to distinct processes around 41 magnetic clouds (MCs) in the period between March 1998 and December 2003 were selected. In this exploratory study, the purpose of this selection is to deal with the cases presenting the three periods: plasma sheath, MC, and post-MC. We calculated one exponent of persistence (e.g., α, β, Hu, Ha) over the previous three time intervals. The persistence exponent values increased inside cloud regions, and it was possible to select the following threshold values: α(j) = 1.392, Ha(j) = 0.327, and Hu(j) = 0.875. These values are useful as another test to evaluate the quality of the identification. If the cloud is well structured, then the persistence exponent values exceed thresholds. In 80.5% of the cases studied, these tools were able to separate the region of the cloud from neighboring regions. The Hausdorff exponent (Ha) provides the best results.
Kristen Rundle: Legal Subjects and Juridical Persons: Developing Public Legal Theory through Fuller and Arendt
Authors: Goodwin Morag , Besters Michiel , Rijgersberg Rudolf
Published: October 2014

Kristen Rundle: Legal Subjects and Juridical Persons: Developing Public Legal Theory through Fuller and Arendt

Introduction to this special issue of NJLP.
Reply
Authors: Rundle Kristen
Published: October 2014

Reply

Author’s reply to four commentaries on ‘Legal Subjects and Juridical Persons: Developing Public Legal Theory through Fuller and Arendt.’
The Influence of Free Hemoglobin and Bilirubin on Heparin Monitoring by Activated Partial Thromboplastin Time and Anti-Xa Assay
Authors: Kostousov Vadim , Nguyen Kim , Hundalani Shilpa G. , Teruya Jun
Published: October 2014

Context

Elevated free hemoglobin (Hb) and bilirubinemia complicate extracorporeal membrane oxygenation and could affect unfractionated heparin (UH) therapy monitoring by anti-Xa assay and activated partial thromboplastin time (aPTT).

Objectives

To compare in vitro response of anti-Xa and aPTT assays to UH in samples with artificial hyperbilirubinemia and hyperhemoglobinemia and to estimate if this interference is also observed in vivo in pediatric extracorporeal membrane oxygenation.

Design

Measurement of aPTT and anti-Xa activity in plasma spiked with UH and increased concentration of free Hb and/or conjugated bilirubin. All samples with anti-Xa activity, antithrombin, free Hb, and bilirubin determination and infused dose of UH from inpatients on extracorporeal membrane oxygenation were extracted from the clinical patient database and analyzed.

Results

Each increment of free Hb by 100 mg/dL significantly shortened aPTT, whereas an increment of bilirubin by 6 mg/dL caused significant prolongation of aPTT and stepwise increase of free Hb and/or bilirubin in plasma decreased anti-Xa activity by 0.03 to 0.05 IU/mL. Extracorporeal membrane oxygenation samples with free Hb 50 mg/dL or greater had significantly lower anti-Xa activity compared with normal ones: 0.33 (0.25–0.42) versus 0.4 (0.31–0.48) IU/mL (P = .01), despite the identical UH infusion and similar antithrombin activity. Moderate increase of free Hb by 59 mg/dL was associated with absolute decrease of anti-Xa activity by 0.07 IU/mL.

Conclusions

Activated partial thromboplastin time and anti-Xa assay are affected by elevated level of free Hb and/or bilirubin in the presence of UH, and lower anti-Xa activity is noted in extracorporeal membrane oxygenation patients with elevated free Hb. Severe hemolysis and/or hyperbilirubinemia could compromise UH monitoring based on these assays.
Phyllodes Tumor of Vulva: A Brief Diagnostic Review
Authors: Lee Solomon , Nodit Laurentia
Published: October 2014

Phyllodes tumors of the vulva are rare proliferations that share morphologic similarities with breast neoplasms. Their histogenetic origin is elusive and may be associated with specialized mammary-like glands of the vulva. Because of their rarity, the clinical and pathologic features, classification, and therapy are not well defined, and their biologic behavior is difficult to predict by histology alone. Immunohistochemical expression of estrogen and progesterone receptors and breast markers provide further support for a common origin. Surgical resection is the current mainstay of therapy and is definitive in most cases.
Quantitative Multiplexed Detection of Common Pulmonary Fungal Pathogens by Labeled Primer Polymerase Chain Reaction
Authors: Gu Zhengming , Buelow Daelynn R. , Petraitiene Ruta , Petraitis Vidmantas , Walsh Thomas J. , Hayden Randall T.
Published: October 2014

Context

Invasive fungal infections are an important cause of morbidity and mortality among immunocompromised patients.

Objective

To design and evaluate a multiplexed assay aimed at quantitative detection and differentiation of the 5 molds that are most commonly responsible for pulmonary infections.

Design

Using labeled primer polymerase chain reaction chemistry, an assay was designed to target the 5.8S and 28S ribosomal RNA genes of Aspergillus spp, Fusarium spp, Scedosporium spp, and members of the order Mucorales (Rhizopus oryzae, Rhizopus microsporus, Cunninghamella bertholletiae, Mucor circinelloides, Lichtheimia corymbifera, and Rhizomucor pusillus). This assay was split into 2 multiplexed reactions and was evaluated using both samples seeded with purified nucleic acid from 42 well-characterized clinical fungal isolates and 105 archived samples (47 blood [45%], 42 bronchoalveolar lavage fluid [40%], and 16 tissue [15%]) collected from rabbit models of invasive pulmonary fungal infections.

Results

Assay detection sensitivity was less than 25 copies of the target sequence per reaction for Aspergillus spp, 5 copies for Fusarium spp and Scedosporium spp, and 10 copies for the Mucorales. The assay showed quantitative linearity from 5 × 101 to 5 × 105 copies of target sequence per reaction. Sensitivities and specificities for bronchoalveolar lavage fluid, tissue, and blood samples were 0.86 and 0.99, 0.60 and 1.00, and 0.46 and 1.00, respectively.

Conclusions

Labeled primer polymerase chain reaction permits rapid, quantitative detection and differentiation of common agents of invasive fungal infection. The assay described herein shows promise for clinical implementation that may have a significant effect on the rapid diagnosis and treatment of patients' severe infections caused by these pulmonary fungal pathogens.
Estrogen Receptor Expression Is High but Is of Lower Intensity in Tubular Carcinoma Than in Well-Differentiated Invasive Ductal Carcinoma
Authors: Jorns Julie M. , Thomas Dafydd G. , Healy Patrick N. , Daignault Stephanie , Vickery Tammi L. , Snider Jacqueline E. , Mardis Elaine R. , Davies Sherri R. , Ellis Matthew J. , Visscher Daniel W.
Published: October 2014

Context

Tubular carcinoma (TC) is a rare, luminal A subtype of breast carcinoma with excellent prognosis, for which adjuvant chemotherapy is usually contraindicated.

Objective

To examine the levels of estrogen receptor (ER) and progesterone receptor expression in cases of TC and well-differentiated invasive ductal carcinoma as compared to normal breast glands and to determine if any significant differences could be detected via molecular testing.

Design

We examined ER and progesterone receptor via immunohistochemistry in tubular (N = 27), mixed ductal/tubular (N = 16), and well-differentiated ductal (N = 27) carcinomas with comparison to surrounding normal breast tissue. We additionally performed molecular subtyping of 10 TCs and 10 ductal carcinomas via the PAM50 assay.

Results

Although ER expression was high for all groups, TC had statistically significantly lower ER staining percentage (ER%) (P = .003) and difference in ER expression between tumor and accompanying normal tissue (P = .02) than well-differentiated ductal carcinomas, with mixed ductal/tubular carcinomas falling between these 2 groups. Mean ER% was 79%, 87%, and 94%, and mean tumor-normal ER% differences were 13.6%, 25.9%, and 32.6% in tubular, mixed, and ductal carcinomas, respectively. Most tumors that had molecular subtyping were luminal A (9 of 10 tubular and 8 of 10 ductal), and no significant differences in specific gene expression between the 2 groups were identified.

Conclusions

Tubular carcinoma exhibited decreased intensity in ER expression, closer to that of normal breast parenchyma, likely as a consequence of a high degree of differentiation. Lower ER% expression by TC may represent a potential pitfall when performing commercially available breast carcinoma prognostic assays that rely heavily on ER-related gene expression.
Hiérarchiser les besoins de diagnostic en mathématique en FP à l’aide d’un modèle de Rasch
Authors: Loye Nathalie , da Costa Carla Barroso
Published: October 2014

Selon le MELS (2008, 2010), 30 % des élèves inscrits dans un programme deformation professionnelle (FP) au Québec n’obtiennent pas leur diplôme. Cettesituation est confirmée par les directeurs et les enseignants de la formation professionnelle,particulièrement lorsque le programme inclut des contenus ma thé -matiques comme, par exemple, en construction. La présente étude a donc pourobjectif de mieux définir la nature des difficultés en mathématique des élèves dela formation professionnelle. En utilisant la modélisation de rasch, l’étude hiérarchiseles besoins de diagnostic en mathématique tels que perçus par les enseignantset directions des établissements scolaires qui ont rempli un questionnaire.Les résultats mettent en évidence les difficultés des élèves dans plusieursdomaines de la mathématique ainsi que les besoins de diagnostic, notamment ence qui a trait au raisonnement logique, aux techniques de calcul, aux démarchesnécessitant plusieurs étapes et à la compréhension de l’énoncé des problèmes.
Estimation des paramètres d’item et de sujet à partir du modèle de Rasch
Authors: Béland Sébastien , Magis David , Raîche Gilles
Published: October 2014

La Théorie de la réponse aux items (TRI) est une classe de modèles de mesure très utilisée en éducation. À ce jour, de nombreux logiciels, tel BILOG-MG, sont disponibles afin de procéder à l’estimation des paramètres d’item et de sujet. Parmi ces logiciels, il ne faut pas négliger ICL et R qui sont gratuits et qui peuvent permettre de produire des analyses diversifiées. Cette étude a pour objectif de comparer la qualité d’estimation des paramètres selon une des modélisations issues de la TRI : le modèle de Rasch. Pour ce faire, nous comparons les estimateurs du paramètre de difficulté et de sujet selon trois logiciels : BILOG-MG, ICL et la librairie ltm, disponible sous le logiciel R. Nous procédons à une analyse par simulation informatique et, dans un second temps, nous analysons un test de classement en anglais, langue seconde. Les résultats démontrent que les logiciels étudiés permettent d’obtenir des estimateurs des paramètres similaires, la différence principale entre ces logiciels étant leur temps d’exécution des procédures d’estimation.
Comment de futurs enseignants évaluent la maîtrise de compétences
Authors: Beckers Jacqueline , François Nathalie
Published: October 2014

L’article analyse le savoir-évaluer de futurs enseignants (FE dans la suite du texte) en sciences humaines dans l’enseignement secondaire supérieur. Le savoirévaluer des FE n’est pas directement observé dans la gestion de pratiques de classe. Il est documenté au travers des outils qu’ils ont construits pour évaluer le degré de maîtrise de compétences de type professionnel chez leurs élèves qui se préparent à un métier de «service aux personnes» et des traces de l’usage de ces outils. Les difficultés les plus récurrentes de même que quelques démarches prometteuses sont relevées et analysées à la lumière du contexte de production de ces pratiques évaluatives. Les données soutiennent l’intérêt de travailler ces pratiques évaluatives en formation. Pour permettre au lecteur de comprendre les critères d’analyse retenus par les auteurs, les premiers chapitres de l’article préciseront, d’une part, le contexte général du développement des compétences en Communauté française de Belgique, ses fondements conceptuels et les exigences liées à leur évaluation, d’autre part, les choix didactiques portés par les formatrices pour travailler le «savoir évaluer» des FE.
Une nouvelle perspective et de nouveaux défis pour les enquêtes internationales
Authors: Martin Romain , Blais Jean-Guy
Published: October 2014

Le présent article analyse les changements qui ont été introduits dans les enquêtes comparatives internationales (plus spécifiquement celles de l’OCDE) par suite de l’introduction du testing assisté par ordinateur. On passera en revue les différents instruments de mesure administrés par ordinateur qui ont été utilisés dans les différents cycles de ces enquêtes et on discutera si elles ont réellement impliqué une valeur ajoutée, notamment par le fait de fournir des données sur des compétences qui sont inaccessibles à travers des instruments classiques sous format papier-crayon. On analysera également les relations spécifiques que les mesures assistées par ordinateur entretiennent avec des variables d’arrière-fond tel le genre. Finalement, l’article mettra en évidence les défis et les risques qui sont associés avec une introduction de plus en plus massive d’instruments de mesure assistés par ordinateur, notamment en ce qui concerne deux aspects majeurs: la nécessité de garder une continuité dans les compétences mesurées en vue de mettre en évidence des évolutions, et le manque de cadres théoriques adéquats pour la mise en oeuvre efficace des mesures assistées par ordinateur.
L’évaluation entre « technicité » et « théorisation » ?
Authors: Figari Gérard
Published: October 2014

Cet article cherche à montrer que les relations entre théorie et pratique en matière d’évaluation en général (et d’évaluation de programme, en particulier) constituent, en réalité, une aporie opposant et reliant, à la fois, le « système technicien », privé de sens (Ellul, 2012) et la recherche permanente d’une théorie, génératrice de sens. Pour étayer cette aporie, l’auteur s’appuie notamment, sur un certain nombre de travaux, dont ceux récents, rassemblés par Mottier Lopez et Figari (2012), dressant un bilan épistémologique des recherches sur l’évaluation en éducation. L’auteur rappelle tout d’abord, les critiques apportées aux « évaluations techniciennes » remises en question par des chercheurs parce qu’insuffisamment théorisées. L’auteur fait le point, ensuite, sur l’avancée de la « pensée théorique » qui s’élabore autour de l’évaluation, en questionnant les écrits d’auteurs qui, faute de proposer une « théorie générale », construisent des « théorisations ». C’est pourquoi, dans les écrits analysés, les éléments constitutifs d’une théorisation émergente de l’évaluation sont classés selon trois niveaux : 1- un carrefour de disciplines de sciences sociales et humaines s’attachant à expliquer, de leur point de vue, les phénomènes liés à l’évaluation : 2- une méthodologie de la mesure en pleine évolution dans le sens d’une plus grande intégration de cadres théoriques à son développement; 3- l’émergence d’une configuration de paradigmes de l’évaluation de plus en plus restreints et fédérateurs. À défaut de résoudre l’aporie initiale, il est possible de disposer d’un aperçu : celui d’une préthéorie de l’évaluation qui serait en train de naître.
Dialogues entre théories spontanées et théories académiques de l’évaluation
Authors: Tourmen Claire , Droyer Nathalie
Published: October 2014

Théories de l’évaluation, oui, mais de qui et sur quoi ? Les auteurs partiront de l’hypothèse de Shadish, Cook, et Leviton (1991) selon laquelle il existerait à la fois des « théories spontanées » de l’évaluation chez les praticiens, ainsi que des « théories académiques » de l’évaluation dans la littérature. Cet article vise à mieux décrire, comparer et discuter les différentes théories de l’évaluation sur la base de cette distinction. Seront examinées tout d’abord les « théories spontanées » de l’évaluation, à travers les traces décelées chez des évaluateurs rencontrés à l’occasion d’une thèse. Les théories (formes, contenus) des praticiens seront analysées pour tenter d’en comprendre l’origine et le développement. Par la suite, cet article montrera qu’il existe aussi des tentatives d’avancer sur des « théories académiques » de l’évaluation dans la littérature. La forme, le contenu et le mode de constitution de ces théories seront réexaminés. Enfin seront discutés les atouts et les limites de chaque forme de théorisation de l’évaluation pour aboutir sur les liens qui peuvent unir les théories spontanées et les théories académiques de l’évaluation, en tentant de comprendre comment elles circulent et peuvent potentiellement s’enrichir les unes et les autres.
Cushions, Copy-books and Computers: Ann Griffiths (1776-1805), her Hymns and Letters and their Transmission
Authors: James E. Wyn
Published: October 2014

Ann Griffiths (1776-1805), was until comparatively recently the only female poet
of any real prominence in the Welsh literary tradition. Born Ann Thomas, she
lived all her life in rural Montgomeryshire. Ann experienced evangelical
conversion aged 20 and joined the Calvinistic Methodists. She became noted for
the depth of her spirituality and began producing verses encapsulating her
insights and experiences. Of the seventy-three stanzas and eight letters
attributed to her, only one letter and one verse survive in her own hand, most
of the extant verses having been transmitted orally to her maidservant, Ruth
Evans. About two-thirds were published in early 1806, a few months after Anns
death following childbirth, and were immediately acknowledged as religious verse
of the highest order. They are characterized by a fervent subjectivism blended
with an objective wondering and a plethora of biblical allusions and typology.
The transmission of her hymns and letters has taken various forms - oral,
manuscript and print - and most recently electronically, on the ‘Ann Griffiths
Website’ in particular.
‘My Immense Mass of Manuscripts’: Fanny Burney as Archivist, Biographer and Autobiographer
Authors: Harman Claire
Published: October 2014

This article looks at Frances Burneys contribution to life writing through her
composition, preservation and curatorship of her own personal archive and
management of family papers. It charts Burneys chronic anxieties about the
possible interpretation of the record that she had created, and the tension
between self-expression and self-exposure which underlay her very revealing
difficulties with editing, archivism and publication.
Writing Pain: Sensibility and Suffering in the Late Letters of Anna Seward and Mary Robinson
Authors: Cross Ashley
Published: October 2014

‘Writing Pain’ argues that Anna Seward‘s Letters (1811) and Mary
Robinson‘s letters (1800) create alternative models of sensibility from the
suffering poet of Charlotte Smith‘s Elegiac Sonnets. Immensely
popular, Smith‘s sonnets made feminine suffering a source of poetic agency by
aestheticizing and privatizing it. However, despite their sincerity, her sonnets
effaced the physical, nervous body of sensibility on which Seward‘s and
Robinsons early poetic reputations had depended and for which they had been
mocked. The popularity of Smith‘s model made it an important model for women
poets, but, by the end of the eighteenth century, sensibility was also
associated with sickness and artifice. For Seward and Robinson, who wanted to
build their literary reputations but were living with disabled bodies, Smiths
example needed to be reimagined to account for the reciprocity of body and mind
as they struggled to write through pain.
Gender, Class and Epistolary Suffering: Narrating the Bodily Self in Women‘s Medical Consultation Letters to Samuel-Auguste Tissot
Authors: Boon Sonja
Published: October 2014

In this article I use conceptual frames drawn from autobiography studies and
feminist theory to examine the relationships between bodily experience and the
social construction of sex, gender and class as they play themselves out in a
selection of womens medical consultation letters written to the eminent Swiss
physician, Samuel-Auguste Tissot, during the second half of the eighteenth
century. My analysis of a selection of consultation letters - all of which are
situated and read in the context of a rich archival collection of some 1,200
letters - considers the role that bodily experience plays in the construction of
self and suggests that not only the experience, but also the textual
articulation of the body, were imagined both through and against accepted
understandings of sex, gender and class during this period.
Changes in the North Pacific wave climate since the mid‐1990s
Authors: Sasaki Wataru
Published: October 2014

Since the mid‐1990s, ocean wave reanalysis and in situ wave observations have revealed marked downward trends in wave height, exceeding −0.1 m per decade in the midlatitude North Pacific. The wave period in the tropical Pacific is also on a downward trend, exceeding −0.4 s per decade during this period. These changes in wave climate in the Pacific are attributable to recently strengthened trade winds and La Niña‐like conditions in the tropical Pacific. The downward trend in significant wave height in the midlatitude North Pacific is due to strengthening of the negative phase of the Pacific‐North American teleconnection. Numerical experimentations with a wave model also showed that the downward trend in the wave period in the eastern equatorial Pacific was induced not only by increased wind waves due to strengthened trade winds but also by weakened propagating swells from the midlatitude North Pacific.
Has the number of Indian summer monsoon depressions decreased over the last 30 years?
Authors: Cohen Naftali Y. , Boos William R.
Published: October 2014

Monsoon depressions are cyclonic atmospheric vortices with outer radii near 1000 km that form within the larger‐scale monsoon circulations of India and other regions. Recent studies have reported a downward trend in recent decades in the number of Indian summer monsoon depressions. In particular, the years 2002, 2010, and 2012 were noted for having the first summers, in over a century, in which no depressions formed. Here satellite and reanalysis data are used to document the existence of multiple storms in the summers of 2002, 2010, and 2012 that meet traditional criteria for classification as monsoon depressions. Furthermore, the number of extreme synoptic events occurring each summer over the Bay of Bengal is estimated from satellite scatterometers and exhibits no statistically significant trend over the last three decades. These results raise questions about the validity of previously claimed large trends in monsoon depression activity in the Indian summer monsoon.
Strain accumulation in the New Madrid and Wabash Valley seismic zones from 14 years of continuous GPS observation
Authors: Craig Timothy J. , Calais Eric
Published: October 2014

The mechanical behavior—and hence earthquake potential—of faults in continental interiors is an issue of critical importance for the resultant seismic hazard, but no consensus has yet been reached on this controversial topic. The debate has focused on the central and eastern United States, in particular, the New Madrid Seismic Zone, struck by four magnitude 7 or greater earthquakes in 1811–1812, and to a lesser extent the Wabash Valley Seismic Zone just to the north. A key aspect of this issue is the rate at which strain is currently accruing on those plate interior faults, a quantity that remains debated. Here we address this issue with an analysis of up to 14.6 years of continuous GPS data from a network of 200 sites in the central United States centered on the New Madrid and Wabash Valley seismic zones. We find that the high‐quality sites in these regions show motions that are consistently within the 95% confidence limit of zero deformation. These results place an upper bound on strain accrual on faults of 0.2 mm/yr and 0.6 mm/yr in the New Madrid and Wabash Valley Seismic Zones, respectively. For the New Madrid region, where a paleoseismic record is available for the past ∼5000 years, we argue that strain accrual—if any—does not permit the 500–900 year repeat time of paleo‐earthquakes observed in the Upper Mississippi Embayment. These results, together with increasing evidence for temporal clustering and spatial migration of earthquake sequences in continental interiors, indicate that either tectonic loading rates or fault properties vary with time in the New Madrid Seismic Zone and possibly plate wide.
Eruptions at Lone Star geyser, Yellowstone National Park, USA: 2. Constraints on subsurface dynamics
Authors: Vandemeulebrouck Jean , Sohn Robert A. , Rudolph Maxwell L. , Hurwitz Shaul , Manga Michael , Johnston Malcolm J. S. , Soule S. Adam , McPhee Darcy , Glen Jonathan M. G. , Karlstrom Leif , Murphy Fred
Published: October 2014

We use seismic, tilt, lidar, thermal, and gravity data from 32 consecutive eruption cycles of Lone Star geyser in Yellowstone National Park to identify key subsurface processes throughout the geyser's eruption cycle. Previously, we described measurements and analyses associated with the geyser's erupting jet dynamics. Here we show that seismicity is dominated by hydrothermal tremor (~5–40 Hz) attributed to the nucleation and/or collapse of vapor bubbles. Water discharge during eruption preplay triggers high‐amplitude tremor pulses from a back azimuth aligned with the geyser cone, but during the rest of the eruption cycle it is shifted to the east‐northeast. Moreover, ~4 min period ground surface displacements recur every 26 ± 8 min and are uncorrelated with the eruption cycle. Based on these observations, we conclude that (1) the dynamical behavior of the geyser is controlled by the thermo‐mechanical coupling between the geyser conduit and a laterally offset reservoir periodically filled with a highly compressible two‐phase mixture, (2) liquid and steam slugs periodically ascend into the shallow crust near the geyser system inducing detectable deformation, (3) eruptions occur when the pressure decrease associated with overflow from geyser conduit during preplay triggers an unstable feedback between vapor generation (cavitation) and mass discharge, and (4) flow choking at a constriction in the conduit arrests the runaway process and increases the saturated vapor pressure in the reservoir by a factor of ~10 during eruptions.
Electromagnetic activity before initial breakdown pulses of lightning
Authors: Marshall T. , Stolzenburg M. , Karunarathna N. , Karunarathne S.
Published: October 2014

Lightning flash initiation is studied using electric field change (E‐change) measurements made in Florida. An initial E‐change (IEC) was found immediately before the first initial breakdown (IB) pulse in both cloud‐to‐ground (CG) and intracloud (IC) flashes if the E‐change sensor was within 80% of the reversal distance of the IEC. For 18 CG flashes, the IECs had an average point dipole moment of 23 C m and an average duration of 0.18 ms; these parameters for 18 IC flashes were −170 C m and 1.53 ms. The IECs of CG flashes began with a change in the slope of the E‐change (with respect to time) from zero slope to a positive slope, consistent with downward motion of negative charge and/or upward motion of positive charge. For IECs of IC flashes, the beginning slope change was from zero to negative slope, consistent with upward motion of negative charge and/or downward motion of positive charge. During an IEC, the E‐change monotonically increased for CG flashes and monotonically decreased for IC flashes. In 14 of 36 cases, the IEC beginning was coincident with a discrete, impulsive source of VHF radiation; another 13 cases had at least one VHF source during the IEC or the first IB pulse. Before the IECs, there were no preliminary variations detected in the 36 flashes. It is hypothesized that lightning initiation begins with an ionizing event that causes the IEC and that the IEC enhances the ambient electric field to produce the first IB pulse.
Distal 22q11.2 microduplication combined with typical 22q11.2 proximal deletion: A case report
Authors: Molck Miriam Coelho , Vieira Társis Paiva , Simioni Milena , Sgardioli Ilária Cristina , Santos Ana Paula dos , Xavier Ana Carolina , Gil‐da‐Silva‐Lopes Vera Lúcia
Published: October 2014

The 22q11 chromosomal region contains low copy repeats (LCRs) sequences that mediate non‐allelic homologous recombination, which predisposes to copy number variations (CNVs) at this locus. Hemizygous deletions of the proximal 22q11.2 region result in the 22q11.2 deletion syndrome (22q11.2 DS). In addition, 22q11.2 duplications involving the distal LCR22s have been reported. This article describes a patient presenting a 2.5‐Mb de novo deletion at proximal 22q11.21 region (between LCRs A‐D), combined with a 1.3‐Mb maternally inherited duplication at distal 22q11.23 region (between LCRs F‐H). The presence of concomitant chromosomal imbalances found in this patient has not been reported previously. Clinical and molecular data were compared with literature, in order to contribute to genotype‐phenotype correlation. These findings exemplify the complexity and genetic heterogeneity observed in 22q11.2 deletion syndrome and highlights the difficulty to make genetic counseling and predict phenotypic consequences in these situations. © 2014 Wiley Periodicals, Inc.
Enhanced π‐Backdonation from Gold(I): Isolation of Original Carbonyl and Carbene Complexes
Authors: Joost Maximilian , Estévez Laura , Mallet‐Ladeira Sonia , Miqueu Karinne , Amgoune Abderrahmane , Bourissou Didier
Published: October 2014

The specific electronic properties of bent o‐carborane diphosphine gold(I) fragments were exploited to obtain the first classical carbonyl complex of gold [(DPCb)AuCO]+ (ν(CO)=2143 cm−1) and the diphenylcarbene complex [(DPCb)Au(CPh2)]+, which is stabilized by the gold fragment rather than the carbene substituents. These two complexes were characterized by spectroscopic and crystallographic means. The [(DPCb)Au]+ fragment plays a major role in their stability, as substantiated by DFT calculations. The bending induced by the diphosphine ligand substantially enhances π‐backdonation and thereby allows the isolation of carbonyl and carbene complexes featuring significant π‐bond character.
Total Synthesis of Gracilioether F: Development and Application of Lewis Acid Promoted Ketene–Alkene [2+2] Cycloadditions and Late‐Stage CH Oxidation
Authors: Rasik Christopher M. , Brown M. Kevin
Published: October 2014

The first synthesis of gracilioether F, a polyketide natural product with an unusual tricyclic core and five contiguous stereocenters, is described. Key steps of the synthesis include a Lewis acid promoted ketene–alkene [2+2] cycloaddition and a late‐stage carboxylic acid directed C(sp3)H oxidation. The synthesis requires only eight steps from norbornadiene.
Trifluoromethoxylation of Arenes: Synthesis of ortho‐Trifluoromethoxylated Aniline Derivatives by OCF3 Migration
Authors: Hojczyk Katarzyna N. , Feng Pengju , Zhan Chengbo , Ngai Ming‐Yu
Published: October 2014

Aryl trifluoromethoxylation by a two‐step sequence of O‐trifluoromethylation of N‐aryl‐N‐hydroxylamine derivatives and intramolecular OCF3 migration is presented. This protocol allows easy access to a wide range of synthetically useful ortho‐OCF3 aniline derivatives. In addition, it utilizes bench‐stable reagents, is operationally simple, shows high functional‐group tolerance, and is amenable to gram‐scale as well as one‐pot synthesis. A reaction mechanism of a heterolytic cleavage of the NOCF3 bond followed by recombination of the resulting nitrenium ion and trifluoromethoxide is proposed for the OCF3‐migration reaction.
Molybdenum Phosphosulfide: An Active, Acid‐Stable, Earth‐Abundant Catalyst for the Hydrogen Evolution Reaction
Authors: Kibsgaard Jakob , Jaramillo Thomas F.
Published: October 2014

Introducing sulfur into the surface of molybdenum phosphide (MoP) produces a molybdenum phosphosulfide (MoP|S) catalyst with superb activity and stability for the hydrogen evolution reaction (HER) in acidic environments. The MoP|S catalyst reported herein exhibits one of the highest HER activities of any non‐noble‐metal electrocatalyst investigated in strong acid, while remaining perfectly stable in accelerated durability testing. Whereas mixed‐metal alloy catalysts are well‐known, MoP|S represents a more uncommon mixed‐anion catalyst where synergistic effects between sulfur and phosphorus produce a high‐surface‐area electrode that is more active than those based on either the pure sulfide or the pure phosphide. The extraordinarily high activity and stability of this catalyst open up avenues to replace platinum in technologies relevant to renewable energies, such as proton exchange membrane (PEM) electrolyzers and solar photoelectrochemical (PEC) water‐splitting cells.
Acetamide‐modified hyper‐cross‐linked resin: Synthesis, characterization, and adsorption performance to phenol from aqueous solution
Authors: Wang Xiaomei , Patil Prafulla D. , He Chunlian , Huang Jianhan , Liu You‐Nian
Published: October 2014

Acetamide‐modified hyper‐cross‐linked resin, HCP‐HMTA‐AA, was prepared and its adsorption performance was evaluated using phenol as the adsorbate. The prepared HCP–HMTA–AA owned predominant micro/mesopores and medium polarity, making it possess a superior adsorption to phenol as compared with polystyrene (PS), chloromethylated polystyrene (CMPS), hyper‐cross‐linked polymer (HCP) and amino‐modified hyper‐cross‐linked resin (HCP–HMTA). The adsorption enthalpy was −99.56 kJ/mol at zero fractional loading, multiple hydrogen bonding contributed to such a great adsorption enthalpy and an approximately planar hexahydric ring was formed between acetamide of HCP–HMTA–AA and phenol. The dynamic capacity of phenol on HCP–HMTA–AA was 291.3 mg/g at a feed concentration of 946.2 mg/L and a flow rate of 48 mL/h and the resin column was almost regenerated by a mixed solvent including 50% of ethanol (v/v) and 0.01 mol/L of sodium hydroxide (w/v). HCP–HMTA–AA was repeatedly used for five times and the equilibrium adsorption capacity for the five time reached 94.2% of the equilibrium adsorption capacity for the first time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41597.
Cellulose nanocrystal driven crystallization of poly(d,l‐lactide) and improvement of the thermomechanical properties
Authors: Camarero‐Espinosa Sandra , Boday Dylan J. , Weder Christoph , Foster E. Johan
Published: October 2014

The technological exploitation of polylactide in fields requiring wide range of operating conditions is limited by the low crystallization rate of the polymer and therewith the low thermomechanical stability. Here we report the crystallization and consequent improvement of the thermomechanical properties of originally amorphous poly(d,l‐lactide) (d : l ratio 11 : 89) loaded with cellulose nanocrystals (CNCs). Isothermal treatment of samples with different CNC contents and at various temperatures, showed up to 6 wt % crystalline phase formation, as confirmed by differential scanning calorimetry and X‐ray diffraction measurements. Under a particular set of annealing conditions, CNCs promote the formation of a lamellar structure. This provides the system with higher order and cohesion which in combination with stress‐transfer between CNCs, led to an increase of the storage modulus in the rubbery plateau up to 30 times (from 2.7 MPa up to 79 MPa), a rise of the melting temperature up to 50°C, and an improvement of the Young's modulus up to 40%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41607.
Synthesis, characterization, and properties of acrylate‐modified tung‐oil waterborne insulation varnish
Authors: Ge Qing , Wang Hualin , She Yi , Jiang Suwei , Cao Mengye , Zhai Linfeng , Jiang Shaotong
Published: October 2014

An acrylate‐modified tung‐oil waterborne insulation varnish was synthesized from tung oil, maleic anhydride, and acrylates via a Diels–Alder reaction and free‐radical polymerization, and the varnish could be solidified at a relatively low temperature with blocked hexamethylene diisocyanate as a curing agent. The resulting films were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The insulation properties (electrical insulation strength, volume resistivity, and surface resistivity) of the varnish films were tested, and the resistances of films to salted water were evaluated. With an increase in the maleic anhydride content, the thermal stability of the film was improved, whereas the electrical insulation strength, volume resistivity, and surface resistivity decreased. The electrical insulation strength of the film after it was immersed in the NaCl solution was lower than that in dry state, and it decreased as the immersed time was prolonged. In particular, the electrical insulation strength loss of the film increased significantly at maleic anhydride contents beyond 25 wt %. Furthermore, the hardness of the film increased with increasing methyl methacrylate/N‐butyl acrylate ratio, whereas the flexibility and adhesion of film decreased to a certain degree at the same time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41608.
Studies on thermal behavior, moisture absorption, and biodegradability of ginger spent incorporated polyurethane green composites
Authors: Chethana M. , Prashantha Kalappa , Siddaramaiah
Published: October 2014

Ecological concern on accumulation of neutraceutical industrial waste material and the demands for newer composite materials have promoted extensive research on utilizing industrial wastes materials. Therefore, in the present study finely powdered ginger spent (GS), filled polyurethane (PU) green composites with varying amount viz., 0, 2.5, 5, 7.5, and 10 wt % of GS have been fabricated. The prepared PU/GS green composites have been characterized for their mechanical properties, density and void content. Interaction between filler and matrix has been confirmed from Fourier transform infrared spectroscopy studies. Moisture absorption and desorption studies have been performed at different relative humidity (RH). The moisture absorption and desorption studies, shows that as the hydrophilic GS content increases in the matrix the RH also increases. Water uptake behavior of PU/GS were measured in different chemical environments such as 5% sodium chloride solution, cold water at different temperature and in hydrochloric acid solution. The water uptake values increases as increase in GS concentration. Equilibrium water content, diffusivity and equilibrium time taken for all PU/GS composites have been investigated. Biodegradation studies reveals that as the GS content increases the weight loss also increases. Thermal properties have been performed using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). From DSC and DMA thermograms it is revealed that increase inTgwith increase in GS content. RH and contact angle measurement have been performed to understand the hydrophilic nature of the prepared composite. The morphological behavior of composites has been studied using scanning electron microscopy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2015,132, 41614.
A Necessary and Sufficient Condition for Stabilization of Switched Descriptor Time‐Delay Systems Under Arbitrary Switching
Authors: Zhao Jiemei , Zhang Lijun , Qi Xue
Published: October 2014

In this paper, a necessary and sufficient condition for generalized quadratic stabilization of switched descriptor time‐delay (SDT) systems under arbitrary switching is investigated. Based on the linear matrix inequality (LMI) method, some results are given: (i) the SDT system is regular, impulse‐free, and stable under arbitrary switching; (ii) the necessary and sufficient condition for switched generalized quadratic stability (stabilization) of the uncertain SDT systems is derived. Finally, a numerical example is provided to illustrate the effectiveness of the method.
Role of surgery in the treatment of renal secondary hyperparathyroidism
Authors: Schneider R , Bartsch D K
Published: October 2014

Surgery is cost-effective
Selective extraction based on poly(MAA‐VB‐EGMDA) monolith followed by HPLC for determination of hordenine in plasma and urine samples
Authors: Chen Yonggang , Meng Junhua , Zou Jili , An Jing
Published: October 2014

Hordenine is an active compound found in several foods, herbs and beer. In this work, a novel sorbent was fabricated for selective solid‐phase extraction (SPE) of hordenine in biological samples. The organic polymer sorbent was synthesized in one step in the plastic barrel of a syringe by a pre‐polymerization solution consisting of methacrylic acid (MAA), 4‐vinylphenylboronic acid (VB) and ethylene glycol dimethacrylate (EGDMA). The conditions for preparation were optimized to generate a poly(MAA‐VB‐EGMDA) monolith with good permeability. The monolith exhibited good enrichment efficiency towards hordenine. By using tyramine as the internal standard, a poly(MAA‐VB‐EGMDA)‐based SPE‐HPLC method was established for analysis of hordenine. Conditions for SPE, including volume of eluting solvent, pH of sample solution, sampling rate and sample volume, were optimized. The proposed SPE‐HPLC method presented good linearity (R2 = 0.9992) within 10–2000 ng/mL and the detection limits was 3 ng/mL, which is significantly more sensitive than reported methods. The method was also applied in plasma and urine samples; good capability of removing matrices was observed, while hordenine in low content was well extracted and enriched. The recoveries were from 90.6 to 94.7% and from 89.3 to 91.5% for the spiked plasma and urine samples, respectively, with the relative standard deviations <4.7%. Copyright © 2014 John Wiley & Sons, Ltd.
Qualitative and quantitative analysis of the major constituents in Acorus tatarinowii Schott by HPLC/ESI‐QTOF‐MS/MS
Authors: Zhang Feng , Qi Peng , Xue Rui , Li Zhixiong , Zhu Kaicheng , Wan Ping , Huang Chenggang
Published: October 2014

Acorus tatarinowii Schott (ATS) is a well‐known traditional Chinese medicine (TCM) for the treatment of epilepsy, amnesia and insomnia. In this study, a methodology utilizing high‐performance liquid chromatography (HPLC) coupled with electrospray ionization quadrupole time‐of‐flight mass spectrometry (ESI‐QTOF‐MS/MS) was established for the separation and structural identification of the major chemical constituents in ATS for the first time. Overall, 46 major constituents including flavonoid glycosides, phenylpropane derivatives, amides and lignans were identified or tentatively characterized. Seven major constituents, including four phenylpropane derivatives and three lignans, were further quantified as marker substances, which showed good linearity within the test ranges. These results indicated that the developed quantitative method was linear, sensitive, and precise for quality control of ATS. Copyright © 2014 John Wiley & Sons, Ltd.
Vismodegib, an antagonist of hedgehog signaling, directly alters taste molecular signaling in taste buds
Authors: Yang Hyekyung , Cong Wei‐na , Yoon Jeong Seon , Egan Josephine M.
Published: October 2014

Vismodegib, a highly selective inhibitor of hedgehog (Hh) pathway, is an approved treatment for basal‐cell carcinoma. Patients on treatment with vismodegib often report profound alterations in taste sensation. The cellular mechanisms underlying the alterations have not been studied. Sonic Hh (Shh) signaling is required for cell growth and differentiation. In taste buds, Shh is exclusively expressed in type IV taste cells, which are undifferentiated basal cells and the precursors of the three types of taste sensing cells. Thus, we investigated if vismodegib has an inhibitory effect on taste cell turnover because of its known effects on Hh signaling. We gavaged C57BL/6J male mice daily with either vehicle or 30 mg/kg vismodegib for 15 weeks. The gustatory behavior and immunohistochemical profile of taste cells were examined. Vismodegib‐treated mice showed decreased growth rate and behavioral responsivity to sweet and bitter stimuli, compared to vehicle‐treated mice. We found that vismodegib‐treated mice had significant reductions in taste bud size and numbers of taste cells per taste bud. Additionally, vismodegib treatment resulted in decreased numbers of Ki67‐ and Shh‐expressing cells in taste buds. The numbers of phospholipase Cβ2‐ and α‐gustducin‐expressing cells, which contain biochemical machinery for sweet and bitter sensing, were reduced in vismodegib‐treated mice. Furthermore, vismodegib treatment resulted in reduction in numbers of T1R3, glucagon‐like peptide‐1, and glucagon‐expressing cells, which are known to modulate sweet taste sensitivity. These results suggest that inhibition of Shh signaling by vismodegib treatment directly results in alteration of taste due to local effects in taste buds.
Cytochrome P450 OxyBtei Catalyzes the First Phenolic Coupling Step in Teicoplanin Biosynthesis
Authors: Haslinger Kristina , Maximowitsch Egle , Brieke Clara , Koch Alexa , Cryle Max J.
Published: October 2014

Bacterial cytochrome P450s form a remarkable clade of the P450 superfamily of oxidative hemoproteins, and are often involved in the biosynthesis of complex natural products. Those in a subgroup known as “Oxy enzymes” play a crucial role in the biosynthesis of glycopeptide antibiotics, including vancomycin and teicoplanin. The Oxy enzymes catalyze crosslinking of aromatic residues in the non‐ribosomal antibiotic precursor peptide while it remains bound to the non‐ribosomal peptide synthetase (NRPS); this crosslinking secures the three‐dimensional structure of the glycopeptide, crucial for antibiotic activity. We have characterized OxyBtei, the first of the Oxy enzymes in teicoplanin biosynthesis. Our results reveal that OxyBtei possesses a structure similar to those of other Oxy proteins and is active in crosslinking NRPS‐bound peptide substrates. However, OxyBtei displays a significantly altered activity spectrum against peptide substrates compared to its well‐studied vancomycin homologue.
Ni–Co/Al2O3Bimetallic Catalysts for CH4Steam Reforming: Elucidating the Role of Co for Improving Coke Resistance
Authors: You Xiaojuan , Wang Xiang , Ma Youhe , Liu Jianjun , Liu Wenming , Xu Xianglan , Peng Honggen , Li Changqing , Zhou Wufeng , Yuan Ping , Chen Xiaohong
Published: October 2014

A series of supported Ni–Co/γ‐Al2O3bimetallic catalysts with a fixed 12 % Ni loading but different Co contents were prepared by using the coimpregnation method and investigated for methane steam reforming. The addition of Co can significantly improve the coke resistance and the reaction stability of Ni/Al2O3at a mild loss of the reforming activity. XPS and TEM results prove the existence of strong interaction between Ni and Co species. XRD and high‐angle annular dark‐field scanning transmission electron microscopy mapping results of the reduced catalysts provide direct evidence for surface Ni–Co alloy formation upon Co addition onto Ni/Al2O3, which can block part of the active low coordinated Ni sites and lower the metal dispersion, thus effectively suppressing coking and improving the reaction stability in comparison with the unmodified Ni/Al2O3catalyst.