bluuebunny/crossref_metadata_2025 huggingface dataset:
Robust Fault Detection Using Subspace Aided Data Driven Design
Authors: Hussain Abrar , Khan Abdul Qayyum , Abid Muhammad
Published: January 2015

The paper deals with the design of robust fault detection system using subspace aided data driven techniques. Because of unavailability of system matrices for the complex processes, a new algorithm has been proposed to identify a robust parity vector directly from the process data. The identified parity vector is used to construct a residual generator having robustness against the process and sensor noises and increased sensitivity to actuator and sensor faults. The performance of the proposed fault detection scheme has been analyzed by simulation studies on a coupled liquid three tank system (CLTS).
Gravitational entropy of cosmic expansion
Authors: Sussman R. A.
Published: January 2015

We apply a recent proposal to define “gravitational entropy” to the expansion of cosmic voids within the framework of nonperturbative General Relativity. By considering CDM void configurations compatible with basic observational constraints, we show that this entropy grows from post‐inflationary conditions towards a final asymptotic value in a late time fully nonlinear regime described by the Lemaître‐Tolman‐Bondi (LTB) dust models. A qualitatively analogous behavior occurs if we assume a positive cosmological constant consistent with a Λ‐CDM background model. However, the Λ term introduces a significant suppression of entropy growth with the terminal equilibrium value reached at a much faster rate. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Neutrino emissivity, strong magnetic fields and cooling of neutron stars
Authors: Coelho E. L. , Chiapparini M. , Bracco M. E. , Negreiros R. P.
Published: January 2015

The direct Urca process is an extremely efficient mechanism for cooling a proto neutron star after its formation. It is believed to be the process responsible for the cooling of proto‐neutron stars after the first 100 years of life. One of the most interesting kind of neutron stars are the pulsars, which are highly magnetized neutron stars with fields up to 1014 G at the surface. In this work we investigate the influence of strong magnetic fields on the cooling of pulsars due to the neutrino emissivity coming from the direct Urca process. The matter is described using a relativistic mean‐field model at zero temperature. We calculate numerically the emissivity of neutrinos for different magnetic fields as a function of the baryon density and compare the results for the case without a magnetic field. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A possible 130 GeV gamma‐ray line from annihilating singlet fermionic dark matter
Authors: Franarin T. H. , Vasconcellos C. A. Z. , Hadjimichef D.
Published: January 2015

There is evidence for a spectral line at Eγ ≈ 130 GeV in the Fermi ‐LAT data that can be explained as dark mater particles annihilating into photons. We review a well known dark matter model that consists in a singlet Dirac fermion and a singlet scalar. The scalar implements spontaneous symmetry breaking in the dark sector, and is responsible for the communication between dark matter and standard model particles through a coupling to the Higgs. These interactions are suppressed by the mixing between the scalar and the Higgs. Therefore, the singlet fermionic dark matter is naturally a weakly interacting massive particle (WIMP) and can explain the observed relic density. We show that this model cannot produce the signal identified in the Fermi ‐LAT data. Thus, we propose a modification in the model by introducing a new scalar multiplet that carries electric charge and couples to the singlet scalar. It enhances the annihilation into two photons and succeeds in producing the observed signal. We also discuss the resulting increase of the branching ratio of the h → γγ process, which is consistent with measurements from the CMS experiments. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Predicted values of braking indexes and second frequency derivatives for magnetars
Authors: Gao Z. F. , Zhao X. J. , Song D. L. , Liu N. , Wang N.
Published: January 2015

To date, the observational determination of braking indexes of magnetars is still an open question due to the lack of long‐term radio emission and strong timing noise. Based on the assumption that the real ages of magnetars are the ages of their host supernova remnants (SNRs), expanding diffuse gaseous nebulae resulting from explosions of massive stars, we obtain the sizes of the braking index n for 11 magnetar candidates with SNRs. According to our calculations, the magnetar braking indexes will be constrained within the range of about 1–40, assuming the measurements of SNRs are reliable. We also investigate the frequency parameters of magnetars with associated SNRs, and estimate possible wind luminosities for magnetars with n < 3 and magnetic field decay rates for magnetars with n > 3. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Effects of AMM on the EoS of magnetized dense systems
Authors: Manreza Paret D. , Perez Martinez A. , Ferrer E. J. , de la Incera V.
Published: January 2015

We investigate the effects of the anomalous magnetic moment (AMM) in the EoS of a fermion system in the presence of a magnetic field. In the region of strong magnetic fields (B > m2) the AMM is found from the one‐loop fermion selfenergy. In contrast to the weak‐field AMM found by Schwinger, in the strong magnetic field case, the AMM depends on the Landau level (LL) and decreases with it. The effects of the AMM in the EoS at intermediate‐to‐large fields can be found introducing the one‐loop, LL‐dependent AMM in the effective Lagrangian that is then used to find the thermodynamical potential of the system. We compare the plots of the parallel and perpendicular pressures versus the magnetic field in the strong field region considering the LL‐dependent AMM, the Schwinger AMM, and no AMM at all. The results clearly show a separation between the physical magnitudes found using the Schwinger AMM and the LL‐dependent AMM. This is an indication of the inconsistency of considering the Schwinger AMM beyond the weak field region B < m2 where it was originally found. The curves for the EoS, pressures and magnetization at different fields give rise to the well‐known de Haas van Alphen oscillations, associated to the change in the number of LL contributing at different fields. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Ultra‐Luminous X‐ray sources and intermediate‐mass black holes
Authors: Motch C.
Published: January 2015

The extremely high X‐ray luminosity of non‐nuclear Ultra Luminous X‐ray sources (ULXs) may be evidence of the existence of black holes with masses intermediate between those produced by stellar evolution and those encountered in active galactic nuclei. Alternatively, they may reflect the existence of stellar mass black holes undergoing steady super‐Eddington accretion. In this short review, we will describe the main X‐ray and optical observational properties of these ULXs and discuss their likely accretion regimes. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Gravitational waves from the cosmological QCD transitio
Authors: Mouräo Roque V. R. C. , Lugones G.
Published: January 2015

We determine the minimum fluctuations in the cosmological QCD phase transition that could be detectable by the eLISA/NGO gravitational wave observatory. To this end, we performed several hydrodynamical simulations using a stateof‐the‐art equation of state derived from lattice QCD simulations. Based on the fact that the viscosity per entropy density of the quark gluon plasma obtained from heavy‐ion collision experiments at the RHIC and the LHC is extremely small, we considered a non‐viscous fluid in our simulations. Several previous works about this transition considered a first order transition that generates turbulence which follows a Kolmogorov power law. We show that for the QCD crossover transition the turbulent spectrum must be very different because there is no viscosity and no source of continuous energy injection. As a consequence, a large amount of kinetic energy accumulates at the smallest scales. From the hydrodynamic simulations, we have obtained the spectrum of the gravitational radiation emitted by the motion of the fluid, finding that, if typical velocity and temperature fluctuations have an amplitude Δv/c 10–2 and/or ΔT/Tc 10–3, they would be detected by eLISA/NGO at frequencies larger than ∼10–4 Hz. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Bouncing models and inflation
Authors: Pinto‐Neto N.
Published: January 2015

In this contribution I will make a critical comparison among viable inflationary, and bouncing models for the primordial Universe which I will describe, and I will discuss how the usual problems and features of the standard cosmological model are addressed by them in order to investigate if they can be distinguished by future observations. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Strangeness content of neutron stars with strong Σ–‐hyperon repulsion
Authors: Razeira M. , Mesquita A. , Vasconcellos C.A.Z. , Ruffini R. , Rueda J.A. , Gomes R.O.
Published: January 2015

A new constraint on the equation of state and composition of the matter on neutron stars has been provided by the measurement of the mass 2.01 ± 0.04 M⊙ for PSR J0348 +0432. In this contribution we investigate the role of many‐body correlations in the maximum mass of neutron stars using the effective relativistic QHD‐model with parameterized couplings. The complete expression of our QHD interaction Lagrangian exhausts the whole fundamental baryon octet (n, p, Σ–, Σ0, Σ+, Λ, Ξ–, Ξ0) and includes many‐body forces simulated by nonlinear self‐couplings and meson‐meson interaction terms involving scalar‐isoscalar (σ, σ*), vector‐isoscalar (ω, ϕ), vector‐isovector (∼), and scalar‐isovector (δ). We study the behavior of the asymmetry parameter, which describes the relative neutron excess in the system as well as the behavior of the strangeness asymmetry parameter, which specifies the strangeness content in the system and is strictly connected with the appearance of a particular hyperon species in the extreme case where the Σ– experiences such a strong repulsion that it does not appear at all in nuclear matter. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Effective field theory for neutron stars with genuine many‐body forces
Authors: Vasconcellos C. A. Z. , Gomes R. O. , Dexheimer V. , Negreiros R. P. , Horvath J. , Hadjimichef D.
Published: January 2015

The aim of our contribution is to shed some light on open questions facing the high density nuclear many‐body problem. We focus our attention on the conceptual issue of naturalness and its role for the baryon‐meson coupling for nuclear matter at high densities. As a guideline for the strengths of the various couplings the concept of naturalness has been adopted. In order to encourage possible new directions of research, we discuss relevant aspects of a relativistic effective theory for nuclear matter with “natural” parametric couplings and genuine many‐body forces. Among other topics, we discuss in this work the connection of this theory with other known effective Quantum Hadrodynamics (QHD) models found in literature and how we can potentially use our approach to describe new physics for neutron stars. We also show some preliminary results for the equation of state, population profiles and mass‐radius relation for neutron stars assuming local charge neutrality and beta equilibrium. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Non‐radial fluid oscilation modes of color superconducting self‐bound stars
Authors: Väsquez Flores C. , Lugones G.
Published: January 2015

We investigate the effect of color superconductivity on the non‐radial oscillations of pure self‐bound quark stars using an equation of state in the framework of the MIT bag model. The equations of non‐radial oscillations are integrated within the Cowling approximation in order to determine the frequency of the fundamental mode and of the first and second pressure modes. We employ several parametrizations of the equation of state that result in a maximum mass larger than the mass of the recently observed PSR J1614–2230 and PSR J0348–0432 with M ≈ 2 M⊙. The pulsation frequencies are compared with the corresponding modes of quark stars without pairing. For the fundamental mode, the oscillation frequency is typically 2–3 kHz. Parametrizations of the equations of state with larger values of the pairing gap Δ tend to give smaller values of the frequency. For the first and second pressure modes, the frequencies lie in the range 5–10 kHz for stars with masses above 1.5 M⊙ and diverge as the mass of the star tends to zero. From the numerical results we obtain parabolic fittings of the frequency of the fundamental mode as a function of the gravitational redshift at the surface of the star. For the p1 and p2 modes we find power law fittings that are rather independent of the parametrization of the equations of state. The here obtained results can be used to extract details about the internal composition of compact stars from observed modes of pulsation. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Childhood Facial Recognition Predicts Adolescent Symptom Severity in Autism Spectrum Disorder
Authors: Eussen Mart L. J. M. , Louwerse Anneke , Herba Catherine M. , Van Gool Arthur R. , Verheij Fop , Verhulst Frank C. , Greaves‐Lord Kirstin
Published: January 2015

Limited accuracy and speed in facial recognition (FR) and in the identification of facial emotions (IFE) have been shown in autism spectrum disorders (ASD). This study aimed at evaluating the predictive value of atypicalities in FR and IFE for future symptom severity in children with ASD. Therefore we performed a seven‐year follow‐up study in 87 children with ASD. FR and IFE were assessed in childhood (T1: age 6–12) using the Amsterdam Neuropsychological Tasks (ANT). Symptom severity was assessed using the Autism Diagnostic Observation Schedule (ADOS) in childhood and again seven years later during adolescence (T2: age 12–19). Multiple regression analyses were performed to investigate whether FR and IFE in childhood predicted ASD symptom severity in adolescence, while controlling for ASD symptom severity in childhood. We found that more accurate FR significantly predicted lower adolescent ASD symptom severity scores (ΔR2 = .09), even when controlling for childhood ASD symptom severity. IFE was not a significant predictor of ASD symptom severity in adolescence. From these results it can be concluded, that in children with ASD the accuracy of FR in childhood is a relevant predictor of ASD symptom severity in adolescence. Test results on FR in children with ASD may have prognostic value regarding later symptom severity. Autism Res 2015, 8: 261–271. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
Effect of several PEO–PPO amphiphiles on bax, bcl‐2, and hTERT mRNAs: An insight into apoptosis and cell immortalization induced in hepatoma cells by these polymeric excipients
Authors: Castronuovo Cynthia Celeste , Cuestas María Luján , Oubiña José Raúl , Mathet Verónica Lidia
Published: January 2015

Recent data have shown that synthetic polymers and nanomaterials display phenotypic effects in cells and signal transduction mechanisms involved in inflammation, differentiation, proliferation, and apoptosis. Aim: This article aims to investigate the effect of poly(ethylene oxide)–poly(propylene oxide) (PEO–PPO) block copolymers with a wide range of biomedical and pharmaceutical applications on apoptosis and/or cell immortalization, by flow cytometry and multiplex RT‐PCR for bax, bcl‐2, and human telomerase reverse transcriptase (hTERT). Results: PEO–PPO amphiphiles upregulated bax and hTERT and induced apoptosis of two human hepatoma cell lines. Conclusions: PEO–PPO block copolymers—considered safe for human use—can drastically alter gene expression profiles of genes related to apoptosis/cell proliferation.
Purification and characterization of a new neutral metalloprotease from marine Exiguobacterium sp. SWJS2
Authors: Lei Fenfen , Cui Chun , Zhao Haifeng , Tang Xuelu , Zhao Mouming
Published: January 2015

Among the protease‐producing bacterial strains isolated from deep‐sea sediments, SWJS2 was finally selected and identified as genus Exiguobacterium. Plackett–Burman and orthogonal array designs were applied to optimize the fermentation conditions, and the results are as follows: Glucose 5g, yeast extract 15g, glycerin 2g and CaCl2⋅2H2O 0.5 g dissolved in 1 L artificial seawater; temperature 25 °C, original pH 7, inoculum rate 2%, seed age 12 H, loading volume 25 mL (250‐mL Erlenmeyer flask), shaking speed 150 rpm, and fermentation time 44 H. The protease activity production was improved from about 80 to 660 U/mL under the optimized parameters. The protease was purified fourfold with specificity activity of 30,654.1 U/mg protein and a total yield of 16.2%. The protease exhibited the maximum activity at 40–45 °C and pH 7. Moreover, the enzyme activity was found to be inhibited by Cu2+, Ba2+, Cd2+, Hg2+, and Al3+ at 5 mM, whereas it can be increased by Mg2+, Mn2+, and Ca2+ at 0.5–5 mM. The enzyme was totally inactivated by 1 or 5 mM ethylenediaminetetraacetic acid but not by phenylmethanesulfonyl fluoride, tyrpsin inhibitor from Glycine max (STI), benzamidine, 5,5′‐dithio‐bis‐(2‐nitro benzoic acid), or pepstatin A, suggesting that it belonged to metalloprotease.
The estimation and use of predictions for the assessment of model performance using large samples with multiply imputed data
Authors: Wood Angela M. , Royston Patrick , White Ian R.
Published: January 2015

Multiple imputation can be used as a tool in the process of constructing prediction models in medical and epidemiological studies with missing covariate values. Such models can be used to make predictions for model performance assessment, but the task is made more complicated by the multiple imputation structure. We summarize various predictions constructed from covariates, including multiply imputed covariates, and either the set of imputation‐specific prediction model coefficients or the pooled prediction model coefficients. We further describe approaches for using the predictions to assess model performance. We distinguish between ideal model performance and pragmatic model performance, where the former refers to the model's performance in an ideal clinical setting where all individuals have fully observed predictors and the latter refers to the model's performance in a real‐world clinical setting where some individuals have missing predictors. The approaches are compared through an extensive simulation study based on the UK700 trial. We determine that measures of ideal model performance can be estimated within imputed datasets and subsequently pooled to give an overall measure of model performance. Alternative methods to evaluate pragmatic model performance are required and we propose constructing predictions either from a second set of covariate imputations which make no use of observed outcomes, or from a set of partial prediction models constructed for each potential observed pattern of covariate. Pragmatic model performance is generally lower than ideal model performance. We focus on model performance within the derivation data, but describe how to extend all the methods to a validation dataset.
Neural basis of nonanalytical reasoning expertise during clinical evaluation
Authors: Durning Steven J. , Costanzo Michelle E. , Artino Anthony R. , Graner John , van der Vleuten Cees , Beckman Thomas J. , Wittich Christopher M. , Roy Michael J. , Holmboe Eric S. , Schuwirth Lambert
Published: January 2015

Introduction

Understanding clinical reasoning is essential for patient care and medical education. Dual‐processing theory suggests that nonanalytic reasoning is an essential aspect of expertise; however, assessing nonanalytic reasoning is challenging because it is believed to occur on the subconscious level. This assumption makes concurrent verbal protocols less reliable assessment tools.

Methods

Functional magnetic resonance imaging was used to explore the neural basis of nonanalytic reasoning in internal medicine interns (novices) and board‐certified staff internists (experts) while completing United States Medical Licensing Examination and American Board of Internal Medicine multiple‐choice questions.

Results

The results demonstrated that novices and experts share a common neural network in addition to nonoverlapping neural resources. However, experts manifested greater neural processing efficiency in regions such as the prefrontal cortex during nonanalytical reasoning.

Conclusions

These findings reveal a multinetwork system that supports the dual‐process mode of expert clinical reasoning during medical evaluation.
Periprocedural myocardial infarction is associated with increased mortality in patients with coronary artery bifurcation lesions after implantation of a drug‐eluting stent
Authors: Chen Shao‐Liang , Zhang Jun‐Jie , Ye Fei , Tian Nai‐Liang , Sheiban Imad , Jepson Nigel , Paiboon Chitprapai , Sansoto Teugh , Kwan Tak W. , Wen Shang‐Yu , Wang Hai‐Chang , Jiang Tie‐Ming , Wang Yan , Chen Liang‐Long , Qiu Chun‐Guang , Zhang Yao‐Jun , Chen Meng‐Xuan , De Maria Anthony
Published: January 2015

Objectives

The present study aimed to investigate the association between periprocedural myocardial infarction (PMI), defined by creatine kinase (CK)‐MB or troponin I (TNI) level elevations >5 times the 99th percentile of the upper reference limit (URL) within 48 hr after implantation of a drug‐eluting stent (DES), and one‐year mortality in patients with coronary bifurcation.

Background

PMI is reported to be associated with increased one‐year mortality after DES implantation. However, the prevalence and association of PMI with mortality after stenting bifurcation lesions remains unclear.

Methods

We prospectively followed 1,971 patients with true coronary bifurcations who underwent DES implantation as part of the multicenter DEFINITION study. These patients were grouped into categories based on PMI outcome: Non‐PMI, CKMB‐PMI, TNI‐PMI, and CKMB/TNI‐PMI. The primary endpoint was the rate of all‐cause mortality at one year.

Results

PMI occurred in 11.4% of patients by CKMB criteria and 41.3% of patients by TNI criteria. At one‐year follow‐up, the mortality rate was 2.3% in the entire patient population. However, mortality was significantly higher in the CKMB‐PMI (6.4%) and CKMB/TNI‐PMI (6.1%) groups compared to the Non‐PMI (1.7%) and TNI‐PMI (2.1%) groups (all P < 0.05). A 10‐fold increase in TNI levels resulted in similar PMI rate (5.2%) and mortality risk (adjusted HR 2.7, 95% CI 3.0–5.2) as a fivefold increase in CKMB levels.

Conclusions

PMI, as defined by CKMB elevations following coronary bifurcation lesion stenting, was associated with increased one‐year mortality. Additionally, to attain an equal frequency of PMI, the elevation in TNI levels needed to be twice as high as the elevation in CKMB levels. © 2015 Wiley Periodicals, Inc.
Morphological characteristics of severe aortic stenosis in China: Imaging corelab observations from the first Chinese transcatheter aortic valve trial
Authors: Jilaihawi Hasan , Wu Yongjian , Yang Yuejin , Xu Liang , Chen Mao , Wang Jianan , Kong Xiangqing , Zhang Ruiyan , Wang Moyang , Lv Bin , Wang Wei , Xu Bo , Makkar Raj R. , Sievert Horst , Gao Runlin
Published: January 2015

Objectives

We sought to describe the morphological characteristics of aortic valve disease in a Chinese population presenting for transcatheter aortic valve replacement (TAVR).

Background

Racial and regional differences are known to exist in aortic stenosis (AS), but limited data exist comparing the specific anatomical variations between populations.

Methods

Patients were prospectively evaluated in a Chinese population presenting for TAVR in the Venus A‐Valve trial, the first trial evaluating TAVR in China. A systematic anatomical assessment protocol employed contrast‐enhanced computed tomography (CT) in all the cases.

Results

A total of 120 consecutive patients were studied. Of these, 61 (50.7%) were patients with tricuspid, 57 (47.5%) bicuspid, and 2 (1.7%) unicuspid valve morphologies. Of the 57 cases with bicuspid valve, 31 (54.4%) had no raphe (Sievers classification, type 0) and 26 (45.6%) were of raphe type. Although the incidence of bicuspid valve morphology was more than a third in the northern Chinese population, this was lower than the eastern Chinese population (P = 0.035), in whom the incidence was more than half. A comparison of tricuspid morphologies in China versus a Western series of 229 consecutive patients undergoing TAVR assessed with CT showed a threefold excess of leaflet calcium burden in China, with a leaflet calcium volume of 421 mm3 (IQR, 188–688 mm3) versus 142 mm3 (IQR, 58–267 mm3).

Conclusions

Patients presenting for TAVR in China have a very high frequency of bicuspid valve morphology. Even in tricuspid disease, there are clear differences to Western patients, with a high calcium burden, which presents challenges for TAVR in this population (ClinicalTrials.gov NCT01683474). © 2015 Wiley Periodicals, Inc.
Highly Effective Pt‐Based Water–Gas Shift Catalysts by Surface Modification with Alkali Hydroxide Salts
Authors: Kusche Matthias , Bustillo Karen , Agel Friederike , Wasserscheid Peter
Published: January 2015

Herein, we describe an economical and convenient method to improve the performance of Pt/alumina catalysts for the water–gas shift reaction through surface modification of the catalysts with alkali hydroxides according to the solid catalyst with ionic liquid layer approach. The results are in agreement with our findings reported earlier for methanol steam reforming. This report indicates that alkali doping of the catalyst plays an important role in the observed catalyst activation. In addition, the basic and hygroscopic nature of the salt coating contributes to a significant improvement in the performance of the catalyst. During the reaction, a partly liquid film of alkali hydroxide forms on the alumina surface, which increases the availability of H2O at the catalytically active sites. Kinetic studies reveal a negligible effect of the KOH coating on the rate dependence of CO and H2O partial pressures. TEM studies indicate an agglomeration of the active Pt clusters during catalyst preparation; restructuring of Pt nanoparticles occurs under reaction conditions, which leads to a highly active and stable system over 240 h time on stream. Excessive pore fillings with KOH introduce a mass transfer barrier as indicated in a volcano‐shaped curve of activity versus salt loading. The optimum KOH loading was found to be 7.5 wt %.
Sulfur‐Tolerant Hierarchically Porous Ceramic Anode‐Supported Solid‐Oxide Fuel Cells with Self‐Precipitated Nanocatalyst
Authors: Chen Yu , Zhang Yanxiang , Xiao Guoliang , Yang Zhibin , Han Minfang , Chen Fanglin
Published: January 2015

A hierarchically porous Sr2Fe1.5Mo0.5O6−δ–Gd0.1Ce0.9O1.95 (SFM–GDC) ceramic anode‐supported solid‐oxide fuel cell with a GDC electrolyte film was fabricated by freeze‐drying tape‐casting and drop coating. 3D X‐ray computed tomography analysis indicated that the SFM–GDC anode has a high porosity and low tortuosity factor, facilitating gas diffusion in the anode during fuel cell operation. Peak power density of cells with a La0.6Sr0.4Co0.2Fe0.8O3–GDC (LSCF–GDC) cathode can reach 0.22 W cm−2 at 700 °C when using H2 as the fuel and ambient air as the oxidant. The SFM–GDC anode shows excellent sulfur tolerance when using H2 with 50 ppm H2S. SEM analysis demonstrates that the nanocatalyst (iron) can precipitate from the parent SFM phase upon reduction and iron nanoparticles can react with sulfur species to form needle‐like nanosulfide. Both the nanocatalyst and sulfide show a graded distribution along the thickness direction, owing to a graded local oxygen chemical potential within the anode.
Molybdenum Disulfide/Reduced Graphene Oxide–Carbon Nanotube Hybrids as Efficient Catalytic Materials in Dye‐Sensitized Solar Cells
Authors: Lin Jeng‐Yu , Su An‐Lin , Chang Chin‐Yu , Hung Kuan‐Chung , Lin Tsung‐Wu
Published: January 2015

A hybrid material has been fabricated by combining MoS2/reduced graphene oxide (RGO) nanocomposites with carbon nanotubes (CNTs) (designated MoS2/RGO‐CNTs) through facile electrophoretic deposition. The MoS2/RGO‐CNTs hybrid benefits from the advantages of both MoS2/RGO and CNTs as a counter electrode (CE) in dye‐sensitized solar cells (DSCs). According to a series of electrochemical results, the incorporation of conductive networks of CNTs provides additional pathways for electron transport in the MoS2/RGO‐CNTs hybrid, which increases the charge‐transfer rate at the CE/electrolyte interface. As a result, the MoS2/RGO‐CNTs CE exhibits greatly improved electrocatalytic activity compared with that of MoS2/RGO alone. A DSC incorporating the MoS2/RGO‐CNTs CE achieves impressive cell performance of 7.46 %, which is higher than those measured with DSCs incorporating MoS2/RGO CE (6.82 %) and Pt CE (7.23 %).
Improving the Photocatalytic Reduction of CO2 to CO through Immobilisation of a Molecular Re Catalyst on TiO2
Authors: Windle Christopher D. , Pastor Ernest , Reynal Anna , Whitwood Adrian C. , Vaynzof Yana , Durrant James R. , Perutz Robin N. , Reisner Erwin
Published: January 2015

The photocatalytic activity of phosphonated Re complexes, [Re(2,2′‐bipyridine‐4,4′‐bisphosphonic acid) (CO)3(L)] (ReP; L=3‐picoline or bromide) immobilised on TiO2 nanoparticles is reported. The heterogenised Re catalyst on the semiconductor, ReP–TiO2 hybrid, displays an improvement in CO2 reduction photocatalysis. A high turnover number (TON) of 48 molCO molRe−1 is observed in DMF with the electron donor triethanolamine at λ>420 nm. ReP–TiO2 compares favourably to previously reported homogeneous systems and is the highest TON reported to date for a CO2‐reducing Re photocatalyst under visible light irradiation. Photocatalytic CO2 reduction is even observed with ReP–TiO2 at wavelengths of λ>495 nm. Infrared and X‐ray photoelectron spectroscopies confirm that an intact ReP catalyst is present on the TiO2 surface before and during catalysis. Transient absorption spectroscopy suggests that the high activity upon heterogenisation is due to an increase in the lifetime of the immobilised anionic Re intermediate (t50 %>1 s for ReP–TiO2 compared with t50 %=60 ms for ReP in solution) and immobilisation might also reduce the formation of inactive Re dimers. This study demonstrates that the activity of a homogeneous photocatalyst can be improved through immobilisation on a metal oxide surface by favourably modifying its photochemical kinetics.
New Tetracobalt Cluster Compounds for Electrocatalytic Proton Reduction: Syntheses, Structures, and Reactivity
Authors: Li Ping , Zaffaroni Riccardo , de Bruin Bas , Reek Joost N. H.
Published: January 2015

Reaction of Co2(CO)8 and 1,3‐propanedithiol in a 1:1 molar ratio in toluene affords a novel tetracobalt complex, [(μ2‐pdt)2(μ3‐S)Co4(CO)6] (pdt=‐SCH2CH2CH2S‐, 1), which possesses some of the structural features of the active site of [FeFe]‐hydrogenase. Carbonyl displacement reaction of complex 1 in the presence of mono‐ or diphosphine ligands leads to the formation of [(μ2‐pdt)2(μ3‐S)Co4(CO)5(PCy3)] (2) and [(μ2‐pdt)2(μ3‐S)Co4(CO)4(L)] [L=Ph2PCHCHPPh2, 3; Ph2PCH2N(Ph)CH2PPh2, 4; Ph2PCH2N(iPr)CH2PPh2, 5]. Complexes 1–5 have been fully characterized by spectroscopy and single‐crystal X‐ray diffraction studies. Cyclic voltammetry has revealed that complexes 1–5 show a reversible first reduction wave and are active for electrocatalytic proton reduction in the presence of CF3COOH. Protonation reactions have been monitored by 31P and 1H NMR and infrared spectroscopies, which revealed the formation of different protonated species. The mono‐reduced species of 1–5 have been spectroscopically characterized by EPR and spectro‐electro‐infrared techniques.
Ultrathin FeSe2 Nanosheets: Controlled Synthesis and Application as a Heterogeneous Catalyst in Dye‐Sensitized Solar Cells
Authors: Huang Shoushuang , He Qingquan , Chen Wenlong , Qiao Qiquan , Zai Jiantao , Qian Xuefeng
Published: January 2015

Two‐dimensional (2D) semiconducting nanosheets have emerged as an important field of materials, owing to their unique properties and potential applications in areas ranging from electronics to catalysis. However, the controlled synthesis of ultrathin 2D nanosheets remains a great challenge, due to the lack of an intrinsic driving force for anisotropic growth. High‐quality ultrathin 2D FeSe2 nanosheets with average thickness below 7 nm have been synthesized on large scale by a facile solution method, and a formation mechanism has been proposed. Due to their favorable structural features, the as‐synthesized ultrathin FeSe2 nanosheets exhibit excellent electrocatalytic activity for the reduction of triiodide to iodide and low charge‐transfer resistance at the electrolyte–electrode interface in dye‐sensitized solar cells (DSSCs). The DSSCs with FeSe2 nanosheets as counter electrode material achieve a high power conversion efficiency of 7.53 % under a simulated solar illumination of 100 mW cm−2 (AM 1.5), which is comparable with that of Pt‐based devices (7.47 %).
Tetraloop‐like Geometries Could Form the Basis of the Catalytic Activity of the Most Ancient Ribooligonucleotides
Authors: Stadlbauer Petr , Šponer Jiří , Costanzo Giovanna , Di Mauro Ernesto , Pino Samanta , Šponer Judit E.
Published: January 2015

The origin of the catalytic activity of ancient oligonucleotides is a largely unexplored field of contemporary science. In the current work we use molecular dynamics simulations to investigate the plausibility of tetraloop‐like overhang geometries to initiate transphosphorylation reactions that lead to ligation and terminal cleavage in simple, Watson–Crick (WC) complementary oligoC/oligoG sequences observed experimentally. We show a series of examples of known tetraloop architectures, which can be adopted by the unpaired overhangs of short oligonucleotide sequences for a sufficiently long time to enable chemical reactions that lead to simple ribozyme‐like catalytic activity. Thus, our computations demonstrate that the role of non‐WC interactions at the emergence of the most ancient catalytic oligonucleotides could be more significant than ever believed.
Ratiometric Fluorescent Nanosensors for Copper(II) Based on Bis(rhodamine)‐Derived PMOs with J‐Type Aggregates
Authors: Qiu Xiaoyong , Han Shuhua , Hu Yongfeng , Sun Baowen
Published: January 2015

By using pentyl‐linked bis(rhodamine)‐derived tetra‐siloxane (PRh‐Si4) as the organosilica precursor, highly ordered PRh‐bridged periodic mesoporous organosilicas (PRhPMOs) were prepared. When excited at λ=500 nm, the PRhPMO suspension that contained metal ions showed two separate emission peaks at λ=550 and 623 nm. The first peak, located at λ=550 nm, was due to ring‐opening of the spiro structure in the rhodamine moiety and the second, located at λ=623 nm, originated from fluorescent aggregates of the PRh units embedded in the silica framework of the PRhPMO. By using the different intensity ratios of the two fluorescence signals (FI550/623), PRhPMOs could be used as turn‐ON type fluorescent ratiometric chemosensors for Cu2+. Furthermore, based on the single‐exciton theory, it was deduced that the fluorescent aggregates formed were of the J‐type and had a coplanar configuration. Consequently, PRhPMOs display a longer fluorescence lifetime and greater fluorescent quantum yield than the respective monomers dissolved in solution, which is consistent with the experimental results.
ChemInform Abstract: Ab initio Structure Determination of Barium Periodate, Ba5I2O12, from Powder XRD Data.
Authors: Kubel Frank , Pantazi Mariana , Hagemann Hans
Published: January 2015

Ba5I2O12 is prepared from a precipitate obtained from an aq.
ChemInform Abstract: Hydrothermal Synthesis and Multiferroic Properties of Y2NiMnO6.
Authors: Zhang Chenyang , Zhang Tingsong , Ge Lei , Wang Shan , Yuan Hongming , Feng Shouhua
Published: January 2015

The title compound is hydrothermally prepared from a solution of Y(NO3)3, NiSO4, MnO2, and KOH (autoclave, 533 K, 3 d) and characterized by powder XRD, SEM, XPS, and electric and magnetic measurements.
ChemInform Abstract: Synthesis and Magnetic Properties of MNb2O6 (M: Fe, Co, Ni) Nanoparticles.
Authors: Lei Shuijin , Wang Chuanning , Guo Donghai , Gao Xijie , Cheng Di , Zhou Jianliang , Cheng Baochang , Xiao Yanhe
Published: January 2015

Nanoparticles of the title ceramics are hydrothermally synthesized from aqueous solutions of K7HNb6O19 and FeSO4, CoCl2, or NiCl2 (autoclave, 180 °C, 12 h), followed by calcination at 800 °C for 2 h under N2.
ChemInform Abstract: Solvothermal Synthesis of Pyrite FeS2 Nanocubes and Their Superior High Rate Lithium Storage Properties.
Authors: Liu W. L. , Rui X. H. , Tan H. T. , Xu C. , Yan Q. Y. , Hng H. H.
Published: January 2015

The title nanocubes with particle sizes of around 80—120 nm are solvothermally synthesized from mixtures of FeCl2, sulfur powder, 1,2‐dodecanediol, and oleylamine (autoclave, 180 °C, 18 h), and characterized by powder XRD, SEM, TEM, Raman spectroscopy, and electrochemical measurements.
ChemInform Abstract: Nano‐Sized Quaternary CuGa2In3S8 as an Efficient Photocatalyst for Solar Hydrogen Production.
Authors: Kandiel Tarek A. , Anjum Dalaver H. , Takanabe Kazuhiro
Published: January 2015

Quaternary CuGa2In3S8 photocatalysts with a primary particle size of 4 nm are prepared by using a solution of Cu(acac)2, Ga(acac)3, In(acac)3, trioctylphosphine oxide, and oleylamine to which 1‐dodecanethiol is injected under Ar atmosphere (150 °C, aging at 285 °C for 2—24 h).
ChemInform Abstract: Novel 3‐D Nanoporous Graphitic‐C3N4 Nanosheets with Heterostructured Modification for Efficient Visible‐Light Photocatalytic Hydrogen Production.
Authors: Yuan Jielin , Gao Qiongzhi , Li Xin , Liu Yingju , Fang Yueping , Yang Siyuan , Peng Feng , Zhou Xiaosong
Published: January 2015

Phosphorus‐doped graphitic‐C3N4 nanosheets coupled with BiPO4 nanorods are hydrothermally synthesized from aqueous solutions containing CH2N2, NaH2PO4, Bi(NO3)3, and HNO3 (autoclave, 483 K, 4 h), followed by calcination at 823 K for 4 h.
ChemInform Abstract: Syntheses and Characterization of One‐Dimensional Alkali Metal Antimony(III) Thiostannates(IV), A2Sb2Sn3S10 (A: K, Rb, Cs).
Authors: Yohannan Jinu P. , Vidyasagar Kanamaluru
Published: January 2015

K2SbIII2SnIV3 S10 is prepared from an alkali thiosulfate flux using K2CO3, Sn, Sb, and S in the molar ratio of 0.75:1.5:1:5.5, resp.
ChemInform Abstract: Solid‐State Syntheses and Single‐Crystal Characterizations of Three Tetravalent Thorium and Uranium Silicates.
Authors: Jin Geng Bang , Soderholm L.
Published: January 2015

Colorless crystals of ThSiO4 (I) and (Ca0.5Na0.5) 2NaThSi8O20 (II) are prepared by solid state reactions of ThO2, CaSiO3, and Na2WO4 (evacuated silica ampoules, 1073 K, 140 h).
ChemInform Abstract: Synthesis, Structural and Electrical Properties of a New Cobalt Arsenate NaCo2As3O10.
Authors: Ben Smida Y. , Marzouki R. , Guesmi A. , Georges S. , Zid M. F.
Published: January 2015

The title compound is prepared by calcination of a mixture of NaNO3, Co(NO3)2, and As2O5 in air (Na:Co:As = 8:5:10, silica crucible, 670 °C, 3 d, 5 K/h cooling rate).
ChemInform Abstract: Discovery of the Last Remaining Binary Platinum‐Group Pernitride RuN2.
Authors: Niwa Ken , Suzuki Kentaro , Muto Shunsuke , Tatsumi Kazuyoshi , Soda Kazuo , Kikegawa Takumi , Hasegawa Masashi
Published: January 2015

Marcasite‐type RuN2 is synthesized by direct reaction between ruthenium metal and molecular nitrogen above a minimum pressure of 32 GPa (laser‐heated diamond‐anvil cell, <2000 K).
ChemInform Abstract: Diamidophosphites with Remote P*‐Stereocentres and Their Performance in Pd‐Catalyzed Enantioselective Reactions.
Authors: Gavrilov Konstantin N. , Zheglov Sergey V. , Gavrilov Vladislav K. , Chuchelkin Ilya V. , Novikov Ivan M. , Shiryaev Alexei A. , Volov Alexandr N. , Zamilatskov Ilya A.
Published: January 2015

Only the relative but not the absolute configuration of compound (X) was determined.
ChemInform Abstract: A Solar Light‐Driven, Eco‐Friendly Protocol for Highly Enantioselective Synthesis of Chiral Alcohols via Photocatalytic/Biocatalytic Cascades.
Authors: Choudhury Sumit , Baeg Jin‐Ook , Park No‐Joong , Yadav Rajesh K.
Published: January 2015

An asymmetric artificial photosynthesis system that comprises an efficient method of nicotinamide cofactor regeneration under visible light employing a graphene‐based light harvesting photocatalyst and its subsequent utilization in an enzyme‐catalyzed asymmetric reduction of prochiral ketones is described.
ChemInform Abstract: Effect of Conformational Rigidity on the Stereoselectivity of Nucleophilic Additions to Five‐Membered Ring Bicyclic Oxocarbenium Ion Intermediates.
Authors: Lavinda Olga , Tran Vi Tuong , Woerpel K. A.
Published: January 2015

On the basis of four substrates, the influence of structural perturbations of a fused seven‐membered ring on the selectivity of nucleophilic substitution of bicyclic acetals is studied.
ChemInform Abstract: N‐Heterocyclic Carbene/Broensted Base Cascade Catalysis: Base‐Controlled Selective Synthesis of Multifunctional Benzofuran‐3‐ones or Flavone Derivatives from the Reaction of 3‐(2‐Formylphenoxy)propenoates with Imines.
Authors: Zhao Yuan , Wang Zi‐Tian , Cheng Ying
Published: January 2015

Depending on the amount of base used, this method yields either benzofurans (III) and (V) with high diastereoselectivity or benzopyrans (VI) and (VII).
ChemInform Abstract: Intramolecular Dehydro‐Diels—Alder Reaction Affords Selective Entry to Arylnaphthalene or Aryldihydronaphthalene Lignans.
Authors: Kocsis Laura S. , Brummond Kay M.
Published: January 2015

Depending on the choice of the reaction solvent the microwave promoted intramolecular Diels—Alder reaction of cinnamyl esters of arylpropiolic acids [cf.
ChemInform Abstract: Facile Conversion of Cyclopropanols into Linear Conjugate Enones.
Authors: Han Wei‐Bo , Li Shao‐Gang , Lu Xiao‐Wei , Wu Yikang
Published: January 2015

Oxidative rearrangement of a variety of 1,2‐disubstituted cyclopropanols in the presence of air and Co(acac)2 as the catalyst offers a practical method for the synthesis of functionalized α,β‐unsaturated ketones after reductive workup of the intermediate peroxides, mesylation of the resulting β‐hydroxy ketones, and β‐elimination.
ChemInform Abstract: Development of a Metal‐Free Oxidation of Alcohols with Dimethyl Sulfoxide (DMSO) Activated by Tosyl Chloride.
Authors: Saadati Fariba , Yousefi Kobra
Published: January 2015

Primary and secondary alcohols can be oxidized to the corresponding aldehydes or ketones using the system DMSO/tosyl chloride/triethylamine in toluene as solvent.
ChemInform Abstract: An Efficient and Reusable Vanadium Based Catalytic System for Room Temperature Oxidation of Alcohols to Aldehydes and Ketones.
Authors: Sarmah Gayatri , Bharadwaj Saitanya K. , Dewan Anindita , Gogoi Ankur , Bora Utpal
Published: January 2015

A facile protocol using tBuOOH as oxidating agent and vanadyl sulfate as the catalyst allows the oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones.
ChemInform Abstract: Indium(III) Catalyzed Regio‐ and Stereoselective Hydrothiolation of Bromoalkynes.
Authors: Rajesh Nimmakuri , Prajapati Dipak
Published: January 2015

For the first time metal catalyzed hydrothiolation of bromoalkynes to generate (Z)‐β‐bromo vinyl sulfides is demonstrated.
ChemInform Abstract: Palladium‐Catalyzed Regioselective Arylation of 1,1,3‐Triaryl‐2‐azaallyl Anions with Aryl Chlorides.
Authors: Li Minyan , Berritt Simon , Walsh Patrick J.
Published: January 2015

The optimized conditions render possible the regioselective arylation of ketimines and aldimines with aryl chlorides to give the target products in high yields.
ChemInform Abstract: Cu‐Catalyzed Fe‐Driven Csp—Csp and Csp—Csp2 Cross‐Coupling: An Access to 1,3‐Diynes and 1,3‐Enynes.
Authors: Ahammed Sabir , Kundu Debasish , Ranu Brindaban C.
Published: January 2015

Aliphatic, aromatic, and heteroaromatic alkynyl bromides are easily coupled with various aromatic alkynyl boronates, but the reaction fails for alkyl substituted alkynyl boronic esters as substrates (not shown).
ChemInform Abstract: Modified Yamaguchi Reagent: Convenient and Efficient Esterification.
Authors: Okuno Yoshinori , Isomura Shigeki , Nishibayashi Akihiro , Hosoi Aiko , Fukuyama Kei , Ohba Masashi , Takeda Kazuyoshi
Published: January 2015

2,4,6‐Trichlorobenzoyl‐4‐dimethylaminopyridine (modified Yamaguchi reagent) is shown to be an efficient reagent for the esterification, that allows to avoid the use of intractable acid chlorides as well as acid anhydrides.
ChemInform Abstract: Preparation of Nano Silica Supported Sodium Hydrogen Sulfate: As an Efficient Catalyst for the Trimethyl, Triethyl and t‐Butyldimethyl Silylations of Aliphatic and Aromatic Alcohols in Solution and under Solvent‐Free Conditions.
Authors: Abri Abdolreza , Ranjdar Somayeh
Published: January 2015

The silylation reactions are fast and with good functional group tolerance.
ChemInform Abstract: Photoredox‐Induced Three‐Component Azido‐ and Aminotrifluoromethylation of Alkenes.
Authors: Dagousset Guillaume , Carboni Aude , Magnier Emmanuel , Masson Geraldine
Published: January 2015

A wide range of styrenes and functionalized olefins undergo regioselective azidotrifluoromethylation with a combination of TmsN3 and Umemoto′s reagent as CF3‐source in the presence of [Ru(bipy)3](PF6)2 as catalyst.
ChemInform Abstract: Oxetanyl Peptides: Novel Peptidomimetic Modules for Medicinal Chemistry.
Authors: McLaughlin Martin , Yazaki Ryo , Fessard Thomas C. , Carreira Erick M.
Published: January 2015

Novel peptidomimetics bearing a non‐hydrolyzable oxetanylamine fragment instead of the normal amide bond are synthesized in different ways.
ChemInform Abstract: Nucleophilic Addition Reactions of Nitriles to Nitrones under Mild Silylation Conditions.
Authors: Yoshimura Fumihiko , Abe Taiki , Tanino Keiji
Published: January 2015

The synthetic versatility of the addition products is further examined by the transformation of the cyano group in (XIa) into a carboxamide, a carboxylic acid or an aminomethyl functionality.
ChemInform Abstract: Cyanuric Chloride—Dimethylformamide Mediated Cleavage of Cyclopropylcarbinols‐Synthesis of Phenolic Antioxidant and Construction of a New Vinylcyclopropane Skeleton.
Authors: Khan Sagar , Roy Sanchita , Roy Rimi , Ghatak Avishek , Pramanik Amit , Bhar Sanjay
Published: January 2015

In general, the ring cleavage of substituted cyclopropylcarbinols produces homoallylic chlorides.
ChemInform Abstract: Palladium‐Catalyzed Oxidative Domino Carbocyclization—Carbonylation—Alkynylation of Enallenes.
Authors: Volla Chandra M. R. , Baeckvall Jan‐E.
Published: January 2015

An operationally simple protocol for the Pd‐catalyzed oxidative carbocyclization followed by the carbonylative Sonogashira reaction of enallenes is developed to yield functionalized cyclopentenes in good to excellent yields.
ChemInform Abstract: Tandem Prins/Pinacol Reaction for the Synthesis of Oxaspiro[4.5]decan‐1‐one Scaffolds.
Authors: Subba Reddy B. V. , Gopal Reddy S. , Ramana Reddy M. , Pal Bhadra Manika , Sarma A. V. S.
Published: January 2015

The reaction can be scaled up.
ChemInform Abstract: An Improved Synthesis of 10‐Isobornylsultone.
Authors: Lewis Frank W. , Grayson David H.
Published: January 2015

Target compound (VI) is prepared in 81% overall yield via a 3‐step sequence comprising esterification, stereoselective reduction, and base‐catalyzed intramolecular cyclization.
ChemInform Abstract: Facile and Efficient Synthesis of 1‐Haloalkynes via DBU‐Mediated Reaction of Terminal Alkynes and N‐Haloimides under Mild Conditions.
Authors: Li Mengru , Li Yueju , Zhao Baozhong , Liang Fushun , Jin Long‐Yi
Published: January 2015

The advantages of this new halogenation reaction of alkynes are high yields, cheap and easily available reagents, mild conditions, short reaction time, and broad halogen scope.
ChemInform Abstract: Palladium‐Catalyzed Amination of Aryl Sulfides with Anilines.
Authors: Sugahara Tomohiro , Murakami Kei , Yorimitsu Hideki , Osuka Atsuhiro
Published: January 2015

The synthesis of a wide variety of diarylamines from aryl sulfides and anilines is presented.