bluuebunny/crossref_metadata_2025 huggingface dataset:
VxOy Supported on Hydrophobic Poly(Ionic Liquid)s as an Efficient Catalyst for Direct Hydroxylation of Benzene to Phenol
Authors: Han Hongling , Jiang Tao , Wu Tianbin , Yang Dexin , Han Buxing
Published: September 2015

Supported vanadium oxides (VxOy) on hydrophobic poly(ionic liquid)s (PILs), for which the PILs were obtained by copolymerization of the ionic liquid (IL) 1‐hexadecyl‐3‐vinylimidazolium bromide and the cross‐linker divinylbenzene (DVB), are reported. The VxOy/PIL catalyst was characterized by different techniques, and the performance of the catalyst for the selective oxidation of benzene to phenol was studied with H2O2 as the oxidant. It was demonstrated that VxOy/PIL had much better catalytic performance than the analogous catalyst VxOy/P, prepared with the polymer support (P) obtained from DVB and vinyl imidazole, without the IL. The high activity and selectivity of the VxOy/PIL catalyst could be attributed to the incorporation of the IL during the polymerization, which endowed the VxOy/PIL catalyst with increased specific surface area, stronger absorbent ability, and more active sites than the smooth and bulky VxOy/P. Furthermore, the hydrophobic side chain of the IL in the catalyst was beneficial for the access of benzene and the removal of the generated phenol from the surface of the catalyst, which also played an important role in improving the catalytic performance of VxOy/PIL. Up to 13.4 % yield of phenol was achieved, with a high selectivity of 97.5 %. In addition, the catalyst could be easily separated and recycled at least three times without significant decline in the phenol yield.
General Strategy to Fabricate Ternary Metal Nitride/Carbon Nanofibers for Supercapacitors
Authors: Xu Yunling , Wang Jie , Ding Bing , Shen Laifa , Dou Hui , Zhang Xiaogang
Published: September 2015

In this work, ternary metal nitrides are proposed as novel electrode materials for supercapacitors. We selectively fabricate ternary vanadium titanium nitride/carbon (VTiN/C) nanofibers through a facile electrospinning strategy and investigate their electrochemical performance for the first time. The obtained well‐interconnected VTiN/C nanofibers with VTiN nanoparticles embedded into carbon ensure rapid electron/ion transfer and offer a highly ion‐accessible surface. Appealingly, the VTiN‐4/C nanofibers exhibit a greatly improved performance, with a high specific capacitance (430.7 F g−1, 0.5 A g−1) and a good rate capability. Furthermore, the performance of the VTiN/C nanofibers is found to be controllable by adjusting the V/Ti atomic ratio. The encouraging electrochemical performance suggests that ternary VTiN could be a promising electrode material for supercapacitors.
Signal‐Amplified Analysis of Molecular Layers Prepared through Bipolar Electrochemistry
Authors: Shida Naoki , Kitamura Fusao , Fuchigami Toshio , Tomita Ikuyoshi , Inagi Shinsuke
Published: September 2015

In this article, we investigate the surface modification of an indium tin oxide (ITO) plate as a bipolar electrode (BPE) by bipolar electrolysis with the well‐established electrochemistry of aryl diazonium salts. To study in detail the formation behavior of a molecular layer of the aryl groups, we employ two different approaches, namely, the direct analysis of the layer and the indirect analysis based on the idea of signal amplification by the surface‐initiated polymerization (SIP) technique. For the direct analysis, we made X‐ray photoelectron spectroscopy (XPS) measurements of the molecular layer and find that the amount of the aryl group introduced is in a gradient manner, reflecting the potential slope generated on the BPE. After the SIP process, signals amplified by the grafting polymers can be detected by infrared reflection absorption spectroscopy (IR–RAS) and film thickness measurement with a stylus‐type tester. Atomic force microscopy (AFM) measurement of the surface of the polymer brush was also carried out. These indirect methods afford detailed information on the modification behavior of the original molecular layer prepared through the bipolar electrolysis process.
Mechanistic Aspects of Aryl–Halide Oxidative Addition, Coordination Chemistry, and Ring‐Walking by Palladium
Authors: Zenkina Olena V. , Gidron Ori , Shimon Linda J. W. , Iron Mark A. , van der Boom Milko E.
Published: September 2015

This contribution describes the reactivity of a zero‐valent palladium phosphine complex with substrates that contain both an aryl halide moiety and an unsaturated carbon–carbon bond. Although η2‐coordination of the metal center to a CC or CC unit is kinetically favored, aryl halide bond activation is favored thermodynamically. These quantitative transformations proceed under mild reaction conditions in solution or in the solid state. Kinetic measurements indicate that formation of η2‐coordination complexes are not nonproductive side‐equilibria, but observable (and in several cases even isolated) intermediates en route to aryl halide bond cleavage. At the same time, DFT calculations show that the reaction with palladium may proceed through a dissociation–oxidative addition mechanism rather than through a haptotropic intramolecular process (i.e., ring walking). Furthermore, the transition state involves coordination of a third phosphine to the palladium center, which is lost during the oxidative addition as the Chalide bond is being broken. Interestingly, selective activation of aryl halides has been demonstrated by adding reactive aryl halides to the η2‐coordination complexes. The product distribution can be controlled by the concentration of the reactants and/or the presence of excess phosphine.
Versatile Tailoring of Paddle‐Wheel ZnII Metal–Organic Frameworks through Single‐Crystal‐to‐Single‐Crystal Transformations
Authors: Pal Tapan K. , Neogi Subhadip , Bharadwaj Parimal K.
Published: September 2015

A new tetracarboxylate ligand having short and long arms formed 2D layer ZnII coordination polymer 1 with paddle‐wheel secondary building units under solvothermal conditions. The framework undergoes solvent‐specific single crystal‐to‐single crystal (SC‐SC) transmetalation to produce 1Cu. With a sterically encumbered dipyridyl linker, the same ligand forms non‐interpenetrated, 3D, pillared‐layer ZnII metal–organic framework (MOF) 2, which takes part in SC‐SC linker‐exchange reactions to produce three daughter frameworks. The parent MOF 2 shows preferential incorporation of the longest linker in competitive linker‐exchange experiments. All the 3D MOFs undergo complete SC‐SC transmetalation with CuII, whereby metal exchange in different solvents and monitoring of X‐ray structures revealed that bulky solvated metal ions lead to ordering of the shortest linker in the framework, which confirms that the solvated metal ions enter through the pores along the linker axis.
Separation of Ofloxacin and Its Six Related Substances Enantiomers by Chiral Ligand‐Exchange Chromatography
Authors: Liang Xinlei , Zhao Longshan , Deng Miaoduo , Liu Lijie , Ma Yongfu , Guo Xingjie
Published: September 2015

A chiral ligand‐exchange high‐performance liquid chromatography method was developed for the enantioseparation of ofloxacin and its six related substances termed impurities A, B, C, D, E, and F. The separation was performed on a conventional C18 column. Different organic modifiers, copper salts, amino acids, the ratio of Cu2+ to amino acid, pH of aqueous phase, and column temperature were optimized. The optimal mobile phase conditions were methanol‐water systems consisting of 5 mmol/L copper sulfate and 10 mmol/L L‐isoleucine (L‐Ile). Under such conditions, good enantioseparation of ofloxacin and impurities A, C, E, and F could be observed with resolutions (RS) of 3.54, 1.97, 3.21, 3.50, and 2.12, respectively. On the relationship between the thermodynamic parameters and structures of analytes, the mechanism of chiral recognition was investigated. It was concluded that ofloxacin and impurities A, C, E, and F were all enthalpically driven enantioseparation and that low column temperature was beneficial to enantioseparation. Furthermore, the structure–separation relationship of these analytes is also discussed. Chirality 27:843–849, 2015. © 2015 Wiley Periodicals, Inc.
Discovery of Inhibitors of Trypanosoma brucei by Phenotypic Screening of a Focused Protein Kinase Library
Authors: Woodland Andrew , Thompson Stephen , Cleghorn Laura A. T. , Norcross Neil , De Rycker Manu , Grimaldi Raffaella , Hallyburton Irene , Rao Bhavya , Norval Suzanne , Stojanovski Laste , Brun Reto , Kaiser Marcel , Frearson Julie A. , Gray David W. , Wyatt Paul G. , Read Kevin D. , Gilbert Ian H.
Published: September 2015

A screen of a focused kinase inhibitor library against Trypanosoma brucei rhodesiense led to the identification of seven series, totaling 121 compounds, which showed >50 % inhibition at 5 μm. Screening of these hits in a T. b. brucei proliferation assay highlighted three compounds with a 1H‐imidazo[4,5‐b]pyrazin‐2(3H)‐one scaffold that showed sub‐micromolar activity and excellent selectivity against the MRC5 cell line. Subsequent rounds of optimisation led to the identification of compounds that exhibited good in vitro drug metabolism and pharmacokinetics (DMPK) properties, although in general this series suffered from poor solubility. A scaffold‐hopping exercise led to the identification of a 1H‐pyrazolo[3,4‐b]pyridine scaffold, which retained potency. A number of examples were assessed in a T. b. brucei growth assay, which could differentiate static and cidal action. Compounds from the 1H‐imidazo[4,5‐b]pyrazin‐2(3H)‐one series were found to be either static or growth‐slowing and not cidal. Compounds with the 1H‐pyrazolo[3,4‐b]pyridine scaffold were found to be cidal and showed an unusual biphasic nature in this assay, suggesting they act by at least two mechanisms.
Imidazotriazines: Spleen Tyrosine Kinase (Syk) Inhibitors Identified by Free‐Energy Perturbation (FEP)
Authors: Lovering Frank , Aevazelis Cristina , Chang Jeanne , Dehnhardt Christoph , Fitz Lori , Han Seungil , Janz Kristin , Lee Julie , Kaila Neelu , McDonald Joseph , Moore William , Moretto Alessandro , Papaioannou Nikolaos , Richard David , Ryan Mark S. , Wan Zhao‐Kui , Thorarensen Atli
Published: September 2015

There has been significant interest in spleen tyrosine kinase (Syk) owing to its role in a number of disease states, including autoimmunity, inflammation, and cancer. Ongoing therapeutic programs have resulted in several compounds that are now in clinical use. Herein we report our optimization of the imidazopyrazine core scaffold of Syk inhibitors through the use of empirical and computational approaches. Free‐energy perturbation (FEP) methods with MCPRO+ were undertaken to calculate the relative binding free energies for several alternate scaffolds. FEP was first applied retrospectively to determine if there is any predictive value; this resulted in 12 of 13 transformations being predicted in a directionally correct manner. FEP was then applied in a prospective manner to evaluate 17 potential targets, resulting in the realization of imidazotriazine 17 (3‐(4‐(3,4‐dimethoxyphenylamino)imidazo[1,2‐f][1,2,4]triazin‐2‐yl)benzamide), which shows a tenfold improvement in activity relative to the parent compound and no increase in atom count. Optimization of 17 led to compounds with nanomolar cellular activity.
Discovery of Novel Allosteric Non‐Bisphosphonate Inhibitors of Farnesyl Pyrophosphate Synthase by Integrated Lead Finding
Authors: Marzinzik Andreas L. , Amstutz René , Bold Guido , Bourgier Emmanuelle , Cotesta Simona , Glickman J. Fraser , Götte Marjo , Henry Christelle , Lehmann Sylvie , Hartwieg J. Constanze D. , Ofner Silvio , Pellé Xavier , Roddy Thomas P. , Rondeau Jean‐Michel , Stauffer Frédéric , Stout Steven J. , Widmer Armin , Zimmermann Johann , Zoller Thomas , Jahnke Wolfgang
Published: September 2015

Farnesyl pyrophosphate synthase (FPPS) is an established target for the treatment of bone diseases, but also shows promise as an anticancer and anti‐infective drug target. Currently available anti‐FPPS drugs are active‐site‐directed bisphosphonate inhibitors, the peculiar pharmacological profile of which is inadequate for therapeutic indications beyond bone diseases. The recent discovery of an allosteric binding site has paved the way toward the development of novel non‐bisphosphonate FPPS inhibitors with broader therapeutic potential, notably as immunomodulators in oncology. Herein we report the discovery, by an integrated lead finding approach, of two new chemical classes of allosteric FPPS inhibitors that belong to the salicylic acid and quinoline chemotypes. We present their synthesis, biochemical and cellular activities, structure–activity relationships, and provide X‐ray structures of several representative FPPS complexes. These novel allosteric FPPS inhibitors are devoid of any affinity for bone mineral and could serve as leads to evaluate their potential in none‐bone diseases.
Control over Water Adhesion on Nanostructured Parahydrophobic Films Using Mesh Substrates
Authors: Darmanin Thierry , Diouf Alioune , El‐Maiss Janwa , Yandé Dieng Samba , Guittard Frédéric
Published: September 2015

Control over water adhesion is extremely necessary for many applications in water harvesting, liquid transportation, and water/oil separation, for example. Inspired by natural species such as rose petals and gecko feet, these properties can be controlled with the topography of surface structures. Here, we report for the first time the electrodeposition of sticking conducting polymers forming nanofilaments or nanosheets on textured mesh substrates. We show that the presence of mesh textures can reduce the water adhesion, although the adhesion still remains relatively high. This is probably due to a high amount of air between the mesh wires and a low amount of air on them. Moreover, it is also possible to control the water adhesion with the mesh opening or by modifying the shape of the nanostructures. This work opens new strategies for the control of water adhesion.
Photo‐electrochemical Oxidation of Organic C1 Molecules over WO3 Films in Aqueous Electrolyte: Competition Between Water Oxidation and C1 Oxidation
Authors: Reichert Robert , Zambrzycki Christian , Jusys Zenonas , Behm R. Jürgen
Published: September 2015

To better understand organic‐molecule‐assisted photo‐electrochemical water splitting, photo‐electrochemistry and on‐line mass spectrometry measurements are used to investigate the photo‐electrochemical oxidation of the C1 molecules methanol, formaldehyde, and formic acid over WO3 film anodes in aqueous solution and its competition with O2 evolution from water oxidation O2+ and CO2+ ion currents show that water oxidation is strongly suppressed by the organic species. Photo‐electro‐oxidation of formic acid is dominated by formation of CO2, whereas incomplete oxidation of formaldehyde and methanol prevails, with the selectivity for CO2 formation increasing with increasing potential and light intensity. The mechanistic implications for the photo‐electro‐oxidation of the organic molecules and its competition with water oxidation, which could be derived from this novel approach, are discussed.
The conservation value of elevation data accuracy and model sophistication in reserve design under sea‐level rise
Authors: Zhu Mingjian , Hoctor Tom , Volk Mike , Frank Kathryn , Linhoss Anna
Published: September 2015

Many studies have explored the value of using more sophisticated coastal impact models and higher resolution elevation data in sea‐level rise (SLR) adaptation planning. However, we know little about to what extent the improved models and data could actually lead to better conservation outcomes underSLR. This is important to know because high‐resolution data are likely to not be available in some data‐poor coastal areas in the world and running more complicated coastal impact models is relatively time‐consuming, expensive, and requires assistance by qualified experts and technicians. We address this research question in the context of identifying conservation priorities in response toSLR. Specifically, we investigated the conservation value of using more accurate light detection and ranging (Lidar)‐based digital elevation data and process‐based coastal land‐cover change models (Sea Level Affecting Marshes Model,SLAMM) to identify conservation priorities versus simple “bathtub” models based on the relatively coarse National Elevation Dataset (NED) in a coastal region of northeast Florida. We compared conservation outcomes identified by reserve design software (Zonation) using three different model dataset combinations (Bathtub–NED, Bathtub–Lidar, andSLAMM–Lidar). The comparisons show that the conservation priorities are significantly different with different combinations of coastal impact models and elevation dataset inputs. The research suggests that it is valuable to invest in more accurate coastal impact models and elevation datasets inSLRadaptive conservation planning because this model–dataset combination could improve conservation outcomes underSLR. Less accurate coastal impact models, including ones created using coarser Digital Elevation Model (DEM) data can still be useful when better data and models are not available or feasible, but results need to be appropriately assessed and communicated. A future research priority is to investigate how conservation priorities may vary among differentSLRscenarios when different combinations of model‐data inputs are used.
Carbocation Catalysis: Oxa‐Diels–Alder Reactions of Unactivated Aldehydes and Simple Dienes
Authors: El Remaily Mahmoud Abd El Aleem Ali Ali , Naidu Veluru Ramesh , Ni Shengjun , Franzén Johan
Published: September 2015

The versatility of the trityl cation (TrBF4) as a highly efficient Lewis acid organocatalyst is demonstrated in the oxa‐Diels–Alder reaction of various unactivated aromatic and aliphatic aldehydes and simple unactivated dienes, such as isoprene and 2,3‐dimethylbutadiene. The transformation proceeds smoothly to give 3,6‐dihydropyrane adducts in high to moderate yields with catalyst loadings down to 1.0 mol‐% under mild reaction conditions. In contrast to most previously reported strategies, this protocol does not require substrate functional group activation, neither by electron‐deficient aldehydes (2‐oxo aldehydes) or electron‐rich dienes (methoxy or amino‐butadiene).
Thermal Performance Improvement of Tractor Radiator Using CuO/Water Nanofluid
Authors: Ravisankar R. , Venkatachalapathy V. S. K. , Alagumurthy N.
Published: September 2015

This research work discusses the heat transfer improvement in a tractor radiator with nanosized particles of CuO with water as base fluid. The nano materials and its suspension in fluids as particles have been the subject of intensive study worldwide recently since pioneering researchers recently discovered the anomalous thermal behavior of these fluids. The engine cooling in heavy vehicles is an important factor for their performance in the intended application. Here, the tractor engine radiator cooling is enhanced by the nanofluid mechanism of heat transfer for its improved performance in agricultural work. Through the improvement of tractor engine cooling through the radiator a greater area can be ploughed and cultivated within a short time span. Heat transfer in automobiles is achieved through radiators. In this research work an experimental and numerical investigation for the improved heat transfer characteristics of a radiator using CuO/water nanofluid for 0.025 and 0.05% volume fraction is done with an inlet temp of 50 °C to 60 °C under the turbulent flow regime (8000 ≤ Re ≤ 25000). The overall heat transfer coefficient decreases with an increase in nanofluid inlet temperature of 50 °C to 60°C. The experimental results of the heat transfer using the CuO nanofluid is compared with the numerical values. The results in this work suggest that the best heat transfer enhancement can be obtained compared with the base fluid by using a system with CuO/ water nanofluid‐cooled radiators.
Using magnetic resonance imaging to quantify the inflammatory response following allergen challenge in allergic rhinitis
Authors: Leaker Brian R. , Scadding Glenis , Jones C. Richard , Barnes Peter J.
Published: September 2015

Current rhinometric and flow assessments measure nasal patency and are often poorly correlated with rhinitis symptoms. To evaluate magnetic resonance imaging (MRI) as a new method to measure inflammatory changes in nasal and sinus mucosa following nasal allergen challenge. A pilot study (n = 6) determined the optimal technical settings for MRI to measure inflammatory change which were then adopted for the main study. This study was a single blind, placebo‐controlled, three‐way crossover trial in 14 subjects with seasonal allergic rhinitis. Effects of cetirizine, cetirizine and pseudoephedrine (Cet+PE), or placebo on total nasal symptom scores (TNSS), peak nasal inspiratory flow (PNIF), nasal nitric oxide (nNO), acoustic rhinometry, and MRI end points following nasal intranasal allergen challenge were measured. There were significant changes in all parameters after allergen challenge (P < 0.01), except for nNO. MRI end points were less variable and more consistent than PNIF and acoustic rhinometry in detecting changes after allergen challenge. Total nasal airspace volume was the most sensitive and reproducible MRI measurement, with a mean reduction from −5.37 cm3 (95%CI −7.35, −3.38; P < 0.001), which was maximal 60 min after allergen challenge. A change of one in TNSS corresponded to a change in MRI volume of −0.57 cm3. There was an improvement in all parameters (except nNO) in subjects taking Cet+PE compared with placebo, however this did not achieve significance probably because of the small study size (overall analysis P > 0.07; comparison of active versus placebo P > 0.09). MRI provides novel insights into the anatomical inflammatory changes post allergen challenge and provides a new method for assessment of nasal patency and objective measurement of inflammatory responses.
Physicochemical and Redox Characteristics of Fe Ion‐doped CeO2 Nanoparticles
Authors: Ansari Anees A. , Labis J. , Alam Manawwer , Ramay Shahid M. , Ahmad Naushad , Mahmood Asif
Published: September 2015

We report the structural, thermal, optical, and redox properties of Fe‐doped cerium oxide (CeO2) nanoparticles, obtained using the polyol‐co‐precipitation process. X‐ray diffraction data reveal the formation of single‐phase structurally isomorphous CeO2. The presence of Fe3+ may act as electron acceptor and/or hole donor, facilitating longer lived charge carrier separation in Fe‐doped CeO2 nanoparticles as confirmed by optical band gap energy. The increased content of localized defect states in the ceria gap and corresponding shift of the optical absorption edge towards visible range in Fe‐doped samples can significantly improve the optical activity of nanocrystalline ceria. The better‐quality redox performances of the Fe‐doped CeO2 nanoparticles, compared with undoped CeO2 nanoparticles, were ascribed mainly to a decrease in band gap energy and an increase in specific surface area of the material. As observed from TPR studies all Fe ‐doped CeO2 nanoparticles, particularly the 10 mol % Fe doped CeO2 nanoproduct, exhibit excellent reduction performance.
Quantum Mechanical Study of Substituent Dependence on the Structure, Spectroscopic (13C, 1H NMR and UV), NBO, Hyperpolarizability and HOMOLUMO Analysis of Ru(NHC)2Cl2(CH‐p‐C6H4X) Complexes
Authors: Ghiasi Reza , Abdolmohammadi Shahrzad , Moslemizadeh Sara
Published: September 2015

In this work, we have explored the structural, electronic properties, 13C and 1H NMR parameters and first hyperpolarizability of Ru(NHC)2Cl2(CH‐p‐C6H4X) complexes (XH, F, Cl, Me, NH2, OH, CN, NO2, CHO, COOH) by mpw1pw91 quantum method. The X‐substituent effect on structural parameters, frontier orbital energies, spectroscopic (1H and 13C NMR, UV) of complex was carried out. The results indicate that the substituent has played a significant role on the structures and properties of complex. 1H and 13C NMR chemical shifts were calculated by using the gauge‐invariant atomic orbital (GIAO) method. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (OPDOS) diagrams analysis were exhibited. In analyzing the bonding characteristics of this structure, Ru‐Ccarbene and Ru‐CNHC bonds were identified and characterized in details by Natural bond orbital (NBO) analysis.
Microwave‐Assisted Organic Synthesis in Ionic Liquids
Authors: Pathak Arpit Kumar , Ameta Chetna , Ameta Rakshit , Punjabi Pinki B.
Published: September 2015

Revolution in organic compound synthesis has been promoted by microwave‐assisted organic syntheses (MAOS) by which small molecules are built up into large polymers in a fraction of time. Ionic liquids (ILs), considered being a relatively recent magical chemical due to their unique properties, have a large variety of applications in all areas of the chemical industries. Nonvolatility and nonflammability are their common characteristics giving them an advantageous edge in various applications. This common advantage, when considered with the possibility of tuning the chemical and physical properties of ILs by changing anion–cation combination, is a great opportunity to obtain task‐specific ILs for a multitude of specific applications. In previous reviews on this subject, the focus of MAOS has been on the process of MAOS reactions rather than the importance given to the related applications. This review focuses on properties of ILs and their use in organic synthesis of heterocyclic compounds under microwave exposure. In this review, a general description of ILs and historical background are given; basic properties of ILs such as solvent properties are discussed; structure of ILs, cation, anion types, and synthesis methods in the related literature and synthesis of different heterocyclic compounds in ILs are briefly summarized.
Experimental evidence of hepatitis A virus infection in pigs
Authors: Song Young‐Jo , Park Woo‐Jung , Park Byung‐Joo , Kwak Sang‐Woo , Kim Yong‐Hyeon , Lee Joong‐Bok , Park Seung‐Yong , Song Chang‐Seon , Lee Sang‐Won , Seo Kun‐Ho , Kang Young‐Sun , Park Choi‐Kyu , Song Jae‐Young , Choi In‐Soo
Published: September 2015

Hepatitis A virus (HAV) is the leading cause of acute viral hepatitis worldwide, with HAV infection being restricted to humans and nonhuman primates. In this study, HAV infection status was serologically determined in domestic pigs and experimental infections of HAV were attempted to verify HAV infectivity in pigs. Antibodies specific to HAV or HAV‐like agents were detected in 3.5% of serum samples collected from pigs in swine farms. When the pigs were infected intravenously with 2 × 105 50% tissue culture infectious dose (TCID50) of HAV, shedding of the virus in feces, viremia, and seroconversion were detected. In pigs orally infected with the same quantity of HAV, viral shedding was detected only in feces. HAV genomic RNA was detected in the liver and bile of intravenously infected pigs, but only in the bile of orally infected pigs. In further experiments, pigs were intravenously infected with 6 × 105 TCID50 of HAV. Shedding of HAV in feces, along with viremia and seroconversion, were confirmed in infected pigs but not in sentinel pigs. HAV genomic RNA was detected in the liver, bile, spleen, lymph node, and kidney of the infected pigs. HAV antigenomic RNA was detected in the spleen of one HAV‐infected pig, suggesting HAV replication in splenic cells. Infiltration of inflammatory cells was observed in the livers of infected pigs but not in controls. This is the first experimental evidence to demonstrate that human HAV strains can infect pigs. J. Med. Virol. 88:631–638, 2016. © 2015 Wiley Periodicals, Inc.
Changes in annual, seasonal and monthly precipitation events and their link with elevation in Sichuan province, China
Authors: Zeng Wei , Yu Zhen , Wu Shihu , Qin Jianbo
Published: September 2015

This study performs the spatial and temporal trend analysis of the annual, seasonal and monthly time series of a set of uniformly distributed 36 stations precipitation data in Sichuan Province during 1960–2013. The result indicates that the annual precipitation amount and precipitation days across the region have decreasing trends, but the last is significant. The annual precipitation intensity and maximum 1‐day precipitation have slightly increasing trends. Although annual precipitation amount and precipitation days decline, annual precipitation intensity and maximum 1‐day precipitation rise. This reflects that droughts and floods increase in Sichuan Province in recent years. Seasonally, precipitation amount has decreased in all seasons, while autumn precipitation amount is statistically significant. Regionally average trends in precipitation days also show large differences in all seasons. The temporal variability in regional precipitation intensity increases except for autumn, but significant increases are found in spring and summer. Regional maximum 1‐day precipitation has significantly increasing trends in spring and summer, but slightly decreasing trend in autumn and winter. On a monthly basis, trends of precipitation amount show tremendous differences. Spatial changes in annual, seasonal and monthly precipitation events are not the same, and they are not clustered, either. Additionally, the correlations between elevation and the magnitudes of the trends in annual precipitation amount and precipitation days are statistically significant whereas the correlations are not perfect in precipitation intensity and maximum 1‐day precipitation. As can be seen from the seasonal and monthly precipitation amount, the correlations between elevation and the magnitudes of the trends in precipitation amount are higher in spring and autumn, but not perfect in summer and winter. April, October and December precipitation amount shows the strongest positive correlations with elevation. On the whole, the increasing trend of precipitation is relatively prominent at higher elevations, while the decrease trend is more significant at low elevation stations.
Organizational Ethnographic Research: Intersections of Place, Cultural Identities, Constructed Memories, and Sense Making Within Institutions
Authors: Gavin Diane
Published: September 2015

In the article, the author presents a discussion on the value of incorporating institutional ethnographic studies in a researcher's repertoire. Researchers who conduct institutional ethnographies provide critical cultural examinations of organizations, companies, schools, or other establishments that give insights into the values, mores, and belief systems that may not be apparent at first glance. Gavin draws upon her experience as an ethnographer to explain her approach to institutional ethnography and the benefits she has gleaned from such research. Those qualitative researchers who are considering new research venues to explore may find institutional ethnography to be a challenging yet fruitful area.
The Phenomenon of Later‐Life Recareering by Well‐Educated Baby Boomers
Authors: Rice Candy K.
Published: September 2015

As well‐educated Boomer professionals reach later life they are engaging in activities such as recareering that defy the normal expectation for older workers in the late adulthood life stage of adult development. Recareering is embarking on a new career in a new industry later in life, after leaving a long‐term primary career. Growing numbers of Boomers are redefining normal work activities as they reach traditional retirement age.

A qualitative phenomenological analysis explored the experience of well‐educated Baby Boomer professionals who have recareered. From the dominant thematic findings emerged seven essences of the shared experience of recareering for this population. Results strikingly defied much of common knowledge of the older worker experience.

Implications suggested a critical need to embrace a new paradigm of work activities in positive aging. Insights from these Baby Boomer professionals have the potential to redefine adult development theory. Findings have wide benefits for practitioners, academicians, organizations, and governments in terms of the development and implementation of new products, services, and policies for older workers. Future recommendations and limitations are outlined.
Combined uncertainty estimation for the determination of the dissolved iron amount content in seawater using flow injection with chemiluminescence detection
Authors: Floor Geerke H. , Clough Robert , Lohan Maeve C. , Ussher Simon J. , Worsfold Paul J. , Quétel Christophe R.
Published: September 2015

This work assesses the components contributing to the combined uncertainty budget associated with the measurement of the Fe amount content by flow injection chemiluminescence (FI‐CL) in <0.2 μm filtered and acidified seawater samples. Amounts of loaded standard solutions and samples were determined gravimetrically by differential weighing. Up to 5% variations in the loaded masses were observed during measurements, in contradiction to the usual assumptions made when operating under constant loading time conditions. Hence signal intensities (V) were normalised to the loaded mass and plots of average normalised intensities (in V kg−1) vs. values of the Fe amount content (in nmol kg−1) added to a “low level” iron seawater matrix were used to produce the calibration graphs. The measurement procedure implemented and the uncertainty estimation process developed were validated from the agreement obtained with consensus values for three SAFe and GEOTRACES reference materials (D2, GS, and GD). Relative expanded uncertainties for peak height and peak area based results were estimated to be around 12% and 10% (coverage factor k = 2), respectively. The most important contributory factors were the uncertainty on the sensitivity coefficient (i.e., calibration slope) and the within‐sequence‐stability (i.e., the signal stability over several hours of operation; here 32 h). For GD, using peak height measurements, these factors contributed respectively 69.7% and 21.6% while the short‐term repeatability accounted for only 7.9%. Therefore, an uncertainty estimation based on the intensity repeatability alone, as is often done in FI‐CL studies, is not a realistic estimation of the overall uncertainty of the procedure.
Erosive wear behavior and dynamic mechanical analysis of textile material reinforced polymer composites
Authors: Tejyan Sachin , Patnaik Amar
Published: September 2015

The present analysis intends to look into the needlepunched nonwoven textile material reinforced polymer composites. The solid particle erosion wear behavior of needlepunched nonwoven fabric mat reinforced epoxy composites were assessed using silica sand particles with the size of 250, 350, and 450 μm. Taguchi analysis was also carried out on the basis of design of experiments (DoE) approach to establish the interdependence of operating parameters. Mechanical and physical properties of composites were also evaluated experimentally, and the storage modulus (E′), loss modulus (E″) and damping factor (tan δ) characteristics were analyzed with the help of dynamic mechanical analyzer (DMA) in the temperature range of 20–200°C. Surface morphology of the eroded surfaces of composites were also analyze by scanning electron microscopic (SEM) to discuss the feasible erosion mechanism on composite surfaces. The result reveals that fiber content and impact velocity has an invulnerable impact on the erosion rate of needlepunched nonwoven fabric mat‐epoxy composites. The mechanical and physical properties are meliorating with incorporation of fabric mat weight percentage in composites, and the measured damping factor (tan δ) peaks of Tg for needlepunched nonwoven fabric mat epoxy composites ranged from 100 to 110°C. POLYM. COMPOS., 38:2201–2211, 2017. © 2015 Society of Plastics Engineers
Effects of all‐sky assimilation of GCOM‐W/AMSR2 radiances in the ECMWF numerical weather prediction system
Authors: Kazumori Masahiro , Geer Alan J. , English Stephen J.
Published: September 2015

This article assesses the impact of Advanced Microwave Scanning Radiometer 2 (AMSR2) radiances in the all‐sky assimilation of the European Centre for Medium‐Range Weather Forecasts (ECMWF). Individual impacts of three microwave imagers including AMSR2 were examined by using a baseline experiment that had no microwave imager data. The three microwave imagers brought similar improvements in humidity, temperature and wind first‐guess (FG) fields in the troposphere. Improvements were found in fits to both analyses and other observations. Moreover, significant improvements in wind and geopotential height fields in the troposphere were found in day 3–6 forecasts. AMSR2 made larger improvements than other microwave imagers to geopotential height forecasts in the Northern Hemisphere. The use of AMSR2 radiance data in addition to the other existing microwave imagers gave mixed results. Consistent improvements in the FG fit to humidity observations were confirmed. However, the FG fit for several channels of the microwave temperature sounding instruments was degraded. The mean FG departure of AMSR2 showed biases that varied according to the time of day and meteorological conditions. The causes of the biases were identified as insufficient representation of the cloud liquid water path (LWP) in the forecast model under unstable conditions and insufficient amplitude of LWP diurnal variation in stratocumulus areas in the Tropics. The assimilation of too much biased data might start to bring negative effects for the analyses and forecasts, which for some parameters could outweigh the improvements in the assimilation. However, despite this, AMSR2 brought significant improvements of the geopotential height field in the Southern Hemisphere lower troposphere for day 5–7 forecasts.
Improving the Laplace transform integration method
Authors: Lynch Peter , Clancy Colm
Published: September 2015

We consider the Laplace transform filtering integration scheme applied to the shallow‐water equations, and demonstrate how it can be formulated as a finite‐difference scheme in the time domain. In addition, we investigate a more accurate treatment of the nonlinear terms. The advantages of the resulting algorithms are demonstrated by means of numerical integrations.
Theoretical prediction of the electronic and thermodynamic properties of YN‐ZrN solid solutions
Authors: Ramírez‐Montes Luz , López‐Pérez William , González‐García Alvaro , González‐Hernández Rafael
Published: September 2015

In this study, the results of structural parameters, electronic structure, and thermodynamic properties of the ZrxY1–xN solid solutions are presented. The effect of zirconium composition on lattice constant, and bulk modulus shows nonlinear dependence on concentration. Deviations of the lattice constant from Vegard's law and deviations of the bulk modulus from linear concentration dependence were found. Our findings indicate that the ZrxY1–xN solid solutions are metallic for x = 0.25, 0.5, 0.75. The calculated excess mixing enthalpy is positive over the entire zirconium composition range. The positive mixing enthalpies for ZrxY1–xN alloys indicate the existence of miscibility gaps and spinodal decompositions. The effect of temperature on the volume, bulk modulus, Debye temperature, and the heat capacity for ZrxY1–xN alloys were analyzed using the quasi‐harmonic Debye model. Results show that the heat capacity is slightly sensitive to composition as temperature increases. © 2015 Wiley Periodicals, Inc.
CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results
Authors: Jorge Francisco E. , de Oliveira Amanda Z. , Silva Thiago P.
Published: September 2015

A hierarchical sequence of basis sets along with one long‐range corrected functional (CAM‐B3LYP) were used to calculate electronic optical rotations (OR) at three wavelengths (355.0, 589.3, and 633.0 nm) of 14 rigid chiral molecules whose experimental values are available in the literature. As the results showed to be sensitive to the basis set quality, complete basis set limits were estimated. Special attention was given to five particularly difficult compounds. In these cases, one verifies that vibrational corrections (taken from the literature) must be added to the CAM‐B3LYP equilibrium OR to correct signs. In general, the complete basis set limits reported in this work are in good agreement with the experimental data and with those obtained at a higher level of theory. For some compounds, solvent effects are taken into account by means of the polarizable continuum model. For the solvated systems, the dependence between OR and cavity size is also examined. © 2015 Wiley Periodicals, Inc.
Incorporation of nested frailties into semiparametric multi‐state models
Authors: Rotolo Federico , Rondeau Virginie , Legrand Catherine
Published: September 2015

Proportional hazards models are among the most popular regression models in survival analysis. Multi‐state models generalize them by jointly considering different types of events and their interrelations, whereas frailty models incorporate random effects to account for unobserved risk factors, possibly shared by clusters of subjects. The integration of multi‐state and frailty methodology is an interesting way to control for unobserved heterogeneity in the presence of complex event history structures and is particularly appealing for multicenter clinical trials. We propose the incorporation of correlated frailties in the transition‐specific hazard function, thanks to a nested hierarchy. We studied a semiparametric estimation approach based on maximum integrated partial likelihood. We show in a simulation study that the nested frailty multi‐state model improves the estimation of the effect of covariates, as well as the coverage probability of their confidence intervals. We present a case study concerning a prostate cancer multicenter clinical trial. The multi‐state nature of the model allows us to evidence the effect of treatment on death taking into account intermediate events. Copyright © 2015 JohnWiley & Sons, Ltd.
Pharmacokinetic Profile of Subcutaneous Testosterone Enanthate Delivered via a Novel, Prefilled Single-Use Autoinjector: A Phase II Study
Authors: Kaminetsky Jed , Jaffe Jonathan S. , Swerdloff Ronald S.
Published: September 2015

Introduction

Hypogonadism is one of the most common male endocrine problems. Although many treatments are currently available, unmet need exists for new testosterone (T) replacement therapies that are simple to administer and use, are safe, and mimic physiologic T levels.

Aim

The study aim was to determine the pharmacokinetics (PK), safety, and tolerability of T enanthate (TE) administered via a novel single-use autoinjector system, which was designed to eject high-viscosity solutions from a prefilled syringe fitted with a five-eighths-inch 27-gauge needle.

Methods

Thirty-nine men with hypogonadism entered this dose-finding, open-label, parallel-group study. Patients were washed out of their topical T regimens and randomized to receive 50 or 100 mg of subcutaneous (SC) TE weekly. The reference group were patients with hypogonadism who were maintained on standard 200-mg intramuscular (IM) TE.

Main Outcome Measure

The primary outcome measure was the PK profile of SC TE, analyzed in reference to T levels used by the Food and Drug Administration to approve T products. Secondary outcome measures were safety and tolerability assessments.

Results

Both doses of SC TE achieved normal average concentrations of serum T within a 168-h dosing interval after injection. Concentration ranges were similar at all time points following 50-mg SC TE injections and following the third injection in the 100-mg arm. Mean steady-state T concentration at week 6 was 422.4 and 895.5 ng/dL for the 50- and 100-mg SC TE arms, respectively. SC TE demonstrated PK dose proportionality. SC TE restored normal serum T with low variation relative to 200-mg IM without clinically significant adverse events.

Conclusions

Administration of TE via this novel injection system restored T levels to normal range in men with hypogonadism. SC TE dosed weekly demonstrated steady, dose-proportional measures of exposure and was well-tolerated.
A QoE centric distributed caching approach for vehicular video streaming in cellular networks
Authors: Sun Fei , Liu Bo , Hou Fen , Zhou Haibo , Chen Jiacheng , Rui Yun , Gui Lin
Published: September 2015

Distributed caching‐empowered wireless networks can greatly improve the efficiency of data storage and transmission and thereby the users' quality of experience (QoE). However, how this technology can alleviate the network access pressure while ensuring the consistency of content delivery is still an open question, especially in the case where the users are in fast motion. Therefore, in this paper, we investigate the caching issue emerging from a forthcoming scenario where vehicular video streaming is performed under cellular networks. Specifically, a QoE centric distributed caching approach is proposed to fulfill as many users' requests as possible, considering the limited caching space of base stations and basic user experience guarantee. Firstly, a QoE evaluation model is established using verified empirical data. Also, the mathematic relationship between the streaming bit rate and actual storage space is developed. Then, the distributed caching management for vehicular video streaming is formulated as a constrained optimization problem and solved with the generalized–reduced gradient method. Simulation results indicate that our approach can improve the users' satisfaction ratio by up to 40%. Copyright © 2015 John Wiley & Sons, Ltd.
Between democracy and putsch? — Censure motions in Romania (1989–2012)
Authors: Stan Lavinia
Published: September 2015

Though vilified as instances of “parliamentary putsch,” no-confidence censure motions remain significant constitutional tools through which the opposition can challenge the government in Romania, and publicly underscore its policy ineffectiveness in certain areas of activity. An overview of censure motions debated in the Romanian parliament from 1989 to 2012 reveals that center-left cabinets faced fewer challenges than their centerright counterparts, anti-communist forces were less skilled in articulating criticisms against cabinets, not all adopted motions led to cabinet removal, and motions became increasingly complex over time. Two motions adopted in 2009 and 2012, tabled by the center-left opposition against center-right cabinets, turned these parliamentary tools into powerful censure instruments.
The Hawthorne Effect in Infection Prevention and Epidemiology
Authors: Chen Luke F. , Vander Weg Mark W. , Hofmann David A. , Reisinger Heather Schacht
Published: September 2015

The Hawthorne Effect is a prevalent observer effect that causes behavioral changes among participants of epidemiological studies or infection control interventions. The purpose of the review is to describe the origins of the Hawthorne Effect, to understand the term in relation to current scientific literature, to describe characteristics of the Hawthorne effect, and to discuss methods to quantify and overcome limitations associated with the Hawthorne Effect.

Infect. Control Hosp. Epidemiol.2015;36(12):1444–1450