bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reactions of [Cp2Ti(η2‐Me3SiC2SiMe3)] with 1,4‐Bis(diphenylphosphanyl)but‐2‐yne: Coupling and Isomerization versus Phosphorylation
Authors: Altenburger Kai , Reiß Fabian , Schubert Kathleen , Baumann Wolfgang , Spannenberg Anke , Arndt Perdita , Rosenthal Uwe 
Published: February 2015

AbstractThe reactions of [Cp2Ti(η2‐Me3SiC2SiMe3)] (1; Cp = η5‐cyclopentadienyl) with 1,4‐bis(diphenylphosphanyl)but‐2‐yne (2) have been investigated and found to yield a mixture of products. From these, through the coupling of 2, the tetrasubstituted titanacyclopentadiene [Cp2Ti(CCH2PPh2)4] (3) was isolated. In addition, small amounts of very unusual complexes were obtained and characterized. In one case, the substrate 2 isomerized to the allene Ph2PC(H)=C=C(H)CH2PPh2, which formed the complex [Cp2Ti{η3‐Ph2PC(H)=C=C(H)CH2PPh2}] (4) through the coordination of a double bond and one of the phosphorus atoms. Another complex, [Cp2Ti{‐C(CH2PPh2)=C(CH2PPh2)P(Ph2)H‐}] (5), was identified to be the result of a formal hydrophosphorylation of the substrate 2 by HPPh2, and features a Ti–H–P bridge. It is not clear how HPPh2 was formed. One possible explanation is the dehydrophosphorylation of the substrate with the formation of HPPh2 and the butatriene H2C=C=C=C(H)PPh2 [tautomer of the but‐2‐en‐3‐yne HC≡C‐CH=C(H)PPh2]. The molecular structures of complexes 4 and 5 were determined by X‐ray analysis.
Organocatalytic Asymmetric Fluorination of 4‐Substituted Isoxazolinones
Authors: Zhang Huanrui , Wang Baomin , Cui Longchen , Bao Xiaoze , Qu Jingping , Song Yuming 
Published: February 2015

AbstractA straightforward method for the asymmetric fluorination of 4‐substituted isoxazolinones catalyzed by a bis‐cinchona alkaloid catalyst was developed. A series of 4‐fluoroisoxazolinone derivatives with a fluorine‐containing quaternary stereocenter were obtained in good to high yields with good enantioselectivities (up to 91 % yield, 85 % ee).
Racemization of Olefinic Alcohols by a Carbonyl(cyclopentadienyl)ruthenium Complex: Inhibition by the Carbon–Carbon Double Bond
Authors: Warner Madeleine C. , Bäckvall Jan‐E. 
Published: February 2015

AbstractIn this article, racemization of various olefinic sec‐alcohols by Ru(CO)2(η5‐C5Ph5)Cl was investigated. The racemization of three aliphatic sec‐alcohols with different chain lengths containing terminal double bonds was studied. A dramatic decrease of the racemization rate was found for these sec‐alcohols compared to that of the corresponding saturated substrates. The slow racemization rate of the former alcohols is ascribed to coordination of the double bond to the ruthenium centre, which blocks the free site needed for β‐hydride elimination. This mechanism was supported by a recent study, in which 5‐hexen‐2‐ol was found to form an alkoxycarbonyl complex having the double bond coordinated to the ruthenium atom. Aliphatic sec‐alcohol substrates with a di‐ or trisubstituted double bond were found to give a lower degree of inhibition of the racemization rate than the substrates with a monosubstituted double bond.
Experimental study of vertically upward flame spread over polymethyl methacrylate slabs at different altitudes
Authors: Liang Canjun , Cheng Xudong , Yang Hui , Zhang Heping , Yuen Kwok Kit 
Published: February 2015

SummaryExperiments of vertically upward flame spread over polymethyl methacrylate slabs were conducted in Hefei (with an altitude of 29.8 m) and Lhasa (with an altitude of 3658.0 m). Measurements were taken for the flame heights, the flame heat flux to the fuel surface and the flame spread rate. Two regions were identified for the dependence of the flame height on the heat release rate per unit width
. When
is less than 22 kW/m, the flame height scales as
while it scales as
, when
is greater than 22 kW/m. The flame heights in Lhasa are approximately 1.34 and 1.25 times, respectively, of those in Hefei for these two regions. The flame heat flux to the fuel surface decreases significantly from the pyrolysis front to the flame tip, whereas it decreases slowly above the flame tip. In both regions, it can be correlated reasonably well with (x − xp)/(xf − xp) using the form of
. The flame heat flux to the fuel surface in Lhasa is approximately 0.75 times of that in Hefei. The flame spread process can be divided into three stages, which correspond to a flow region of laminar, transitional, and turbulent, respectively. The transition to a turbulent flow is delayed in Lhasa compared with Hefei. The flame spread rate in Lhasa is about half of that in Hefei because of the lower flame heat flux caused by the lower ambient pressure. Copyright © 2015 John Wiley & Sons, Ltd.
Catalytic Influence of Oxide Component in Ni‐Based Cermet Anodes for Ammonia‐Fueled Solid Oxide Fuel Cells
Authors: Yang J. , Akagi T. , Okanishi T. , Muroyama H. , Matsui T. , Eguchi K. 
Published: February 2015

AbstractRecently, the promising prospect of ammonia as a hydrogen carrier for solid oxide fuel cells (SOFCs) has attracted significant interests. In this work, the effects of temperature, fuel content, and total flow rate of anode gas on the performance of Ni/yttria‐stabilized zirconia (Ni/YSZ) anode for ammonia‐fueled SOFCs were investigated. Based on obtained results, the utilization route of ammonia on Ni/YSZ anode was discussed; the results of electrochemical experiments were related with the catalytic decomposition bahavior of ammonia over Ni/YSZ. Moreover, the catalytic activity for ammonia decomposition and anode performance of Ni/samarium‐doped ceria (Ni/SDC) and Ni/yttrium‐doped barium cerate (Ni/BCY) were also investigated. Among these anode materials, Ni/BCY exhibited the highest ammonia decomposition activity and anode performance for ammonia‐fueled SOFCs at intermediate temperatures.
Influence of the Temperature for the Ethanol Oxidation Reaction (EOR) on Pt/C, Pt‐Rh/C and Pt‐Rh‐SnO2/C
Authors: Bach Delpeuch A. , Asset T. , Chatenet M. , Cremers C. 
Published: February 2015

AbstractThe electrocatalytic activity of Pt/C, Pt‐Rh/C and Pt‐Rh‐SnO2/C electrocatalysts toward the ethanol oxidation reaction (EOR) was investigated in a three‐electrode assembly at 25 °C, 40 °C and 70 °C in acidic medium. The 10 wt.% electrocatalysts were prepared with a modified polyol method and physically characterized by both X‐Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). The CO‐stripping study revealed that COad oxidation initiates at lower potential on Pt‐Rh/C and Pt‐Rh‐SnO2/C than on Pt/C and shifts negatively when the temperature increases. The positive effect of the temperature is maintained for the EOR: the three electrocatalysts exhibit a higher activity and a negative shift of the EOR wave at higher temperature. Pt‐Rh‐SnO2/C demonstrates the lowest EOR onset potential of the three electrocatalysts. The steady‐state Tafel slopes and apparent activation energies Ea were determined in 0.5 M H2SO4 + 0.1 M EtOH between E = 0.4 and 0.7 V vs. RHE in the temperature range 25–70 °C. The results show rather comparable rate determining steps (rds) for the ethanol electrooxidation on Pt/C and Pt‐Rh/C in the ranges of potential and temperature studied. The EOR on Pt‐Rh‐SnO2/C seems less influenced by the potential than on Pt/C and Pt‐Rh/C electrocatalysts, but is more temperature sensitive.
Towards Comprehensive Description of Stack Durability/Reliability Behavior
Authors: Yokokawa H. 
Published: February 2015

AbstractA new five‐year NEDO project on durability, on the basis of past two projects on SOFC durability/reliability, places an emphasis on simulation technologies to be utilized in comparison with measured long term stack behaviors and in prediction for 90,000 h durability. To extract true degradation issues, use is made of stack materials tested for a long term operation or for thermal cycles; to further confirm the mechanisms, use is made of single cells or button cells for specified issues. This makes it possible to correlate degradation behaviors of cell components with operational conditions such as temperature and oxygen potential with an aid of predetermination of microstructures of electrodes by FIB‐SEM or of the impurity levels inside major components at the beginning of cell operation. There are two major streams in such a comprehensive treatment of degradation; one is to predict the stack performance, the other being the prediction of mechanical instability. These will be described in details with special emphases on impurity effects and anomalous diffusion properties associated with respective extracted degradation issues.
Measuring vascular reactivity with breath‐holds after stroke: A method to aid interpretation of group‐level BOLD signal changes in longitudinal fMRI studies
Authors: Geranmayeh Fatemeh , Wise Richard J.S. , Leech Robert , Murphy Kevin 
Published: February 2015

AbstractBlood oxygenation level‐dependent (BOLD) contrast functional magnetic resonance imaging (fMRI) is a widely used technique to map brain function, and to monitor its recovery after stroke. Since stroke has a vascular etiology, the neurovascular coupling between cerebral blood flow and neural activity may be altered, resulting in uncertainties when interpreting longitudinal BOLD signal changes. The purpose of this study was to demonstrate the feasibility of using a recently validated breath‐hold task in patients with stroke, both to assess group level changes in cerebrovascular reactivity (CVR) and to determine if alterations in regional CVR over time will adversely affect interpretation of task‐related BOLD signal changes. Three methods of analyzing the breath‐hold data were evaluated. The CVR measures were compared over healthy tissue, infarcted tissue and the peri‐infarct tissue, both sub‐acutely (∼2 weeks) and chronically (∼4 months). In this cohort, a lack of CVR differences in healthy tissue between the patients and controls indicates that any group level BOLD signal change observed in these regions over time is unlikely to be related to vascular alterations. CVR was reduced in the peri‐infarct tissue but remained unchanged over time. Therefore, although a lack of activation in this region compared with the controls may be confounded by a reduced CVR, longitudinal group‐level BOLD changes may be more confidently attributed to neural activity changes in this cohort. By including this breath‐hold‐based CVR assessment protocol in future studies of stroke recovery, researchers can be more assured that longitudinal changes in BOLD signal reflect true alterations in neural activity. Hum Brain Mapp 36:1755–1771, 2015. © 2015 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc.
Effect of cloth stoma covers on tracheal climate of laryngectomy patients
Authors: Quail Gavin , Fagan Johannes J. , Raynham Oliver , Krynauw Hugo , John Lester Ryan , Carrara Henri 
Published: February 2015

ABSTRACTBackgroundThe purpose of this study was to evaluate the efficacy of cloth stoma covers (bibs) to compensate for breathing unconditioned air after laryngectomy and loss of heat‐moisture‐exchange (HME) functions of the upper airways, which, to the best of our knowledge, has never been reported. In addition, we compared the efficacy of inexpensive, simple, locally made, noncommercial fabric bibs with commercial bibs and stick‐over‐the‐stoma HME devices and to determine whether wetting the bib improves the tracheal climate.MethodsTracheal temperature and humidity were studied in 25 patients who underwent a laryngectomy with a purpose‐built sampling device.ResultsNoncommercial and commercial bibs effectively heat and humidify inspired air (p < .05). Both bibs compare favorably with commercial HME devices. There is no benefit in using a commercially produced Buchanan Bib over an inexpensive noncommercial bib. Wetting a bib proved to be counterproductive.ConclusionInexpensive, noncommercial bibs are effective and improve tracheal climate and benefit patients with laryngectomies. © 2015 Wiley Periodicals, Inc. Head Neck 38: E480–E487, 2016
The effect of Fe2O3 and ZnO nanoparticles on cytotoxicity and glucose metabolism in lung epithelial cells
Authors: Lai Xiaofeng , Wei Yifang , Zhao Hu , Chen Suning , Bu Xin , Lu Fan , Qu Dingding , Yao Libo , Zheng Jianyong , Zhang Jian 
Published: February 2015

AbstractMetallic nanoparticles (NPs) have potential applications in industry and medicine, but they also have the potential to cause many chronic pulmonary diseases. Mechanisms for their cytotoxicity, glucose and energy metabolism responses need to be fully explained in lung epithelial cells after treatment with metallic nanoparticles. In our study, two different metallic nanoparticles (Fe2O3 and ZnO) and two cell‐based assays (BEAS‐2B and A549 cell lines) were used. Our findings demonstrate that ZnO nanoparticles, but not Fe2O3 nanoparticles, induce cell cycle arrest, cell apoptosis, reactive oxygen species (ROS) production, mitochondrial dysfunction and glucose metabolism perturbation, which are responsible for cytotoxicity. These results also suggest that the glucose metabolism and bioenergetics had a great potential in evaluating the cytotoxicity and thus were very helpful in understanding their underlying molecular mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.
Non‐clinical safety and biodistribution of AS03‐adjuvanted inactivated pandemic influenza vaccines
Authors: Segal Lawrence , Wouters Sandrine , Morelle Danielle , Gautier Gaëlle , Le Gal Julien , Martin Thomas , Kuper Frieke , Destexhe Eric , Didierlaurent Arnaud M. , Garçon Nathalie 
Published: February 2015

AbstractPandemic‐influenza vaccines containing split‐inactivated‐virus antigen have been formulated with the immunostimulatory Adjuvant System AS03 to enhance the antigen immunogenicity and reduce antigen content per dose. AS03 is an oil‐in‐water emulsion containing α‐tocopherol, squalene and polysorbate 80. To support the clinical development of AS03‐adjuvanted pandemic‐influenza vaccines, the local and systemic toxicity of test articles containing split‐influenza A(H5N1) and/or AS03 were evaluated after 3–4 intramuscular (i.m.) injections in rabbits. Treatment‐related effects were restricted to mild inflammatory responses and were induced primarily by the test articles containing AS03. The injection‐site inflammation was mild at 3 days, and minimal at 4 weeks after the last injection; and was reflected by signs of activation in the draining lymph nodes and by systemic effects in the blood including a transient increase of neutrophils. In addition, a study in mice explored the biodistribution of A(H5N1) vaccines or AS03 through radiolabelling the antigen or constituents of AS03 prior to injection. In this evaluation, 57–73% of AS03's principal constituents had cleared from the injection site 3 days after injection, and their different clearance kinetics were suggestive of AS03's dissociation. All these AS03 constituents entered into the draining lymph nodes within 30 min after injection. In conclusion, the administration of repeated doses of the H5N1/AS03 vaccine was well tolerated in the rabbit, and was primarily associated with transient mild inflammation at the injection site and draining lymph nodes. The biodistribution kinetics of AS03 constituents in the mouse were consistent with AS03 inducing this pattern of inflammation. Copyright © 2015 John Wiley & Sons, Ltd.
MRT letter: A unified accelerated maximum likelihood technique for widefield, confocal, and super‐resolution 4Pi microscopy
Authors: Chelur K Rasmi , Kanhirodan Rajan , Mondal Partha Pratim 
Published: February 2015

ABSTRACTWe propose an algorithmic technique for accelerating maximum likelihood (ML) algorithm for image reconstruction in fluorescence microscopy. This is made possible by integrating Biggs–Andrews (BA) method with ML approach. The results on widefield, confocal, and super‐resolution 4Pi microscopy reveal substantial improvement in the speed of 3D image reconstruction (the number of iterations has reduced by approximately one‐half). Moreover, the quality of reconstruction obtained using accelerated ML closely resembles with nonaccelerated ML method. The proposed technique is a step closer to realize real‐time reconstruction in 3D fluorescence microscopy. Microsc. Res. Tech. 78:331–335, 2015. © 2015 Wiley Periodicals, Inc.
Postural vital capacity difference with aging in duchenne muscular dystrophy
Authors: Won Yu Hui , Choi Won Ah , Kim Dong Hyun , Kang Seong‐Woong 
Published: February 2015

ABSTRACTIntroduction: A change in vital capacity (VC) from standing to supine can be an index of diaphragm paralysis if it exceeds 25%. We aimed to verify whether the postural VC difference increases with age and reflects diaphragm weakness in DMD. Methods: VCs were measured in DMD. Postural VC difference and percentage were calculated from the VC data. Maximal inspiratory pressure (MIP) and MIP percentage were measured as an indirect index of diaphragm weakness. Results: A total of 220 patients and 544 measurements were collected. MIP and MIP percentage decreased significantly with age (P < 0.001 for both). Estimated postural VC difference and percentage also decreased (P < 0.001, P = 0.006, respectively). Age group comparisons showed a significant decrease in younger, but not older subjects. Conclusions: This study shows that the postural VC difference tended to decrease with age and might not reflect diaphragmatic weakness in DMD; however, this should be interpreted cautiously. Muscle Nerve 52: 722–727, 2015
Sonographic characteristics of the facial nerve in healthy volunteers
Authors: TAWFIK EMAN A. 
Published: February 2015

ABSTRACTIntroduction: Peripheral nerve ultrasound has become an effective imaging technique. However, imaging of cranial nerves, especially in healthy volunteers, has received minimal attention. The objectives of this study were to describe the sonographic characteristics of the facial nerve and to establish average values of its diameter. Methods: The extra‐cranial part of the facial nerve was scanned bilaterally along its longitudinal axis inside the parotid gland using a 13‐MHz probe in 50 healthy adults. The diameter was measured at the nerve's thickest region. Results: The facial nerve appeared as a thin, tubular, hypoechoic structure inside the parotid gland. The mean facial nerve diameter was 0.5 ± 0.1 mm, and the mean side‐to‐side difference in diameter was 0.1 ± 0.1 mm. Conclusions: The average facial nerve diameter values may provide help with identification of nerve abnormalities using ultrasound. Muscle Nerve 52: 767–771, 2015
Exposing the subunit diversity and modularity of protein complexes by structural mass spectrometry approaches
Authors: Chorev Dror S. , Ben‐Nissan Gili , Sharon Michal 
Published: February 2015

Although the number of protein‐encoding genes in the human genome is only about 20 000 not far from the amount found in the nematode worm genome, the number of proteins that are translated from these sequences is larger by several orders of magnitude. A number of mechanisms have evolved to enable this diversity. For example, genes can be alternatively spliced to create multiple transcripts; they may also be translated from different alternative initiation sites. After translation, hundreds of chemical modifications can be introduced in proteins, altering their chemical properties, folding, stability, and activity. The complexity is then further enhanced by the various combinations that are generated from the assembly of different subunit variants into protein complexes. This, in turn, confers structural and functional flexibility, and endows the cell with the ability to adapt to various environmental conditions. Therefore, exposing the variability of protein complexes is an important step toward understanding their biological functions. Revealing this enormous diversity, however, is not a simple task. In this review, we will focus on the array of MS‐based strategies that are capable of performing this mission. We will also discuss the challenges that lie ahead, and the future directions toward which the field might be heading.
Suppressing the long‐chain branching in the synthesis of poly(styrene‐b‐butyl acrylate‐b‐styrene) in RAFT emulsion polymerization by tuning the interfacial properties
Authors: Guo Yunlong , Gao Xiang , Luo Yingwu 
Published: February 2015

ABSTRACTReversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization is becoming an important technique to synthesize the latex of block copolymers. A previous study showed that in the synthesis of polystyrene‐b‐poly(butyl acrylate)‐b‐polystyrene triblock copolymer via RAFT emulsion polymerization using amphiphilic oligo(acrylic acid‐styrene) macroRAFT as surfactant and mediator, the molecular weight distribution could be much broadened to PDI higher than 2. In this study, an in‐depth investigation was performed to decrease PDI. It was found that long‐chain branches could be formed in the synthesis of triblock block copolymer, leading to the appearance of a higher molecular weight shoulder in the GPC curve of the final product. The lower neutralization degree of acrylic acid (AA) units on the macroRAFT and shorter AA chains would help to suppress the formation the long‐chain branches, leading to PDI around 1.5. It is evidenced that the successful suppression is due to the promotion of radical entry as a result of decreased interfacial transport impedance. It is also evidenced that the presence of styrene during the polymerization of butyl acrylate could promote the formation of long chain branches. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1464–1473
Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer
Authors: Calame Jeffrey P. 
Published: February 2015

ABSTRACTMolecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 740–759