bluuebunny/crossref_metadata_2025 huggingface dataset:
Rhodium‐Catalyzed Decarbonylative Direct C2‐Arylation of Indoles with Aryl Carboxylic Acids
Authors: Zhang Lingjuan , Xue Xiao , Xu Conghui , Pan Yixiao , Zhang Guang , Xu Lijin , Li Huanrong , Shi Zhangjie
Published: September 2014

A RhI‐catalyzed direct C2‐arylation of indoles with diversely substituted aryl carboxylic acids has been developed using 2‐pyrimidyl group as an easily installable and readily removable N‐directing group. The reaction proceeded smoothly without the need for any external oxidants under relatively mild conditions to produce the C2‐arylated indoles in high yields with excellent regioselectivity. A range of functional groups in both coupling partners were tolerated regardless of their electronic properties and positions. With the assistance of the 2‐pyrimidyl group, these C2‐functionalized products could further undergo C7‐arylation to give the C7‐aryl indole products. Mechanistic evidence supports that the reaction involves a decarbonylation step, and the carboxylic acids could be activated in situ by treatment with (tBuCO)2O to generate the active anhydrides.
Use of Diode Analogy in Explaining the Voltammetric Characteristics of Immobilized Ferrocenyl Moieties on a Silicon Surface
Authors: Herrera Marvin U. , Ichii Takashi , Murase Kuniaki , Sugimura Hiroyuki
Published: September 2014

The creation of a model that explains the dependency of the voltammetric characteristics of ferrocene‐terminated Si (Si‐Fc) samples on the type of substrate (n‐ or p‐type) would be helpful in understanding the electronic characteristics of these materials. To explain the dependency, Si‐Fc samples are treated like diodes. As diodes, the samples may allow charge flow in a certain direction while inhibiting the opposite flow. The treatment of a sample as a diode is done to facilitate analysis of charge flow within the sample, thus enabling easy prediction of its electrochemical characteristics. Likewise, the trend of the anodic peak potential versus light intensity plot (of the samples with n‐type substrate) is also associated with the sample’s diode characteristics. Our proposed model opens many scientific possibilities, especially in relating the voltammetric characteristics of electroactive molecules on a Si surface with the properties of a diode (e.g., open‐circuit voltage).
Distinctive Potential Behavior at Oxidized Surface of Semiconductor Device in Concentrated Aqueous Salt Solution
Authors: Maekawa Yuki , Shibuta Yasushi , Sakata Toshiya
Published: September 2014

The cover artwork is provided by the Sakata laboratory. The image shows the SiO2/NaCl(aq) interface obtained in silico by molecular dynamics simulation, reflecting the electrical measurement obtained on silico from a semiconductor‐based biosensor. Read the full text of the article at 10.1002/celc.201402069.
Tailoring the Structure of Two‐Dimensional Self‐Assembled Nanoarchitectures Based on NiII–Salen Building Blocks
Authors: Viciano‐Chumillas Marta , Li Dongzhe , Smogunov Alexander , Latil Sylvain , Dappe Yannick J. , Barreteau Cyrille , Mallah Talal , Silly Fabien
Published: September 2014

The synthesis of a series of NiII–salen‐based complexes with the general formula of [Ni(H2L)] (H4L=R2‐N,N′‐bis[R1‐5‐(4′‐benzoic acid)salicylidene]; H4L1: R2=2,3‐diamino‐2,3‐dimethylbutane and R1=H; H4L2: R2=1,2‐diaminoethane and R1=tert‐butyl and H4L3: R2=1,2‐diaminobenzene and R1=tert‐butyl) is presented. Their electronic structure and self‐assembly was studied. The organic ligands of the salen complexes are functionalized with peripheral carboxylic groups for driving molecular self‐assembly through hydrogen bonding. In addition, other substituents, that is, tert‐butyl and diamine bridges (2,3‐diamino‐2,3‐dimethylbutane, 1,2‐diaminobenzene or 1,2‐diaminoethane), were used to tune the two‐dimensional (2D) packing of these building blocks. Density functional theory (DFT) calculations reveal that the spatial distribution of the LUMOs is affected by these substituents, in contrast with the HOMOs, which remain unchanged. Scanning tunneling microscopy (STM) shows that the three complexes self‐assemble into three different 2D nanoarchitectures at the solid–liquid interface on graphite. Two structures are porous and one is close‐packed. These structures are stabilized by hydrogen bonds in one dimension, while the 2D interaction is governed by van der Waals forces and is tuned by the nature of the substituents, as confirmed by theoretical calculations. As expected, the total dipolar moment is minimized
Self‐Directed Orientation of Molecular Columns Based on n‐Type Hexaazatrinaphthylenes (HATNAs) for Electron Transport
Authors: Liu Xu‐Ying , Usui Takayuki , Hanna Junichi
Published: September 2014

Self‐organizing n‐type hexaazatrinaphthylenes (HATNAs) with various bay‐located side chains have been synthesized. The HATNA derivatives are able to form long‐range molecular columns with self‐directed growth directions. In particular, alkyl‐substituted HATNAs showed in‐plane molecular columns with axes parallel to substrates, whereas the columnar orientation of the HATNAs with alkylethynyl or alkylthio groups strongly depended on the length of the introduced side chains. Interestingly, the derivative with octylthio chains exhibited out‐of‐plane molecular columns, in which electron mobility of up to 10−3 cm2 V−1 s−1 was determined through the time‐of‐flight technique, highlighting the fact that such molecular columns based on bay‐substituted HATNAs are promising n‐type semiconductors for device applications.
Broadband Visible‐Light‐Harvesting trans‐Bis(alkylphosphine) Platinum(II)‐Alkynyl Complexes with Singlet Energy Transfer between BODIPY and Naphthalene Diimide Ligands
Authors: Liu Lianlian , Guo Song , Ma Jie , Xu Kejing , Zhao Jianzhang , Zhang Tierui
Published: September 2014

A heteroleptic bis(tributylphosphine) platinum(II)‐alkynyl complex (Pt‐1) showing broadband visible‐light absorption was prepared. Two different visible‐light‐absorbing ligands, that is, ethynylated boron‐dipyrromethene (BODIPY) and a functionalized naphthalene diimide (NDI) were used in the molecule. Two reference complexes, Pt‐2 and Pt‐3, which contain only the NDI or BODIPY ligand, respectively, were also prepared. The coordinated BODIPY ligand shows absorption at 503 nm and fluorescence at 516 nm, whereas the coordinated NDI ligand absorbs at 594 nm; the spectral overlap between the two ligands ensures intramolecular resonance energy transfer in Pt‐1, with BODIPY as the singlet energy donor and NDI as the energy acceptor. The complex shows strong absorption in the region 450 nm–640 nm, with molar absorption coefficient up to 88 000 M−1 cm−1. Long‐lived triplet excited states lifetimes were observed for Pt‐1–Pt‐3 (36.9 μs, 28.3 μs, and 818.6 μs, respectively). Singlet and triplet energy transfer processes were studied by the fluorescence/phosphorescence excitation spectra, steady‐state and time‐resolved UV/Vis absorption and luminescence spectra, as well as nanosecond time‐resolved transient difference absorption spectra. A triplet‐state equilibrium was observed for Pt‐1. The complexes were used as triplet photosensitizers for triplet–triplet annihilation upconversion, with upconversion quantum yields up to 18.4 % being observed for Pt‐1.
Partial Charge Transfer in the Shortest Possible Metallofullerene Peapod, La@C82⊂[11]Cycloparaphenylene
Authors: Iwamoto Takahiro , Slanina Zdenek , Mizorogi Naomi , Guo Jingdong , Akasaka Takeshi , Nagase Shigeru , Takaya Hikaru , Yasuda Nobuhiro , Kato Tatsuhisa , Yamago Shigeru
Published: September 2014

[11]Cycloparaphenylene ([11]CPP) selectively encapsulates La@C82 to form the shortest possible metallofullerene–carbon nanotube (CNT) peapod, La@C82⊂[11]CPP, in solution and in the solid state. Complexation in solution was affected by the polarity of the solvent and was 16 times stronger in the polar solvent nitrobenzene than in the nonpolar solvent 1,2‐dichlorobenzene. Electrochemical analysis revealed that the redox potentials of La@C82 were negatively shifted upon complexation from free La@C82. Furthermore, the shifts in the redox potentials increased with polarity of the solvent. These results are consistent with formation of a polar complex, (La@C82)δ−⊂[11]CPPδ+, by partial electron transfer from [11]CPP to La@C82. This is the first observation of such an electronic interaction between a fullerene pea and CPP pod. Theoretical calculations also supported partial charge transfer (0.07) from [11]CPP to La@C82. The structure of the complex was unambiguously determined by X‐ray crystallographic analysis, which showed the La atom inside the C82 near the periphery of the [11]CPP. The dipole moment of La@C82 was projected toward the CPP pea, nearly perpendicular to the CPP axis. The position of the La atom and the direction of the dipole moment in La@C82⊂[11]CPP were significantly different from those observed in La@C82⊂CNT, thus indicating a difference in orientation of the fullerene peas between fullerene–CPP and fullerene–CNT peapods. These results highlight the importance of pea–pea interactions in determining the orientation of the metallofullerene in metallofullerene–CNT peapods.
Asymmetric Reduction of α‐Amino Ketones with a KBH4 Solution Catalyzed by Chiral Lewis Acids
Authors: He Peng , Zheng Haifeng , Liu Xiaohua , Lian Xiangjin , Lin Lili , Feng Xiaoming
Published: September 2014

An efficient enantioselective reduction of α‐amino ketones with potassium borohydride solution catalyzed by chiral N,N′‐dioxide–metal complex catalysts was accomplished under mild reaction conditions for the first time. It provided a simple, convenient, and practical approaches for obtaining synthetically important chiral β‐amino alcohols in good to excellent yields (up to 98 %) and enantioselectivities (up to 97 % ee).
Synthesis of Cs2.5H0.5PW12O40/TiO2 Nanocomposites with Dominant TiO2 {001} Facets and Related Photocatalytic Properties
Authors: Hu Yichen , Ren Yuanhang , Tang Gangfeng , Wang Cheng , Tang Min , Yue Bin , He Heyong
Published: September 2014

TiO2 nanosheets with dominant {001} facets, coupled with Cs2.5H0.5PW12O40, were successfully synthesized by a one‐step hydrothermal reaction. The photocatalytic activity of nanocatalysts was evaluated by the degradation of Rhodamine B under UV light irradiation. The results showed that both the addition of Cs2.5H0.5PW12O40 and the exposed {001} facets of TiO2 have a positive effect on the photocatalytic activity. The improved photoactivity of nanocomposites in comparison with that of TiO2 nanosheets could be attributed to the synergistic effect between Cs2.5H0.5PW12O40 and TiO2 which facilitates the separation of photo‐induced hole‐electron pairs.
Synthesis of 6‐Alkylidene‐5,6‐dihydro‐4H‐1,3‐thiazine Derivatives via the Cyclization of N‐3‐Bromo‐3‐alkenylthioamides
Authors: Shen Shusu , Liu Yu
Published: September 2014

By the treatment of N‐3‐bromo‐3‐alkenylthioamides with sodium hydroxide in DMF‐H2O in the presence of tetra‐butylammonium bromide, series of 6‐alkylidene‐5,6‐dihydro‐4H‐1,3‐thiazine derivatives were prepared in moderate to good yields. The cyclization is supposed to proceed via both the intramolecular vinylic nucleophilic substitution and the elimination‐addition mechanisms (formation of acetylenic intermediates) in a competitive manner.
In Situ Preparation of Au‐SH@SO3H‐SBA‐15 Catalyst with Enhanced Activity and Durability in Alkyne Hydration
Authors: Zhu Fengxia , Li Hexing
Published: September 2014

A facile approach was developed for synthesizing Au‐SH@SO3H‐SBA‐15 with ordered mesoporous channels by reducing Au3+ to Au nanoparticles with SH‐group bonded to silica support, followed by in situ coordinating Au with the unreacted SH‐groups. This catalyst exhibited high efficiency in alkyne hydration owing to the high activity of uniformly dispersed ultrasmall Au nanoparticles, the diminished diffusion limit due to the mesoporous structure, and the promoting effect of acidic SO3H‐groups resulting from oxidation of the SH‐group by Au3+. Meanwhile, the catalyst could be easily recycled and displayed strong durability owing to the strong hydrothermal stability of mesoporous structure and the enhanced stability against Au leaching due to the Au‐SH coordination bond.
Light Induced Inhibition of Protein Phosphatase Calcineurin
Authors: Quintero Andres , Lin Weilin , Hermann Sophia , Zhang Yixin
Published: September 2014

Light‐induced switching of drug activity can be used to realize spatio‐temporal control of biological activity in cells and in vivo. In our study of light‐switchable derivatives of immunosuppressive drug cyclosporin A (CsA) in their inhibition of protein phosphatase calcineurin (CaN), we have discovered that 7‐methyl‐6‐thioguanosine (MESG) inhibits CaN under light irradiation through a photo‐crosslinking mechanism. The inhibition has shown selectivity over other enzymes such as phosphatase PP2A, protease chymotrypsin, and cyclophilin 18, the receptor protein for CsA. The discovery could pave the way to discover new covalent inhibitors for protein phosphtase, to design immunophilin‐independent CaN inhibitors, and to design new light controlled inhibitors to modulate signal transduction.
Is there an increased risk of second primary malignancy after diagnosis of thyroid cancer?
Authors: Mathur Aarti , Schneider Eric B. , Zeiger Martha A.
Published: September 2014

Recent reports on the risk of developing second primary malignancies have raised concern about whether enhanced surveillance is warranted in patients with thyroid cancer. An excellent review of the incidences and types of second primary malignancies in a Korean population treated for thyroid cancer is provided in this issue of Cancer.
POLE mutations as an alternative pathway for microsatellite instability in endometrial cancer: Implications for Lynch syndrome testing
Authors: Konstantinopoulos Panagiotis A. , Matulonis Ursula A.
Published: September 2014

In endometrial cancer, the presence of polymerase ɛ (POLE) exonuclease domain mutations in immunohistochemically abnormal/microsatellite unstable/mutL homolog1‐unmethylated tumors may serve as a marker of somatic origin. These mutations may be important in making determinations and recommendations for mismatch repair gene mutation testing in women with endometrial cancer.
Using Aqueous Ammonia in Hydroaminomethylation Reactions: Ruthenium‐Catalyzed Synthesis of Tertiary Amines
Authors: Wu Lipeng , Fleischer Ivana , Zhang Min , Liu Qiang , Franke Robert , Jackstell Ralf , Beller Matthias
Published: September 2014

The direct synthesis of tertiary amines from ammonia and olefins is presented. Using a combination of Ru3(CO)12 and 2‐phosphino‐substituted imidazole ligand as catalyst system allows for hydroaminomethylation reactions of bulk aliphatic and functionalized olefins. Tertiary amines are obtained in an atom‐efficient domino process in moderate to good isolated yields (45–76 %) with excellent regioselectivities (n/iso up to 99:1).
Antimycobacterial evaluation of novel [4,5‐dihydro‐1H‐pyrazole‐1‐carbonyl]pyridine derivatives synthesized by microwave‐mediated Michael addition
Authors: Sedighi Vida , Azerang Parisa , Sardari Soroush
Published: September 2014

The focus of this study is the synthesis and biological activity evaluation of a series of dibenzalaceton derivatives (3a‐3n) and novel [4,5‐dihydro‐1H‐pyrazole‐1‐carbonyl]pyridine derivatives (5a‐5g) against Mycobacterium bovis, Bacillus Calmette–Guerin (BCG). Dibenzalacetone derivatives were synthesized by benzaldehyde derivatives. The [4,5‐dihydro‐1H‐pyrazole‐1‐carbonyl]pyridine derivatives were synthesized by Michael addition reaction and using green chemistry microwave‐mediated method. All compounds were evaluated against BCG and the activity expressed as minimum inhibitory concentration (MIC) in μM. The result showed good activity for all the compounds especially compounds (3a), (3n), and (5a) illustrated high activity (7.03, 8.10 and 5.37 μM, respectively). Copyright © 2014 John Wiley & Sons, Ltd.
Comparison of volatile compounds of hot‐pressed, cold‐pressed and solvent‐extracted flaxseed oils analyzed by SPME‐GC/MS combined with electronic nose: Major volatiles can be used as markers to distinguish differently processed oils
Authors: Wei Chang Q. , Liu Wen Y. , Xi Wan P. , Cao Dong , Zhang Hui J. , Ding Ming , Chen Lu , Xu Ya Y. , Huang Ke X.
Published: September 2014

Analysis of volatile profiles from differently processed flaxseed oils (FSO) was performed by SPME‐GC‐MS, electronic nose (E‐nose) and descriptive sensory analysis. A total of 61 volatiles were tentatively identified and then quantified. Among these components, 51 volatiles were obtained from the hot‐pressed FSO, 47 from cold‐pressed FSO, and 40 by solvent extraction. Principal component analysis (PCA) demonstrated that three FSO samples tested resulted in significant differences of three treatments (p<0.05) and the marker compounds that contributed to discrimination of different processed FSO were hexanal, (E, E)‐2, 4‐pentadienal, (E, E)‐2, 4‐heptadienal, 6‐hydroxy‐2‐hexanone, 1‐hexanol, methyl‐pyrazine, nonanal, 2,3‐pentanedione, 1‐butanol, acetic acid, hexanoic acid, and ethyl acetate. In addition, there was good consistency among GS‐MS, sensory evaluation and E‐nose analysis results. These results indicated that the process method has a significant effect on the aroma quality of FSO and may be helpful in evaluating aroma quality and the detection of frauds.

Practical applications: The results showed that the major volatile components could be used as chemical markers to distinguish differently processed FSOs by the chemometric method. There was good consistency among GS‐MS, sensory evaluation and E‐nose analysis results, suggesting that E‐nose technique combined with a PCA of the data provided by the sensor arrays has the good potential to evaluate FSO quality and the detection of frauds.

Sixty‐one volatiles were identified and significant differences were found in different processed flaxseed oils. Twelve major volatile compounds contributed to discrimination of different processed flaxseed oils. Flaxseed oil samples were distinguished from each other through PCA of E‐nose data, suggesting that the E‐nose can successfully discriminate different processed flaxseed oils.
Addition–Elimination versus Direct Substitution Mechanisms for Arene Chlorination
Authors: Galabov Boris , Koleva Gergana , Kong Jing , Schaefer Henry F. , v. R. Schleyer Paul
Published: September 2014

Theoretical modelling of the chlorination of arenes (benzene, toluene and naphthalene) in a nonpolar solvent (CCl4) at the B3LYP‐D3/6‐311+G(2d,2p) level reveals two alternative reaction pathways, namely, direct substitution and addition–elimination, both of which lead to the same substitution products. The closeness of their barriers indicates competition between these alternative routes. Neither of these mechanistic pathways includes a σ‐complex intermediate, which is traditionally believed to be a key feature of electrophilic aromatic substitution (SEAr) mechanisms. Instead, the direct substitution pathway involves a single concerted transition state following the barrierless formation of a π‐complex between the reactants. The reported catalytic effect of HCl catalysis on the reaction product is modelled systematically and considerably decreases the transition‐state energies. The computed reaction barriers are in excellent accord with the experimentally established reactivity trends for the arenes investigated.
Determination of α‐Lipoic acid on a Pyrolytic Graphite Electrode Modified with Cobalt Phthalocyanine
Authors: Ferreira Ana Paula M. , dos Santos Pereira Laise N. , da Silva Iranaldo Santos , Tanaka Sônia M. C. N. , Tanaka Auro A. , Angnes Lúcio
Published: September 2014

In this work voltammetric techniques were explored for quantification of α‐Lipoic acid (ALA) using a pyrolytic graphite electrode modified with cobalt phthalocyanine. Cyclic voltammograms recorded in phosphate buffer solution containing 1×10−3 mol L−1 of ALA presented an oxidation peak located at +0.8 V vs. SCE. The modification of the electrode produced a 100 mV shift of the onset oxidation potential to less positive value and a substantial increase in the ALA oxidation current. Among the voltammetric techniques explored, differential pulse voltammetry showed the best performance for quantifications of the analyte in low concentrations. Limits of detection and quantification of ALA obtained corresponds to 3.4×10−9 mol L−1 and 1.2×10−8 mol L−1, respectively.
Fine‐tuning of electromembrane extraction selectivity using 18‐crown‐6 ethers as supported liquid membrane modifiers
Authors: Šlampová Andrea , Kubáň Pavel , Boček Petr
Published: September 2014

Selectivity of electromembrane extractions (EMEs) was fine‐tuned by modifications of supported liquid membrane (SLM) composition using additions of various 18‐crown‐6 ethers into 1‐ethyl‐2‐nitrobenzene. Gradually increased transfer of K+, the cation that perfectly fits the cavity of 18‐crown‐6 ethers, was observed for EMEs across SLMs modified with increasing concentrations of 18‐crown‐6 ethers. A SLM containing 1% w/v of dibenzo‐18‐crown‐6 in 1‐ethyl‐2‐nitrobenzene exhibited excellent selectivity for EMEs of K+. The established host–guest interactions between crown ether cavities in the SLM and potassium ions in donor solution ensured their almost exhaustive transfer into acceptor solution (extraction recovery ∼92%) within 30 min of EME at 50 V. Other inorganic cations were not transferred across the SLM (Ca2+ and Mg2+) or were transferred negligibly (NH4+, Na+; extraction recovery < 2%) and had only subtle effect on EMEs of K+. The high selectivity of the tailor‐made SLM holds a great promise for future applications in EMEs since the range of similar selective modifiers is very broad and may be applied in various fields of analytical chemistry.
A simple technique to improve the resolution of membrane acidic proteins of the haloarchaeon Haloferax volcanii by 2D electrophoresis
Authors: Paggi Roberto A. , Giménez María Inés , De Castro Rosana E. , Cesari Andreina
Published: September 2014

Proteins present in the archaeal cell envelope play key roles in a variety of processes necessary for survival in extreme environments. The haloarchaeon Haloferax volcanii is a good model for membrane proteomic studies because its genome sequence is known, it can be genetically manipulated, and a number of studies at the “omics” level have been performed in this organism. This work reports an easy strategy to improve the resolution of acidic membrane proteins from H. volcanii by 2DE. The method is based on the solubilization, delipidation, and salt removal from membrane proteins. Due to the abundance of the S‐layer glycoprotein (SLG) in membrane protein extracts, other proteins from the envelope are consequently underrepresented. Thus, a protocol to reduce the amount of the SLG by EDTA treatment was applied and 11 cm narrow range pH (3.9–5.1) IPG strips were used to fractionate the remaining proteins. Using this method, horizontal streaking was substantially decreased and at least 75 defined spots (20% of the predicted membrane proteome within this pI/Mw range) were reproducibly detected. Two of these spots were identified as thermosome subunit 1 and NADH dehydrogenase from H. volcanii, confirming that proteins from the membrane fraction were enriched. Removal of the SLG from membrane protein extracts can be applied to increase protein load for 2DE as well as for other proteomic methods.
Experimental studies on the effect of fire accelerants during living room fires and detection of ignitable liquids in fire debris
Authors: Krüger Simone , Deubel Jan H. , Werrel Martin , Fettig Ina , Raspe Tina
Published: September 2014

Reconstructing the course of a fire and performing chemical analysis of ignitable liquids in fire debris is an important tool to conduct fire investigations in suspected arson cases. Here, a total of five fire tests has been performed to investigate the effect of fire accelerants on the fire development of a room fire and to prove the capability of analytical methods. Different experimental scenarios have been realized (no accelerant, accelerant applied at different positions, and different amounts of fire accelerant). Each test room was equipped with an identical set of living room furnishing. The location and amount of the fire accelerant applied löschen varied in four of five tests. One experiment was carried out without fire accelerant. Fire quantities such as mass loss (of the entire room), gas temperatures (at several locations in the room), and heat release were determined during the experiments, and chemical‐analytical studies were carried out. A headspace solid phase micro extraction procedure, using gas chromatography–mass spectrometry, was used to analyze fire debris samples to potentially detect ignitable liquids. Beside the analysis of fire debris samples, swipe soot samples were analyzed and the detectability of the fire accelerant used was demonstrated. Results show that it is possible to provide evidence of ignitable liquids in soot samples collected from walls. This allows an additional sampling strategy at potential crime scenes, besides taking fire debris samples. Copyright © 2014 John Wiley & Sons, Ltd.
Forecasting Death Rates Using Exogenous Determinants
Authors: French Declan , O'Hare Colin
Published: September 2014

Mortality models used for forecasting are predominantly based on the statistical properties of time series and do not generally incorporate an understanding of the forces driving secular trends. This paper addresses three research questions: Can the factors found in stochastic mortality‐forecasting models be associated with real‐world trends in health‐related variables? Does inclusion of health‐related factors in models improve forecasts? Do resulting models give better forecasts than existing stochastic mortality models? We consider whether the space spanned by the latent factor structure in mortality data can be adequately described by developments in gross domestic product, health expenditure and lifestyle‐related risk factors using statistical techniques developed in macroeconomics and finance. These covariates are then shown to improve forecasts when incorporated into a Bayesian hierarchical model. Results are comparable or better than benchmark stochastic mortality models. Copyright © 2014 John Wiley & Sons, Ltd.
Proton Exchange Membrane Fuel Cell Operation and Degradation in Short‐Circuit
Authors: Silva R. E. , Harel F. , Jemeï S. , Gouriveau R. , Hissel D. , Boulon L. , Agbossou K.
Published: September 2014

Hybridization of proton exchange membrane fuel cells (PEMFC) and ultra capacitors (UC) are considered as an alternative way to implement high autonomy, high dynamic, and reversible energy sources. PEMFC allow high efficiency and high autonomy, however their dynamic response is limited and this source does not allow recovering energy. UC appears to be a complementary source to fuel cell systems (FCS) due to their high power density, fast dynamics, and reversibility. A direct hybridization of these sources could allow reducing the number of power converters and then the total cost of the hybridized system. Simulations show the behavior of the hybrid source when the fuel cell and ultra capacitors are interconnected and the natural energy management when a charge is connected. The results show that the magnitude of the transient current supplied by the fuel cell to charge the UC can be much higher than its nominal value. An experimental setup is implemented to study the effects of these high currents in a PEMFC. This is done by imposing a controlled short‐circuit between the electrodes. The PEMFC degradation is quantified by using electrochemical impedance spectroscopy.
SAXS Analysis of Catalyst Degradation in High Temperature PEM Fuel Cells Subjected to Accelerated Ageing Tests
Authors: Valle F. , Zuliani N. , Marmiroli B. , Amenitsch H. , Taccani R.
Published: September 2014

The loss in performance during fuel cell operation is one of the critical factors that hamper fuel cells commercialization. This paper presents a research activity related to high temperature polymer electrode membrane fuel cell (HT‐PEMFC) degradation. The aim of the study is to investigate catalyst degradation of membrane electrode assemblies (MEAs) subjected to load cycles. Two HT‐PEM MEAs have been subjected to accelerated ageing tests based on load cycling. The cycles profile has been chosen in order to enhance catalyst degradation. Both the tests show a fuel cell performance loss lower than 30 mV after 100,000 cycles at 600 mA cm−2. In order to analyze the catalyst evolution, synchrotron small angle X‐ray scattering (SAXS) has been employed. The catalyst degradation of the two conditioned samples has been compared with the data obtained from a new MEA that has been used as reference sample. The SAXS results showed a mean size increase of the platinum nanoparticles up to the 100%.
Effects of PH3 and CH3Cl Contaminants on the Performance of Solid Oxide Fuel Cells
Authors: Li T. S. , Gao C. , Xu M. , Li B. , Wu M. , Wang W. G.
Published: September 2014

Solid oxide fuel cells (SOFCs) have been considered as one of the most efficient power generators that can directly convert chemical energy in the natural gas, biomass, or coal‐derived gas to electrical energy. Various contaminants in syngas are capable to cause catalyst malfunction and cell performance drop, limiting fuel cell to a wide application. The effects of PH3 and CH3Cl fuel impurities on the electrochemical performance of SOFCs are investigated at various testing conditions. Performance drop caused by the addition of 10 ppm PH3 remains identical in pure hydrogen and simulated coal‐derived syngas at 750 °C, but a slight increase is observed when the cells are fueled syngas at 850 °C. The presence of CH3Cl in syngas causes cell degradation to a larger extent at 850 °C. Moreover, the cooperative influences of PH3 and CH3Cl impurities in hydrogen are also studied at 750, 800, and 850 °C. The addition of CH3Cl can stop and remove PH3 poisoning behavior, which is associated with each contaminant concentrations and operational temperatures. The related mechanism has been deeply analyzed and diagnosed.
Co‐synthesis of Sm0.5Sr0.5CoO3‐Sm0.2Ce0.8O1.9 Composite Cathode with Enhanced Electrochemical Property for Intermediate Temperature SOFCs
Authors: Jiang W. , Wei B. , Lü Z. , Wang Z. H. , Zhu X. B. , Zhu L.
Published: September 2014

A 70 wt.% Sm0.5Sr0.5CoO3 – 30 wt.% Sm0.2Ce0.8O1.9 (SSC–SDC73) composite cathode was co‐synthesized by a facile one‐step sol–gel method, which showed lower polarization resistance and overpotential than those of physically mixed SSC–SDC73 cathode. The polarization resistance of co‐synthesized SSC–SDC73 cathode at 800 °C was as low as 0.03 Ω cm2 in air. Scanning electron microscopy (SEM) images showed that the enhanced electrochemical property was mainly attributed to the smaller grains and good dispersion of SSC and SDC phases within the composite cathode, leading to an increase in three‐phase boundary length. The dependence of polarization resistance with oxygen partial pressure indicated that the rate‐limiting step for oxygen reduction reaction was the dissociation of molecular oxygen to atomic oxygen process. An anode supported fuel cell with a co‐synthesized SSC–SDC73 cathode exhibited a peak power density of 924 mW cm−2 at 800 °C. Our results suggested that co‐synthesized composite was a promising cathode for intermediate temperature solid oxide fuel cells (IT‐SOFCs).
Interfacial Stability between Air Electrode and Ceria‐Based Electrolyte under Cathodic Polarization in Solid Oxide Fuel Cells
Authors: Matsui T. , Komoto M. , Muroyama H. , Eguchi K.
Published: September 2014

The stability of interfacial structure between air electrode and ceria‐based electrolyte (Sm2O3–CeO2, SDC) was evaluated under various polarization conditions at 1,000 °C. This is because the structural change at the interface is strongly related to the diffusion of constituent elements and has the potential to affect the long‐term stability. In this study, (La,Sr)MnO3 (LSM) and (La,Sr)(Co,Fe)O3 (LSCF) were applied as air electrodes. The cell with LSM/SDC interface showed the performance enhancement after cathodic polarization for 5 h, accompanied with the change in interfacial structure. The magnitude of the microstructural change as well as activation was dependent on the current density and the oxygen partial pressure. However, the active triple phase boundary (TPB)‐length decreased at every condition studied. On the other hand, no appreciable change in interfacial structure was confirmed for the LSCF/SDC system regardless of polarization conditions. In response to this phenomenon, the total TPB‐length was almost identical to the active one. The difference in morphological evolution at the interface depending on the electrode material was discussed.
Curvature Reversal and Residual Stress in Solid Oxide Fuel Cell Induced by Chemical Shrinkage and Expansion
Authors: Xiang Z. , Haibo S. , Fenghui W. , Kang L. , Jianye H.
Published: September 2014

Structural stability of layered functional ceramic composites is challenged by curvature effects and residual stresses caused by the thermal mismatch and chemical strains. In this study, a phenomenon of curvature reversal is found in the half‐cell structure of solid oxide fuel cell (SOFC) during the reduction of the half‐cell from NiO‐YSZ to Ni‐YSZ. An analytical model is derived to study the curvature and residual stress caused by the chemical shrinkage and expansion of anode. With reducing to Ni‐YSZ, the curvature of the half‐cell changes from the initial direction to an opposite direction, then back to the initial direction. This curvature reversal is inevitable during reduction while the thickness ratio of electrolyte to anode is between 0 and 0.102. The residual stress in electrolyte, calculated by the analytical model, is well agreement with the experiment result using X‐ray stress analysis. The YSZ layer is always subjected to compressive stress in despite of curvature reversal existing in half‐cell. It is impossible to get the residual stress by measuring the curvature unless the half‐cell was reduced completely.
Coffee, tea and decaffeinated coffee in relation to hepatocellular carcinoma in a European population: Multicentre, prospective cohort study
Authors: Bamia Christina , Lagiou Pagona , Jenab Mazda , Trichopoulou Antonia , Fedirko Veronika , Aleksandrova Krasimira , Pischon Tobias , Overvad Kim , Olsen Anja , Tjønneland Anne , Boutron‐Ruault Marie‐Christine , Fagherazzi Guy , Racine Antoine , Kuhn Tilman , Boeing Heiner , Floegel Anna , Benetou Vasiliki , Palli Domenico , Grioni Sara , Panico Salvatore , Tumino Rosario , Vineis Paolo , Bueno‐de‐Mesquita H.B(as) , Dik Vincent K. , Bhoo‐Pathy Nirmala , Uiterwaal Cuno S. P. M. , Weiderpass Elisabete , Lund Eiliv , Quirós J. Ramón , Zamora‐Ros Raul , Molina‐Montes Esther , Chirlaque Maria‐Dolores , Ardanaz Eva , Dorronsoro Miren , Lindkvist Björn , Wallström Peter , Nilsson Lena Maria , Sund Malin , Khaw Kay‐Tee , Wareham Nick , Bradbury Kathryn E. , Travis Ruth C. , Ferrari Pietro , Duarte‐Salles Talita , Stepien Magdalena , Gunter Marc , Murphy Neil , Riboli Elio , Trichopoulos Dimitrios
Published: September 2014

Inverse associations of coffee and/or tea in relation to hepatocellular carcinoma (HCC) risk have been consistently identified in studies conducted mostly in Asia where consumption patterns of such beverages differ from Europe. In the European Prospective Investigation into Cancer and nutrition (EPIC), we identified 201 HCC cases among 486,799 men/women, after a median follow‐up of 11 years. We calculated adjusted hazard ratios (HRs) for HCC incidence in relation to quintiles/categories of coffee/tea intakes. We found that increased coffee and tea intakes were consistently associated with lower HCC risk. The inverse associations were substantial, monotonic and statistically significant. Coffee consumers in the highest compared to the lowest quintile had lower HCC risk by 72% [HR: 0.28; 95% confidence intervals (CIs): 0.16–0.50, p‐trend < 0.001]. The corresponding association of tea with HCC risk was 0.41 (95% CI: 0.22–0.78, p‐trend = 0.003). There was no compelling evidence of heterogeneity of these associations across strata of important HCC risk factors, including hepatitis B or hepatitis C status (available in a nested case–control study). The inverse, monotonic associations of coffee intake with HCC were apparent for caffeinated (p‐trend = 0.009), but not decaffeinated (p‐trend = 0.45) coffee for which, however, data were available for a fraction of subjects. Results from this multicentre, European cohort study strengthen the existing evidence regarding the inverse association between coffee/tea and HCC risk. Given the apparent lack of heterogeneity of these associations by HCC risk factors and that coffee/tea are universal exposures, our results could have important implications for high HCC risk subjects.
Improvement in population‐based survival of stage IV NSCLC due to increased use of chemotherapy
Authors: Aarts Mieke J. , van den Borne Ben E. , Biesma Bonne , Kloover Jeroen S. , Aerts Joachim G. , Lemmens Valery E.P.P.
Published: September 2014

This study aimed to investigate which factors were associated with the administration of chemotherapy for patients with stage IV non‐small cell lung cancer (NSCLC), and their relation to survival at a population‐based level. All patients with NSCLC stage IV from 2001 to 2012 were identified in the Netherlands Cancer Registry in the Eindhoven area (n = 5,428). Chemotherapy use and survival were evaluated by logistic and Cox regression analyses, respectively. The proportion of patients receiving chemotherapy increased from 30% in 2001 to 48% in 2012. Higher rates were found among younger patients [multivariable odds ratio (OR≤64_vs._≥75_years): 1.8 (95%CI 1.6–2.1)], high socioeconomic status [ORhigh_vs._low: 1.8 (95%CI 1.6–2.2)], no comorbidity [OR0_vs._≥2: 1.5 (95%CI 1.3–1.8)], diagnosed in recent years [OR2010–2012_vs._2001–2003: 2.0 (95%CI 1.6–2.3)] and adenocarcinoma [ORsquamous_vs._adenocarcinoma: 0.8 (95%CI 0.6–0.9)]. Having liver metastasis was associated with reduced odds (ORliver_vs._brain: 0.8 (95%CI 0.7–1.0). The variation between hospitals was large, up to OR 2.0 (95%CI 1.5–2.6). Median survival increased from 18 weeks in 2001–2003 to 21 weeks in 2010–2012 (log‐rank p = 0.007), and was 35 weeks in patients with and 10 weeks without chemotherapy. The multivariable hazard of death reduced significantly over time [HR2001–2003_vs._2010–2012: 1.1 (95%CI 1.0–1.2), HR2004–2005_vs._2010–2012: 1.2 (95%CI 1.1–1.3)] and only remained significant for 2004–2006 after additional adjustment for chemotherapy [final multivariable model, HR2004–2006_vs._2010–2012: 1.1 (95%CI 1.0–1.2)]. Besides, prognostic factors were having chemotherapy [final multivariable model: HR 0.4 (95%CI 0.4–0.4)], female sex [HRmale_vs._female: 1.1 (95%CI 1.0–1.1)], socioeconomic status [HRintermediate_and_high_vs._low both 0.9 (95%CI 0.9–1.0)], comorbidity [HRunknown_vs._≥2: 1.3 (95%CI 1.2–1.5)], histology [HRother_vs._adenocarcinoma: 1.1 (95%CI 1.1–1.2)], and location of metastasis [range: 1.2 (HRlymph_nodes_vs._brain) − 1.6 (HRliver_vs._brain)]. In conclusion, population‐based survival increased due to increasing administration rates of chemotherapy. The administration of chemotherapy was affected by hospital of diagnosis and both patient and tumour characteristics. Identifying patients who benefit from chemotherapy should become a key issue.
The Research and Design of A Land Reclamation Supervisory Information System in A Mining Area
Authors: Guo Xiaozhong , Pan Jian , Wu Ganguo , Xue Fanxiu , Lu Yuanqing
Published: September 2014

Using an overall document data comprehensive analysis system and a structure analysis, this study preliminarily classified technical indicators, structured the regulatory index database on construction of land reclamation, and explicated the information operation process and main content of land reclamation. From the perspective of module design, this article describes the most significant details about information query and release process, engineering construction quality monitoring and control, the land reclamation engineering acceptance process, and post‐project evaluation. From the perspective of user management, this article details the most significant features of the operation flow for the department of land and resources management, land reclamation obligations, and system management supervisors. Using the technology of Struts, Spring, and Hibernate, this article develops and designs the Land Reclamation Supervision Information System Alpha (LRSIS Alpha Version) and tests the interface and path, function, and performance of the system. Copyright © 2014 John Wiley & Sons, Ltd.
Optimized demineralization of human cancellous bone by application of a vacuum
Authors: Eagle Mark J. , Rooney Paul , Kearney John N.
Published: September 2014

Human demineralized bone matrix derived from cortical bone is used by surgeons due to its ability to promote bone formation. There is also a need for shaped demineralized bone matrices made from cancellous bone, where the properties of the material allow its insertion into defects, therefore acting as a void filler and scaffold onto which new bone can form. In this study, we report that demineralized bone sponges were prepared by dissecting and cutting knee bone into cancellous bone cubes of 1 cm3. These cubes were then taken through a series of warm water washes, some with sonication, centrifugation, and two decontamination chemical washes. The cubes were optimally demineralized into sponges with 0.5N hydrochloric acid under vacuum with constant pH measurement. Demineralization was confirmed by quantitative measurement of calcium and qualitatively by compression. The sponges were freeze dried before terminal sterilisation with a target dose of 25 kGy gamma radiation whilst frozen. Samples of the sponges were histologically examined for calcium and collagen and also tested for osteoinductivity. Data showed well defined collagen staining in the sponges, with little residual calcium. Sponges from two out of three donors demonstrated osteoinductivity when implanted into the muscle of an athymic mouse. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1023–1029, 2015.
WNT5A Has Anti-Prostate Cancer Effects In Vitro and Reduces Tumor Growth in the Skeleton In Vivo
Authors: Thiele Stefanie , Göbel Andy , Rachner Tilman D , Fuessel Susanne , Froehner Michael , Muders Michael H , Baretton Gustavo B , Bernhardt Ricardo , Jakob Franz , Glüer Claus C , Bornhäuser Martin , Rauner Martina , Hofbauer Lorenz C
Published: September 2014

Prostate cancer is the most frequent malignancy in men, and a major cause of prostate cancer–related death is attributable to bone metastases. WNT5A is known to influence the clinical outcome of various cancer types, including prostate cancer, but the exact mechanisms remain unknown. The goal of this study was to assess the relevance of WNT5A for the development and progression of prostate cancer. WNT5A expression was determined in a cDNA and tissue microarray of primary tumor samples in well-defined cohorts of patients with prostate cancer. Compared with benign prostate tissue, the expression of WNT5A and its receptor Frizzled-5 was higher in prostate cancer, and patients with a WNT5A expression above the median had a higher probability of survival after 10 years. Using different osteotropic human prostate cancer cell lines, the influence of WNT5A overexpression and knock-down on proliferation, migration, and apoptosis was assessed. In vitro, WNT5A overexpression induced prostate cancer cell apoptosis and reduced proliferation and migration, whereas WNT5A knock-down showed opposite effects. In vivo, different xenograft models were used to determine the effects of WNT5A on tumor growth. Local tumor growth and tumor growth in the bone microenvironment was considerably diminished after WNT5A overexpression in PC3 cells. WNT5A exhibits antitumor effects in prostate cancer cells and may be suitable as a prognostic marker and therapeutic target for prostate cancer and associated skeletal metastases. © 2014 American Society for Bone and Mineral Research.
A new set of atomic radii for accurate estimation of solvation free energy by Poisson–Boltzmann solvent model
Authors: Yamagishi Junya , Okimoto Noriaki , Morimoto Gentaro , Taiji Makoto
Published: September 2014

The Poisson–Boltzmann implicit solvent (PB) is widely used to estimate the solvation free energies of biomolecules in molecular simulations. An optimized set of atomic radii (PB radii) is an important parameter for PB calculations, which determines the distribution of dielectric constants around the solute. We here present new PB radii for the AMBER protein force field to accurately reproduce the solvation free energies obtained from explicit solvent simulations. The presented PB radii were optimized using results from explicit solvent simulations of the large systems. In addition, we discriminated PB radii for N‐ and C‐terminal residues from those for nonterminal residues. The performances using our PB radii showed high accuracy for the estimation of solvation free energies at the level of the molecular fragment. The obtained PB radii are effective for the detailed analysis of the solvation effects of biomolecules. © 2014 The Authors Journal of Computational Chemistry Published by Wiley Periodicals, Inc.
Informal Sources of Supervision in Clinical Training
Authors: Farber Barry A. , Hazanov Valery
Published: September 2014

Although formal, assigned supervision is a potent source of learning and guidance for psychotherapy trainees, many beginning psychotherapists use other, informal sources of supervision or consultation for advice and support. Results of an online survey of beginning trainees (N = 146) indicate that other than their formally assigned supervisor, trainees most often consult with colleagues in their program, their own psychotherapist, and their significant other; that they're most likely to seek these other sources of help when they're feeling stuck or feel they've made a clinical mistake; that they do so because they need extra reassurance and suggestions; that they feel the advice given from these sources is helpful; and that they don't especially regret sharing this information. Several case examples are used to illustrate these points. Discussing clinical material with informal sources is, apparently, a great deal more common than typically acknowledged, and as such, has implications for training programs (including discussions of ethics) and formal supervision.
Disciplinary Supervision Following Ethics Complaints: Goals, Tasks, and Ethical Dimensions
Authors: Thomas Janet T.
Published: September 2014

Clinical supervision is considered an integral component of the training of psychologists, and most of the professional literature is focused on this type of supervision. But psychologists also may supervise fully credentialed colleagues in other circumstances. One such context occurs when licensing boards mandate supervision as part of a disciplinary order. When supervision is provided in disciplinary cases, there are significant implications for the ethical dimensions of the supervisory relationship and concomitant ethical challenges for supervisors. Not only are the goals, objectives, and supervisory tasks of disciplinary supervision distinct from other types of supervision, but the supervisor's ethical responsibilities also encompass unique dimensions. Competence, informed consent, boundaries, confidentiality, and documentation are examined. Recommendations for reports to licensing boards include a statement of the clinical or ethical problems instigating discipline, description of how these problems have been addressed, and an assessment of the supervisee's current practices and ability to perform competently.