bluuebunny/crossref_metadata_2025 huggingface dataset:
A Molecular Rotor that Measures Dynamic Changes of Lipid Bilayer Viscosity Caused by Oxidative Stress
Authors: Vyšniauskas Aurimas , Qurashi Maryam , Kuimova Marina K.
Published: August 2016

Oxidation of cellular structures is typically an undesirable process that can be a hallmark of certain diseases. On the other hand, photooxidation is a necessary step of photodynamic therapy (PDT), a cancer treatment causing cell death upon light irradiation. Here, the effect of photooxidation on the microscopic viscosity of model lipid bilayers constructed of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine has been studied. A molecular rotor has been employed that displays a viscosity‐dependent fluorescence lifetime as a quantitative probe of the bilayer's viscosity. Thus, spatially‐resolved viscosity maps of lipid photooxidation in giant unilamellar vesicles (GUVs) were obtained, testing the effect of the positioning of the oxidant relative to the rotor in the bilayer. It was found that PDT has a strong impact on viscoelastic properties of lipid bilayers, which ‘travels’ through the bilayer to areas that have not been irradiated directly. A dramatic difference in viscoelastic properties of oxidized GUVs by Type I (electron transfer) and Type II (singlet oxygen‐based) photosensitisers was also detected.
3‐Bromo‐2‐Pyrone: An Alternative and Convenient Route to Functionalized Phosphinines
Authors: Habicht Marija H. , Wossidlo Friedrich , Weber Manuela , Müller Christian
Published: August 2016

The facile access to 3‐bromo‐2‐pyrone allows the preparation of 6‐bromo‐2‐trimethylsilyl‐phosphinine by a [4+2] cycloaddition with Me3Si‐C≡P for the first time. The regioselectivity of this reaction could be verified by means of single crystal X‐ray diffraction of the corresponding W0 complex. In the presence of ZnBr2 and dppp (1,3‐bis(diphenylphosphino)propane) as a bidentate ligand, the bromo‐phosphinine quantitatively undergoes a Negishi cross‐coupling reaction with PhLi that selectively leads to 6‐phenyl‐2‐trimethylsilyl‐phosphinine. This heterocycle could again be characterized by means of X‐ray diffraction as a W0 complex. These results describe a new and convenient route to 2,6‐disubstituted phosphinines that makes use of readily available starting materials.
Enhanced Photocatalytic Performance of ZnO Nanorods Coupled by Two‐Dimensional α‐MoO3 Nanoflakes under UV and Visible Light Irradiation
Authors: Hang Da‐Ren , Sharma Krishna Hari , Chen Chun‐Hu , Islam Sk Emdadul
Published: August 2016

We exploit the utilization of two‐dimensional (2D) molybdenum oxide nanoflakes as a co‐catalyst for ZnO nanorods (NRs) to enhance their photocatalytic performance. The 2D nanoflakes of orthorhombic α‐MoO3 were synthesized through a sonication‐aided exfoliation technique. The 2D MoO3 nanoflakes can be further converted to substoichiometric quasi‐metallic MoO3−x by using UV irradiation. Subsequently, 1D–2D MoO3/ZnO NR and MoO3−x/ZnO NR composite photocatalysts have been successfully synthesized. The photocatalytic performances of the novel nanosystems in the decomposition of methylene blue are studied by using UV‐ and visible‐illumination setup. The incorporated 2D nanoflakes show a positive influence on the photocatalytic activity of the ZnO. The obtained rate constant values follow the order of pristine ZnO NR<MoO3/ZnO NR<MoO3−x/ZnO NR composites. The enhancement of the photocatalytic efficiency can be ascribed to a fast charge carrier separation and transport within the heterojunctions of the MoO3/ZnO NRs. In particular, the best photocatalytic performance of the MoO3−x/ZnO NR composite can be additionally attributed to a quasi‐metallic conductivity and substoichiometry‐induced mid‐gap states, which extend the light absorption range. A tentative photocatalytic degradation mechanism was proposed. The strategy presented in this work not only demonstrates that coupling with nanoscale molybdenum oxide nanoflakes is a promising approach to significantly enhance the photocatalytic activity of ZnO but also hints at new type of composite catalyst with extended applications in energy conversion and environmental purification.
Spectroscopically Characterized Synthetic Mononuclear Nickel–Oxygen Species
Authors: Corona Teresa , Company Anna
Published: August 2016

Iron, copper, and manganese are the predominant metals found in oxygenases that perform efficient and selective hydrocarbon oxidations and for this reason, a large number of the corresponding metal–oxygen species has been described. However, in recent years nickel has been found in the active site of enzymes involved in oxidation processes, in which nickel–dioxygen species are proposed to play a key role. Owing to this biological relevance and to the existence of different catalytic protocols that involve the use of nickel catalysts in oxidation reactions, there is a growing interest in the detection and characterization of nickel–oxygen species relevant to these processes. In this Minireview the spectroscopically/structurally characterized synthetic superoxo, peroxo, and oxonickel species that have been reported to date are described. From these studies it becomes clear that nickel is a very promising metal in the field of oxidation chemistry with still unexplored possibilities.
Asymmetric Assembly of All‐Carbon Tertiary/Quaternary Nonadjacent Stereocenters through Organocatalytic Conjugate Addition of α‐Cyanoacetates to a Methacrylate Equivalent
Authors: Iriarte Igor , Vera Silvia , Badiola Eider , Mielgo Antonia , Oiarbide Mikel , García Jesús M. , Odriozola José M. , Palomo Claudio
Published: August 2016

An efficient, highly diastereo‐ and enantioselective assembly of acyclic carbonyl fragments possessing nonadjacent all‐carbon tertiary/quaternary stereoarrays is reported based on a Brønsted base catalyzed Michael addition/α‐protonation sequence involving α‐cyanoacetates and 2,4‐dimethyl‐4‐hydroxypenten‐3‐one as novel methacrylate equivalent.
Vogelspinne zeigt neue Schmerz‐Wege
Authors: Groß Michael
Published: August 2016

Im Gift einer handtellergroßen westafrikanischen Vogelspinne fanden Forscher zwei Peptide, die in Nervenzellen gezielt einen Ionenkanal blockieren, dessen Funktion bisher unbekannt war, aber nun mit diesen Molekülen untersucht werden kann.
Das Eis ist heiß
Authors: Neidlinger Andreas
Published: August 2016

Wer Eiswürfel herstellt, ist schneller am Ziel, wenn er kaltes Wasser ins Gefrierfach stellt und nicht heißes. Oder doch nicht?
CO2 – ein janusköpfiges Molekül
Authors: Offermanns Heribert , Bertau Martin
Published: August 2016

“Klimakiller” und Basis für eine Weltwirtschaft ohne fossile Rohstoffe
Metal–Organic Coordination versus Hydrogen Bonding: Highly Efficient Templated Photocycloadditions of Trisubstituted Isomeric Olefins in the Solid State
Authors: Elacqua Elizabeth , Sinnwell Michael A. , Loren Bradley P. , Jurgens Paul T. , Groeneman Ryan H. , Reinheimer Eric W. , MacGillivray Leonard R.
Published: August 2016

Trisubstituted olefins are reactants in template‐directed, solid‐state [2+2] photocycloaddition reactions. Whereas hydrogen‐bond‐based templates afford crystalline assemblies with olefins that are photostable, AgI coordination results in carbon–carbon double bonds that react stereoselectively and result in quantitative yield.
The Synthesis of Ketone‐Derived Enamides by Elimination of HCN from Cyanoamides
Authors: Coussanes Guilhem , Gaus Katharina , O'Sullivan Anthony C.
Published: August 2016

Treatment of easily available ketone‐derived cyanoamides with NaOtBu leads to enamides in a simple, scalable, and inexpensive one‐step operation in good yield. Enamides not stabilized by conjugation or by inclusion in a ring can also be prepared. An E1cB mechanism consistent with all results and observations, is proposed. The Z geometry of the product enamide is highly favoured, and the regioselectivity can be directed by one′s choice of protecting group.
Direct Synthesis of Perylene‐Fused Cyclic Ketones from Perylene and 2‐Alkenoic Acids
Authors: Głodek Marta , Makal Anna , Kłys Arkadiusz , Zakrzewski Janusz , Plażuk Damian
Published: August 2016

An efficient, one‐pot methodology of direct synthesis of perylene‐fused cyclic ketones from perylene and 2‐alkenoic acids under acidic catalytic conditions has been developed. The reaction of perylene with 2,3‐disubstituted 2‐alkenoic acid leads, via Friedel–Crafts acylation followed by Nazarov cyclization, to the formation of disubstituted 5,6‐dihydro‐4H‐cyclopenta[b]perylen‐4‐ones in high yield (up to 97 %) and high diastereoselectivity, whereas the reaction with acrylic acid leads, via alkylation followed by intramolecular Friedel–Crafts acylation, to 2,3‐dihydro‐1H‐benzo[cd]perylen‐1‐one.
Covalent Attachment of the Water‐insoluble Ni(PCy2NPhe2)2 Electrocatalyst to Electrodes Showing Reversible Catalysis in Aqueous Solution
Authors: Rodríguez‐Maciá Patricia , Priyadarshani Nilusha , Dutta Arnab , Weidenthaler Claudia , Lubitz Wolfgang , Shaw Wendy J. , Rüdiger Olaf
Published: August 2016

Hydrogenases are a diverse group of metalloenzymes which catalyze the reversible conversion between molecular hydrogen and protons at high rates. The catalytic activity of these enzymes does not require overpotential because their active site has been evolutionarily optimized to operate fast and efficiently. These enzymes have inspired the development of molecular catalysts, which have dramatically improved in efficiency in recent years, to the point that some synthetic catalysts even outperform hydrogenases under certain conditions. In this work, we use a reversible noble‐metal‐free homogeneous catalyst, the [Ni(PCy2NPhe2)2]2+ complex, and we covalently immobilize it on a functionalized highly oriented pyrolytic graphite “edge” (HOPGe) electrode surface. This catalyst is not water soluble, but once it is surface‐confined on the electrode, it maintains its catalytic properties in aqueous solutions, showing reversibility for H2 oxidation/reduction. Immobilization of the [Ni(PCy2NPhe2)2]2+ complex onto a multi‐walled carbon nanotubes coated electrode leads to even higher catalytic current densities and enhanced stability.
Cost‐effective non‐metric photogrammetry from consumer‐grade sUAS: implications for direct georeferencing of structure from motion photogrammetry
Authors: Carbonneau Patrice E. , Dietrich James T.
Published: August 2016

The declining costs of small Unmanned Aerial Systems (sUAS), in combination with Structure‐from‐Motion (SfM) photogrammetry have triggered renewed interest in image‐based topography reconstruction. However, the potential uptake of sUAS‐based topography is limited by the need for ground control acquired with expensive survey equipment. Direct georeferencing (DG) is a workflow that obviates ground control and uses only the camera positions to georeference the SfM results. However, the absence of ground control poses significant challenges in terms of the data quality of the final geospatial outputs. Notably, it is generally accepted that ground control is required to georeference, refine the camera calibration parameters, and remove any artefacts of optical distortion from the topographic model. Here, we present an examination of DG carried out with low‐cost consumer‐grade sUAS. We begin with a study of surface deformations resulting from systematic perturbations of the radial lens distortion parameters. We then test a number of flight patterns and develop a novel error quantification method to assess the outcomes. Our perturbation analysis shows that there exists families of predictable equifinal solutions of K1‐K2 which minimize doming in the output model. The equifinal solutions can be expressed as K2 = f (K1) and they have been observed for both the DJI Inspire 1 and Phantom 3 sUAS platforms. This equifinality relationship can be used as an external reliability check of the self‐calibration and allow a DG workflow to produce topography exempt of non‐affine deformations and with random errors of 0.1% of the flying height, linear offsets below 10 m and off‐vertical tilts below 1°. Whilst not yet of survey‐grade quality, these results demonstrate that low‐cost sUAS are capable of producing reliable topography products without recourse to expensive survey equipment and we argue that direct georeferencing and low‐cost sUAS could transform survey practices in both academic and commercial disciplines. Copyright © 2016 John Wiley & Sons, Ltd.
Tricoordinate Organochromium(III) Complexes Supported by a Bulky Silylamido Ligand Produce Ultra‐High‐Molecular Weight Polyethylene in the Absence of Activators
Authors: Liu Hsueh‐Ju , Cai Irene C. , Fedorov Alexey , Ziegler Micah S. , Copéret Christophe , Tilley T. Don
Published: August 2016

Low‐coordinate organoCr(III) complexes supported by the silylamido ligand –N(SiMe3)DIPP (DIPP = 2,6‐diisopropylphenyl) are ethylene polymerization catalyst precursors without the need of additional cocatalyst. The reaction of CrCl3(THF)3 with 3 or 2 equiv. of LiN(SiMe3)DIPP yields either a four‐membered cyclometalated Cr complex or Cr[N(SiMe3)DIPP]2Cl, respectively, with no trace of Cr[N(SiMe3)DIPP]3. Addition of 1 equiv. of LiN(SiMe3)DIPP to Cr[N(SiMe3)DIPP]2Cl also leads to the four‐membered metallacycle, which upon heating transforms to a new six‐membered Cr metallacycle, likely via a σ‐bond metathesis step. Cr[N(SiMe3)DIPP]2Cl can be readily converted to bis(amido)Cr(III) vinyl and alkyl complexes Cr[N(SiMe3)DIPP]2R (R = vinyl, Bn, and Me). All of these structurally characterized low‐coordinate Cr(III) complexes with a Cr–C bond initiate the polymerization of ethylene in the absence of activators or cocatalysts, producing ultra‐high‐molecular weight polyethylene.
Metabolomic study of wild and cultivated caper (Capparis spinosa L.) from different areas of Sardinia and their comparative evaluation
Authors: Maldini Mariateresa , Foddai Marzia , Natella Fausta , Addis Roberta , Chessa Mario , Petretto Giacomo Luigi , Tuberoso Carlo I. G. , Pintore Giorgio
Published: August 2016

Capparis spinosa L. (Capparidaceae), also known as caper, is widely known for its very aromatic flower buds (capers),that are largely employed as a flavouring in cooking. Capparis species are regarded as a potential source of important bioactive compounds, in fact, due to their botanical relationship with Brassica species; they contain glucosinolates, secondary plant metabolites, that have been studied for their potential anticarcinogenic properties. In addition, the presence of other numerous beneficial compounds such as polyphenols, alkaloids, lipids, vitamins and minerals have been reported. The aim of this study was to individuate and determinate the principal bioactive compounds occurring in different part (leaves, buds and flowers) of wild and cultivated C. spinosa collected from different area of Sardinia (Italy).

Ultra‐high performance liquid chromatography‐triple quadrupole/linear ion trap tandem mass spectrometry methods were used for identification and simultaneous determination of 27 bioactive molecules.

Analysis of different samples revealed qualitative and quantitative differences in the content of flavonoids, glucosinolates, anthocyanins and phenolic acids. In particular, glucocapparin resulted the most abundant with values ranging from 112 to 364 mg/100 g Fresh Weight (FW); followed by rutin with highest value of 126 mg/100 g FW, 4‐hydroxyglucobrassicin with highest value of 42 mg/100 g FW and isorhamnetin 3‐O‐rutinoside with highest value of 24 mg/100 g FW.

Based on this metabolomic targeted approach, quantitative results were treated by principal component analysis to explore and visualise correlation and discrimination among collections of C. spinosa samples. Copyright © 2016 John Wiley & Sons, Ltd.
Observed spatio‐temporal changes of winter snow albedo over the north‐west Himalaya
Authors: Negi H. S. , Datt P. , Thakur N. K. , Ganju A. , Bhatia V. K. , Vinay Kumar G.
Published: August 2016

ABSTRACT

This study presents the spatio‐temporal winter snow albedo analysis over different mountain ranges of north‐west Himalaya (NWH) for a period of approximately 24 years. Here we assess the temporal albedo variations in past two decades (1991–2010) in comparison to the recent 14 years (2000–2014). The field collected manual data of two representative observatories of Lower Himalaya (LH) and Great Himalaya (GH), and six automatic weather stations in LH, GH and Karakoram Himalaya (KH) were analysed. Satellite derived MODIS albedo data (MOD10A1) over these stations between 2001 and 2014 were analysed. A good correlation (r = 0.59) was observed between monthly average MODIS retrieved albedo and field collected albedo for GH with a relative error of 11%. In past two decades, a statistically significant (99%) decreasing rate of −0.011 per year in winter snow albedo was observed over GH (1993–2010), while in recent decade (2001 onward), no statistically significant increasing trend was observed. The change in albedo of GH is attributed to winter mean air temperature, which shows a significant rise in the past two decades, but there has been a hiatus in winter mean air temperature rise in recent decade. The higher winter mean air temperature above 0 °C since beginning of the study period (1991 onward) kept albedo of moist/wet snow approximately stable in LH. Further, insignificant increasing trend of albedo was observed over KH range in recent decade, and it is attributed to persistent very low temperatures and an increase in the frequency of snowfall days. This albedo study over NWH supports the recently reported findings on Himalayan snow cover and glacier variations during different durations.
Amino‐methyl coumarin as a potential SERS@Ag probe for the evaluation of protease activity and inhibition
Authors: Soualmia Feryel , Touhar Si Ammar , Guo Liangfeng , Xu Qisong , V. Garland Marc , Colomban Philippe , Percot Aline , El Amri Chahrazade
Published: August 2016

Proteases are found deregulated in many diseases including cancer and neurodegenerative diseases. They thus represent good therapeutical targets for the development of inhibitors mainly small organic molecules. Peptide substrates containing fluorogenic groups constitute central tools for the monitoring of protease activities and inhibitor screening platforms. Amino‐methyl coumarin (AMC) is a well‐known fluorogenic group that functionalized a huge number of peptide substrates used for kinetics in vitro but also in vivo. However, either autofluorescence or quenching of the AMC fluorescence could compromise selection and accurate evaluation of these inhibitors. It is thus needed to explore alternative spectroscopic tools to unravel these limitations. Here, we investigate whether AMC could constitute a valuable Surface Enhanced Raman Spectroscopy probe in the presence of Creighton' silver colloids under 532‐nm excitation to monitor protease activity and to evaluate inhibitors. The kallikrein‐related peptidase 8 was used as model of proteolytic enzyme. Band‐Target Entropy Minimization analysis was successfully used to validate the present Surface Enhanced Raman Spectroscopy approach. Copyright © 2016 John Wiley & Sons, Ltd.
Protein glycation and aggregation inhibitory potency of biomolecules from black gram milled by‐product
Authors: Girish Talakatta K , Prasada Rao Ummiti JS
Published: August 2016

BACKGROUND

Persistent hyperglycaemia causes increased advanced glycation end products (AGEs), which contribute to the pathogenesis of diabetic complication. Therefore, effect of black gram milled by‐product (BGBP) extract on inhibition of AGE formation in a bovine serum albumin (BSA)/glucose system was investigated.

RESULTS

BGBP extract had a total polyphenol content of 82 mg GAE g−1 and flavonoid content of 46 mg CE g−1. Ferulic acid, protocatechuic acid, gallic acid, gentisic acid, isovitexin, vitexin and epicatechin were the major bioactives in the extract. BGBP extract exhibited an effective Fe2+ chelating activity. Size exclusion–high‐performance liquid chromatographic studies indicated that upon BSA‐AGE formation the BSA monomer content was 38%; however, in the presence of BGBP extract at 50 and 100 µg levels, the monomer content increased and it was found to be 48% and 73%, respectively. BGBP extract at 50 and 100 µg levels decreased the protein carbonyl and fructosamine contents, and quenched the fluorescence intensity of glycated BSA in a dose‐dependent manner. Further, fluorescence and transmission electron microscopic studies confirmed the decrease in formation of AGEs by BGBP extract.

CONCLUSION

As BGBP extract inhibited the formation of AGEs, the extract can be used as a nutraceutical or it can be incorporated into food products to obtain functional foods. © 2016 Society of Chemical Industry
Acclimation settings with identical or similar sensation and functional thresholds
Authors: Kezirian Eric J.
Published: August 2016

Hypoglossal nerve stimulation with an activated implanted device does not awaken individuals from sleep once they have acclimated to the new sensation of the resulting tongue movement. This case report illustrates the importance of an acclimation period, allowing a patient to become accustomed to stimulation settings below the level at which there is gross tongue movement. Laryngoscope, 126:S20–S21, 2016
Particle Nucleation in the Initial Stage of Emulsifier‐Free, Emulsion Organotellurium‐Mediated Living Radical Polymerization (Emulsion TERP) of Styrene: Kinetic Approach
Authors: Kitayama Yukiya , Yamashita Nobuko , Okubo Masayoshi
Published: August 2016

Kinetic simulations of polymer chain propagation in an aqueous medium in an initial stage of emulsifier‐free, emulsion organotellurium‐mediated living radical polymerization (emulsion TERP) of styrene with sodium poly(methacrylic acid)‐methyltellanyl (PMAA‐TeMe) as a control agent and 4,4′‐azobis(4‐cyanovaleric acid) as a water‐soluble azo‐initiator at various polymerization temperatures, which is carried out experimentally at pH > 9 in a previous article, is performed using PREDICI software from CiTGmbH. The approach based on α‐chain end‐separated kinetic simulation leads us to get important aspects of individual polymer chain growths from both α‐end groups, i.e., initiator and PMAA end groups. The larger number percentage of polystyrene (PS) chain having PMAA end group relative to all PS chains is generated at lower polymerization temperature. In addition, the PS chain growth is also pronounced at lower temperature. In other words, the self‐assembly nucleation, in which the control agents are contained, predominantly occurs at the lower polymerization temperature than the homogeneous nucleation, in which they are not contained. This indicates that the emulsion TERP effectively proceeds at lower temperature, which is well accorded with the experimental result in the previous article.

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The transport dynamics in complex systems governing by anomalous diffusion modelled with Riesz fractional partial differential equations
Authors: Ray Santanu Saha
Published: August 2016

In this paper, numerical solutions of fractional Fokker–Planck equations with Riesz space fractional derivatives have been developed. Here, the fractional Fokker–Planck equations have been considered in a finite domain. In order to deal with the Riesz fractional derivative operator, shifted Grünwald approximation and fractional centred difference approaches have been used. The explicit finite difference method and Crank–Nicolson implicit method have been applied to obtain the numerical solutions of fractional diffusion equation and fractional Fokker–Planck equations, respectively. Numerical results are presented to demonstrate the accuracy and effectiveness of the proposed numerical solution techniques. Copyright © 2016 John Wiley & Sons, Ltd.
Numerical recovery strategies for parallel resilient Krylov linear solvers
Authors: Agullo Emmanuel , Giraud Luc , Guermouche Abdou , Roman Jean , Zounon Mawussi
Published: August 2016

As the computational power of high‐performance computing systems continues to increase by using a huge number of cores or specialized processing units, high‐performance computing applications are increasingly prone to faults. In this paper, we present a new class of numerical fault tolerance algorithms to cope with node crashes in parallel distributed environments. This new resilient scheme is designed at application level and does not require extra resources, that is, computational unit or computing time, when no fault occurs. In the framework of iterative methods for the solution of sparse linear systems, we present numerical algorithms to extract relevant information from available data after a fault, assuming a separate mechanism ensures the fault detection. After data extraction, a well‐chosen part of missing data is regenerated through interpolation strategies to constitute meaningful inputs to restart the iterative scheme. We have developed these methods, referred to as interpolation–restart techniques, for Krylov subspace linear solvers. After a fault, lost entries of the current iterate computed by the solver are interpolated to define a new initial guess to restart the Krylov method. A well‐suited initial guess is computed by using the entries of the faulty iterate available on surviving nodes. We present two interpolation policies that preserve key numerical properties of well‐known linear solvers, namely, the monotonic decrease of the A‐norm of the error of the conjugate gradient or the residual norm decrease of generalized minimal residual algorithm for solving. The qualitative numerical behavior of the resulting scheme has been validated with sequential simulations, when the number of faults and the amount of data losses are varied. Finally, the computational costs associated with the recovery mechanism have been evaluated through parallel experiments. Copyright © 2016 John Wiley & Sons, Ltd.
Quintic spline technique for time fractional fourth‐order partial differential equation
Authors: Tariq Hira , Akram Ghazala
Published: August 2016

Higher order non‐Fickian diffusion theories involve fourth‐order linear partial differential equations and their solutions. A quintic polynomial spline technique is used for the numerical solutions of fourth‐order partial differential equations with Caputo time fractional derivative on a finite domain. These equations occur in many applications in real life problems such as modeling of plates and thin beams, strain gradient elasticity, and phase separation in binary mixtures, which are basic elements in engineering structures and are of great practical significance to civil, mechanical, and aerospace engineering. The quintic polynomial spline technique is used for space discretization and the time‐stepping is done using a backward Euler method based on the L1 approximation to the Caputo derivative. The stability and convergence analysis are also discussed. The numerical results are given, which demonstrate the effectiveness and accuracy of the numerical method. The numerical results obtained in this article are also compared favorably well with the results of (S. S. Siddiqi and S. Arshed, Int. J. Comput. Math. 92 (2015), 1496–1518). © 2016 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 445–466, 2017
Design of novel plasticizers for nylon: from molecular modeling to experimental verification
Authors: Alperstein David , Knani Dafna
Published: August 2016

Polyamides are semi‐crystalline polymers useful in a wide range of applications in the plastics industry. Some applications require higher flexibility and workability of the polyamides. Therefore, plasticizers are added to ease compounding and processing procedures and produce the desired product properties. The goal of the present work was to study experimentally a series of four esters of 4‐hydroxybenzoate with linear side chain as plasticizers for the random copolymer nylon 66/6 and to compare the experimental results to computational results that were obtained in a previous work. The plasticizers used were the methyl, ethyl, propyl, and butyl esters of 4‐hydroxybenzoate (M4HB, E4HB, P4HB, and B4HB, respectively). Four properties of the plasticizer‐polymer blends were examined: area under the loss modulus curve; impact energy; the decrease in Tg, which is related to the plasticization efficiency, and static modulus that serves as an indication to the mechanical properties or the polymer. It was found that P4HB and B4HB offer the optimal combination of plasticization efficiency and mechanical properties and that M4HB is inferior to the other three plasticizers, as was predicted computationally. This study verifies that computational design of plasticizers for nylon is valid and can serve as an important tool to develop new plasticizers specifically and new additives to polymers generally. Copyright © 2016 John Wiley & Sons, Ltd.
Dihydroxylation of styrene by sodium chlorite with scandium triflate
Authors: Ohkubo Kei , Hirose Kensaku , Shibata Takekatsu , Takamori Kiyoto , Fukuzumi Shunichi
Published: August 2016

Dihydroxylation of styrene by chlorite (ClO2−) with scandium triflate [Sc(OTf)3] occurs efficiently to produce 1‐phenylethane‐1,2‐diol under the ambient conditions. Scandium triflate acting as a strong Lewis acid is found to accelerate the disproportionation of ClO2− to produce ClO− and ClO3−. A scandium‐chlorine dioxide complex (Sc3+ClO2•) is generated by the reaction of ClO− with ClO2− in the presence of Sc3+. The binding of Sc3+ to ClO2• was detected by the electron paramagnetic resonance measurements, enhancing the reactivity and selectivity of styrene hydroxylation.
Potential Energetic Plasticizers on the Basis of 2,2‐Dinitropropane‐1,3‐diol and 2,2‐Bis(azidomethyl)propane‐1,3‐diol
Authors: Hafner Sven , Hartdegen Vera A. , Hofmayer Maximilian S. , Klapötke Thomas M.
Published: August 2016

Different carboxylic acid derivatives of 2,2‐dinitropropane‐1,3‐diol (DNPD) and 2,2‐bis(azidomethyl)propane‐1,3‐diol (BAMP) were synthesized to investigate their suitability as energetic plasticizers. The syntheses were carried out using acyl chlorides of acetic, propionic, and butyric acid. The obtained products were characterized by elemental analysis, NMR, and IR spectroscopy. The energetic properties of the synthesized compounds were calculated on the basis of the computed heats of formation at the CBS‐4M level of theory using the EXPLO5 version 6.02 computer code. Investigations of physical stabilities were carried out using BAM drop hammer and friction tester. Low and high temperature behavior was determined by differential scanning calorimetry (DSC). The energetic and physical properties of the synthesized compounds were compared to the literature known energetic plasticizers N‐butyl nitratoethylnitramine (BuNENA) and diethylene glycol bis(azidoacetate) ester (DEGBAA). For analyzing the plasticizing abilities, mixtures of glycidyl azide polymer (GAP) and poly(3‐nitratomethyl‐3‐methyloxetan) (polyNIMMO) were prepared with both propionyl based compounds in different ratios and investigated regarding their glass transition temperatures and viscosity. Both compounds showed plasticizing effects in the range of BuNENA.
Effect of n‐ and p‐type doping concentrations and compensation on the electrical properties of semiconducting diamond
Authors: Traoré Aboulaye , Koizumi Satoshi , Pernot Julien
Published: August 2016

We report an exhaustive description of electrical properties of mono‐crystalline diamond epilayers doped with boron and phosphorus impurities. Carrier density, carrier mobility, and resistivity have been calculated for boron and phosphorus doped diamond as a function doping level and a compensation for values ranging between 10 and 10 at two different temperatures of 300 and 500 K. The calculated values are graphically compared with experimental data from the literature and discussed in terms of device performances. Finally, an example of use of the graphics is given by comparing the IV characteristics of the first pn diamond junction with our calculations.

Theoretical hole mobility as function of acceptor concentration and compensation at 300 and 500 K. The symbols are experimental data from references given in the text.
Combined experimental and theoretical studies of pressure effects in La2Sb
Authors: Knöner Stephan , Gati Elena , Wolf Bernd , de Souza Mariano , Haghighirad Amir , Kuhnt Markus , Assmus Wolf , Jeschke Harald O. , Tomić Milan , Valentí Roser , Lang Michael
Published: August 2016

The 5 K superconductor LaSb shares some structural similarities with the iron‐pnictides and ‐chalgogenides, especially the so‐called 122‐compounds, despite lacking a 3d‐metal component. In order to look for similarities and dissimilarities of this layered metal pnictide with the higher‐ Fe‐based superconductors, we have performed a combined experimental and theoretical investigation of the effects of hydrostatic pressure. Magnetic measurements reveal a linear increase of with pressure at a rate d/d. Band  structure  calculations show that (i) the states at the Fermi level have predominantly La 5d character and (ii) that the density of states increases linearly with increasing pressure. By using these theoretical results and a BCS formalism, a quantitative description of the experimentally revealed pressure dependence of is possible within a reasonable range of parameters. Our results indicate that LaSb, despite its structural similarities to the 122 Fe‐based superconductors, exhibits a BCS‐type of superconductivity.
Dirac‐mode guidance in silica‐based hollow‐core photonic crystal fiber with high‐index dielectric rings
Authors: Biswas Tushar , Chattopadhyay Rik , Bhadra Shyamal K.
Published: August 2016

Transmission of light in hollow‐core photonic crystal fiber (HC‐PCF) is traditionally based on the out‐of‐plane photonic bandgap of the crystal cladding that usually consists of periodically arranged air holes in silica glass. A new kind of wave guidance relying on a special point (Dirac point) of eigenfrequency dispersion plot in high‐index glass‐based HC‐PCF has been reported recently. Pure silica‐based HC‐PCF is not suitable for this kind of guidance. The existence of the Dirac point in a triangular lattice of air holes surrounded by a germania (GeO2)‐doped high‐index ring in pure silica host has been demonstrated. The addition of the high‐index layer provides a control over the density of states around the Dirac point. The operating wavelength can be tuned precisely by controlling the doping concentration and thickness of the doped glass rings. The structure is very simple and can be fabricated through a conventional stack and draw method.
A regime analysis of Atlantic winter jet variability applied to evaluate HadGEM3‐GC2
Authors: Masato G. , Woollings T. , Williams K. D. , Hoskins B. J. , Lee R. W.
Published: August 2016

The behaviour of the eddy‐driven jet over the Atlantic sector during the winter season is analyzed for the ERA‐Interim reanalysis and the coupled and atmosphere‐only configuration of HadGEM3‐GC2—the climate model in use at the Met Office. The trimodal distribution that characterizes the jet‐stream structure in terms of its preferred locations is reproduced with good accuracy by the model, although a distinct bias towards the high‐latitude position is observed. Two different scenarios are found to contribute to this bias. One occurs when the jet shifts from its southern regime, whereby it settles too far north and for too long compared with the reanalysis. The other is associated with the exit from the central latitude regime, with too many events shifting poleward rather than equatorward. Excessively large lower tropospheric eddy heat fluxes during these transitions may account for the jet errors, even though the heat fluxes do not exhibit a climatological bias. Interestingly, these biases are weaker when the atmosphere model is forced with observed sea‐surface temperatures (SSTs), suggesting that either it is vital to have the correct SST distribution or ocean–atmosphere coupling plays a key role in the biases. Additional analysis revealed that the Pacific jet exit is biased south in the coupled model and that this contributes to the Atlantic bias. Anomalously warm SSTs in the Gulf Stream region may be acting together with the Pacific bias in fostering anomalous activity in low‐level eddy heat fluxes.
TOF‐SIMS imaging of polyester/melamine resin with bismuth cluster ions
Authors: Nishinomiya S. , Toshin K. , Shishido R. , Suzuki S.
Published: August 2016

In recent years, secondary ion mass spectrometry (SIMS) with a time‐of‐flight (TOF) mass analyzer has been widely used for analyzing the structures of organic molecules. In particular, TOF‐SIMS with a cluster ion beam (Aun, Bin, C60, Arn, etc.) has been drawing attention as the technique can be used without destroying the structures of organic molecules. In this study, we imaged polyester/melamine resin using TOF‐SIMS with bismuth cluster ions. By secondary ion imaging, we confirmed that the melamine formaldehyde resin was concentrated on the surface of the paint film. By comparing the difference between C5H7N6+ (m/z = 151) and the other ions, we estimated that the degree of condensation of the melamine formaldehyde resin increased with a catalyst. Copyright © 2016 John Wiley & Sons, Ltd.
Effect of height and atomic arrangement of the super‐tip of a gas field ion emitter on helium ion beam current
Authors: Nagai Shigekazu , Katoh Shu , Iwata Tatsuo , Kajiwara Kazuo , Hata Koichi
Published: August 2016

The optimal height and atomic arrangement of a nano‐protrusion on a gas field ion emitter were investigated with the aim of obtaining higher He ion currents. The nano‐protrusion was fabricated on the center of a <111 > ‐oriented tungsten emitter tip with a large radius of curvature by field‐induced oxygen etching. The optimal height of the nano‐protrusion was determined to be a balance between enhancing the total gas supply, due to higher applied voltages to the emitter, and partition of the gas supply to atoms, including the trimer, at protruding positions where field ionization of He can occur. It was found that higher He ion currents could be obtained from the triangular trimer when the corners were orientated to the {110}‐planes, with the maximum current from the trimer found on the relatively larger (111)‐plane regardless of orientation. The results showed that a higher He ion current could be obtained when the height of the nano‐protrusion was lowered, allowing for a higher voltage to be applied while minimizing the number of the protruding atoms. Copyright © 2016 John Wiley & Sons, Ltd.
From Modular to Distributed Open Architectures: A Unified Decision Framework
Authors: Heydari Babak , Mosleh Mohsen , Dalili Kia
Published: August 2016

This paper introduces a conceptual, yet quantifiable, architecture framework by extending the notion of system modularity in its broadest sense. Acknowledging that modularity is not a binary feature and comes in various types and levels, the proposed framework introduces higher levels of modularity that naturally incorporate decentralized architecture on the one hand and autonomy in agents and subsystems on the other. This makes the framework suitable for modularity decisions in Systems of Systems and for analyzing the impact of modularity on broader surrounding ecosystems. The stages of modularity in the proposed framework are naturally aligned with the level of variations and uncertainty in the system and its environment, a relationship that is central to the benefits of modularity. The conceptual framework is complemented with a decision layer that makes it suitable to be used as a computational architecture decision tool to determine the appropriate stage and level of modularity of a system, for a given profile of variations and uncertainties in its environment. We further argue that the fundamental systemic driving forces and trade‐offs of moving from monolithic to distributed architecture are essentially similar to those for moving from integral to modular architectures. The spectrum, in conjunction with the decision layer, could guide system architects when selecting appropriate parameters and building a system‐specific computational tool from a combination of existing tools and techniques. To demonstrate the applicability of the framework, a case for fractionated satellite systems based on a simplified demo of the DARPAF6 program is presented where the value of transition from a monolithic architecture to a fractionated architecture, as two consecutive levels of modularity in the proposed spectrum, is calculated and ranges of parameters wherefractionationincreases systems value are determined.
Anxiety associated with diagnostic uncertainty in early pregnancy
Authors: Richardson A. , Raine‐Fenning N. , Deb S. , Campbell B. , Vedhara K.
Published: August 2016

Objectives

To determine anxiety levels of women presenting to an early pregnancy assessment unit (EPAU) with abdominal pain and/or vaginal bleeding and to assess how these levels change over time and according to ultrasonographic diagnosis.

Methods

We undertook a prospective cohort study in an EPAU in a large UK teaching hospital. Women with abdominal pain and/or vaginal bleeding in early pregnancy (< 12 weeks' gestation) presenting for the first time were eligible for inclusion in the study. State anxiety levels were assessed using the standardized short form of Spielberger's state–trait anxiety inventory (STAI) on three occasions (before, immediately after and 48–72 hours after an ultrasound scan). Scores were correlated with ultrasonographic diagnosis. The diagnosis was either certain or uncertain. Certain diagnoses were either positive, i.e. a viable intrauterine pregnancy (IUP), or negative, i.e. a non‐viable IUP or ectopic pregnancy. Uncertain diagnoses included pregnancy of unknown location and pregnancy of uncertain viability. Statistical analysis involved mixed ANOVAs and the post‐hoc Tukey–Kramer test.

Results

A total of 160 women were included in the study. Anxiety levels decreased over time for women with a certain diagnosis (n = 128), even when negative (n = 64), and increased over time for women with an uncertain diagnosis (n = 32). Before the ultrasound examination, anxiety levels were high (STAI value, 21.96 ± 1.11) and there was no significant difference between the five groups. Immediately after the ultrasound examination, anxiety levels were lower in the viable IUP group (n = 64; 7.75 ± 1.13) than in any other group. The difference between the five groups was significant (P < 0.005). After 48–72 hours, women with a certain diagnosis had significantly lower anxiety levels than had those with an uncertain diagnosis (10.77 ± 4.30 vs 22.94 ± 1.65; P < 0.005).

Conclusions

The experience of abdominal pain and/or vaginal bleeding in early pregnancy is highly anxiogenic. Following an ultrasound examination, the certainty of the diagnosis affects anxiety levels more than does the positive or negative connotations associated with the diagnosis per se. Healthcare providers should be aware of this when communicating uncertain diagnoses. Copyright © 2016 ISUOG. Published by John Wiley & Sons Ltd.
Near infrared photoimmunotherapy of B‐cell lymphoma
Authors: Nagaya Tadanobu , Nakamura Yuko , Sato Kazuhide , Harada Toshiko , Choyke Peter L. , Kobayashi Hisataka
Published: July 2016

Near infrared photoimmunotherapy (NIR‐PIT) is a new, highly‐selective cancer theranostics that employs an antibody‐photo absorber conjugate (APC). NIR‐PIT has successfully treated preclinical tumor models with APCs and is now in the first‐in‐human phase 1 clinical trial for head and neck cancer patients against EGFR. CD20 is highly expressed in many B‐cell lymphomas and is emerging as a molecular target for this disease. Here, we describe the use of the anti‐CD20 monoclonal antibody (mAb), rituximab‐IR700 APC for NIR‐PIT of B‐cell lymphoma in two CD20‐expressing lymphoma mouse models. CD20 expressing B‐cell lymphoma cell lines (Daudi and Ramos) were used in this study. Rituximab‐IR700, rituximab conjugated with IRDye700DX, showed specific binding, and cell‐specific killing only after exposure of NIR light to both cells in vitro. To evaluate effects of NIR‐PIT in vivo, tumor‐bearing mice were separated into 4 groups: (1) control; (2) APC i.v. only; (3) NIR light exposure only; (4) APC and NIR light (NIR‐PIT). These were performed every week for up to 3 weeks. Rituximab‐IR700 showed high tumor accumulation and high target‐to‐background ratio in vivo. Tumor growth was significantly inhibited by NIR‐PIT in comparison with the other groups (p < 0.001 for both tumors), and survival was significantly prolonged in both tumors (p < 0.001 for Daudi tumors and p < 0.0001 for Ramos tumors vs other groups). More than half of tumors were cured with this single regimen of NIR‐PIT. In conclusion, anti‐CD20 rituximab‐IR700 works as a highly effective APC for NIR‐PIT against B‐cell lymphoma.
A Regional Outbreak of Clostridium difficile PCR-Ribotype 027 Infections in Southeastern France from a Single Long-Term Care Facility
Authors: Cassir Nadim , Delarozière Jean-Christophe , Dubourg Gregory , Delord Marion , Lagier Jean-Christophe , Brouqui Phillipe , Fenollar Florence , Raoult Didier , Fournier Pierre Edouard
Published: August 2016

OBJECTIVE

To describe and analyze a large outbreak of Clostridium difficile 027 (CD-027) infections.

METHODS

Confirmed CD-027 cases were defined as CD infection plus real-time polymerase chain reaction assay (PCR) positive for CD-027. Clinical and microbiological data on patients with CD-027 infection were collected from January 2013 to December 2015 in the Provence-Alpes-Côte-d’Azur region (southeastern France).

RESULTS

In total, 19 healthcare facilities reported 144 CD-027 infections (112 confirmed and 32 probable CD-027 infections) during a 22-month period outbreak. Although the incidence rate per 10,000 bed days was lower in long-term care facilities (LTCFs) than in acute care facilities (0.05 vs 0.14; P<.001), cases occurred mainly in LTCFs, one of which was the probable source of this outbreak. After centralization of CD testing, the rate of confirmed CD-027 cases from LTCFs or residential-care homes increased significantly (69% vs 92%; P<.001). Regarding confirmed CD-027 patients, the sex ratio and the median age were 0.53 and 84.2 years, respectively. The 30-day crude mortality rate was 31%. Most patients (96%) had received antibiotics within 3 months prior to the CD colitis diagnosis. During the study period, the rate of patients with CD-027 (compared with all patients tested in the point-of-care laboratories) decreased significantly (P=.03).

CONCLUSIONS

A large CD-027 outbreak occurred in southeastern France as a consequence of an initial cluster of cases in a single LTCF. Successful interventions included rapid isolation and testing of residents with potentially infectious diarrhea and cohorting of case patients in a specialized infectious diseases ward to optimize management.

Infect Control Hosp Epidemiol 2016;1–5
On mixing a density interface by a bubble plume
Authors: Lima Neto Iran E. , Cardoso Silvana S. S. , Woods Andrew W.
Published: August 2016

We describe new experiments in which a bubble plume, produced from a point source of bubbles, rises through an ambient fluid composed of two layers of fluid of different density. In the lower layer, the speed of the plume exceeds the bubble rise speed and the motion is well described using classical theory of turbulent buoyant plumes. As the mixture enters the upper layer, it is either buoyant and rises to the top of the layer, or is negatively buoyant and forms a fountain. In our experiments, in which a fountain forms in the upper layer, the bubble rise speed exceeds the characteristic speed of this fountain, and a separated flow develops. The bubbles rise to the top of the system, while the lower layer fluid in the fountain rises a finite distance into the upper layer, entrains some of the upper layer fluid, and then collapses. This mixture of fluids then feeds a growing layer of density which is intermediate between the upper and lower layer. The height of rise of the fountain scales with the square of the Froude number of the fountain and the rate of entrainment of upper layer fluid into the fountain is directly proportional to the height of the fountain. This is analogous to the scaling for single-phase fountains with Froude numbers in the same range, $1<Fr<7$, but the constants of proportionality are smaller. We illustrate the relevance of the work for the design of mixing and aeration systems in freshwater reservoirs.