bluuebunny/crossref_metadata_2025 huggingface dataset:
Book Review Editorial Statement: Mapping the Emerging Field of Media Innovation Research
Authors: Krumsvik Arne H.
Published: March 2014

The aim of this journal is to serve the professional and research communities involved in the cross-disciplinary field of media innovations, and the Book Review section will be an indispensable part of the Journal of Media Innovations from its inception, contributing to mapping this emerging field.
Santé organisationnelle
Authors: Dagenais-Desmarais Véronique , Dufour Marie-Ève , St-Hilaire France , Hébert Rachèle
Published: March 2014

Dans un contexte où la qualité de vie au travail, le bien-être et la santé psychologique des employés sont actuellement au coeur des préoccupations des gestionnaires et des milieux de travail, les enjeux de santé organisationnelle deviennent incontournables. Or, malgré l’intérêt grandissant des chercheurs et des praticiens, la notion de santé organisationnelle a été l’objet de diverses conceptualisations et représente encore aujourd’hui un objet d’étude en pleine évolution. Dans cet ordre d’idées, cet article propose de faire une synthèse des approches contemporaines de la santé organisationnelle et d’investiguer comment cette thématique est abordée par les chercheurs québécois. Pour ce faire, une recension des écrits a d’abord été effectuée afin d’établir un portrait des connaissances acquises à ce jour. Ensuite, une enquête consultative a été réalisée auprès d’experts scientifiques québécois. À la fois les écrits et les experts consultés rapportent que la santé organisationnelle est un concept qui prend plusieurs sens, qui nécessite l’adoption d’une perspective plus globale et qui s’élargit à d’autres sphères que le travail. Or, contrairement à la documentation, les experts abordent surtout les aspects de la santé psychologique et moins la santé physique, et ils considèrent essentiellement les facteurs organisationnels comme des préoccupations de recherche future dans le domaine. Les résultats obtenus permettent de dresser un état des connaissances sur le concept de santé organisationnelle et son évolution, tout en identifiant les tendances émergentes susceptibles d’influencer les orientations scientifiques futures pour le regroupement stratégique en santé psychologique au travail du Réseau de recherche en santé et sécurité du travail du Québec.
Bilan relatif aux dispositions de la LSST
Authors: Baril-Gingras Geneviève , Vézina Michel , Lippel Katherine
Published: March 2014

Plus de trente ans après l’adoption de la loi québécoise sur la santé et la sécurité du travail (LSST), la réglementation concernant le programme de prévention (PP), le programme de santé (PSSE), le comité de santé et de sécurité (CSS) et le représentant à la prévention (RP) n’a pas été étendue à tous les secteurs d’activité, tel que prévu, et les dispositions concernant les comités et les représentants sur les chantiers de construction n’ont pas été promulguées. Cela peut-il se justifier, compte tenu des connaissances scientifiques disponibles et de l’adoption de ces dispositions ailleurs? Voilà les questions auxquelles ce texte veut répondre. Dans la grande majorité des autres juridictions canadiennes, des dispositions similaires au PP, au CSS et au RP (dans les petits établissements) sont obligatoires dans tous les secteurs. Les études sur des systèmes similaires au PP montrent des résultats positifs; c’est le cas au Québec lorsque les études prennent en compte l’implantation effective et le contenu des programmes. Les revues des écrits sur les programmes de santé signalent des résultats positifs, dont l’implantation de mesures de prévention primaire, ce qu’indiquent les études québécoises. Au plan international, on observe que les résultats en SST sont plus favorables lorsqu’il y a participation représentative des travailleurs que si l’employeur s’en occupe seul. Les études soutiennent la pertinence de dispositifs comme les CSS, tout en identifiant les conditions nécessaires à leur efficacité. Les études québécoises indiquent aussi généralement des effets intermédiaires et finaux positifs. Quant aux représentants des travailleurs en SST, ils dynamisent l’action préventive. Sur les chantiers de construction, ces mécanismes de représentation ont un rôle favorable et important. Les travaux recensés démontrent le rôle déterminant du contexte et des conditions d’implantation, ce qui peut orienter les politiques publiques. Au total, le fait que ces dispositions au coeur de la LSST ne couvrent pas l’ensemble des secteurs d’activité économique ne peut se justifier sur la base des connaissances scientifiques et des obligations que l’on retrouve ailleurs. L’adoption de ces dispositions pourrait, dans les années à venir, servir de fondement à d’autres mesures nécessaires pour faire face aux changements de la relation d’emploi et de la nature du travail.
Autorité démocratique et contestation. L’apport d’une approche épistémique
Authors: Le Goff Alice , Nadeau Christian
Published: March 2014

Ce texte constitue une introduction au dossier. Il introduit les différentes contributions en mettant en relief leurs principales orientations. Ce faisant, il propose donc une cartographie conceptuelle, forcément partielle, des enjeux associés à la notion de démocratie épistémique et des enjeux du croisement de cette notion avec celle de démocratie de contestation. En un premier temps, nous revenons sur l’apport du procéduralisme épistémique et sur les questions qu’il soulève. Ensuite, nous revenons sur le néo-pragmatisme et la façon dont il permet d’envisager une justification épistémique de la démocratie. Puis nous mettons l’accent sur les enjeux d’un dialogue entre modèle républicain de la démocratie contestataire et modèle épistémique. Enfin, le texte propose un résumé du parcours proposé dans le cadre de ce dossier.
Hippocampal neurons wait their turn
Authors: Gao Yuan , Davison Ian
Published: March 2014

Imaging large groups of neurons as mice learn to respond to an event after a time delay shows that the brain encodes the passage of time using ordered sequences of neural activity.
Intercalated multilayer graphene wires and metal/multilayer graphene hybrid wires obtained by annealing sputtered amorphous carbon
Authors: Sato Motonobu , Takahashi Makoto , Nakano Haruhisa , Takakuwa Yuji , Nihei Mizuhisa , Sato Shintaro , Yokoyama Naoki
Published: March 2014

We have fabricated an intercalated multilayer graphene (i-MLG) wire and a cobalt metal/multilayer graphene (Co/MLG) hybrid wire with decreased resistivity relative to a multilayer graphene (MLG) wire by annealing sputtered amorphous carbon. The resistances of the i-MLG and Co/MLG wires decrease by 1 and 2 orders of magnitude relative to that of the MLG wire, respectively. The breakdown tests of the i-MLG and MLG wires indicate that the current tolerance per graphene layer remains almost the same, independent of whether the wires are intercalated. On the other hand, the Co/MLG hybrid wire exhibits not only decreased resistivity but also increased current tolerance. Moreover, with the optimization of the film thickness and annealing temperature, the obtained resistivities of Co/MLG, MLG, and i-MLG are 10, 80, and 6 µΩ cm, respectively.
Associative memory architecture for word-parallel smallest Euclidean distance search using distance mapping into clock-number domain
Authors: Akazawa Toshinobu , Sasaki Seiryu , Mattausch Hans Jürgen
Published: March 2014

A scalable word-parallel associative memory for smallest Euclidean distance (ED) search is presented. Due to the applied concept of distance to clock-number mapping, the reported architecture is digital in nature and scalable to advanced technology. Furthermore, the reference data of feature vectors can be scaled in principle to any vector dimension and number. Handling of the numerical complexity of the ED without large consumption of Silicon area is achieved by an area-efficient circuit, which uses the same adder for absolute-difference calculation of vector components and subsequent square calculation by sequential addition of partial products. Additionally, a clock-number minimization algorithm is proposed to significantly reduce the clock-number needed for the search when the smallest ED is a large value. The concept of the proposed architecture has been experimentally verified by measurement results from real chips fabricated in a 180 nm CMOS technology, in which the architecture is configured for parallel smallest ED search among 32 reference vectors with each vector having 16 8-bit elements. For the application example of codebook-based data compression, the fabricated test chip achieved 1.19 µs average search time, 5.77 µs worst-case search time and low power consumption of 8.75 mW at the maximum clock frequency of 47 MHz and nominal power supply voltage V
dd = 1.8 V. At reduced power supply voltage V
dd = 1.2 V, a smaller power consumption of 2.80 mW at an also smaller maximum clock frequency of 24 MHz is measured. In comparison to previous analog–digital architecture, a reduction of the normalized power-delay product per matching operation by about a factor 1.6 at V
dd = 1.8 V (about factor 2.5 at V
dd = 1.2 V) is obtained with best-case data for the analog–digital architecture and average-case data for the proposed fully-digital architecture.
Low-power output-capacitorless low-dropout regulator with adjustable charge injection technique for on–off-keying transmitters
Authors: Akita Ippei , Asai Shochi , Ishida Makoto
Published: March 2014

In this paper a low-power low-dropout (LDO) regulator for p power amplifier (PA) in on–off-keying (OOK) transmitters is proposed. The proposed technique needs no external output capacitors, enabling small-area and low-cost implementation. The response of a rapid load change in an OOK transmitter is improved by the proposed adjustable charge injection (ACI) technique that uses timing information of a transmitted data signal. The designed regulator with the ACI technique has been fabricated in a standard 180 nm CMOS process and achieves 100 mVpp dropout voltage ripple. The measured current dissipation is 65 µA at a power supply of 1.8 V.
Gate oxide reliability on trapezoid-shaped defects and obtuse triangular defects in 4H-SiC epitaxial wafers
Authors: Ishiyama Osamu , Yamada Keiichi , Sako Hideki , Tamura Kentaro , Kitabatake Makoto , Senzaki Junji , Matsuhata Hirofumi
Published: March 2014

The reliability of the gate oxide on large-area surface defects (trapezoid-shaped and obtuse triangular defects) in 4H-SiC epitaxial wafers is discussed. Time-dependent dielectric breakdown measurements revealed that a reduction in charge-to-breakdown (Q
bd) occurred at a MOS capacitor including the downstream line of those defects. The deterioration of Q
bd was at the same level in trapezoid-shaped defects and obtuse triangular defects. A cross-sectional transmission electron microscope (TEM) image and the simulation of the electric field distribution for the MOS structure indicated that the local fluctuation of the oxide thickness and/or the roughness of the interface on the downstream lines caused the degradation of the reliability of the MOS capacitors.
Measuring the effect of water vapor on climate warming
Authors: Schultz Colin
Published: March 2014

Water vapor is a potent greenhouse gas. In the atmosphere, the concentration of water vapor increases with the temperature, setting up a powerful positive feedback loop. This water vapor feedback is the strongest known positive feedback, with the potential to roughly double the effect of warming caused by other sources. Determining the exact strength of the water vapor feedback, then, is incredibly important to limiting uncertainty in future climate change projections.
Local Area Cartilage Segmentation: A Semiautomated Novel Method of Measuring Cartilage Loss in Knee Osteoarthritis
Authors: Duryea Jeffrey , Iranpour‐Boroujeni Tannaz , Collins Jamie E. , Vanwynngaarden Case , Guermazi Ali , Katz Jeffrey N. , Losina Elena , Russell Ruby , Ratzlaff Charles
Published: March 2014

Objective

To assess the responsiveness and reader time of a novel semiautomated tool to detect knee cartilage loss over 2 years in subjects with knee osteoarthritis.

Methods

A total of 122 subjects from the Osteoarthritis Initiative progression cohort were selected. A reader used the software method to segment cartilage on double‐echo steady‐state sequence scans in the medial compartment of the femur from the baseline and 24‐month visits. Change in cartilage volume (ΔV) was measured at a fixed weight‐bearing (WB) location with respect to the 3‐dimensional coordinate system based on cylindrical coordinates. Change was measured for 5 regions of varying WB surface area centered on the fixed point. The average change (ΔV), the SD of ΔV, and the standardized response mean (SRM) are reported.

Results

The SRM was −0.52 for the largest region and decreased in magnitude as smaller regions of cartilage were probed. The average evaluation time was <20 minutes per knee compartment, split approximately evenly between a technician and a trained reader.

Conclusion

The results establish that measurement of cartilage loss in a local region can be done efficiently and that the resultant measures are responsive to loss of cartilage over time. The coordinate system can potentially be used to objectively examine and establish a consistent location for all knees that is most responsive to change in cartilage volume. This technique can provide rapidly an objective quantitative measure of cartilage loss and could substantially reduce study costs for large trials and data sets.
Stable SiOC/Sn Nanocomposite Anodes for Lithium‐Ion Batteries with Outstanding Cycling Stability
Authors: Kaspar Jan , Terzioglu Caglar , Ionescu Emanuel , Graczyk‐Zajac Magdalena , Hapis Stefania , Kleebe Hans‐Joachim , Riedel Ralf
Published: March 2014

Silicon oxycarbide/tin nanocomposites (SiOC/Sn) are prepared by chemical modification of polysilsesquioxane Wacker‐Belsil PMS MK (SiOCMK) and polysiloxane Polyramic RD‐684a (SiOCRD) with tin(II)acetate and subsequent pyrolysis at 1000 °C. The obtained samples consist of an amorphous SiOC matrix and in‐situ formed metallic Sn precipitates. Galvanostatic cycling of both composites demonstrate a first cycle reversible capacity of 566 mAhg−1 for SiOCMK/Sn and 651 mAhg−1 for SiOCRD/Sn. The superior cycling stability and rate capability of SiOCRD/Sn as compared to SiOCMK/Sn is attributed to the soft, carbon‐rich SiOC matrix derived from the RD‐684a polymer, which accommodates the Sn‐related volume changes during Li‐uptake and release. The poor cycling stability found for SiOCMK/Sn relates to mechanical failure of the rather stiff and fragile, carbon‐poor matrix produced from PMS MK. Incremental capacity measurements outline different final Li–Sn alloy stages, depending on the matrix. For SiOCRD/Sn, alloying up to Li7Sn2 is registered, whereas for SiOCMK/Sn Li22Sn5 stoichiometry is reached. The suppression of Li22Sn5 phase in SiOCRD/Sn is rationalized by an expansion restriction of the matrix and thus prevention of a higher Li content in the alloy. For SiOCMK/Sn on the contrary, the matrix severely ruptures, providing an unlimited free volume for expansion and thus formation of Li22Sn5 phase.
Charge Transport Anisotropy in Highly Oriented Thin Films of the Acceptor Polymer P(NDI2OD‐T2)
Authors: Tremel Kim , Fischer Florian S. U. , Kayunkid Navaphun , Pietro Riccardo Di , Tkachov Roman , Kiriy Anton , Neher Dieter , Ludwigs Sabine , Brinkmann Martin
Published: March 2014

The nanomorphology of the high mobility polymer poly{[N,N′‐bis(2‐octyldodecyl)‐1,4,5,8‐naphthalenedicarboximide‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} P(NDI2OD‐T2) in thin films is explored as a function of different annealing conditions and correlated to optical and electrical properties. While nanofibrils with face‐on orientation in form I are obtained directly after spin‐coating and annealing below the melt transition temperature, clear evidence of lamellar structures is found after melt‐annealing followed by slow cooling to room temperature. Interestingly these structural changes are accompanied by distinct changes in the absorption patterns. Electron diffraction measurements further show clear transitions towards predominant edge‐on oriented chains in form II upon melt‐annealing. Large‐scale alignment with dichroic ratios up to 10 and improved order is achieved by high temperature rubbing and subsequent post‐rubbing annealing. These highly oriented morphologies allow anisotropic in‐plane charge transport to be probed with top‐gate transistors parallel and perpendicular to the polymer chain direction. Mobilities up to 0.1 cm2 V‐1 s‐1 are observed parallel to the polymer chain, which is up to 10 times higher than those perpendicular to the polymer chain.
A model for the devolatilization of EPDM rubber in a series of steam stripping vessels
Authors: Francoeur Angelica J. B. , Karimi Hadiseh , McAuley Kim B. , D'Agnillo Luigi
Published: March 2014

A mathematical model was developed for the multitank stripping section of industrial ethylene propylene diene monomer (EPDM) rubber processes. Experiments were conducted to determine Henry's law coefficients and diffusivities for hexane solvent and 5‐ethylidene‐2‐norbornene (ENB) comonomer in EPDM particles. Equivalent radii for diffusion within the particles were also determined. A model was developed to predict solvent and comonomer concentrations in a single particle as it moves through a series of tanks with different operating conditions. A second, more‐complicated model was then developed to account for a continuous flow stirred tank residence time distribution for the particles in the tanks. Data from three industrial plants were used to estimate parameters and assess the models' predictive ability. Typical prediction errors are 0.90 wt % for residual hexane and 0.14 wt % for residual ENB. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2596–2606, 2014
Solubilities of small hydrocarbons, viscosities of diluted tetraalkylphosphonium bis(2,4,4‐trimethylpentyl) phosphinates
Authors: Liu Xiangyang , Afzal Waheed , He Maogang , Prausnitz John M.
Published: March 2014

Tetraalkylphosphonium bis(2,4,4‐trimethylpentyl)phosphinates show large solubilities for methane, ethane, ethylene, and propane. In these ionic liquids, solubilities of ethane are larger than those of ethylene. Therefore, these ionic liquids may be useful solvents for separation of ethane and ethylene; because the vapor pressure of ethylene is higher than that of ethane, the relative volatility ethylene/ethane is enhanced. However, the viscosities of these ionic liquids are too high for an industrial process. Low‐viscosity 1‐butyl‐3‐H‐imidazolium acetate([BHMIM][AC]) is a suitable diluent for reducing the large viscosities of trihexyl tetradecylphosphonium bis(2,4,4‐trimethylpentyl) phosphinate ([P(14)666][TMPP]) and tetrabutylphosphonium bis(2,4,4‐trimethylpentyl) phosphinate ([P4444][TMPP]). Addition of 20 wt % [BHMIM][AC] gives a dramatic drop in the viscosities of these ionic liquids. Mixtures of [P(14)666][TMPP] or [P4444][TMPP] with 20 or 50 wt % [BHMIM][AC] show high solubilities for the four solutes when compared with those in other ionic liquids. In these mixtures, the solubility for ethane is higher than that for ethylene. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2607–2612, 2014
Engraftment syndrome after allogeneic hematopoietic cell transplantation in adults
Authors: Omer Aazim K. , Kim Haesook T. , Yalamarti Bhargavi , McAfee Steven L. , Dey Bimalangshu R. , Ballen Karen K. , Attar Eyal , Chen Yi‐Bin , Spitzer Thomas R.
Published: March 2014

We performed a retrospective study of the engraftment syndrome (ES) as defined by the Spitzer Criteria in adult patients undergoing allogeneic hematopoietic cell transplantation (HCT) for various hematological malignancies at a single institution, over a decade, and analyzed its relationship to acute GVHD; 217 patients underwent either myeloablative (38.7%) or reduced intensity (61.3%) HCT; 22.1% met the criteria for ES. Acute GVHD prophylaxis (P = 0.006) and transplants prior to 2006 (P < 0.0001) were significantly associated with a risk of ES in univariable analysis. Early aGVHD within 4 weeks of engraftment was significantly more common in the ES compared to the non ES cohort (21 vs. 8.3% respectively, P = 0.02). ES did not predict for future GVHD, as at day +180, the cumulative incidences of grades II–IV aGVHD (31 vs. 23%, P = 0.19) and of chronic GVHD at 2 years of engraftment (42 vs. 36%, P = 0.28) were not significantly different between the ES and non ES groups, respectively. No significant differences in NRM, overall survival and progression‐free survival were observed between the two groups. Although predictive of early aGVHD, ES occurred independently of GVHD in 79% of the patients. Survival outcomes should be evaluated in a larger randomized study to investigate if there is a correlation with ES. Am. J. Hematol. 89:698–705, 2014. © 2014 Wiley Periodicals, Inc.
Successful treatment of intravenously abused oral Opana ER‐induced thrombotic microangiopathy without plasma exchange
Authors: Miller Peter John , Farland Andrew Matthew , Knovich Mary Ann , Batt Katharine Marie , Owen John
Published: March 2014

In January 2013, the Centers for Disease Control and Prevention reported an illness associated with intravenous (IV) abuse of oral Opana ER (oxymorphone) in Tennessee. The clinical presentation of this syndrome was reported to resemble that of thrombotic thrombocytopenic purpura in the 15 patients reported; 12 were treated with plasma exchange. We report a similar case series of 15 patients with 18 episodes of thrombotic microangiopathy associated with recent IV abuse of oral Opana ER. In our series, we demonstrate that therapeutic plasma exchange is unnecessary; supportive care and treatment of underlying infections and renal dysfunction (without use of plasma exchange) resulted in clinical improvement in all patients. Thus, it appears that plasma exchange with associated costs and risks can be safely omitted in patients with thrombotic microangiopathy resulting from IV abuse of oral Opana ER. Am. J. Hematol. 89:695–697, 2014. © 2014 Wiley Periodicals, Inc.
Collecting women's reproductive histories
Authors: Beall Cynthia M. , Leslie Paul W.
Published: March 2014

The importance of women's reproductive histories for scientific questions mandates rigor in collecting data. Unfortunately, few studies say much about how histories were constructed and validated. The aim of this report, therefore, is to illustrate the elements of a rigorous system of data collection. It focuses particularly on potential sources of inaccuracy in collecting reproductive histories and on options for avoiding them and evaluating the results. A few studies are exemplary in their description of methods of data collection and evaluation of data quality because they clearly address the main issues of ascertaining whether or not an event occurred and, if so, its timing. Fundamental variables such as chronological age, live birth, or marriage may have different meanings in different cultures or communities. Techniques start with asking the appropriate people meaningful questions that they can and will answer, in suitable settings, about themselves and others. Good community relations and well‐trained, aware interviewers who check and cross‐check, are fundamental. A range of techniques estimate age, date events, and optimize the value of imperfect data. Robust data collection procedures rely on skillful and knowledgeable interviewing. Reliability can be improved, evaluated and explained. Researchers can plan to implement robust data collection procedures and should assess their data for the scientific community to raise confidence in reproductive history data. Am. J. Hum. Biol. 26:577–589, 2014. © 2014 Wiley Periodicals, Inc.
Analysis of two candidate genes for Basan syndrome
Authors: Marks Katherine C. , Banks Wesley R. , Cunningham David , Witman Patricia M. , Herman Gail E.
Published: March 2014

Basan syndrome is an extremely rare ectodermal dysplasia with autosomal dominant inheritance and variable expressivity. The etiology of Basan syndrome remains unknown. To identify the Basan syndrome gene, we sequenced keratin 14 (KRT14) and SMARCAD1 in a previously unreported kindred with the disease. Sequencing of the coding regions and splice junctions of KRT14 and SMARCAD1 was performed using PCR‐amplified genomic DNA isolated from blood or saliva and standard PCR protocols. In vitro functional studies were performed for a variant identified in SMARCAD1. While direct sequencing of KRT14 failed to reveal any likely pathogenic sequence alterations or splice site variants, a heterozygous splicing variant (c.378+3A>T) that segregated with the disease was identified in the skin‐specific isoform of SMARCAD1. In vitro studies failed to demonstrate a splicing defect in SMARCAD1. We screened two candidate genes for Basan syndrome in a 3‐generation pedigree. The skin‐specific isoform of SMARCAD1 remains a good candidate for this disease. © 2014 Wiley Periodicals, Inc.
A tortuous proximal urethra in urorectal septum malformation sequence?
Authors: Lin Henry J. , Lugo Hector , Tran Thu , Tovar Jason P. , Corral Julia , Zork Noelia M. , Smith Lynne M. , French Samuel W. , Barajas Luciano
Published: March 2014

We observed a newborn boy with urorectal septum malformation sequence. Anomalies of the genitalia and rectum were present. He expired on the first day of life, due to severe lung hypoplasia. Autopsy showed a colon that ended in a blind sac, an enlarged bladder with no grossly visible urethra, and dysplastic kidneys. A cone‐shaped tissue at the usual site of the bladder outlet contained tortuous and slit‐like lumina, suggesting an undeveloped proximal urethra. The urethral structure was lined by transitional epithelium with squamous metaplasia. Many small buds—lined with columnar epithelium—branched from the urethral structure. These ductal buds lined with columnar epithelium stained for prostatic acid phosphatase. Basal cells surrounding the ductal buds stained for p63 and high molecular weight cytokeratin—supporting an interpretation that the buds were early prostatic ducts with normal histology. To our knowledge, these are the first histological images of an undeveloped, obstructed urethra associated with the urorectal septum malformation sequence. © 2014 Wiley Periodicals, Inc.
Segmental overgrowth syndrome due to an activating PIK3CA mutation identified in affected muscle tissue by exome sequencing
Authors: Rasmussen Maria , Sunde Lone , Weigert Karen Petra , Bogaard Pauline Wilhemina , Lildballe Dorte L.
Published: March 2014

Mosaic PIK3CA‐mutations have been described in an increasing number of overgrowth syndromes. We describe a patient with a previously unreported segmental overgrowth syndrome with the mutation, PIKCA3 c.3140A>G (p.His1047Arg) in affected tissue diagnosed by exome sequencing. This PIK3CA‐associated segmental overgrowth syndrome overlaps with CLOVES syndrome and fibroadipose hyperplasia but is distinct from each of these entities. © 2014 Wiley Periodicals, Inc.
Exome analysis of connective tissue dysplasia: Death and rebirth of clinical genetics?
Authors: Wilson Golder N.
Published: March 2014

Exome results are reported for two patients with connective tissue dysplasia, one refining a clinical diagnosis of Ehlers–Danlos to Marfan syndrome, the other suggesting arthrogryposis derived from maternofetal Stickler syndrome. Patient 1 had mutations in transthyretin (TTR), fibrillin (FBN1), and a calcium channel (CACNA1A) gene suggesting diagnoses of transthyretin amyloidosis, Marfan syndrome, and familial hemiplegic migraines, respectively. Patient 2 presented with arthrogryposis that was correlated with his mother's habitus and arthritis once COL2A1 mutations suggestive of Stickler syndrome were defined. Although DNA results often defy prediction by the best of clinicians, these patients illustrate needs for ongoing clinical scholarship (e.g., to delineate guidelines for management of mutations like that for hyperekplexia in Patient 2) and for interpretation of polygenic change that is optimized by clinical genetic/syndromology experience (e.g., suggesting acetazolamide therapy for Patient 1 and explaining arthrogryposis in Patient 2). © 2014 Wiley Periodicals, Inc.
L1CAM whole gene deletion in a child with L1 syndrome
Authors: Chidsey Brandalyn A. , Baldwin Erin E. , Toydemir Reha , Ahles Lauren , Hanson Heather , Stevenson David A.
Published: March 2014

L1 syndrome is a group of overlapping, X‐linked disorders caused by mutations in L1CAM. Clinical phenotypes within L1 syndrome include X‐linked hydrocephalus with stenosis of the aqueduct of sylvius (HSAS); mental retardation, adducted thumbs, shuffling gait, and aphasia (MASA) syndrome; spastic paraplegia type 1; and agenesis of the corpus callosum. Over 200 mutations in L1CAM have been reported; however, only a few large gene deletions have been observed. We report on a 4‐month‐old male with a de novo whole gene deletion of L1CAM presenting with congenital hydrocephalus, aqueductal stenosis, and adducted thumbs. Initial failure of L1CAM gene sequencing suggested the possibility of a whole gene deletion of L1CAM. Further investigation through chromosome microarray analysis showed a 62Kb deletion encompassing the first exon of the PDZD4 gene and the entire L1CAM gene. Investigations into genotype–phenotype correlations have suggested that mutations leading to truncated or absent L1 protein cause more severe forms of L1 syndrome. Based on the presentation of the proband and other reported patients with whole gene deletions, we provide further evidence that L1CAM whole gene deletions result in L1 syndrome with a severe phenotype, deletions of PDZD4 do not cause additional manifestations, and that X‐linked nephrogenic diabetes insipidus reported in a subset of patients with large L1CAM deletions results from the loss of AVPR2. © 2014 Wiley Periodicals, Inc.
An Alternative Synthesis of Chiral (S)‐Proline Derivatives that Contain a Thiohydantoin Moiety and Their Application as Organocatalysts in the Asymmetric Michael Addition Reaction under Solvent‐Free Conditions.
Authors: Vega‐Peñaloza Alberto , Sánchez‐Antonio Omar , Ávila‐Ortiz C. Gabriela , Escudero‐Casao Margarita , Juaristi Eusebio
Published: March 2014

A convenient synthetic procedure for the preparation of chiral thiohydantoins derived from natural α‐amino acids is reported. Salient features of this method include ready availability of the starting materials, mild reaction conditions, and high yields of the desired products. The prepared thiohydantoins were tested as organocatalysts in asymmetric Michael addition reactions, under solvent‐free reaction conditions. Thiohydantoin 10 d turned out to be the most efficient catalyst, and its catalytic activity can be significantly enhanced by the use of an equimolar amount of salicylic acid as additive. Furthermore, highest diastereo‐ and enantioselectivity is achieved when the reaction is carried out at −5.5 °C, without detriment of the reaction rate. Regarding the reaction’s scope, the asymmetric Michael reaction catalyzed by 10 d was found to maintain its efficiency with various Michael acceptors.
Asymmetric Synthesis of Efavirenz via Organocatalyzed Enantioselective Trifluoromethylation
Authors: Okusu Satoshi , Kawai Hiroyuki , Yasuda Yoshimasa , Sugita Yutaka , Kitayama Takashi , Tokunaga Etsuko , Shibata Norio
Published: March 2014

We demonstrate a metal‐free catalytic process for the synthesis of anti‐HIV drug efavirenz in 99 % ee, which was achieved by an organocatalyzed enantioselective trifluoromethylation with Me3SiCF3 as a key reaction. The combination of cinchona alkaloid‐derived phase‐transfer catalysts modified with long chain ethers and tetramethylammonium fluoride enables the enantioselective trifluoromethylation of 1‐(5‐chloro‐2‐nitrophenyl)‐3‐cyclopropylprop‐2‐yn‐1‐one to be improved, and provides a desired (S)‐trifluoromethyl carbinol, which is a two‐step key precursor for the synthesis of efavirenz, in up to 80 % ee. As our method is a metal‐free process, it would provide an alternative industrial manufacturing process for efavirenz.
Synthese von Cyano‐substituierten Diaryltetracenen ausgehend von Tetraaryl[3]cumulenen
Authors: Gawel Przemyslaw , Dengiz Cagatay , Finke Aaron D. , Trapp Nils , Boudon Corinne , Gisselbrecht Jean‐Paul , Diederich François
Published: March 2014

Wir berichten über eine vielseitig anwendbare, zweistufige Synthese hochsubstituierter, cyanofunktionalisierter Diaryltetracene ausgehend von leicht zugänglichen Tetraaryl[3]cumulenen. Diese beispiellose Umsetzung beginnt mit der [2+2]‐Cycloaddition von Tetracyanoethylen (TCNE) an die proacetylenische zentrale Doppelbindung der Cumulene unter Bildung eines zwitterionischen Zwischenprodukts, welches über eine Elektrocyclisierungskaskade und nachfolgende Dehydrierung in einer Eintopfreaktion 5,5,11,11‐Tetracyano‐5,11‐dihydro‐6,12‐diaryltetracene liefert. Eine nachfolgende Kupfer‐unterstützte Decyanierung/Aromatisierung ergab die 5,11‐Dicyano‐6,12‐diaryltetracen‐Zielverbindungen. Alle postulierten Strukturen werden von Röntgenstrukturanalysen gestützt. Die neuen Chromophore sind thermisch hochstabil und zeigen vielversprechende Fluoreszenzeigenschaften, die für potenzielle Anwendungen in der Optoelektronik von Interesse sind. Sie sind selektive Chemosensoren für CuI‐Ionen, die an einen der CN‐Substituenten koordinieren und 1:1‐Komplexe mit Assoziationskonstante Ka=1.5×105 L mol−1 bei 298 K bilden.
Construction of Quaternary Stereogenic Carbon Centers through Copper‐Catalyzed Enantioselective Allylic Cross‐Coupling with Alkylboranes
Authors: Hojoh Kentaro , Shido Yoshinori , Ohmiya Hirohisa , Sawamura Masaya
Published: March 2014

A combination of an in situ generated chiral CuI/DTBM‐MeO‐BIPHEP catalyst system and EtOK enabled the enantioselective SN2′‐type allylic cross‐coupling between alkylborane reagents and γ,γ‐disubstituted primary allyl chlorides with enantiocontrol at a useful level. The reaction generates a stereogenic quaternary carbon center having three sp3‐alkyl groups and a vinyl group. This protocol allowed the use of terminal alkenes as nucleophile precursors, thus representing a formal reductive allylic cross‐coupling of terminal alkenes. A reaction pathway involving addition/elimination of a neutral alkylcopper(I) species with the allyl chloride substrate is proposed.
Innovative direct nanoparticle dispersion injection into injection molding processing
Authors: Hassinger Irene , Becker Thorsten , Walter Rolf , Burkhart Thomas , Kopnarski Michael , Brodyanski Alexander
Published: March 2014

Nanoparticles are applied in polymer matrices because of building up an inorganic network within an organic network resulting in a simultaneous increase of stiffness and toughness provided that a good degree of dispersion with a very low amount of agglomerates can be realized. To prevent these kinds of agglomerates, the incorporation of appropriate nanoparticle dispersions is promising. Using nanoparticle containing dispersions, we can produce nanocomposites via a direct injection molding process with excellent nanoparticle dispersion in the resulting nanocomposite. TiO2‐ (15 nm and 300 nm) and Al2O3‐ (13 nm) particle containing dispersions were manufactured and incorporated in polyamide 6 (PA6) via the addition of a nanoparticle containing dispersion within an injection molding process (IM). Agglomeration has to be suppressed during injection molding process and the nanoparticles have to cross over from the dispersing agent to the polymer matrix melt in which they have to be well distributed. The resulting mechanical (tensile and Charpy impact) and morphological (SEM and TEM) properties of those nanocomposites are discussed. The impact toughness and Young's modulus could be enhanced with slightly decreasing tensile strength. The nanoparticles could be well distributed in the polymer matrix. The achievable distribution quality is equal to the distribution achieved in a melt kneading process. Thus, materials with enhanced elongation at break with a very good dispersion quality were produced in a single production process. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40641.
The Computational Road to Better Catalysts
Authors: Jover Jesús , Fey Natalie
Published: March 2014

Computational studies, especially those that use density functional theory (DFT), have become pervasive in the characterization, mechanistic study, and optimization of homogeneous organometallic catalysts, and the “rational” design of such catalysts seems within reach once more. But how advanced, user‐friendly, and reliable are the computational tools that are currently available? Here we summarize the current state of the art for predictive computational organometallic chemistry in reference to the different stages of catalyst development by considering characterization, mechanistic studies, fine‐tuning/optimization, and evaluation of novel designs. We also assess critically where the strengths and weaknesses of computational studies lie and hence map out the road ahead for the design and discovery of novel catalysts in silico and in combination with targeted experimental studies.
Neoadjuvant chemotherapy with S-1 and cisplatin followed by D2 gastrectomy with para-aortic lymph node dissection for gastric cancer with extensive lymph node metastasis
Authors: Tsuburaya A , Mizusawa J , Tanaka Y , Fukushima N , Nashimoto A , Sasako M
Published: March 2014

Background

Locally advanced gastric cancer with extensive regional and/or para-aortic lymph node (PAN) metastases is typically unresectable and associated with poor outcomes. This study investigated the safety and efficacy of S-1 plus cisplatin followed by extended surgery with PAN dissection for gastric cancer with extensive lymph node metastasis.

Methods

Patients with gastric cancer with bulky lymph node metastasis along the coeliac artery and its branches and/or PAN metastasis received two or three 28-day cycles of S-1 plus cisplatin, followed by gastrectomy with D2 plus PAN dissection. The primary endpoint was the percentage of complete resections with clear margins in the primary tumour (R0 resection). A target sample size of 50 with one-sided α of 0·105 and β of approximately 0·2 corresponded to an expected R0 rate of 65 per cent and a threshold of 50 per cent.

Results

Between February 2005 and June 2007, 53 patients were enrolled, of whom 51 were eligible. The R0 resection rate was 82 per cent. Clinical and pathological response rates were 65 and 51 per cent respectively. The 3- and 5-year overall survival rates were 59 and 53 per cent respectively. During chemotherapy, grade 3/4 neutropenia occurred in 19 per cent and grade 3/4 non-haematological adverse events in 15·4 per cent. The incidence of grade 3/4 adverse events related to surgery was 12 per cent. There were no reoperations or treatment-related deaths.

Conclusion

For locally advanced gastric cancer with extensive lymph node metastasis, 4-weekly S-1 plus cisplatin followed by surgery including PAN dissection was safe and effective for some patients. Further investigation of this treatment strategy is warranted.
A 10‐year survey of trace metals in sediments using self‐organizing maps
Authors: Besada Victoria , Quelle Cristina , Andrade José Manuel , Gutiérrez Noemí , Gómez‐Carracedo María Paz , Schultze Fernando
Published: March 2014

Self‐organizing maps (SOMs) (in particular, Matrix reOrganization Layout to Map Analytical Patterns (MOLMAP)) were used to unravel the main patterns in a three‐way dataset after a preliminary unfolding of the cube. Eleven sites of the ría of Vigo (NW of Spain) were monitored during the last decade (from 2000 to 2010) to assess pollution trends in this area. Twelve trace metals (Hg, Pb, Cd, Cu, Zn, Cr, As, Li, Fe, Al, Ni and Mn), the total organic carbon and the percentage of fine particles were measured. Results from MOLMAP, the SOM‐based approach, were compared to those of three established alternatives: parallel factor analysis, matrix‐augmented principal component analysis and generalized Procrustes rotation, the latter two employing unfolding as well. MOLMAP showed the best capabilities to differentiate groups of samples. The spatial and temporal trends, as well as the analytical variables causing them, were almost the same for all methods, which confirms MOLMAP as a simple and reliable methodology to treat three‐way environmental datasets. Copyright © 2014 John Wiley & Sons, Ltd.
A New Approach to Prepare Efficient Blue AIE Emitters for Undoped OLEDs
Authors: Huang Jing , Tang Runli , Zhang Tian , Li Qianqian , Yu Gui , Xie Shuyi , Liu Yunqi , Ye Shanghui , Qin Jingui , Li Zhen
Published: March 2014

Two aggregation‐induced emission active luminogens (TPE–pTPA and TPE–mTPA) were successfully synthesized. For comparison, another six similar compounds were prepared. Because of the introduced hole‐dominated triphenylamine (TPA), fluorene groups with high luminous efficiency, and unconjugated linkages, the π conjugation length of the obtained luminogens is effectively restricted to ensure their blue emission. The undoped organic light‐emitting diodes based on TPE–pTPA and TPE–mTPA exhibited blue or deep‐blue emissions, low turn‐on voltages (3 V), and high electroluminescence efficiencies with Lmax, ηC,max, and ηP,max values of up to 26 697 cd m−2, 3.37 cd A−1, and 2.40 Lm W−1.
Kilogram‐Scale Production of SnO2 Yolk–Shell Powders by a Spray‐Drying Process Using Dextrin as Carbon Source and Drying Additive
Authors: Choi Seung Ho , Kang Yun Chan
Published: March 2014

A simple and general method for the large‐scale production of yolk–shell powders with various compositions by a spray‐drying process is reported. Metal salt/dextrin composite powders with a spherical and dense structure were obtained by spray drying and transformed into yolk–shell powders by simple combustion in air. Dextrin plays a key role in the preparation of precursor powders for fabricating yolk–shell powders by spray drying. Droplets containing metal salts and dextrin show good drying characteristics even in a severe environment of high humidity. Sucrose, glucose, and polyvinylpyrrolidone are widely used as carbon sources in the preparation of metal oxide/carbon composite powders; however, they are not appropriate for large‐scale spray‐drying processes because of their caramelization properties and adherence to the surface of the spray dryer. SnO2 yolk–shell powders were studied as the first target material in the spray‐drying process. Combustion of tin oxalate/dextrin composite powders at 600 °C in air produced single‐shelled SnO2 yolk–shell powders with the configuration SnO2@void@SnO2. The SnO2 yolk–shell powders prepared by the simple spray‐drying process showed superior electrochemical properties, even at high current densities. The discharge capacities of the SnO2 yolk–shell powders at a current density of 2000 mA g−1 were 645 and 570 mA h g−1 for the second and 100th cycles, respectively; the corresponding capacity retention measured for the second cycle was 88 %.
Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene, Methyl Methacrylate, and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling
Authors: Nakanishi So‐ichiro , Kawamura Mitsunobu , Kai Hidetomo , Jin Ren‐Hua , Sunada Yusuke , Nagashima Hideo
Published: March 2014

Environmentally friendly iron(II) catalysts for atom‐transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N‐trialkylated‐1,4,9‐triazacyclononane (R3TACN) ligands. Two types of structures were confirmed by crystallography: “[(R3TACN)FeX2]” complexes with relatively small R groups have ionic and dinuclear structures including a [(R3TACN)Fe(μ‐X)3Fe(R3TACN)]+ moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R3TACN)FeX2]n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)3TACN}FeBr2] (4 b) was the best catalyst for the well‐controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined.
Iron Fluoride Hollow Porous Microspheres: Facile Solution‐Phase Synthesis and Their Application for Li‐Ion Battery Cathodes
Authors: Liu Jun , Liu Wei , Ji Shaomin , Wan Yanling , Gu Mingzhe , Yin Huaqi , Zhou Yichun
Published: March 2014

Iron fluoride cathodes have been attracting considerable interest due to their high electromotive force value of 2.7 V and their high theoretical capacity of 237 mA h g−1 (1 e− transfer). In this study, uniform iron fluoride hollow porous microspheres have been synthesized for the first time by using a facile and scalable solution‐phase route. These uniform porous and hollow microspheres show a high specific capacity of 210 mA h g−1 at 0.1 C, and excellent rate capability (100 mA h g−1 at 1 C) between 1.7 and 4.5 V versus Li/Li+. When in the range of 1.3 to 4.5 V, stable capacity was achieved at 350 mA h g−1 at a current of 50 mA g−1.
Photodynamics of [26]‐ and [28]Hexaphyrin–Bodipy Hybrids
Authors: Shin Ji‐Young , Kim Kilsuk , Lim Jong Min , Tanaka Takayuki , Kim Dongho , Kim Kimoon , Shinokubo Hiroshi , Osuka Atsuhiro
Published: March 2014

A set of hybrids having gradual variation in distances between hexaphyrin and bodipy moieties, given by uses of phenylene, biphenylene, and triphenyelene bridges was prepared. Efficient PET processes from bodipy (donor) to [26]‐ or [28]hexaphyrin (acceptor) were successfully observed, where the PET speed was controlled by intramolecular distances between the donor and the acceptor. UV irradiation at 515 nm raised a band corresponding to the bodipy absorption. As the time delayed, the bodipy bands decreased and new absorption bands at 615 and 580 nm corresponding to respective absorption bands of [28]‐ and [26]‐hybrids gradually appeared. Whereas the femtosecond transient absorption spectra of [28]/[26]‐hybrids having terphenylene bridges completely showed energy transfers from bodipy to hexaphyrin, irradiation of the hybrids using 615 and 580 nm pulses did not induce opposite ways of the PET process. On the basis of enlarged center‐to‐center‐distances of [26]‐hybrids than those of [28]‐hybrids, the set of [26]‐hybrids resulted in slow decay/rise processes. PET parameters obtained with the experiments were fairly consistent with the PET parameters calculated.