bluuebunny/crossref_metadata_2025 huggingface dataset:
Influence of Meso and Nanoscale Structure on the Properties of Highly Efficient Small Molecule Solar Cells
Authors: Moench Tobias , Friederich Pascal , Holzmueller Felix , Rutkowski Bogdan , Benduhn Johannes , Strunk Timo , Koerner Christian , Vandewal Koen , Czyrska‐Filemonowicz Aleksandra , Wenzel Wolfgang , Leo Karl
Published: December 2015

The nanoscale morphology of the bulk heterojunction absorber layer in an organic solar cell (OSC) is of key importance for its efficiency. The morphology of high performance vacuum‐processed, small molecule OSCs based on oligothiophene derivatives (DCV5T‐Me) blended with C60 on various length scales is studied. The analytical electron microscopic techniques such as scanning transmission electron microscopy, energy dispersive X‐ray spectroscopy, highly sensitive external quantum efficiency measurements, and meso and nanoscale simulations are employed. Unique insights into the relation between processing, morphology, and efficiency of the final devices are obtained. It is shown that the connectivity of the oligothiophene‐C60 network is independent of the material domain size. The decisive quantity controlling the internal quantum efficiency is the energetic disorder induced by material mixing, strongly limiting charge and exciton transport in the OSCs.
Robust Thin Films‐Based Triboelectric Nanogenerator Arrays for Harvesting Bidirectional Wind Energy
Authors: Quan Zuci , Han Chang Bao , Jiang Tao , Wang Zhong Lin
Published: December 2015

Wind‐driven triboelectric nanogenerators (TENGs) play an important role in harvesting energy from ambient environments. Compared to single‐side‐fixed triboelectric nanogenerator (STENG) arrays for harvesting single‐pathway wind energy, double‐side‐fixed triboelectric nanogenerator (DTENG) arrays are developed to harvest bidirectional wind energy. Electrical performances of the STENG and DTENG can be improved due to sticky, abrasive, and electrical properties of the Ti buffer layers among Al, polytetrafluoroethylene (PTFE), and polyimide (Kapton), configuring in triboelectric PTFE/Ti/Al and Al/Ti/Kapton/Ti/Al thin films. Short‐circuit current (I
SC), open‐circuit voltage (V
OC), and frequencies of the STENG and DTENG increase with increasing wind velocity ranging from 9.2 to 18.4 m s21, revealing that the moderate I
SC, V
OC, frequencies, and output powers of the STENG and DTENG reach 67 μA, 57 μA, 334 V, 296 V, 173 Hz, 162 Hz, 5.5 mW and 3.4 mW with a matched load of 4 MΩ at airflow rate of 15.9 m s21, respectively. Compared with counterparts of the single‐pathway‐harvested STENG arrays, the I
SC, durability, and stability of the bidirectional‐harvested DTENG can be dramatically improved by a 4 3 1 array connected in parallel because of the improved device configuration, stickiness, and abrasion by adhering Ti buffer layers. The durable DTENG arrays present a step toward practical applications in harvesting bidirectional wind energy for self‐powered systems and wireless sensors.
Symptoms of psychosis in schizophrenia, schizoaffective disorder, and bipolar disorder: A comparison of African Americans and Caucasians in the Genomic Psychiatry Cohort
Authors: Perlman Greg , Kotov Roman , Fu Jinmiao , Bromet Evelyn J. , Fochtmann Laura J. , Medeiros Helena ,   Genomic Psychiatry Cohort Consortium, Pato Michele T. , Pato Carlos N.
Published: December 2015

Several studies have reported differences between African Americans and Caucasians in relative proportion of psychotic symptoms and disorders, but whether this reflects racial bias in the assessment of psychosis is unclear. The purpose of this study was to examine the distribution of psychotic symptoms and potential bias in symptoms assessed via semi‐structured interview using a cohort of 3,389 African American and 5,692 Caucasian participants who were diagnosed with schizophrenia, schizoaffective disorder, or bipolar disorder. In this cohort, the diagnosis of schizophrenia was relatively more common, and the diagnosis of bipolar disorder and schizoaffective disorder‐bipolar type was less relatively common, among African Americans than Caucasians. With regard to symptoms, relatively more African Americans than Caucasians endorsed hallucinations and delusions symptoms, and this pattern was striking among cases diagnosed with bipolar disorder and schizoaffective‐bipolar disorder. In contrast, the relative endorsement of psychotic symptoms was more similar among cases diagnosed with schizophrenia and schizoaffective disorder‐depressed type. Differential item function analysis revealed that African Americans with mild psychosis over‐endorsed “hallucinations in any modality” and under‐endorsed “widespread delusions” relative to Caucasians. Other symptoms did not show evidence of racial bias. Thus, racial bias in assessment of psychotic symptoms does not appear to explain differences in the proportion of symptoms between Caucasians and African Americans. Rather, this may reflect ascertainment bias, perhaps indicative of a disparity in access to services, or differential exposure to risk factors for psychosis by race. © 2015 Wiley Periodicals, Inc.
Nanodrähte in Chemo‐ und Biosensoren: aktueller Stand und Fahrplan für die Zukunft
Authors: Fennell John F. , Liu Sophie F. , Azzarelli Joseph M. , Weis Jonathan G. , Rochat Sébastien , Mirica Katherine A. , Ravnsbæk Jens B. , Swager Timothy M.
Published: December 2015

Sensoren auf Basis von chemischen Widerständen gewinnen derzeit stark an Bedeutung. Im Vergleich zu herkömmlichen Analysegeräten sind sie preisgünstig, lassen sich leicht in elektronische Bauteile integrieren und benötigen weniger Strom. Nanodrähte (NWs) spielen für die Entwicklung von Chemosensoren eine zentrale Rolle. Mit ihrer großen Oberfläche, den Übergängen zwischen den Nanodrähten und den definierten Leitungswegen gewährleisten sie eine hervorragende Sensoransprache und verfügen über neuartige Mechanismen, wie ein Bindungsereignis oder eine andere Aktion des Analyten in ein Signal weitergeleitet wird. Dieser Aufsatz erläutert den aktuellen Entwicklungsstand der NW‐Chemosensoren. Wir beginnen mit dem Prinzip der Signalübertragung in NW‐Sensoren. Anschließend erhält der Leser einen Überblick über die Leistungsparameter der Bauelemente. Dann gehen wir auf die verschiedenen NW‐Typen und die Architektur der NW‐Bauelemente ein und erläutern die unterschiedlichen Strategien zur NW‐Funktionalisierung. Zum Abschluss entwerfen wir einen Fahrplan für die weitere Entwicklung, der Selektivität, Drift und Empfindlichkeit, die Analyse der Messantwort sowie neue Anwendungen berücksichtigt.
Kupferhydrid‐katalysierte Hydroaminierung von Alkenen und Alkinen
Authors: Pirnot Michael T. , Wang Yi‐Ming , Buchwald Stephen L.
Published: December 2015

In den vergangenen Jahren wurde die CuH‐katalysierte Hydroaminierung entdeckt und als robuster und konzeptionell neuer Synthesezugang zu enantiomerenangereicherten sekundären und tertiären Aminen entwickelt. Der Erfolg auf diesem Gebiet wurde möglich durch zahlreiche frühere Beispiele für die Katalyse mit Kupfer(I)hydrid und die gut untersuchte Verwendung von Hydroxylaminestern als elektrophile Aminquellen in ähnlichen kupferkatalysierten Reaktionen. Dieser Kurzaufsatz beschreibt Hintergrund, Fortschritte und mechanistische Untersuchungen der CuH‐katalysierten Hydroaminierung.
Synthese kristalliner Chalkogenide in ionischen Flüssigkeiten
Authors: Santner Silke , Heine Johanna , Dehnen Stefanie
Published: December 2015

Kristalline Chalkogenide gehören zu den vielversprechendsten Materialklassen. Außer dicht gepackten Festkörperstrukturen können sie auch Arrangements molekularer Cluster und Netzwerke mit hohen Porositäten bilden, wie in den so genannten zeotypen Chalkogenidometallaten. Sie zeichnen sich durch große Strukturvielfalt und interessante physikalische Eigenschaften aus. Zusätzlich zu Halbleitereigenschaften findet man Photoleitfähigkeit, Ionenleitfähigkeit, die Möglichkeit zum Moleküleinfang sowie chemische und katalytische Aktivität. Das große Interesse an der Entwicklung neuer und maßgeschneiderter Chalkogenide führte im Laufe der Jahre zu der Suche nach immer neuen und besseren Synthesestrategien. Es lässt sich ein klarer Trend in Richtung niedrigerer Synthesetemperaturen erkennen, was auf ökonomische und ökologische Gründe sowie den Wunsch nach einer besseren Reaktionskontrolle zurückzuführen ist. So kam es auch im Bereich der Chalkogenide zu Anwendungen von ionischen Flüssigkeiten als Designermedium für die Materialsynthese. In diesem Aufsatz fassen wir jüngste Entwicklungen zusammen und geben einen Überblick über verschiedene Familien von Chalkogeniden und deren Eigenschaften.
An Electron‐Deficient Building Block Based on the B←N Unit: An Electron Acceptor for All‐Polymer Solar Cells
Authors: Dou Chuandong , Long Xiaojing , Ding Zicheng , Xie Zhiyuan , Liu Jun , Wang Lixiang
Published: December 2015

A double B←N bridged bipyridyl (BNBP) is a novel electron‐deficient building block for polymer electron acceptors in all‐polymer solar cells. The B←N bridging units endow BNBP with fixed planar configuration and low‐lying LUMO/HOMO energy levels. As a result, the polymer based on BNBP units (P‐BNBP‐T) exhibits high electron mobility, low‐lying LUMO/HOMO energy levels, and strong absorbance in the visible region, which is desirable for polymer electron acceptors. Preliminary all‐polymer solar cell (all‐PSC) devices with P‐BNBP‐T as the electron acceptor and PTB7 as the electron donor exhibit a power conversion efficiency (PCE) of 3.38 %, which is among the highest values of all‐PSCs with PTB7 as the electron donor.
Stabile Peptide statt “gestapelte Peptide”: hochaffine αvβ6‐selektive Integrinliganden
Authors: Maltsev Oleg V. , Marelli Udaya Kiran , Kapp Tobias G. , Di Leva Francesco Saverio , Di Maro Salvatore , Nieberler Markus , Reuning Ute , Schwaiger Markus , Novellino Ettore , Marinelli Luciana , Kessler Horst
Published: December 2015

Das Integrin αvβ6 bindet mit hoher Selektivität an das die RGD‐Sequenz enthaltende Peptid des Maul‐und‐Klauenseuche‐Virus. In dieser Arbeit wurde die lange, für die Bindung dieses Liganden wichtige Helix systematisch zu einem enzymatisch stabilen, cyclischen Peptid verkleinert, welches subnanomolare Bindungsaktivität für den αvβ6‐Rezeptor und eine bemerkenswerte Selektivität gegenüber anderen Integrinrezeptoren besitzt. Um die molekularen Grundlagen für die hohe Bindungsaffinität und Rezeptorsubtypselektivität aufzuklären, wurden Dockingexperimente durchgeführt. Des Weiteren wurde auch die Anwendbarkeit des funktionalisierten Liganden in biomedizinischen Studien gezeigt.
Dynamics of Photoelectrons and Structural Changes of Tungsten Trioxide Observed by Femtosecond Transient XAFS
Authors: Uemura Yohei , Kido Daiki , Wakisaka Yuki , Uehara Hiromitsu , Ohba Tadashi , Niwa Yasuhiro , Nozawa Shunsuke , Sato Tokushi , Ichiyanagi Kohei , Fukaya Ryo , Adachi Shin‐ichi , Katayama Tetsuo , Togashi Tadashi , Owada Sigeki , Ogawa Kanade , Yabashi Makina , Hatada Keisuke , Takakusagi Satoru , Yokoyama Toshihiko , Ohtani Bunsho , Asakura Kiyotaka
Published: December 2015

The dynamics of the local electronic and geometric structures of WO3 following photoexcitation were studied by femtosecond time‐resolved X‐ray absorption fine structure (XAFS) spectroscopy using an X‐ray free electron laser (XFEL). We found that the electronic state was the first to change followed by the local structure, which was affected within 200 ps of photoexcitation.
Concise Total Synthesis of Enigmazole A
Authors: Ahlers Andreas , de Haro Teresa , Gabor Barbara , Fürstner Alois
Published: December 2015

An efficient entry into the phosphorylated marine macrolide enigmazole A is described. Enigmazole A interferes with c‐Kit signaling by an as yet unknown mode of action and is therefore a potential lead in the quest for novel anticancer agents. Key to success is a gold‐catalyzed cascade comprising a [3,3]‐sigmatropic rearrangement of a propargyl acetate along the periphery of a macrocyclic scaffold, followed by a transannular hydroalkoxylation of the resulting transient allenyl acetate. This transformation mandated the use of a chiral gold catalyst to ensure a matching double‐asymmetric setting. Other noteworthy steps are the preparation of the oxazole building block by a palladium‐catalyzed C−H activation, as well as the smooth ring‐closing alkyne metathesis of a diyne substrate bearing a propargylic leaving group, which has only little precedent.
Stable Peptides Instead of Stapled Peptides: Highly Potent αvβ6‐Selective Integrin Ligands
Authors: Maltsev Oleg V. , Marelli Udaya Kiran , Kapp Tobias G. , Di Leva Francesco Saverio , Di Maro Salvatore , Nieberler Markus , Reuning Ute , Schwaiger Markus , Novellino Ettore , Marinelli Luciana , Kessler Horst
Published: December 2015

The αvβ6 integrin binds the RGD‐containing peptide of the foot and mouth disease virus with high selectivity. In this study, the long binding helix of this ligand was downsized to an enzymatically stable cyclic peptide endowed with sub‐nanomolar binding affinity toward the αvβ6 receptor and remarkable selectivity against other integrins. Computational studies were performed to disclose the molecular bases underlying the high binding affinity and receptor subtype selectivity of this peptide. Finally, the utility of the ligand for use in biomedical studies was also demonstrated here.
Vacancy‐Engineered Nanoceria: Enzyme Mimetic Hotspots for the Degradation of Nerve Agents
Authors: Vernekar Amit A. , Das Tandrila , Mugesh Govindasamy
Published: December 2015

Organophosphorus‐based nerve agents, such as paraoxon, parathion, and malathion, inhibit acetylcholinesterase, which results in paralysis, respiratory failure, and death. Bacteria are known to use the enzyme phosphotriesterase (PTE) to break down these compounds. In this work, we designed vacancy‐engineered nanoceria (VE CeO2 NPs) as PTE mimetic hotspots for the rapid degradation of nerve agents. We observed that the hydrolytic effect of the nanomaterial is due to the synergistic activity between both Ce3+ and Ce4+ ions located in the active site‐like hotspots. Furthermore, the catalysis by nanoceria overcomes the product inhibition generally observed for PTE and small molecule‐based PTE mimetics.
Water states and thermal processability of boric acid modified poly(vinyl alcohol)
Authors: Wang Ning , Zhao Lipeng , Zhang Chuhong , Li Li
Published: December 2015

To further improve the processability of water plasticized poly(vinyl alcohol) (PVA), boric acid (BA), which can rapidly form reversible crosslinked structure with the hydroxyl groups of PVA, was adopted as a modifier, and the water states, thermal performance, and rheological properties of modified PVA were investigated. The results showed that ascribing to the formation of the crosslinked structure between PVA and BA, the content of nonfreezing water in system increased, indicating that the bondage of PVA matrix on water enhanced, thus retarding the tempestuous evaporation of water in system during melt process and making more water remained in system to play the role of plasticizer. Meanwhile, this crosslinked structure shielded part hydroxyl groups in PVA chains, leading to the further weakening of the self‐hydrogen bonding of PVA, and guaranteeing a lower melting point and higher decomposition temperature, thus obtaining a quite wide thermal processing window, i.e., ≥179°C. The melt viscosity of BA modified PVA slightly increased, but still satisfied the requirements for thermal processing, thus reinforcing the flow stability of the melt at high shearing rate. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43246.
Influence of curing sequence on phase structure and properties of bisphenol A‐aniline benzoxazine/N,N′‐(2,2,4‐trimethylhexane‐1,6‐diyl) bis (maleimide)/imidazole blend
Authors: Wang Zhi , Cao Ni , Miao Yu , Gu Yi
Published: December 2015

The effects of different catalysts on the curing sequences of bisphenol A‐aniline benzoxazine (BA‐a)/N,N′‐(2,2,4‐trimethylhexane‐1,6‐diyl) bis (maleimide) (TBMI) blends were studied, and the influence of curing sequences on the phase structure and properties of products was discussed. In BA‐a/TBMI/adipic acid, BA‐a homopolymerized first, followed by the copolymerization between TBMI and ring‐opened benzoxazine. This curing sequence led to strong copolymerization, which limited the movement of components and resulted in homogeneous structures of the final products. However, in BA‐a/TBMI/imidazole, TBMI homopolymerized firstly, followed by the homopolymerization of BA‐a. BA‐a and TBMI hardly copolymerized, and the products presented phase‐separated (bi‐continuous phase) structures finally. The degree of copolymerization and phase structures of products differed due to different curing sequences when different catalysts were used. Furthermore, the product with phase‐separated structures had improved thermal property and toughness compared to those of the product with homogeneous structures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43259.
Polyurethane foams from alkaline lignin‐based polyether polyol
Authors: Li Hong‐Qiang , Shao Qiang , Luo Hao , Xu Jian
Published: December 2015

As a byproduct produced during biorefining, alkaline lignin (AL) possesses multiple benzene ring and phenol hydroxyl groups with high chemical reactivity, and is renewable and cheaper than petrochemical products. Here, AL was liquefied in polyethylene glycol‐400/glycerol and subsequently used to prepare polyurethane foams (PUFs). The results showed that the AL could be almost completely liquefied. The resulting lignin‐based polyether polyol (LPP) exhibited physicochemical properties similar to a commercial polyether polyol (PP). The PUFs made from LPP presented better thermal stability and higher compressive strength than those PUFs obtained from commercial PP, suggesting this could be a viable commercial application for AL. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43261.
“A red cross appeared in the sky” and other celestial signs: Presumable European aurorae in the mid AD 770s were halo displays
Authors: Neuhäuser D. L. , Neuhäuser R.
Published: December 2015

The interpretation of the strong 14C variation around AD 775 as one (or several) solar super‐flare(s) by, e.g., Usoskin et al. (2013) is based on alleged aurora sightings in the mid AD 770s in Europe: A red cross /crucifix in AD 773/4/6 from the Anglo‐Saxon Chronicle, inflamed shields in AD 776 (both listed in the aurora catalogue of Link 1962), and riders on white horses in AD 773 (newly proposed as aurora in Usoskin et al. 2013), the two latter from the Royal Frankish Annals. We discuss the reports about these three sightings in detail here. We can show that all three can be interpreted convincingly as halo displays: The red cross or crucifix is formed by the horizontal arc and a vertical pillar of light (either with the Sun during sunset or with the moon after sunset); the inflamed shields and the riders on white horses were both two mock suns, especially the latter narrated in form of a Christian adaptation of the antique dioscuri motive. While the latter event took place early in AD 774 (dated AD 773 in Usoskin et al. 2013), the two other sightings have tobe dated AD 776, i.e. anyway too late for being in connection with a 14C rise that started before AD 775. We also sketch the ideological background of those sightings and there were many similar reports throughout that time. In addition, we present a small drawing of a lunar halo display with horizontal arc and vertical pillar forming a cross for shortly later, namely AD 806 June 4, the night of full moon, also from the Anglo‐Saxon Chronicle; we also show historic observations of halo phenomena (mock suns and crosses) from G. Kirch and Hevelius – and a modern photograph. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Dynamo saturation in direct simulations of the multi‐phase turbulent interstellar medium
Authors: Bendre A. , Gressel O. , Elstner D.
Published: December 2015

The ordered magnetic field observed via polarised synchrotron emission in nearby disc galaxies can be explained by a mean‐field dynamo operating in the diffuse interstellar medium (ISM). Additionally, vertical‐flux initial conditions are potentially able to influence this dynamo via the occurrence of the magnetorotational instability (MRI). We aim to study the influence of various initial field configurations on the saturated state of the mean‐field dynamo. This is motivated by the observation that different saturation behaviour was previously obtained for different supernova rates. We perform direct numerical simulations (DNS) of three‐dimensional local boxes of the vertically stratified, turbulent interstellar medium, employing shearing‐periodic boundary conditions horizontally. Unlike in our previous work, we also impose a vertical seed magnetic field. We run the simulations until the growth of the magnetic energy becomes negligible. We furthermore perform simulations of equivalent 1D dynamo models, with an algebraic quenching mechanism for the dynamo coefficients. We compare the saturation of the magnetic field in the DNS with the algebraic quenching of a mean‐field dynamo. The final magnetic field strength found in the direct simulation is in excellent agreement with a quenched α) dynamo. For supernova rates representative of the Milky Way, field losses via a Galactic wind are likely responsible for saturation. We conclude that the relative strength of the turbulent and regular magnetic fields in spiral galaxies may depend on the galaxy's star formation rate. We propose that a mean field approach with algebraic quenching may serve as a simple sub‐grid scale model for galaxy evolution simulations including a prescribed feedback from magnetic fields. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Magnetic field and radius of the innermost stable circular orbit near super‐massive black holes in active galactic nuclei
Authors: Piotrovich M. Yu. , Gnedin Yu. N. , Silant'ev N. A. , Natsvlishvili T. M. , Buliga S. D.
Published: December 2015

Magnetic fields in an accretion disk around the central black hole can modify the size of the innermost stable circular orbit (ISCO) and can produce a difference to the classical Novikov‐Thorne radius. We estimated the ISCO magnetic field strength from the polarimetric observations of the accretion‐disk radiation. This estimate is obtained taking into account the effect of the Faraday rotation of the polarization plane at the distance of the mean free path of photons between successive electron scattering events. We present the new method for estimating the ISCO radius in the accretion disk, i.e. in the nearest vicinity of a central black hole. Our estimates confirmed the Frolov, Shoom & Tzounis (2014) and Ranea‐Sandoval & Garcia (2015) conclusion that the magnetic field in the accretion disk decreases the size of the innermost stable circular orbit. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Chemical composition of a sample of bright solar‐metallicity stars
Authors: Caffau E. , Mott A. , Steffen M. , Bonifacio P. , Strassmeier K. G. , Gallagher A. , Faraggiana R. , Sbordone L.
Published: December 2015

We present a detailed analysis of seven young stars observed with the spectrograph SOPHIE at the Observatoire de Haute‐Provence for which the chemical composition was incomplete or absent in the literature. For five stars, we derived the stellar parameters and chemical compositions using our automatic pipeline optimized for F, G, and K stars, while for the other two stars with high rotational velocity, we derived the stellar parameters by using other information (parallax), and performed a line‐by‐line analysis. Chromospheric emission‐line fluxes from Caii are obtained for all targets. The stellar parameters we derive are generally in good agreement with what is available in the literature. We provide a chemical analysis of two of the stars for the first time. The star HIP 80124 shows a strong Li feature at 670.8 nm implying a high lithium abundance. Its chemical pattern is not consistent with it being a solar sibling, as has been suggested. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Long‐term survival for infants born with orofacial clefts in Western Australia
Authors: Bell Jane C. , Nassar Natasha , Bower Carol , Turner Robin M. , Raynes‐Greenow Camille
Published: December 2015

BACKGROUND

Only two population‐based studies have reported survival beyond 15 years for individuals with orofacial clefts (OFC), and only for individuals with isolated OFC. Compared with the general population, long‐term survival was similar for individuals with cleft lip only, and lower for individuals with cleft palate only. Results for those born with isolated cleft lip and cleft palate were inconsistent.

METHODS

Using linked population‐based health data, including a congenital anomaly register with active surveillance and diagnoses up to 6 years, we compared survival at 1, 5, and 20 years for infants born 1980 to 2010 with, and without OFC.

RESULTS

Of the 8112 live born infants in the cohort, 186 died before 20 years; most (81%) died during infancy. Compared with infants without OFC, infants born with all types of isolated OFC ± additional minor anomalies had similar infant survival (around 99%), but we found lower survival for infants with all cleft types and an additional major anomaly (66–84%). From 1 to 5 years, only infants with cleft palate only and an additional major anomaly had lower survival (97%) compared with children without OFC (99.9%). From 5 to 20 years, children with all cleft types, with or without additional major anomalies had similar survival to children without OFC (98–100%).

CONCLUSION

Parents with a child diagnosed with an OFC ± additional minor anomalies only can be reassured that the OFC does not influence survival rates in infancy, or long‐term. Infant survival was lower only for children with OFC and additional major anomalies. Birth Defects Research (Part A) 106:172–177, 2016. © 2015 Wiley Periodicals, Inc.
Visualizing Compound Distribution during Zebrafish Embryo Development: The Effects of Lipophilicity and DMSO
Authors: de Koning Coco , Beekhuijzen Manon , Tobor‐Kapłon Marysia , de Vries‐Buitenweg Selinda , Schoutsen Dick , Leeijen Nico , van de Waart Beppy , Emmen Harry
Published: December 2015

The predictability of the zebrafish embryo model is highly influenced by internal exposure of the embryo/larva. As compound uptake is likely to be influenced by factors such as lipophilicity, solvent use, and chorion presence, this article focuses on investigating their effects on compound distribution within the zebrafish embryo. To visualize compound uptake and distribution, zebrafish embryos were exposed for 96 hr, starting at 4 hr postfertilization, to water‐soluble dyes: Schiff's reagent (logP –4.63), Giemsa stain (logP –0.77), Van Gierson stain (logP 1.64), Cresyl fast violet (logP 3.5), Eosine Y (logP 4.8), Sudan III (logP 7.5), and Oil red O (logP 9.81), with and without 1% dimethyl‐sulfoxide (DMSO). Three additional compounds were used to analytically determine the uptake and distribution: Acyclovir (logP –1.56), Zidovudine (logP 0.05), and Metoprolol Tartrate Salt (logP 1.8). Examinations were performed every 24 hr. Both methods (visualization and specific analysis) showed that exposure to higher logP values results in higher compound uptake. Specific analysis showed that for lipophilic compounds >90% of compound is taken up by the embryo. For hydrophilic compounds, >90% of compound within the complete egg could not be associated to embryo or chorion and is probably distributed into the perivitelline space. Overall, internal exposure analyses on at least two occasions (i.e., before and after hatching) is crucial for interpretation of zebrafish embryotoxicity data, especially for compounds with extreme logP values. DMSO did not affect exposure when examined with the visualization method, however, this method might be not sensitive enough to draw hard conclusions.
Adenine methylation in eukaryotes: Apprehending the complex evolutionary history and functional potential of an epigenetic modification
Authors: Iyer Lakshminarayan M. , Zhang Dapeng , Aravind L.
Published: December 2015

While N6‐methyladenosine (m6A) is a well‐known epigenetic modification in bacterial DNA, it remained largely unstudied in eukaryotes. Recent studies have brought to fore its potential epigenetic role across diverse eukaryotes with biological consequences, which are distinct and possibly even opposite to the well‐studied 5‐methylcytosine mark. Adenine methyltransferases appear to have been independently acquired by eukaryotes on at least 13 occasions from prokaryotic restriction‐modification and counter‐restriction systems. On at least four to five instances, these methyltransferases were recruited as RNA methylases. Thus, m6A marks in eukaryotic DNA and RNA might be more widespread and diversified than previously believed. Several m6A‐binding protein domains from prokaryotes were also acquired by eukaryotes, facilitating prediction of potential readers for these marks. Further, multiple lineages of the AlkB family of dioxygenases have been recruited as m6A demethylases. Although members of the TET/JBP family of dioxygenases have also been suggested to be m6A demethylases, this proposal needs more careful evaluation.

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Valeric acid induces cell cycle arrest at G1 phase in CHO cell cultures and improves recombinant antibody productivity
Authors: Park Jin Hyoung , Noh Soo Min , Woo Ju Rang , Kim Jong Won , Lee Gyun Min
Published: December 2015

To find a more effective chemical reagent for improved monoclonal antibody (mAb) production, eight chemical reagents (curcumin, quercein, DL‐sulforaphane, thymidine, valeric acid, phenyl butyrate, valproic acid, and lithium chloride) known to induce cell cycle arrest were examined individually as chemical additives to recombinant CHO (rCHO) cell cultures producing mAb. Among these chemical additives, valeric acid showed the best production performance. Valeric acid decreased specific growth rate (μ), but increased culture longevity and specific mAb productivity (qmAb) in a dose‐dependent manner. The beneficial effect of valeric acid on culture longevity and qmAb outweighed its detrimental effect on μ, resulting in 2.9‐fold increase in the maximum mAb concentration when 1.5 mM valeric acid was added to the cultures. Furthermore, valeric acid did not negatively affect the mAb quality attributes with regard to aggregation, charge variation, and galactosylation. Unexpectedly, galactosylation of the mAb increased by the 1.5 mM valeric acid addition. Taken together, the results obtained here demonstrate that valeric acid is an effective chemical reagent to increase mAb production in rCHO cells.
α‐Helix‐peptides comprising the human nuclear receptor ERRγ competitively provoke inhibition of functional homomeric dimerization
Authors: Liu Xiaohui , Nishimura Hirokazu , Fujiyama Akina , Matsushima Ayami , Shimohigashi Miki , Shimohigashi Yasuyuki
Published: December 2015

Estrogen‐related receptor γ (ERRγ) is a constitutively active nuclear receptor functioning as a transcription factor. ERRγ binds to a single half site designated as ERRE that has only a single DNA‐binding motif. However, with regard to the subunit structure, it remains a matter of controversy whether ERRγ binds as a monomer or dimer. Because the ligand‐binding domain (LBD) of ERRγ was in a homodimer form in its X‐ray crystal structure, the peptide fragments present in the dimer interfaces would perturb or destabilize the dimer structure by inhibiting the mutual interaction among ERRγ molecules. Thus, to demonstrate the essential homodimer structure of ERRγ, we utilized the peptides corresponding to the α‐helix peptides 7 (H7), H9, and H10/11 in order to test such inhibitor activity. These selections were done based on a structural analysis of the X‐ray crystal structures of ERRγ‐LBD, which forms a head‐to‐head dimer structure. Peptides were evaluated by means of a luciferase reporter gene assay, in which ERRγ exhibited a high constitutive activity with no ligand. When the peptide was expressed in the HeLa cells together with ERRγ, these peptides clearly showed a concentration‐dependent activity inhibition, indicating that ERRγ is indeed homodimerized as required for DNA transcription activity. The present results strongly suggest that human nuclear receptor ERRγ functions as a genuine homomeric dimer with symmetrical dimeric interface regions. © 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 547–554, 2016.
Outcomes with multimodal therapy for elderly patients with rectal cancer
Authors: Thiels C A , Bergquist J R , Meyers A J , Johnson C L , Behm K T , Hayman A V , Habermann E B , Larson D W , Mathis K L
Published: December 2015

Background

Treatment guidelines for stage II and III rectal cancer include neoadjuvant chemoradiotherapy, surgery and postoperative adjuvant chemotherapy. Although data support this recommendation in younger patients, it is unclear whether this benefit can be extrapolated to elderly patients (aged 75 years or older).

Methods

This was a retrospective review of patients aged at least 75 years with stage II or III rectal cancer who underwent surgery with curative intent from 1996 to 2013 at the Mayo Clinic. Kaplan–Meier analysis and log rank test were used to compare overall survival between therapy groups. Cox proportional hazards model was used to estimate the independent effect of treatment group on survival.

Results

A total of 160 elderly patients (median age 80 years) with stage II (66) and stage III (94) rectal cancer underwent surgical resection. Only 30·0 and 33·8 per cent received neoadjuvant or adjuvant therapy respectively. Among patients with stage II disease, there was no significant difference in 60-month survival between patients who received any additional therapy and those who had surgery alone (55 versus 38 per cent respectively; P = 0·184), whereas additional therapy improved survival in patients with stage III tumours (58 versus 30 per cent respectively; P = 0·007). Multivariable analysis found a survival benefit for additional therapy in elderly patients with stage III disease (hazard ratio 0·58, 95 per cent c.i. 0·34 to 0·98).

Conclusion

A multimodal approach in elderly patients with stage III rectal cancer improved oncological outcomes.
Implications of Teacher Life–Work Histories for Conceptualisations of ‘Care’: Narratives from Rural Zimbabwe
Authors: Coultas Clare , Broaddus Elena , Campbell Catherine , Andersen Louise , Mutsikiwa Alice , Madanhire Claud , Nyamukapa Connie , Gregson Simon
Published: December 2015

Schools are increasingly seen as key sites for support to HIV‐affected and other vulnerable children, and teachers are assigned the critical role of identifying and providing psychosocial support. Drawing on the life–work history narratives of 12 teachers in Zimbabwe, this paper explores the psychosocial processes underpinning teachers' conceptualisations of these caring roles. The influence of prolonged adversity, formative relationships, and broader patterns of social and institutional change in teacher identity formation processes speak to the complex and embodied nature of understandings of ‘care’. In such extreme settings teachers prioritise the material and disciplinary aspects of ‘care’ that they see as essential for supporting children to overcome hardship. This focus not only means that emotional support as envisaged in international policy is commonly overlooked, but also exposes a wider ideological clash about childrearing. This tension together with an overall ambivalence surrounding teacher identities puts further strain on teacher–student relationships. We propose the current trainings on providing emotional support are insufficient and that more active focus needs to be directed at support to teachers in relation with their students. © 2015 The Authors. Journal of Community & Applied Social Psychology published by John Wiley & Sons Ltd.
On the Mechanism of the Digold(I)–Hydroxide‐Catalysed Hydrophenoxylation of Alkynes
Authors: Gómez‐Suárez Adrián , Oonishi Yoshihiro , Martin Anthony R. , Vummaleti Sai V. C. , Nelson David J. , Cordes David B. , Slawin Alexandra M. Z. , Cavallo Luigi , Nolan Steven P. , Poater Albert
Published: December 2015

Herein, we present a detailed investigation of the mechanistic aspects of the dual gold‐catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ‐OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non‐coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co‐catalyst, lowering the energy barriers of several transition states. A gem‐diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an “off‐cycle” rather than an “in‐cycle” intermediate.
Theoretical Study of Pd11Si6 Nanosheet Compounds Including Seven‐Coordinated Si Species and Its Ge Analogues
Authors: Chen Yue , Sunada Yusuke , Nagashima Hideo , Sakaki Shigeyoshi
Published: December 2015

Nanosheet compounds Pd11(SiiPr)2(SiiPr2)4(CNtBu)10 (1) and Pd11(SiiPr)2(SiiPr2)4(CNMes)10 (2), containing two Pd7(SiiPr)(SiiPr2)2(CNR)4 plates (R=tBu or Mes) connected with three common Pd atoms, were investigated with DFT method. All Pd atoms are somewhat positively charged and the electron density is accumulated between the Pd and Si atoms, indicating that a charge transfer (CT) occurs from the Pd to the Si atoms of the SiMe2 and SiMe groups. Negative regions of the Laplacian of the electron density were found between the Pd and Si atoms. A model of a seven‐coordinated Si species, that is, Pd5(Pd−SiMe), is predicted to be a stable pentagonal bipyramidal molecule. Five Pd atoms in the equatorial plane form bonding overlaps with two 3p orbitals of the Si atom. This is a new type of hypervalency. The Ge analogues have geometry and an electronic structure similar to those of the Si compounds. But their formation energies are smaller than those of the Si analogues. The use of the element Si is crucial to synthesize these nanoplate compounds.
Coordination Polymers Derived from Non‐Steroidal Anti‐Inflammatory Drugs for Cell Imaging and Drug Delivery
Authors: Paul Mithun , Dastidar Parthasarathi
Published: December 2015

A new series of MnII coordination polymers, namely, [{Mn(L)(H2O)2}⋅2 Nap]∞ (CP1), [{Mn(L)(Ibu)2(H2O)2}]∞ (CP2), [{Mn(L)(Flr)2(H2O)2}]∞ (CP3), [{Mn(L)(Ind)2(H2O)2}⋅H2O]∞ (CP4), [{Mn2(L)2(μ‐Flu)4(H2O)}⋅L]∞ (CP5), [{Mn2(L)2(μ‐Tol)4(H2O)2}]∞ (CP6) and [{Mn2(L)2(μ‐Mef)4(H2O)2}]∞ (CP7) (Nap=naproxen, Ibu=ibuprofen, Flr=flurbiprofen, Ind=indometacin, Flu=flufenamic acid, Tol=tolfenamic acid and Mef=mefenamic acid) derived from various non‐steroidal anti‐inflammatory drugs (NSAIDs) and the organic linker 1,2‐bis(4‐pyridyl)ethylene (L) have been synthesized with the aim of being used for cell imaging and drug delivery. Single‐crystal X‐ray diffraction (SXRD) studies revealed that the NSAID molecules were part of the coordination polymeric network either through coordination to the metal center (in the majority of the cases) or through hydrogen bonding. Remarkably, all the MnII coordination polymers were found to be soluble in DMSO, thereby making them particularly suitable for the desired biological applications. Two of the coordination polymers (namely, CP1 and CP3) reported herein, were found to be photoluminescent both in the solid as well as in the solution state. Subsequent experiments (namely, MTT (3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide), and PGE2 (prostaglandin E2) assays) established their biocompatibility and anti‐inflammatory response. In vitro studies by using a macrophage cell line (i.e., RAW 264.7) revealed that both CP1 and CP3 were excellent cell imaging agents. Finally, biodegradability studies under simulated physiological conditions in phosphate‐buffered saline (PBS) at pH 7.6 showed that slow and sustained release of the corresponding NSAID was indeed possible from both CP1 and CP3.
Synthesis and Characterization of Phenothiazine‐Based Platinum(II)–Acetylide Photosensitizers for Efficient Dye‐Sensitized Solar Cells
Authors: Siu Chi‐Ho , Lee Lawrence Tien Lin , Yiu Sze‐Chun , Ho Po‐Yu , Zhou Panwang , Ho Cheuk‐Lam , Chen Tao , Liu Jianyong , Han Keli , Wong Wai‐Yeung
Published: December 2015

Three new unsymmetrical phenothiazine‐based platinum(II) bis(acetylide) complexes PT1–PT3 with different electron‐donating arylacetylide ligands were synthesized and characterized. Their photophysical, electrochemical, and photovoltaic properties have been fully investigated and the density functional theory (DFT) calculations have been carried out. Under AM 1.5 irradiation (100 mW cm−2), the PT1‐based dye‐sensitized solar cell (DSSC) device exhibited an attractive power conversion efficiency (η) up to 5.78 %, with a short‐circuit photocurrent density (Jsc) of 10.98 mA cm−2, an open‐circuit photovoltage (Voc) of 0.738 V, and a fill factor (ff) of 0.713. These findings provide strong evidence that platinum–acetylide complexes have great potential as promising photosensitizers in DSSC applications.
Enolate Stabilization by Anion–π Interactions: Deuterium Exchange in Malonate Dilactones on π‐Acidic Surfaces
Authors: Miros François N. , Zhao Yingjie , Sargsyan Gevorg , Pupier Marion , Besnard Céline , Beuchat César , Mareda Jiri , Sakai Naomi , Matile Stefan
Published: December 2015

Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion–π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π‐acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π‐acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α‐protons in the 1H NMR spectra. The reactivity of these protons on π‐acidic surfaces is measured by hydrogen–deuterium (H–D) exchange for 11 different examples, excluding controls. The velocity of H–D exchange increases with π acidity (NDI core substituents: SO2R>SOR>H>OR>OR/NR2>SR>NR2). The H–D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11–13 atoms). Most importantly, H–D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)‐macrocycle is reported). For maximal π acidity, transition‐state stabilizations up to −18.8 kJ mol−1 are obtained for H–D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa=10.9 calculates to a ΔpKa=−5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as “impossible” in biology, the found enolate–π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven‐component π‐acidity gradient over almost 1 eV demonstrates quantitatively that such important anion–π activities can be expected only from strong enough π acids.
ChemInform Abstract: Na2MoO2‐δF4+δ — A Perovskite with a Unique Combination of Atomic Orderings and Octahedral Tilts.
Authors: Ishikawa Hajime , Munao Irene , Bode Bela E. , Hiroi Zenji , Lightfoot Philip
Published: December 2015

The title compound (δ ≈ 0.08) is hydrothermally synthesized from a mixture of NaF, MoO3, MoO2, guanidinium carbonate, and HF in H2O (autoclave, 160 °C, 3 d).
ChemInform Abstract: Crystal Growth and Anisotropic Thermal Properties of the Nonlinear and Polar Oxide Cs2TeW3O12.
Authors: Feng Jiang‐He , Xiang Xu Jiang‐He , Mao Jiang‐Gao
Published: December 2015

Large crystals of Cs2TeW3O12 (20 x 15 x 4 mm) are grown by the top‐seeded solution growth method from mixtures of Cs2TeW3O12 and Cs2O and TeO2 as a flux (molar ratio1:1:4) or Cs2CO3, TeO2, and WO3 (molar ratio of 2:5:3) (Pt crucible, 700 °C, 3 d).
ChemInform Abstract: Chemical Synthesis and Characterization of γ‐Co2NiGa Nanoparticles with a Very High Curie Temperature.
Authors: Felser Claudia , et al.
Published: December 2015

Single‐phase γ‐Co2NiGa nanoparticles (NPs) are prepared by ultrasonication of a nearly stoichiometric MeOH dispersion of CoCl2, Ni(NO3)2, and Ga(NO3)3 hydrates to which colloidal silica is given followed by drying and annealing the resultant solid under H2 (1123 K, 2 h).
ChemInform Abstract: High Performance 5 V LiNi0.5Mn1.5O4 Spinel Cathode Materials Synthesized by an Improved Solid‐State Method.
Authors: Gao Zhi‐Gang , Sun Kai , Cong Li‐Na , Zhang Yu‐Hang , Zhao Qin , Wang Rong‐Shun , Xie Hai‐Ming , Sun Li‐Qun , Su Zhong‐Min
Published: December 2015

LiNi0.5Mn1.5O4 is fabricated by ball milling of a stoichiometric mixture of LiOH, Ni(OAc)2, and Mn(OAc)2 (400 rpm, 20 h) followed by drying (100 °C, 10 h), calcination in either air or pure N2 (450 °C, 3 h), and finally calcination in air at 750 °C (cooling rate of 3 °C/min).
ChemInform Abstract: Prediction and Synthesis of Strain Tolerant RbCuTe Crystals Based on Rotation of One‐Dimensional Nano Ribbons within a Three‐Dimensional Inorganic Network.
Authors: Vermeer Michael J. DeVries , Zhang Xiuwen , Trimarchi Giancarlo , Donakowski Martin D. , Chupas Peter J. , Poeppelmeier Kenneth R. , Zunger Alex
Published: December 2015

Crystals of RbCuTe are synthesized by vacuum annealing of the elements (sealed silica tube, 650 °C, 12 h).
ChemInform Abstract: Diastereoselective Addition of Monoorganocuprates to a Chiral Fumarate: Reaction Development and Synthesis of (‐)‐Dihydroprotolichesterinic Acid.
Authors: Hethcox J. Caleb , Shanahan Charles S. , Martin Stephen F.
Published: December 2015

Recently reported diastereoselective conjugate addition of monoorganocuprates to chiral γ‐alkoxycrotonates and fumarates is applied to the shortest total synthesis of (‐)‐dihydroprotolichesterinic acid (VI) to date.
ChemInform Abstract: Organocatalytic Enantioselective Michael Reaction of Malononitrile with β,β‐Disubstituted Nitroalkenes.
Authors: Chen Shengwei , Lou Qinxin , Ding Yuyang , Zhang Shasha , Hu Wenhui , Zhao Junling
Published: December 2015

An enantioselective Michael reaction of malononitrile with β,β‐disubstituted nitro alkenes is presented.
ChemInform Abstract: A Metal‐Free Approach Toward Saturated N‐Propargyl Heterocycles via an Annulation/Decarboxylative Coupling Sequence.
Authors: Feng Huangdi , Jia Huihui , Sun Zhihua
Published: December 2015

A three‐component reaction of primary 2‐ or 3‐amino alcohols with formaldehyde solution and propiolic acids affords N‐propargyl oxazolidines, 1,3‐oxazinanes and a thiazolidine in good yields.
ChemInform Abstract: Enantioselective Oxidation of Alkenes with Potassium Permanganate Catalyzed by Chiral Dicationic Bisguanidinium.
Authors: Wang Chao , Zong Lili , Tan Choon‐Hong
Published: December 2015

The title catalysts are used for the asymmetric dihydroxylation of α‐aryl acrylates and asymmetric oxohydroxylation of trisubstituted enoates.
ChemInform Abstract: Alkene Migration to the End‐Terminal Carbon Bearing a Phenyl Group over a Chiral Siloxy Carbon Center in Heck Reaction.
Authors: Ida Akiko , Hoshiya Naoyuki , Uenishi Jun'ichi
Published: December 2015

The Heck reaction of aryl bromide with a terminal alkene substrate having a chiral center at the allylic position and a phenyl substituent at another terminal carbon is reported.
ChemInform Abstract: Cross‐Coupling Between Aryl‐ and Alkenyldimethylsilanes and Organic Halides Promoted by a Copper(I) Iodide/Sodium Hydride/Ethylene Glycol System.
Authors: Takeda Takeshi , Takeda Yuichiro , Tsubouchi Akira
Published: December 2015

A versatile cross‐coupling reaction of aryl‐ and alkenylsilanes (I) with various organic halides (II) is developed furnishing the corresponding cross‐coupling products (III) in good to excellent yields.