bluuebunny/crossref_metadata_2025 huggingface dataset:
Broadband meter‐wavelength observations of ionospheric scintillation
Authors: Fallows R. A. , Coles W. A. , McKay‐Bukowski D. , Vierinen J. , Virtanen I. I. , Postila M. , Ulich Th. , Enell C‐F. , Kero A. , Iinatti T. , Lehtinen M. , Orispää M. , Raita T. , Roininen L. , Turunen E. , Brentjens M. , Ebbendorf N. , Gerbers M. , Grit T. , Gruppen P. , Meulman H. , Norden M. J. , de Reijer J‐P. , Schoenmakers A. , Stuurwold K.
Published: November 2014

Intensity scintillations of cosmic radio sources are used to study astrophysical plasmas like the ionosphere, the solar wind, and the interstellar medium. Normally, these observations are relatively narrow band. With Low‐Frequency Array (LOFAR) technology at the Kilpisjärvi Atmospheric Imaging Receiver Array (KAIRA) station in northern Finland we have observed scintillations over a three‐octave bandwidth. “Parabolic arcs,” which were discovered in interstellar scintillations of pulsars, can provide precise estimates of the distance and velocity of the scattering plasma. Here we report the first observations of such arcs in the ionosphere and the first broadband observations of arcs anywhere, raising hopes that study of the phenomenon may similarly improve the analysis of ionospheric scintillations. These observations were made of the strong natural radio source Cygnus‐A and covered the entire 30–250 MHz band of KAIRA. Well‐defined parabolic arcs were seen early in the observations, before transit, and disappeared after transit although scintillations continued to be obvious during the entire observation. We show that this can be attributed to the structure of Cygnus‐A. Initial results from modeling these scintillation arcs are consistent with simultaneous ionospheric soundings taken with other instruments and indicate that scattering is most likely to be associated more with the topside ionosphere than the F region peak altitude. Further modeling and possible extension to interferometric observations, using international LOFAR stations, are discussed.
EUV emissions from solar wind charge exchange in the Earth's magnetosheath: Three‐dimensional global hybrid simulation
Authors: He Fei , Zhang Xiao‐Xin , Wang Xue‐Yi , Chen Bo
Published: November 2014

In this paper, a three‐dimensional (3‐D) global hybrid simulation code and a 3‐D geocoronal hydrogen model are used to systematically study the extreme ultraviolet (EUV) emissions at 30.4 nm produced by solar wind charge exchange (SWCX) in the Earth's magnetosheath, associated with different solar wind‐interplanetary magnetic field (SW‐IMF) conditions and different imaging perspectives. We have found that the EUV emission intensities in the magnetosheath are highly variable from several mR to ~1200 mR and increase with the flow speed, the density, the temperature, and the He2+/H+ density ratio of the solar wind; the northward IMF leads to a minimum emission in the magnetosheath, whereas the southward IMF generates a maximum emission; with the increase of the magnitude of IMF, the emission pattern in the nightside splits from single field‐aligned shape into a butterfly shape around the magnetic equator; and the EUV emissions vary with the imaging positions, reflecting different latitudinal and longitudinal information of the magnetosheath. It is noted that the SWCX EUV emissions in the magnetosheath for highly disturbed solar wind conditions should be considered in processing the Moon‐based plasmaspheric EUV images. We suggest that EUV imaging of the global magnetosheath requires an EUV imager with large field‐of‐view, high‐sensitivity, large dynamic range, and low intrinsic dark count rate. This investigation could provide us with an overall understanding on SWCX EUV emissions in the magnetosheath which can potentially be used to image the global magnetosheath to study the solar wind‐magnetosphere coupling in the future.
Antarctic Bottom Water temperature changes in the western South Atlantic from 1989 to 2014
Authors: Johnson Gregory C. , McTaggart Kristene E. , Wanninkhof Rik
Published: November 2014

Warming of abyssal waters in recent decades contributes to global heat uptake and sea level rise. Repeat oceanographic section data in the western South Atlantic taken mostly in 1989 (1995 across the Scotia Sea), 2005, and 2014 are used to quantify warming in abyssal waters that spread northward through the region from their Antarctic origins in the Weddell Sea. While much of the Scotia Sea warmed between 1995 and 2005, only the southernmost portion, on the north side of the Weddell Gyre, continued to warm between 2005 and 2014. The abyssal Argentine Basin also warmed between 1989 and 2005, but again only the southernmost portion continued to warm between 2005 and 2014, suggesting a slowdown in the inflow of the coldest, densest Antarctic Bottom Waters into the western South Atlantic between 1989 and 2014. In contrast, the abyssal waters of the Brazil Basin warmed both between 1989 and 2005 and between 2005 and 2014, at a rate of about 2 m°C yr−1. This warming is also assessed in terms of the rates of change of heights above the bottom for deep isotherms in each deep basin studied. These results, together with findings from previous studies, suggest the deep warming signal observed in the Weddell Sea after the mid‐1970s Weddell Polynya was followed by abyssal warming in the Argentine Basin from the late 1970s through about 2005, then warming in the deep Vema Channel from about 1992 through at least 2010, and warming in the Brazil Basin from 1989 to 2014.
Insurance Pricing/Nonlife
Authors: Ai Jing , Brockett Patrick L.
Published: November 2014

The essentials of nonlife insurance pricing are based on the same fundamental principles as applied in pricing life insurance. However, distinct characteristics of nonlife risks (e.g., shorter contract duration, more complicated claim structure, and the possibility of multiple occurrences of an event within the contract period) have inspired development of actuarial/financial pricing techniques specific to nonlife risk area, where insurers cope with a more regulated yet highly competitive market. This article serves as a brief introduction to various aspects of nonlife insurance pricing. Manual rates, individual risk rating, and classification are first introduced. Credibility theory and its use in determining rates for individual risks are discussed. Important premium principles and properties of these premium principles are also presented. In addition to traditional actuarial approaches, we ultimately discuss financial models that are widely employed in this area, including insurance capital asset pricing models (CAPMs), discounted cash flow models, and option pricing models. We conclude with a remark on the integration of insurance and financial pricing.
Hazards Insurance: A Brief History
Authors: Kunreuther Howard
Published: November 2014

This article briefly surveys the historical development of insurance against natural hazards and acts of God, including marine, fire, and wind hazards, leading to the rise of modern property‐casualty insurance companies.
Risk Processes: Overview
Authors: Zacks Shelemyahu
Published: November 2014

The article presents stochastic processes, which may lead to catastrophic events, like ruin of an insurance company or failure of systems due to cumulative damage. We focus attention on compound renewal processes, and in particular on compound Poisson processes. Distribution of stopping times associated with these risk processes are derived.
Probability Theory
Authors: Heyde Christopher. C.
Published: November 2014

The sections in this article are
Testosterone and male cognitive performance in Tsimane forager‐horticulturalists
Authors: Trumble Benjamin C. , Stieglitz Jonathan , Thompson Melissa Emery , Fuerstenberg Eric , Kaplan Hillard , Gurven Michael
Published: November 2014

Objective

Testosterone plays a vital role in brain function and behavior. Among humans, age‐related decline in testosterone is associated with declining cognitive functioning, and aging men with higher testosterone maintain better cognitive performance. However, most research focuses on industrialized populations with widespread access to formal schooling, high testosterone, and low parasite and pathogen load. We examine whether men's testosterone is associated with cognitive performance among Tsimane forager‐horticulturalists of Bolivia despite relatively lower levels of testosterone and higher immune burden.

Methods

Ninety‐four Tsimane men aged 36–86 (median = 49) participated in a cognitive battery (assessing short‐ and long‐term recall, digit span, semantic memory, and visual scan) and provided urine and blood samples to measure testosterone and markers of immune activation. Linear mixed effects regressions were used to model associations between cognitive performance and testosterone, controlling for age, years of schooling, Spanish fluency, and village residence. For a subset (n = 66) we included immune activation markers to examine mediator effects.

Results

Testosterone is positively associated with short‐ and long‐term verbal memory (β = 0.267, P = 0.018; β = 0.326, P = 0.005 respectively) and visual scanning (β = 0.306, P = 0.008) after controlling for potential confounders. Markers of immune activation were negatively associated with cognitive function, but did not change the associations between testosterone and cognitive performance.

Conclusion

Tsimane men show positive associations between testosterone and cognitive performance, particularly for recall and visual scanning, despite higher immune burden. Testosterone may help motivate both physical and cognitive capacities that were essential for extracting the difficult‐to‐acquire, high‐quality resources upon which humans relied over evolutionary history. Am. J. Hum. Biol. 27:582–586, 2015. © 2015 Wiley Periodicals, Inc.
Reversible kovalente Vernetzung erzeugt eine “Post‐it”‐DNA
Authors: Tomás‐Gamasa María , Serdjukow Sascha , Su Meng , Müller Markus , Carell Thomas
Published: November 2014

Wir berichten von der Entwicklung eines “Heterobasenpaars”, das durch Bildung einer Schiff'schen Base kovalent verknüpft wird. Diese Vernetzung erzeugt eine hohe Stabilisierung von DNA‐Doppelsträngen, aber kann aufgrund reversibler Iminchemie geöffnet werden. Darüber hinaus ist sogar der enzymatische Einbau der Vernetzung möglich. Unser Heterobasenpaar eröffnet neue Möglichkeiten zur Stabilisierung von DNA‐Doppelsträngen und ‐Nanostrukturen unter Bedingungen, die kompatibel mit biologischen Sytemen sind.
Paraformaldehyd und Methanol als C1‐Rohstoffe in metallkatalysierten C‐C‐Kupplungen π‐ungesättigter Edukte
Authors: Sam Brannon , Breit Bernhard , Krische Michael J.
Published: November 2014

Die rutheniumkatalysierte reduktive Kupplung von Paraformaldehyd mit Dienen, Alkinen und Allenen ermöglicht den Zugang zu hydrohydroxymethylierten Produkten, welche so unter Hydroformylierungsbedingungen nicht selektiv zugänglich sind. In speziellen Fällen, unter der Verwendung von Ni‐Katalysatoren, kann die Regioselektivität dieser C‐C‐Kupplung umgedreht werden. Ir‐Katalysatoren ermöglichen mit Methanol eine redoxneutrale, regioselektive Hydrohydroxymethylierung.
Fluorescent Probes of the Apoptolidins and their Utility in Cellular Localization Studies
Authors: DeGuire Sean M. , Earl David C. , Du Yu , Crews Brenda A. , Jacobs Aaron T. , Ustione Alessandro , Daniel Cristina , Chong Katherine M. , Marnett Lawrence J. , Piston David W. , Bachmann Brian O. , Sulikowski Gary A.
Published: November 2014

Apoptolidin A has been described among the top 0.1 % most‐cell‐selective cytotoxic agents to be evaluated in the NCI 60 cell line panel. The molecular structure of apoptolidin A consists of a 20‐membered macrolide with mono‐ and disaccharide moieties. In contrast to apoptolidin A, the aglycone (apoptolidinone) shows no cytotoxicity (>10 μM) when evaluated against several tumor cell lines. Apoptolidin H, the C27 deglycosylated analogue of apoptolidin A, displayed sub‐micromolar activity against H292 lung carcinoma cells. Selective esterification of apoptolidins A and H with 5‐azidopentanoic acid afforded azido‐functionalized derivatives of potency equal to that of the parent macrolide. They also underwent strain‐promoted alkyne–azido cycloaddition reactions to provide access to fluorescent and biotin‐functionalized probes. Microscopy studies demonstrate apoptolidins A and H localize in the mitochondria of H292 human lung carcinoma cells.
Aufklärung der Solvatationsdynamik eines einzelnen Wassermoleküls durch Infrarotspektroskopie: Theorie und Experiment
Authors: Wohlgemuth Matthias , Miyazaki Mitsuhiko , Weiler Martin , Sakai Makoto , Dopfer Otto , Fujii Masaaki , Mitrić Roland
Published: November 2014

Die Dynamik und Energetik von Wasser an Grenzflächen oder in biologischen Systemen spielt eine grundlegende Rolle bei allen Solvatations‐ und biologischen Phänomenen in wässrigen Lösungen. Insbesondere ist die Migration von Wassermolekülen der erste Schritt, der den Gesamtprozess in zeitlicher Hinsicht steuert. Es ist jedoch fast unmöglich, im Experiment die Dynamik individueller Wassermoleküle in der Lösung zu verfolgen, da sich die Signale der Moleküle in heterogenen Umgebungen überlagern. Auch wenn für Simulationen der Molekulardynamik diese Einschränkung nicht gilt, fehlt es an experimentellen Daten, um die berechnete Dynamik zu validieren. Im Folgenden zeigen wir eine neue Strategie auf, mithilfe derer die berechnete Dynamik durch die Messung zeitaufgelöster Infrarotspektren verifiziert wird. Die Koexistenz von schneller und langsamer Wassermolekül‐Migration um eine CONH‐Peptid‐Bindung wird anhand eines Modellsystems gezeigt, das einen Teil eines hydratisierten Peptids repräsentiert.
Metal‐Atom Impact on the Self‐Assembly of Cup‐and‐Ball Metalloporphyrin–Fullerene Conjugates
Authors: Moreira Luis , Calbo Joaquín , Illescas Beatriz M. , Aragó Juan , Nierengarten Iwona , Delavaux‐Nicot Béatrice , Ortí Enrique , Martín Nazario , Nierengarten Jean‐François
Published: November 2014

A fullerene ammonium derivative has been combined with different metalloporphyrin–crown ether receptors to generate very stable supramolecules. The combination of fullerene–porphyrin and ammonium–crown ether interactions leads to a strong chelate effect as evidenced by a high effective molarity (3.16 M). The different parameters influencing the stability of the supramolecular ensembles, in particular the nature of the metal in the porphyrin moiety, have been rationalized with the help of theoretical calculations thus providing new insights into fullerene–porphyrin interactions.
Hydrolysis of a Lipid Membrane by Single Enzyme Molecules: Accurate Determination of Kinetic Parameters
Authors: Rabe Michael , Tabaei Seyed R. , Zetterberg Henrik , Zhdanov Vladimir P. , Höök Fredrik
Published: November 2014

The accurate determination of the maximum turnover number and Michaelis constant for membrane enzymes remains challenging. Here, this problem has been solved by observing in parallel the hydrolysis of thousands of individual fluorescently labeled immobilized liposomes each processed by a single phospholipase A2 molecule. The release of the reaction product was tracked using total internal reflection fluorescence microscopy. A statistical analysis of the hydrolysis kinetics was shown to provide the Michaelis–Menten parameters with an accuracy better than 20 % without variation of the initial substrate concentration. The combined single‐liposome and single‐enzyme mode of operation made it also possible to unravel a significant nanoscale dependence of these parameters on membrane curvature.
The Isothiocyanato Moiety: An Ideal Protecting Group for the Stereoselective Synthesis of Sialic Acid Glycosides and Subsequent Diversification
Authors: Mandhapati Appi Reddy , Rajender Salla , Shaw Jonathan , Crich David
Published: November 2014

The preparation of a crystalline, peracetyl adamantanyl thiosialoside donor protected by an isothiocyanate group is described. On activation at −78 °C in the presence of typical carbohydrate acceptors, this donor gives high yields of the corresponding sialosides with exquisite α‐selectivity. The high selectivity extends to the 4‐O‐benzyl‐protected 3‐OH acceptors, which are typically less reactive and selective than galactose 3,4‐diols. Treatment of the α‐sialosides with tris(trimethylsilyl)silane or allyltris(trimethylsilyl)silane results in replacement of the C5N5 bond by a CH or a CC bond. The reaction of the isothiocyanate‐protected sialosides with thioacids generates amides, while reaction with an amine gives a thiourea, which can be converted into a guanidine. The very high α‐selectivities observed with the new donor and the rich chemistry of the isothiocyante function considerably extend the scope for optimization at the sialoside 5‐position.
An Alkyne‐Appended, Click‐Ready PtII Complex with an Unusual Arrangement in the Solid State
Authors: White Jonathan D. , Guzman Lindsay E. , Zakharov Lev N. , Haley Michael M. , DeRose Victoria J.
Published: November 2014

To better understand the range of cellular interactions of PtII‐based chemotherapeutics, robust and efficient methods to track and analyze Pt targets are needed. A powerful approach is to functionalize PtII compounds with alkyne or azide moieties for post‐treatment conjugation through the azide–alkyne cycloaddition (click) reaction. Herein, we report an alkyne‐appended cis‐diamine PtII compound, cis‐[Pt(2‐(5‐hexynyl)amido‐1,3‐propanediamine)Cl2] (1), the X‐ray crystal structure of which exhibits a combination of unusual radially distributed CH/π(CC) interactions, PtPt bonding, and NH:O/NH:Cl hydrogen bonds. In solution, 1 exhibits no Ptalkyne interactions and binds readily to DNA. Subsequent click reactivity with nonfluorescent dansyl azide results in a 70‐fold fluorescence increase. This result demonstrates the potential for this new class of alkyne‐modified Pt compound for the comprehensive detection and isolation of Pt‐bound biomolecules.
Intermolecular Dynamic Kinetic Resolution Cooperatively Catalyzed by an N‐Heterocyclic Carbene and a Lewis Acid
Authors: Wu Zijun , Li Fangyi , Wang Jian
Published: November 2014

The ubiquitous structure of δ‐lactones makes the development of new methods for their enantioselective and stereoselective synthesis an important ongoing challenge. The intermolecular dynamic kinetic resolution (DKR) of β‐halo‐α‐ketoesters cooperatively catalyzed by an N‐heterocyclic carbene and a Lewis acid generates two contiguous stereocenters with remarkable diastereoselectivity through an oxidation/lactonization sequence.
Tuning the Reactivity of Isocyano Group: Synthesis of Imidazoles and Imidazoliums from Propargylamines and Isonitriles in the Presence of Multiple Catalysts
Authors: Tong Shuo , Wang Qian , Wang Mei‐Xiang , Zhu Jieping
Published: November 2014

The reaction of propargyl amines with tert‐butylisonitrile in the presence of a catalytic amount of both Yb(OTf)3 and AgOTf afforded imidazoles, whereas the same reaction with primary and secondary alkylisonitriles, as well as arylisonitriles, in the presence of three metal salts [Yb(OTf)3/AgOTf/KOTf] resulted in the 1,3,4,5‐tetrasubstituted imidazoliums in excellent yields. Both chiral amines and chiral isonitriles can be used to provide corresponding chiral heterocycles without racemization. In this multiple catalytic system, Yb(OTf)3 catalyzed the insertion of isonitriles to the NH bond of amines, AgOTf catalyzed the 5‐exo‐dig cyclization of the resulting amidine nitrogen to the tethered triple bond, and KOTf promoted the salt metathesis, thus providing at the same time the counterion to the imidazolium. Against common knowledge, the isocyano group acted in these reactions as a polarized triple bond instead of conventional carbene‐like function.
Switchable Guest Molecular Dynamics in a Perovskite‐Like Coordination Polymer toward Sensitive Thermoresponsive Dielectric Materials
Authors: Du Zi‐Yi , Xu Ting‐Ting , Huang Bo , Su Yu‐Jun , Xue Wei , He Chun‐Ting , Zhang Wei‐Xiong , Chen Xiao‐Ming
Published: November 2014

A new perovskite‐like coordination polymer [(CH3)2NH2][Cd(N3)3] is reported which undergoes a reversible ferroelastic phase transition. This transition is due to varied modes of motion of the [(CH3)2NH2]+ guest accompanied by a synergistic deformation of the [Cd(N3)3]− framework. The unusual two‐staged switchable dielectric relaxation reveals the molecular dynamics of the polar cation guest, which are well controlled by the variable confined space of the host framework. As the material switches from the ferroelastic phase to the paraelastic phase, a remarkable increase of the rotational energy barrier is detected. As a result, upon heating at low temperature, this compound shows a notable change from a low to a high dielectric state in the ferroelastic phase. This thermoresponsive host–guest system may serve as a model compound for the development of sensitive thermoresponsive dielectric materials and may be key to understanding and modulating molecular/ionic dynamics of guest molecules in confined space.
Thiol–Ene “Click” Reaction Triggered by Neutral Ionic Liquid: The “Ambiphilic” Character of [hmim]Br in the Regioselective Nucleophilic Hydrothiolation
Authors: Kumar Rajesh , Saima  , Shard Amit , Andhare Nitin H. , Richa  , Sinha Arun K.
Published: November 2014

Thiol–ene “click” chemistry has emerged as a powerful strategy to construct carbon–heteroatom (CS) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using 1H NMR spectroscopy and quadrupole time‐of‐flight electrospray ionization mass spectrometry (Q‐TOF ESI‐MS) revealed that the “ambiphilic” character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti‐Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol–yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol–yne>thiol–ene>dimerization of thiol in [hmim]Br.
An Allosteric Receptor by Simultaneous “Casting” and “Molding” in a Dynamic Combinatorial Library
Authors: Li Jianwei , Nowak Piotr , Otto Sijbren
Published: November 2014

Allosteric synthetic receptors are difficult to access by design. Herein we report a dynamic combinatorial strategy towards such systems based on the simultaneous use of two different templates. Through a process of simultaneous casting (the assembly of a library member around a template) and molding (the assembly of a library member inside the binding pocket of a template), a Russian‐doll‐like termolecular complex was obtained with remarkable selectivity. Analysis of the stepwise formation of the complex indicates that binding of the two partners by the central macrocycle exhibits significant positive cooperativity. Such allosteric systems represent hubs that may have considerable potential in systems chemistry.
Molecular Chirality in Meteorites and Interstellar Ices, and the Chirality Experiment on Board the ESA Cometary Rosetta Mission
Authors: Myrgorodska Iuliia , Meinert Cornelia , Martins Zita , Le Sergeant d'Hendecourt Louis , Meierhenrich Uwe J.
Published: November 2014

Life, as it is known to us, uses exclusively L‐amino acid and D‐sugar enantiomers for the molecular architecture of proteins and nucleic acids. This Minireview explores current models of the original symmetry‐breaking influence that led to the exogenic delivery to Earth of prebiotic molecules with a slight enantiomeric excess. We provide a short overview of enantiomeric enhancements detected in bodies of extraterrestrial origin, such as meteorites, and interstellar ices simulated in the laboratory. Data are interpreted from different points of view, namely, photochirogenesis, parity violation in the weak nuclear interaction, and enantioenrichment through phase transitions. Photochemically induced enantiomeric imbalances are discussed more specifically in the topical context of the “chirality module” on board the cometary Rosetta spacecraft of the ESA. This device will perform the first enantioselective in situ analyses of samples taken from a cometary nucleus.
Phase Behavior of a Designed Cyclopropyl Analogue of Monoolein: Implications for Low‐Temperature Membrane Protein Crystallization
Authors: Salvati Manni Livia , Zabara Alexandru , Osornio Yazmin M. , Schöppe Jendrik , Batyuk Alexander , Plückthun Andreas , Siegel Jay S. , Mezzenga Raffaele , Landau Ehud M.
Published: November 2014

Lipidic cubic phases (LCPs) are used in areas ranging from membrane biology to biodevices. Because some membrane proteins are notoriously unstable at room temperature, and available LCPs undergo transformation to lamellar phases at low temperatures, development of stable low‐temperature LCPs for biophysical studies of membrane proteins is called for. Monodihydrosterculin (MDS) is a designer lipid based on monoolein (MO) with a configurationally restricted cyclopropyl ring replacing the olefin. Small‐angle X‐ray scattering (SAXS) analyses revealed a phase diagram for MDS lacking the high‐temperature, highly curved reverse hexagonal phase typical for MO, and extending the cubic phase boundary to lower temperature, thereby establishing the relationship between lipid molecular structure and mesophase behavior. The use of MDS as a new material for LCP‐based membrane protein crystallization at low temperature was demonstrated by crystallizing bacteriorhodopsin at 20 °C as well as 4 °C.
An Alternative Mechanism for the Cobalt‐Catalyzed Isomerization of Terminal Alkenes to (Z)‐2‐Alkenes
Authors: Schmidt Anastasia , Nödling Alexander R. , Hilt Gerhard
Published: November 2014

The cobalt‐catalyzed selective isomerization of terminal alkenes to the thermodynamically less‐stable (Z)‐2‐alkenes at ambient temperatures takes place by a new mechanism involving the transfer of a hydrogen atom from a Ph2PH ligand to the starting material and the formation of a phosphenium complex, which recycles the Ph2PH complex through a 1,2‐H shift.
Access to Novel Graphene‐Like Sheet of Hydroboron: First‐Principles Investigation
Authors: Wu Yang‐Yang , Zhao Feng‐Qi , Xu Si‐Yu , Ju Xue‐Hai
Published: November 2014

We designed a cyclic borane (B6H12) molecule with a benzene‐like structure, in which the six B atoms are located in the same plane. Three methods of B3LYP, MP2, and CCSD with the 6‐311++G** basis were used to investigate its structure, electronic property, and stability. Next, we calculated the stability and electronic property of three hydroboron derivatives with fused rings of B10H18, B14H24, and B16H26. Finally, we investigated three types of novel two‐dimensional infinite hydroboron sheets with diborane as a building block. The results of the phonon spectra ensure the dynamic stability of these predicted structures. Furthermore, the three types of hydroboron sheets are shown to have different band gap energies of less than 3.0 eV. Some investigations on the optical properties have also been performed. The predicted sheets are candidates for semiconductors, whose band gap energy can be tuned by the positions of the bridge hydrogen atoms in the sheets.
Alternatives to resolution III regular fractional factorial designs for 9–14 factors in 16 runs
Authors: Jones Bradley , Shinde Shilpa Madhavan , Montgomery Douglas C.
Published: November 2014

Resolution III regular fractional factorial designs for 9–14 factors in 16 runs are standard designs for factor screening in industrial experimentation because of their economical run size. However, for all these designs, the main effects are completely confounded with some two‐factor interaction(s), so experimenters must frequently either augment the original fractional factorial with new runs or rely on assumptions or external information to resolve ambiguities in interpretation. We propose nonregular orthogonal fractions in 16 runs for these situations that have no complete confounding of two‐factor interactions and main effects. These designs allow for the unambiguous estimation of the main effects provided that there are only a few two‐factor interactions. We show how these designs can be selected from the nonisomorphic 16‐run orthogonal fractions and discuss potential analysis methods. Copyright © 2014 John Wiley & Sons, Ltd.
A case of myositis of the deltoid muscle of the upper arm developing 1 week after influenza vaccination: case report
Authors: Urayoshi Shunsuke , Matsumoto Satohiro , Miyatani Hiroyuki , Yoshida Yukio
Published: November 2014

Key Clinical Message

We report a case of an elderly man who developed myositis of the deltoid muscle 8 days after influenza vaccination. Adverse reactions to influenza vaccine are generally immediate reactions. However, delayed‐type hypersensitivity reactions, although rare, can occur after routine influenza vaccination.
Submerged Membrane Bioreactor for Vegetable Oil Wastewater Treatment
Authors: Ma Zhun , Lei Ting , Ji Xiaosheng , Gao Xueli , Gao Congjie
Published: November 2014

A bench‐scale submerged membrane bioreactor (SMBR) was employed to treat vegetable oil plant wastewater with complete sludge retention. Treatment performance and membrane fouling of the SMBR were investigated. The system stably removed high amounts of total organic carbon, oil, and ammonia from vegetable oil wastewater and reduced the chemical oxygen demand, demonstrating the great potential of the SMBR in removing pollutants. The membrane fouling layer was not only governed by deposition of organic substances composed of extracellular polymeric substances like proteins, polysaccharides etc., and oil substances but also by inorganic elements. Organic foulants coupled to inorganic precipitation enhanced the formation of a gel layer and triggered severe membrane fouling in the SMBR.
Predicting Power for a Scaled‐up Non‐Newtonian Biomass Slurry
Authors: Russ David C. , Thomas Jonathan M. D. , Miller Q. Sean , Berson R. Eric
Published: November 2014

High‐solids biomass slurries exhibit non‐Newtonian behavior with a yield stress and require high power input for mixing. The goals were to determine the effect of scale and geometry on power number P0, and estimate the power for mixing a pretreated biomass slurry in a 3.8 million L hydrolysis reactor of conventional design. A lab‐scale computational fluid dynamics model was validated against experimental data and then scaled up. A pitched‐blade turbine and A310 hydrofoil were tested for various geometric arrangements. Flow was transitional; laminar and turbulence models resulted in equivalent P0 which increased with scale. The ratio of impeller diameter to tank diameter affected P0 for both impellers, but impeller clearance to tank diameter affected P0 only for the A310. At least 2 MW is required to operate at this scale.
Environmentally Friendly Solvent‐ and Water‐Based Coatings for Mitigation of Crystallization Fouling
Authors: Al‐Janabi Abdullah , Malayeri M. Reza
Published: November 2014

The surface properties of solvent‐based (SB) and water‐based (WB) coatings and their impact on fouling during convective heat transfer of CaSO4 solutions were investigated. Experiments demonstrated that the SB coatings had generally better non‐adhesive characteristics, especially at higher values of the electron donor component since the deposits could easily be washed away. For the SB coatings, a longer induction period compared to those of untreated surfaces was observed and a significant reduction of the fouling rate could be achieved. Further analysis of surfaces revealed that SB coatings enhanced the acid‐base repulsive force and thus reduced the deposit/solid adhesion energy. For the WB coatings, the Liftshitz‐van der Waals attractive force plays a decisive role in the adhesion process due to the higher apolar component of the surface energy.
Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster
Authors: Cardona‐Serra Salvador , Clemente‐Juan Juan M. , Coronado Eugenio , Gaita‐Ariño Alejandro , Suaud Nicolas , Svoboda Ondrej , Bastardis Roland , Guihéry Nathalie , Palacios Juan J.
Published: November 2014

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV14O40]8− (in short V14) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V14 system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.
Turn‐On Fluorescence and Unprecedented Encapsulation of Large Aromatic Molecules within a Manganese(II)–Triazole Metal–Organic Confined Space
Authors: Wang Ying , Yuan Bin , Xu Yao‐Yao , Wang Xiu‐Guang , Ding Bin , Zhao Xiao‐Jun
Published: November 2014

For the purpose of investigating the coordination behavior of sterically congested alkenes and exploring the possibility of cofacial complexation in the polycyclic aromatic system for the formation of extended polymeric networks, a new tetradentate ligand, 1,1,2,2‐tetrakis[4‐(1H‐1,2,4‐triazol‐1‐yl)phenyl]ethylene (TTPE), has been designed and synthesized. By using TTPE as a building block with regard to the self‐assembly with MnCl2⋅4 H2O, a novel two‐dimensional coordination framework {[Mn(TTPE)Cl2]⋅4 CHCl3}n(1) can be isolated. Anion‐exchange and organic‐group‐functionalized aromatic guest TTPE‐loaded host–guest complex experimental results indicate that coordinated Cl−anions in the 2D framework of1can be completely replaced with dissociative ClO4−groups in an irreversible single‐crystal‐to‐single‐crystal transformation fashion, as evidenced by the anion‐exchange products of {[Mn(TTPE)(H2O)2](ClO4)2⋅0.5 TTPE⋅5.25 H2O}n(2). Interestingly, TTPE, acting as an organic template, was encapsulated in the confined space of the 2D grid of2. To the best of our knowledge, such large organic molecules encapsulated in the reactive organic‐group‐functionalized aromatic‐guest‐loaded host–guest complex are unprecedented up to now. Luminescence measurements illustrate that1and2represent novel examples of sensing materials based on triazole derivatives. Further,2has been demonstrated by tuning the fluorescence response of porous metal–organic frameworks as a function of adsorbed small analytes.
Synthesis, Characterization, and Electrochemistry of the Manganese(I) Complexes of meso‐Substituted [14]Tribenzotriphyrins(2.1.1)
Authors: Xue Zhaoli , Wang Yemei , Mack John , Zhu Weihua , Ou Zhongping
Published: November 2014

Metalation of 6,13,20,21‐tetraaryl‐22H‐[14]tribenzotriphyrins(2.1.1) (TriP, 1 a–d) with [Mn(CO)5Br] provided MnI tricarbonyl complexes of [14]tribenzotriphyrins(2.1.1) 2 a–d in 85–93 % yield. The complexes were characterized by mass spectrometry and UV/Vis absorption, IR, and NMR spectroscopy. Single‐crystal X‐ray analyses revealed that 2 b and 2 c adopt bowl‐shaped conformations. The redox properties of [(TriP)MnI(CO)3] (2 a–d) were studied by cyclic voltammetry. Each compound undergoes two reversible one‐electron reductions to form a porphyrin π anion radical and a dianion in CH2Cl2. Two oxidation waves were observed, the first of which corresponds to a metal‐centered electron‐transfer process. The redox potentials of 2 a–d are consistent with the optical spectroscopic data and the relatively narrow HOMO–LUMO gaps that were predicted in DFT calculations. The optical spectra can be assigned by using Michl’s perimeter model. TDDFT calculations predict the presence of several metal‐to‐ligand charge‐transfer bands in the L‐band region between 500 and 700 nm.
A New Concept for Obtaining SnO2 Fiber‐in‐Tube Nanostructures with Superior Electrochemical Properties
Authors: Hong Young Jun , Yoon Ji‐Wook , Lee Jong‐Heun , Kang Yun Chan
Published: November 2014

Tin oxide (SnO2) nanotubes with a fiber‐in‐tube structure have been prepared by electrospinning and the mechanism of their formation has been investigated. Tin oxide‐carbon composite nanofibers with a filled structure were formed as an intermediate product, which were then transformed into SnO2 nanotubes with a fiber‐in‐tube structure during heat treatment at 500 °C. Nanofibers with a diameter of 85 nm were found to be located inside hollow nanotubes with an outer diameter of 260 nm. The prepared SnO2 nanotubes had well‐developed mesopores. The discharge capacities of the SnO2 nanotubes at the 2nd and 300th cycles at a current density of 1 A g−1 were measured as 720 and 640 mA h g−1, respectively, and the corresponding capacity retention measured from the 2nd cycle was 88 %. The discharge capacities of the SnO2 nanotubes at incrementally increased current densities of 0.5, 1.5, 3, and 5 A g−1 were 774, 711, 652, and 591 mA h g−1, respectively. The SnO2 nanotubes with a fiber‐in‐tube structure showed superior cycling and rate performances compared to those of SnO2 nanopowder. The unique structure of the SnO2 nanotubes with a fiber@void@tube configuration improves their electrochemical properties by reducing the diffusion length of the lithium ions, and also imparts greater stability during electrochemical cycling.
Glucose‐ and Cellulose‐Derived Ni/C‐SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation
Authors: Kasakov Stanislav , Zhao Chen , Baráth Eszter , Chase Zizwe A. , Fulton John L. , Camaioni Donald M. , Vjunov Aleksei , Shi Hui , Lercher Johannes A.
Published: November 2014

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual‐functional Ni catalysts supported on sulfonated carbon (Ni/C‐SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C‐SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C‐SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3–5 nm grafted Ni particles was analysed by in situ X‐ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C‐SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C‐SO3H with the Ni/C‐SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C‐SO3H to the most active of the Ni/C‐SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90 %) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.
The First 3‐Connected SrSi2‐Type 3D Chiral Framework Constructed from {Ni6PW9} Building Units
Authors: Li Xin‐Xiong , Fang Wei‐Hui , Zhao Jun‐Wei , Yang Guo‐Yu
Published: November 2014

A novel 3‐connected SrSi2‐type 3D chiral framework constructed from hexa‐NiII‐cluster‐substituted polyoxometalate (POM) units [Ni(enMe)2]3[WO4]3[Ni6(enMe)3(OH)3PW9O34]2⋅9H2O (1) (enMe=1,2‐diaminopropane) has been made from a hydrothermal synthetic method. This POM represents the first 3D framework based on {Ni6PW9} units and {WO4} connectors.
Catalysis by Aluminum(III) Complexes of Non‐Innocent Ligands
Authors: Berben Louise A.
Published: November 2014

Non‐Innocent ligand complexes of aluminum are described in this Concept article, beginning with a discussion of their synthesis, and then structural and electronic characterization. The main focus concerns the ability of the ligands in these complexes to mediate proton transfer reactions. As examples, aluminum–ligand cooperation in the activation of polar bonds is described, as is the importance of hydrogen bonding to stabilization of a transition state for β‐hydride abstraction. Taken together these reactions enable catalytic processes such as the dehydrogenation of formic acid.
Simple and Versatile Molecular Donors for Organic Photovoltaics Prepared by Metal‐Free Synthesis
Authors: Diac Andreea , Demeter Dora , Allain Magali , Grosu Ion , Roncali Jean
Published: November 2014

Donor–acceptor molecules (D‐π‐A) built by connecting a diphenylhydrazone block to a dicyanovinyl acceptor group via various thiophene‐based π‐conjugating spacers (1–5) were synthesized from mono‐ or dialdehydes by a simple metal‐free procedure. Cyclic voltammetry and UV/Vis absorption spectroscopy show that the extension and/or increase of the donor strength of the spacer produces a decrease of the HOMO and LUMO energy level, a red shift of the absorption spectrum and an increase of the molecular absorption coefficient. Compared to solutions, the optical spectra of spin‐cast thin films of compounds 1–3 show a broadening and red shift of the absorption bands, consistent with the formation of J‐aggregates. In contrast the blue shift observed for the EDOT‐containing compounds 4 and 5 suggests the presence of H‐aggregates. Solution‐cast and vacuum‐deposited films of donors 1–5 were evaluated in solar cells with fullerene C60 as acceptor. A power‐conversion efficiency among the highest reported for bilayer devices of basic configuration was obtained with compound 2. On the other hand, the results obtained with 4 and 5 suggest that the presence of EDOT in the structure can have deleterious effects on the organization and performances of the donor material.
Mesoporous MnCo2O4 with a Flake‐Like Structure as Advanced Electrode Materials for Lithium‐Ion Batteries and Supercapacitors
Authors: Mondal Anjon Kumar , Su Dawei , Chen Shuangqiang , Ung Alison , Kim Hyun‐Soo , Wang Guoxiu
Published: November 2014

A mesoporous flake‐like manganese‐cobalt composite oxide (MnCo2O4) is synthesized successfully through the hydrothermal method. The crystalline phase and morphology of the materials are characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller methods. The flake‐like MnCo2O4 is evaluated as the anode material for lithium‐ion batteries. Owing to its mesoporous nature, it exhibits a high reversible capacity of 1066 mA h g−1, good rate capability, and superior cycling stability. As an electrode material for supercapacitors, the flake‐like MnCo2O4 also demonstrates a high supercapacitance of 1487 F g−1 at a current density of 1 A g−1, and an exceptional cycling performance over 2000 charge/discharge cycles.
Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor
Authors: Cho Seonghwa , Jeon Youngeun , Lee Sangjin , Kim Jineun , Kim Tae Ho
Published: November 2014

The controlled self‐assembly of CuI and an asymmetric ligand with mixed N/S donors, 2‐(tert‐butylthio)‐N‐(pyridin‐3‐yl)acetamide (L), afforded three CuI coordination polymers (CPs), [Cu4I4L2(MeCN)2]n (1), [Cu4I4L2]n (2), and {[Cu4I4L2]⋅MeOH}n (3). X‐ray analyses showed that CPs 1–3 are supramolecular isomers with 1, 2, and 3D structures, respectively. CP 1 adopts a stairstep Cu4I4 cluster, whereas CPs 2 and 3 are composed of cubane‐like Cu4I4 clusters. Crystal‐to‐crystal transformations of 1 to 2 and 3 showed reversible transformations between different Cu4I4 clusters using heat or solvent (acetonitrile or methanol) vapor. CP 2 was reversibly transformed to 3 by the addition of methanol and heat. Therefore, the transformations between supramolecular isomers 1, 2, and 3 are completely reversible.
Platinum trans‐Bis(borirene) Complexes Displaying Coplanarity and Communication Across a Platinum Metal Center
Authors: Braunschweig Holger , Damme Alexander , Dewhurst Rian D. , Kelch Hauke , Macha Bret B. , Radacki Krzysztof , Vargas Alfredo , Ye Qing
Published: November 2014

Ambient‐temperature photolysis of the aminoborylene complex [(OC)5CrBN(SiMe3)2] in the presence of a series of trans‐bis(alkynyl)platinum(II) precursors of the type trans‐[Pt(CCAr)2(PEt3)2] (Ar=Ph, p‐C6H4OMe, and p‐C6H4CF3) successfully leads to twofold transfer of the borylene moiety [:BN(SiMe3)2] onto the alkyne functionalities. The alkynyl precursors and resultant bis(borirene)platinum(II) complexes formed are of the type trans‐[Pt(B{N(SiMe3)2}CCAr)2(PEt3)2] (Ar=Ph, p‐C6H4OMe, and p‐C6H4CF3). These species have all been successfully characterized by NMR, IR, and UV/Vis spectroscopy as well as by elemental analysis. Single‐crystal X‐ray diffraction has verified that these trans‐bis(borirene)platinum(II) complexes display coplanarity between the twin three‐membered rings across the platinum core in the solid state and stand as the first examples of coplanar conformations of twin borirene systems. These complexes were modeled using density functional theory (DFT), providing information helpful in determining the ability of the transition metal core to interact with each individual borirene ring system and allowing for the observed coplanarity of these rings in the solid state. This proposed transition metal interaction with the twin borirene systems is manifested in the electronic characterization of these borirene species, which display divergent photophysical UV/Vis spectroscopic profiles compared to a previously published mono(borirene)platinum(II) complex.
ChemInform Abstract: Overcoming Carbon Deactivation in Biogas Reforming Using a Hydrothermally Synthesised Nickel Perovskite Catalyst.
Authors: Evans S. E. , Good O. J. , Staniforth J. Z. , Ormerod R. M. , Darton R. J.
Published: November 2014

Ni0.2Sr0.8ZrO3 catalyst is hydrothermally prepared from a stoichiometric mixture of ZrOCl2, Sr(NO3)2, and Ni(NO3)2 (autoclave, 180 °C, 72 h).
ChemInform Abstract: Solvothermal Synthesis of Bi2O2CO3 Nanoplates for Efficient Photodegradation of RhB and Phenol under Simulated Solar Light Irradiation.
Authors: Hu Sheng‐Peng , Xu Cheng‐Yan , Zhang Bao‐You , Pei Yi , Zhen Liang
Published: November 2014

The title nanoplates with an average width of 320 nm and thicknesses of 50—90 nm are solvothermally synthesized from mixtures of Bi(NO3)3, sodium dodecyl benzene sulfonate, polyethylene glycol, and H2O (autoclave, 180 °C, 20 h).
ChemInform Abstract: A Practical Source of Chlorodifluoromethyl Radicals. Convergent Routes to gem‐Difluoroalkenes and ‐dienes and (2,2‐Difluoroethyl)indoles, ‐azaindoles, and ‐naphthols.
Authors: Salomon Pierre , Zard Samir Z.
Published: November 2014

An efficient transformation of a diverse range of alkene derivatives (II) and (VI) to chlorodifluoromethyl derivatives (IV) and (VII) is developed using the addition reaction of chlorodifluoromethyl radicals generated from xanthogenate (I).
ChemInform Abstract: Bu4N+ Alkoxide‐Initiated/Autocatalytic Addition Reactions with Organotrimethylsilanes.
Authors: Das Manas , O'Shea Donal F.
Published: November 2014

Tms‐OK/Bu4NCl is used as a general activator of organotrimethylsilanes for addition reaction.
ChemInform Abstract: Palladium‐Catalyzed Oxidative Carbocyclization—Carbonylation of Allenynes and Enallenes.
Authors: Volla Chandra M. R. , Mazuela Javier , Baeckvall Jan‐E.
Published: November 2014

This new domino reaction of substrates of type (I), (VII), and (X) gives various cyclopentene diester derivatives.
ChemInform Abstract: Base‐Mediated Synthesis of Imines and Amines from N‐Phenylureas and Alcohols.
Authors: Yadav Dilip Kumar T. , Bhanage Bhalchandra M.
Published: November 2014

Application of aliphatic instead of benzylic alcohols yields carbamate and no imine derivatives, even in the absence of base.