bluuebunny/crossref_metadata_2025 huggingface dataset:
A Study on the Development of an Integrated Automatic Allocation Algorithms for Multilayer Defense System Intercept Missiles
Authors: Hong Inseob , Kwak Kihoon , Oh Jeongtaek , Shim Donghyouk , Jin Hwajong , Yang Kwangjin
Published: October 2024

This study aims to propose optimal missile interception allocation strategies for constructing a multi-layered missile defense system in situations where a large number of ballistic missiles are launched simultaneously. Specifically, we consider the threat level of ballistic missiles, the importance of defense zones, and the asset value of interception missiles, and develop a damage consumption index based on these factors. Through an algorithm that minimizes the sum of damage consumption indices for intercepting missiles defending upper and lower layers, we allocate them in optimal combinations to achieve maximum effectiveness with minimal cost. Additionally, we propose a decision-making system based on algorithmic integration rather than human decision-making, particularly in complex operational scenarios, to ensure systematic decision-making and maximize efficiency.
Mechanical weathering and rock erosion by climate‐dependent subcritical cracking
Authors: Eppes Martha‐Cary , Keanini Russell
Published: May 2017

This work constructs a fracture mechanics framework for conceptualizing mechanical rock breakdown and consequent regolith production and erosion on the surface of Earth and other terrestrial bodies. Here our analysis of fracture mechanics literature explicitly establishes for the first time that all mechanical weathering in most rock types likely progresses by climate‐dependent subcritical cracking under virtually all Earth surface and near‐surface environmental conditions. We substantiate and quantify this finding through development of physically based subcritical cracking and rock erosion models founded in well‐vetted fracture mechanics and mechanical weathering, theory, and observation. The models show that subcritical cracking can culminate in significant rock fracture and erosion under commonly experienced environmental stress magnitudes that are significantly lower than rock critical strength. Our calculations also indicate that climate strongly influences subcritical cracking—and thus rock weathering rates—irrespective of the source of the stress (e.g., freezing, thermal cycling, and unloading). The climate dependence of subcritical cracking rates is due to the chemophysical processes acting to break bonds at crack tips experiencing these low stresses. We find that for any stress or combination of stresses lower than a rock's critical strength, linear increases in humidity lead to exponential acceleration of subcritical cracking and associated rock erosion. Our modeling also shows that these rates are sensitive to numerous other environment, rock, and mineral properties that are currently not well characterized. We propose that confining pressure from overlying soil or rock may serve to suppress subcritical cracking in near‐surface environments. These results are applicable to all weathering processes.
Electrostatic Design of 3D Covalent Organic Networks
Authors: Obersteiner Veronika , Jeindl Andreas , Götz Johannes , Perveaux Aurelie , Hofmann Oliver T. , Zojer Egbert
Published: May 2017

An innovative strategy for electrostatically designing the electronic structure of 3D bulk materials is proposed to control charge carriers at the nanoscale. This is achieved by shifting the electronic levels of chemically identical semiconducting elements through the periodic arrangement of polar functional groups. For the example of covalent organic networks, by first‐principles calculations, the resulting collective electrostatic effects are shown to allow a targeted manipulation of the electronic landscape such that spatially confined pathways for electrons and holes can be realized. Mimicking donor–acceptor bulk heterojunctions, the new materials hold high promise for photovoltaic applications. The distinct advantage over the conventional approach of splitting excitons through chemically distinct donor and acceptor units is that here the magnitude of the band offset can be continuously tuned by varying the dipole density. A particularly promising feature of the suggested strategy is its structural versatility, which also enables the realization of more complex quantum structures such as quantum‐cascades and quantum‐checkerboards.
Hydrothermal Synthesis of Monolithic Co3Se4 Nanowire Electrodes for Oxygen Evolution and Overall Water Splitting with High Efficiency and Extraordinary Catalytic Stability
Authors: Li Wei , Gao Xuefei , Xiong Dehua , Wei Fang , Song Wei‐Guo , Xu Junyuan , Liu Lifeng
Published: May 2017

Cobalt selenide has been proposed to be an effective low‐cost electrocatalyst toward the oxygen evolution reaction (OER) due to its well‐suited electronic configuration. However, pure cobalt selenide has by far still exhibited catalytic activity far below what is expected. Herein, this paper for the first time reports the synthesis of new monoclinic Co3Se4 thin nanowires on cobalt foam (CF) via a facile one‐pot hydrothermal process using selenourea. When used to catalyze the OER in basic solution, the conditioned monolithic self‐supported Co3Se4/CF electrode shows an exceptionally high catalytic current of 397 mA cm−2 at a low overpotential (η) of 320 mV, a small Tafel slope of 44 mV dec−1, a turnover frequency of 6.44 × 10−2 s−1 at η = 320 mV, and excellent electrocatalytic stability at various current densities. Furthermore, an electrolyzer is assembled using two symmetrical Co3Se4/CF electrodes as anode and cathode, which can deliver 10 and 20 mA cm−2 at low cell voltages of 1.59 and 1.63 V, respectively. More significantly, the electrolyzer can operate at 10 mA cm−2 over 3500 h and at 100 mA cm−2 for at least 2000 h without noticeable degradation, showing extraordinary operational stability.
One‐Electron Bonds in Frustrated Lewis Pair TPB Ligands: Boron Behaving as a Lewis Base
Authors: Kusevska Elena , Montero‐Campillo M. Merced , Mó Otilia , Yáñez Manuel
Published: May 2017

Owing to its versatility in synthetic chemistry, TPB (tris[2‐diisopropylphospino)phenyl]borane) is a very important frustrated Lewis Pair. The unusual stability of the neutral radical (TPB)Cu has been related to the presence of a one‐electron B−Cu bond. Herein we show, through the use of different computational chemistry methods, that the existence and nature of this kind of A⋅⋅⋅M bond (A=donor atom, M=transition metal) depends on the surrounding chemical structure, and can be genuine one‐electron sigma bonds only if appropriate metal ligands (Y), able to trap the charge in the desired region, are chosen. This ability is modulated by the subtle balance between the electronegativity of the different atoms along the A⋅⋅⋅M⋅⋅⋅Y bond paths. Most importantly, contrary to many TPB complexes in which boron acts as a Lewis acid, in one‐electron‐bond‐containing structures boron behaves as a Lewis base.
Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene
Authors: Schwedtmann Kai , Hennersdorf Felix , Bauzá Antonio , Frontera Antonio , Fischer Roland , Weigand Jan J.
Published: May 2017

The polarized, cationic diphosphene [(ClImDipp)P=P(Dipp)]+ as the triflate salt 7[OTf](ClImDipp=4,5‐dichloro‐1,3‐bis(Dipp)‐imidazol‐2‐yl; Dipp=2,6‐diisopropylphenyl) reacts with azides of type RN3 (R=Dipp or Dmp; Dmp=2,5‐dimethylphenyl) in a [2+3] cycloaddition reaction followed by the release of N2 and a subsequent electrocyclic ring‐closing reaction to azadiphosphiridine salts [(ClImDipp)P‐P(Dipp)‐N(R)]10a,b[OTf] (R=Dipp or Dmp). The reaction of 7[X] (X=OTf, GaCl4) with the electron‐rich azides Me3SiN3 and NaN3 give the unusual diphosphenimine derivatives [(ClImDipp)P−P(Dipp)=N(SiMe3)]+ (11[OTf]) and [(ClImDipp)P−P(Dipp)=N(GaCl3)] (12), respectively, featuring an acyclic P2N moiety. Theoretical calculations provide insights into the reaction mechanisms to the cyclic and acyclic forms, in which the thermodynamic stability of the latter prevents the electrocyclic ring closure.
Enantioselective Synthesis of (E)‐δ‐Boryl‐Substituted anti‐Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid
Authors: Miura Tomoya , Nakahashi Junki , Murakami Masahiro
Published: May 2017

(E)‐δ‐Boryl‐substituted anti‐homoallylic alcohols are synthesized in a highly diastereo‐ and enantioselective manner from 1,1‐di(boryl)alk‐3‐enes and aldehydes. Mechanistically, the reaction consists of 1) palladium‐catalyzed double‐bond transposition of the 1,1‐di(boryl)alk‐3‐enes to 1,1‐di(boryl)alk‐2‐enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium‐catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.
N2‐to‐NH3 Conversion by a triphos–Iron Catalyst and Enhanced Turnover under Photolysis
Authors: Buscagan Trixia M. , Oyala Paul H. , Peters Jonas C.
Published: May 2017

Bridging iron hydrides are proposed to form at the active site of MoFe‐nitrogenase during catalytic dinitrogen reduction to ammonia and may be key in the binding and activation of N2 via reductive elimination of H2. This possibility inspires the investigation of well‐defined molecular iron hydrides as precursors for catalytic N2‐to‐NH3 conversion. Herein, we describe the synthesis and characterization of new P2P′PhFe(N2)(H)x systems that are active for catalytic N2‐to‐NH3 conversion. Most interestingly, we show that the yields of ammonia can be significantly increased if the catalysis is performed in the presence of mercury lamp irradiation. Evidence is provided to suggest that photo‐elimination of H2 is one means by which the enhanced activity may arise.
Cooperative Light‐Activated Iodine and Photoredox Catalysis for the Amination of C−H Bonds
Authors: Becker Peter , Duhamel Thomas , Stein Christopher J. , Reiher Markus , Muñiz Kilian
Published: May 2017

An unprecedented method that makes use of the cooperative interplay between molecular iodine and photoredox catalysis has been developed for dual light‐activated intramolecular benzylic C−H amination. Iodine serves as the catalyst for the formation of a new C−N bond by activating a remote C
−H bond (1,5‐HAT process) under visible‐light irradiation while the organic photoredox catalyst TPT effects the reoxidation of the molecular iodine catalyst. To explain the compatibility of the two involved photochemical steps, the key N−I bond activation was elucidated by computational methods. The new cooperative catalysis has important implications for the combination of non‐metallic main‐group catalysis with photocatalysis.
Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)
Authors: Stafford Hannah , Rookes Thomas M. , Wildman Elizabeth P. , Balázs Gábor , Wooles Ashley J. , Scheer Manfred , Liddle Stephen T.
Published: May 2017

The reaction of [Zr(TrenDMBS)(Cl)] [Zr1; TrenDMBS=N(CH2CH2NSiMe2But)3] with NaPH2 gave the terminal parent phosphanide complex [Zr(TrenDMBS)(PH2)] [Zr2; Zr−P=2.690(2) Å]. Treatment of Zr2 with one equivalent of KCH2C6H5 and two equivalents of benzo‐15‐crown‐5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a structurally authenticated transition‐metal terminal parent phosphinidene complex [Zr(TrenDMBS)(PH)][K(B15C5)2] [Zr3; Zr=P=2.472(2) Å]. DFT calculations reveal a polarized‐covalent Zr=P double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic‐type Zr⋅⋅⋅HP interaction [∡ZrPH=66.7°] which is unexpectedly similar to that found in cryogenic, spectroscopically observed phosphinidene species. Surprisingly, computational data suggest that the Zr=P linkage is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues.
CO2 separation performance by chitosan/tetraethylenepentamine/poly(ether sulfone) composite membrane
Authors: Prasad Babul , Mandal Bishnupada
Published: May 2017

CO2 separation from CO2/N2 (20:80) gas mixture has been demonstrated by tetraethylenepentamine blended with chitosan (CS‐TEPA) membrane. Optimization of CS and TEPA weight ratio were carried out based on characterization details involving thermogravimetric analysis, Fourier transform infrared spectroscopy, X‐ray diffraction, atomic force microscope, and field emission scanning electron microscope. Effects of water flow rate, pressure, and temperature were concurrently studied on CS‐TEPA membranes through gas permeation. Almost twofold increase in CO2 permeance (24.7 GPU) was detected in CS blend with 30% (w/w) of TEPA (CS70) as compared to pure CS membrane (12.5 GPU). CS70 yielded CO2/N2 selectivity of 80 whereas CS demonstrated a maximum of 54 at 90 °C. The membrane also exhibited improved stability at temperatures less than 120 °C which was evident from TGA isotherm trace. The proposed composite membrane can be a promising candidate for flue gas separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45206.
Enhancement of interlaminar fracture toughness of carbon fiber–epoxy composites using polyamide‐6,6 electrospun nanofibers
Authors: Beylergil Bertan , Tanoğlu Metin , Aktaş Engin
Published: May 2017

In this study, carbon fiber–epoxy composites are interleaved with electrospun polyamide‐6,6 (PA 66) nanofibers to improve their Mode‐I fracture toughness. These nanofibers are directly deposited onto carbon fabrics before composite manufacturing via vacuum infusion. Three‐point bending, tensile, compression, interlaminar shear strength, Charpy impact, and double cantilever beam tests are performed on the reference and PA 66 interleaved specimens to evaluate the effects of PA 66 nanofibers on the mechanical properties of composites. To investigate the effect of nanofiber areal weight density (AWD), nanointerlayers with various AWD are prepared by changing the electrospinning duration. It is found that the electrospun PA 66 nanofibers are very effective in improving Mode‐I toughness and impact resistance, compressive strength, flexural modulus, and strength of the composites. However, these nanofibers cause a decrease in the tensile strength of the composites. The glass‐transition temperature of the composites is not affected by the addition of PA 66 nanofibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45244.
Low Band Gap Donor–Acceptor Conjugated Systems Based on 3‐Alkoxy or 3‐Pyrrolidino‐4‐cyanothiophene and Benzothiadiazole Units
Authors: Savitha Gurunathan , Moussallem Chady , Allain Magali , Gohier Frédéric , Frère Pierre
Published: May 2017

3‐Hexyloxy‐4‐cyanothiophene, 3‐pyrrolidil‐4‐cyanothiophene, and 3,4‐ethylenedioxythiophene (EDOT) units are used with benzothiadiazole as building blocks for the development of three new conjugated donor–acceptor–donor (DAD) derivatives. The DAD molecules have the central acceptor part, which is formed by combining electron‐withdrawing cyano groups and the benzothiadiazole moiety, in common. Theoretical calculations and UV/Vis and electrochemical data reveal the key role of the end‐capped donor to tune the electronic properties of the derivatives. A study of the electropolymerization process of the three derivatives shows the strong influence of the donor parts on both the reactivity of the precursors and the electronic properties of the resulting polymers. Derivatives end‐capped with pyrrolidinocyano thiophene or EDOT units lead to films of polymers presenting low band gaps of around 0.9–1.4 eV. Upon oxidation, the two polymers present different behavior. In the presence of the pyrrolidinocyano thiophene moieties, oxidation leads to a blueshift of the absorption bands, whereas with EDOT units a classical redshift, giving high absorption in the near‐IR region, is observed for the oxidized states.
Variability in Decision Strategies Across Description‐based and Experience‐based Decision Making
Authors: Yoon Sangsuk , Vo Khoi , Venkatraman Vinod
Published: May 2017

Individuals are known to make systematically different decisions when the probabilities in risky choice problems are described or experienced. This difference, known as the description–experience gap, has been reliably replicated across several studies using binary choice gambles. Yet little is known whether these differences exist in more complex gambles in the absence of rare outcomes, and whether they are associated with systematic differences in the use of decision heuristics and strategies across formats. Using three‐outcome mixed gambles, we found that participants showed a strong preference for alternatives that maximized the overall probability of winning when such an option was available in the description condition, and chose more randomly otherwise. In the experience condition, preferences were more homogenous across trials types, with participants choosing the alternative with extreme values more often relative to the description condition. However, when we controlled for the experienced outcomes, both natural mean heuristic (choosing the alternative with highest sampled mean or expected value) and overall probability of winning heuristic reliably predicted choice on each trial. In fact, expected value was the strongest predictor of preferences in a conditional logistic regression model that included extreme values, expected value, and overall probability of winning variables simultaneously. Yet expected value did not predict preferences in decisions from description. Together, these findings provide evidence for an explicit dissociation in decision strategies across description and experience formats. Copyright © 2017 John Wiley & Sons, Ltd.
Wilderness Schooling: A controlled trial of the impact of an outdoor education programme on attainment outcomes in primary school pupils
Authors: Quibell T. , Charlton J. , Law J.
Published: May 2017

Gaps in education attainment between high and low achieving children in the primary school years are frequently evidenced in educational reports. Linked to social disadvantage, these gaps have detrimental long‐term effects on learning. There is a need to close the gap in attainment by addressing barriers to learning and offering alternative contexts for education. There is increasing evidence for beneficial impacts of education delivered outdoors, yet most programmes are un‐structured, and evidence is anecdotal and lacks experimental rigour. In addition, there is a wealth of social‐emotional outcomes reported yet little in the way of educational attainment outcomes. The current study explores the educational impact of a structured curriculum‐based outdoor learning programme for primary school children: ‘Wilderness Schooling’. A matched‐groups design: Wilderness Schooling (n=223) and conventional schooling (n=217), was used to compare attainment data in English reading, English writing and maths, collected at three time‐points: Pre‐ (T1) and post‐intervention (T2) and at a 6‐week follow up (T3). Data show that children in the Wilderness Schooling group significantly improved their attainment in all three subjects compared to controls. Trajectories of impact indicated attainment continued to increase from baseline in the following weeks after the intervention concluded. These results allow the case to be made for the core curriculum to be conducted outdoors to improve children's learning. However, it is important to consider that there are likely to be various components of the intervention that could form a theory of change essential to reported outcomes.
The error analysis of Lobular and segmental division of right liver by volume measurement
Authors: Zhang Jianfei , Lin Weigang , Chi Yanyan , Zheng Nan , Xu Qiang , Zhang Guowei , Yu Shengbo , Li Chan , Wang Bin , Sui Hongjin
Published: May 2017

The aim of this study is to explore the inconsistencies between right liver volume as measured by imaging and the actual anatomical appearance of the right lobe. Five healthy donated livers were studied. The liver slices were obtained with hepatic segments multicolor‐infused through the portal vein. In the slices, the lobes were divided by two methods: radiological landmarks and real anatomical boundaries. The areas of the right anterior lobe (RAL) and right posterior lobe (RPL) on each slice were measured using Photoshop CS5 and AutoCAD, and the volumes of the two lobes were calculated. There was no statistically significant difference between the volumes of the RAL or RPL as measured by the radiological landmarks (RL) and anatomical boundaries (AB) methods. However, the curves of the square error value of the RAL and RPL measured using CT showed that the three lowest points were at the cranial, intermediate, and caudal levels. The U‐ or V‐shaped curves of the square error rate of the RAL and RPL revealed that the lowest value is at the intermediate level and the highest at the cranial and caudal levels. On CT images, less accurate landmarks were used to divide the RAL and RPL at the cranial and caudal layers. The measured volumes of hepatic segments VIII and VI would be less than their true values, and the measured volumes of hepatic segments VII and V would be greater than their true values, according to radiological landmarks. Clin. Anat. 30:585–590, 2017. © 2017 Wiley Periodicals, Inc.
Statistical molecular identification of kinase inhibitors to disrupt c‐Jun N‐terminal protein kinase involved in paraquat‐mediated toxicological effects
Authors: Yang Yu‐Ping , Jin Yu‐Mei , Zhu Zhi‐Yuan
Published: May 2017

Paraquat is a toxic chemical that is widely used as an herbicide (plant killer), primarily for weed and grass control. Recently, kinase inhibitors have shown great potential against paraquat‐mediated toxicological effects and, specifically, the c‐Jun N‐terminal protein kinase (JNK) was found as a new and promising target for relieving the paraquat toxicity. Here, we developed a statistical molecular identification protocol that systematically profiles a variety of existing kinase inhibitors against JNK. A consensus molecular docking strategy was developed to examine the binding behavior of inhibitor candidates, from which top‐8 hit compounds were selected and tested; several compounds were found to show high or moderate inhibitory potency against JNK with IC50 values at nanomolar level, which are comparable to the sophisticated JNK inhibitor SP600125. We also performed atomistic molecular dynamics simulations and post binding free energy analyses to dissect the structural basis, energetic property, and biological implication underlying the intermolecular interaction of JNK kinase domain with these promising compounds, highlighting the complicated interaction pattern between the kinase and potent hit compounds.
Gold(I)‐Catalysed Asymmetric Hydroamination of Alkenes: A Silver‐ and Solvent‐Dependent Enantiodivergent Reaction
Authors: Abadie Marc‐Antoine , Trivelli Xavier , Medina Florian , Duhal Nathalie , Kouach Mostafa , Linden Bernhard , Génin Eric , Vandewalle Maxence , Capet Frédéric , Roussel Pascal , Del Rosal Iker , Maron Laurent , Agbossou‐Niedercorn Francine , Michon Christophe
Published: May 2017

In the present study, we report the first silver‐dependent enantiodivergent gold‐catalysed reaction. The asymmetric intramolecular hydroamination of alkenes catalysed by the combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate can afford both enantiomers of the products by a simple solvent change from toluene to methanol. Such an enantiodivergent reaction is strictly independent of the reaction temperature or of the nature of the catalyst anion and displays the same first‐order kinetic rate law with respect to substrate concentration in both solvents. Beyond a simple solvent effect the enantioinversion is controlled by gold–silver chloride adducts which occur only in methanol and allow a dual activation of the reagent. While one single gold atom activates the alkene moiety, the other gold atom forms an oxophilic gold–silver chloride adduct which is likely to interact with the carbamate function. By comparison with toluene, which affords (S)‐enantiomer, this proximal and bimetallic activation would allow an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and lead therefore to the (R)‐enantiomer.
Total Syntheses of Lepadiformine Marine Alkaloids with Enantiodivergency, Utilizing Hg(OTf)2‐Catalyzed Cycloisomerization Reaction and their Cytotoxic Activities
Authors: Nishikawa Keisuke , Yamauchi Kengo , Kikuchi Seiho , Ezaki Shinnosuke , Koyama Tomoyuki , Nokubo Haruka , Matsumura Kunihiro , Kodama Takeshi , Kumagai Momochika , Morimoto Yoshiki
Published: May 2017

The enantioselective total syntheses of lepadiformine marine alkaloids, azatricyclic natural products isolated from marine tunicates, were completed. These alkaloids have a unique chemical structure characterized by the trans‐1‐azadecalin (AB ring system) fused with the spirocyclic ring (AC ring system). Here we found that a cycloisomerization reaction from functionalized linear substrates to a 1‐azaspiro[4.5]decane framework corresponding to the AC ring in lepadiformines is promoted by a catalytic amount of mercury(II) triflate (Hg(OTf)2). The total syntheses of (−)‐lepadiformines A and B were achieved in 28 % and 21 % overall yields, respectively, through the novel cycloisomerization reaction. The syntheses of (+)‐ and (−)‐lepadiformine C hydrochloride salts also enabled us to determine the absolute configuration of natural lepadiformine C. It has been found that a phenomenon of enantiodivergence occurs in lepadiformine alkaloids from a single species of marine tunicate, Clavelina moluccensis. The cytotoxic activities of synthesized lepadiformine hydrochloride salts and their synthetic intermediates were evaluated.
Stellar Multi‐Photon Absorption Materials: Beyond the Telecommunication Wavelength Band
Authors: Schwich Torsten , Barlow Adam , Cifuentes Marie P. , Szeremeta Janusz , Samoc Marek , Humphrey Mark G.
Published: May 2017

Very large molecular two‐ and three‐photon absorption cross‐sections are achieved by appending ligated bis(diphosphine)ruthenium units to oligo(p‐phenyleneethynylene) (OPE)‐based “stars” with arms up to 7 phenyleneethynylene (PE) units in length. Extremely large three‐ and four‐photon absorption cross‐sections, through the telecommunications wavelengths range and beyond, are obtained for these complexes upon optimizing OPE length and the ruthenium‐coordinated peripheral ligand. Multi‐photon absorption (MPA) cross‐sections are optimized with stars possessing arms 2 PE units in length. Peripheral ligand variation modifies MPA merit and, in particular, 4‐nitrophenylethynyl ligand incorporation enhances maximal MPA values and “switches on” four‐photon absorption (4PA) in these low molecular‐weight complexes. The 4‐nitrophenylethynyl‐ligated 2PE‐armed star possesses a maximal four‐photon absorption cross‐section of 1.8×10−108 cm8 s3 at 1750 nm, and significant MPA activity extending beyond 2000 nm.
A Fluxional Cu8H6 Cluster Supported by Bis(diphenylphosphino)methane and its Facile Reaction with CO2
Authors: Nakamae Kanako , Tanaka Miho , Kure Bunsho , Nakajima Takayuki , Ura Yasuyuki , Tanase Tomoaki
Published: May 2017

A copper hydride cluster [Cu8(μ‐H)6(μ‐dppm)5](PF6)2 (dppm=bis(diphenylphosphino)methane) was prepared from reaction of [CuH(PPh3)]6 with dppm in the presence of [Cu(CH3CN)4]PF6 and exhibited fluxional behaviors in solution where the hydrides and the phosphines are scrambling around the trans‐bicapped octahedral Cu8 framework. The Cu8H6 complex showed facile reactivity with CO2 (1 atm, RT) to afford a tricopper complex, [Cu3(μ‐H)(μ‐O2CH)(μ‐dppm)3]PF6, which could be developed to unprecedented hydrosilylation of CO2 catalyzed by multinuclear CuH species under mild conditions.
Electroluminescent and Optoelectronic Properties of OLEDs with Bay‐Extended, Distorted Perylene Esters as Emitter Materials
Authors: Vollbrecht Joachim , Blazy Simon , Dierks Philipp , Peurifoy Samuel , Bock Harald , Kitzerow Heinz
Published: May 2017

Three esters with a perylene, a unilaterally, and a bilaterally extended perylene core, respectively, were used as emitter materials for organic light‐emitting diodes. The electroluminescent properties of these devices were studied. Different spectral shifts were found, which can be attributed to the formation of excited dimers (excimers) in the nanofilms of the emitter materials. Thermal treatment of the unilaterally extended derivative resulted in a red‐shift of the electroluminescence owing to the formation of a denser nanofilm. The luminance and efficiency of optoelectronic devices employing the extended perylene esters exceed those of devices using an emitter layer comprised of the perylene ester. Different deposition methods, limitations in the deposition process, and the role of hole‐transporting materials are compared.
Highly Efficient and Uniform 1 cm2 Perovskite Solar Cells with an Electrochemically Deposited NiOx Hole‐Extraction Layer
Authors: Park Ik Jae , Kang Gyeongho , Park Min Ah , Kim Ju Seong , Seo Se Won , Kim Dong Hoe , Zhu Kai , Park Taiho , Kim Jin Young
Published: May 2017

Given that the highest certified conversion efficiency of the organic–inorganic perovskite solar cell (PSC) already exceeds 22 %, which is even higher than that of the polycrystalline silicon solar cell, the significance of new scalable processes that can be utilized for preparing large‐area devices and their commercialization is rapidly increasing. From this perspective, the electrodeposition method is one of the most suitable processes for preparing large‐area devices because it is an already commercialized process with proven controllability and scalability. Here, a highly uniform NiOx layer prepared by electrochemical deposition is reported as an efficient hole‐extraction layer of a p–i–n‐type planar PSC with a large active area of >1 cm2. It is demonstrated that the increased surface roughness of the NiOx layer, achieved by controlling the deposition current density, facilitates the hole extraction at the interface between perovskite and NiOx, and thus increases the fill factor and the conversion efficiency. The electrochemically deposited NiOx layer also exhibits extremely uniform thickness and morphology, leading to highly efficient and uniform large‐area PSCs. As a result, the p–i–n‐type planar PSC with an area of 1.084 cm2 exhibits a stable conversion efficiency of 17.0 % (19.2 % for 0.1 cm2) without showing hysteresis effects.
Impaired myocardial relaxation with exercise determines peak aerobic exercise capacity in heart failure with preserved ejection fraction
Authors: Trankle Cory , Canada Justin M. , Buckley Leo , Carbone Salvatore , Dixon Dave , Arena Ross , Van Tassell Benjamin , Abbate Antonio
Published: May 2017

Background

Heart failure with preserved ejection fraction (HFpEF) is a clinical syndrome characterized by impaired exercise capacity due to shortness of breath and/or fatigue. Assessment of diastolic dysfunction at rest and with exercise may provide insight into the pathophysiology of exercise intolerance in HFpEF.

Aims

To measure echocardio‐Doppler‐derived parameters of diastolic function as they relate to various indices of aerobic exercise capacity in HFpEF.

Methods

We selected 16 subjects with clinically stable HFpEF, no evidence of volume overload, but impaired functional capacity by cardiopulmonary exercise testing [peak oxygen consumption (VO2)]. We measured the transmitral E and A flow velocities, E/A ratio, and E deceleration time (DT) and tissue Doppler E′ velocity. We also indexed the E′ to the DT, as additional measure of impaired relaxation (E′DT), and calculated the diastolic functional reserve index (DFRI), as the product of E′ at rest and change in E′ with exercise.

Results

E′ velocity, at rest and peak exercise, as well as the DFRI positively correlated with peak VO2, whereas DT, E′DT, and E/E′ with exercise inversely correlated with peak VO2. Of note, the E′DT at rest also significantly predicted E′ velocity at peak exercise (R = +0.81, P < 0.001). Exercise E′ was the only independent predictor of peak VO2 at multivariable analysis (R = +0.67, P = 0.005).

Conclusions

The E′ velocity at peak exercise is a strong and independent predictor of aerobic exercise capacity as measured by peak VO2 in patients with HFpEF, providing the link between abnormal myocardial relaxation with exercise and impaired aerobic exercise capacity in HFpEF.
Selective expression of long non‐coding RNAs in a breast cancer cell progression model
Authors: Tracy Kirsten M. , Tye Coralee E. , Page Natalie A. , Fritz Andrew J. , Stein Janet L. , Lian Jane B. , Stein Gary S.
Published: May 2017

Long non‐coding RNAs (lncRNAs) are acknowledged as regulators of cancer biology and pathology. Our goal was to perform a stringent profiling of breast cancer cell lines that represent disease progression. We used the MCF‐10 series, which includes the normal‐like MCF‐10A, HRAS‐transformed MCF‐10AT1 (pre‐malignant), and MCF‐10CA1a (malignant) cells, to perform transcriptome wide sequencing. From these data, we have identified 346 lncRNAs with dysregulated expression across the progression series. By comparing lncRNAs from these datasets to those from an additional set of cell lines that represent different disease stages and subtypes, MCF‐7 (early stage, luminal), and MDA‐MB‐231 (late stage, basal), 61 lncRNAs that are associated with breast cancer progression were identified. Querying breast cancer patient data from The Cancer Genome Atlas, we selected a lncRNA, IGF‐like family member 2 antisense RNA 1 (IGFL2‐AS1), of potential clinical relevance for functional characterization. Among the 61 lncRNAs, IGFL2‐AS1 was the most significantly decreased. Our results indicate that this lncRNA plays a role in downregulating its nearest neighbor, IGFL1, and affects migration of breast cancer cells. Furthermore, the lncRNAs we identified provide a valuable resource to mechanistically and clinically understand the contribution of lncRNAs in breast cancer progression.
Simulated effects of internal mixing of anthropogenic aerosols on the aerosol–radiation interaction and global temperature
Authors: Zhou Chen , Zhang Hua , Zhao Shuyun , Li Jiangnan
Published: May 2017

A partial internal mixing (PIM) treatment of black carbon (BC), organic carbon (OC), and sulphate was examined, and the core‐shell model was used to represent the internally mixed aerosols with BC as the core and sulphate or OC as the shell. The influences of PIM treatment on the effective radiative forcing due to aerosol–radiative interaction (ERFari) and global temperature were examined and compared to those of external mixing (EM) treatment using an aerosol‐climate online coupled model of BCC_AGCM2.0_CUACE/Aero. Radiative forcing due to aerosol–radiation interaction (RFari) of the anthropogenic aerosols since the preindustrial era was −0.34 W m−2 for EM and −0.23 W m−2 for PIM, respectively. The global annual mean ERFari of anthropogenic aerosols since the preindustrial era was −0.42 W m−2 for EM and −0.34 W m−2 for PIM, respectively. The change in global annual mean surface temperature increased accordingly from −0.18 K in the EM case to −0.125 K in the PIM case. Well geographic consistence between the change in low‐level cloud amount and the change in temperature can be found. The atmospheric temperature in the troposphere was markedly less reduced in the PIM case than in the EM case. The RFari/ERFari for 50% and 100% were −0.11/–0.07 and 0.13/0.14 W m−2, respectively. RFari, ERFari, and surface temperature changed approximately linearly with the internal mixing proportion.
Features of polarized Raman spectra for homogeneous and non‐homogeneous compressively strained Ge1−ySny alloys
Authors: Perova T. S. , Kasper E. , Oehme M. , Cherevkov S. , Schulze J.
Published: May 2017

Raman spectra of homogeneous and non‐homogeneous, compressively strained, Ge‐rich Ge1−ySny alloys (with y < 13%), deposited by molecular beam epitaxy (MBE) techniques using various low‐temperature process conditions, were investigated using polarized micro‐Raman spectroscopy. It is demonstrated that collecting Raman spectra using both polarizations (
and
) provides more insight into the structural features of GeSn alloys than Raman spectroscopy using an unpolarized probe beam. Acquiring Raman spectra using polarization offers the advantages of enhancing the behaviour of some modes as well as eliminating the overlap of longitudinal optical (LO) modes with unwanted acoustical phonons from the Ge. Raman spectra of samples, grown at extremely low temperatures and identified by X‐ray diffraction as non‐homogeneous, exhibit a lowering of the Ge–Ge peak position, an increase in linewidth and a decrease of the dichroic ratio. Another type of non‐homogeneity appears when the metastable GeSn separates into two phases after obtaining a Sn content‐dependent thickness. Raman microscopy confirmed that the segregates, obtained as a result of phase separation and Sn diffusion to the surface, are of metallic tin origin. Copyright © 2017 John Wiley & Sons, Ltd.
Pressure‐induced phase transitions of vaterite, a metastable phase of CaCO3
Authors: Maruyama Koji , Kagi Hiroyuki , Komatsu Kazuki , Yoshino Toru , Nakano Satoshi
Published: May 2017

Pressure‐induced phase transitions of vaterite, a metastable phase of CaCO3, were observed from Raman spectra and X‐ray diffraction patterns at high pressure using diamond anvil cells at room temperature. Pressure dependence of Raman peaks assignable to the symmetric stretching vibration modes of carbonate ion indicated the phase transitions of vaterite. At 4.3 GPa, vaterite (vaterite I) transformed to a high‐pressure form of vaterite (vaterite II). With increasing pressure, a part of vaterite II gradually transformed to calcite III, and the remainder of vaterite II transformed to another new phase (vaterite III). The phase transition from vaterite II to calcite III was irreversible, and calcite III back‐transformed to calcite I during decompression. Moreover, at the pressures higher than 13.1 GPa, several diffraction spots were observed on an imaging plate, indicating another phase transition from vaterite III to a phase having coarse grains (vaterite IV). Our results indicate that vaterite undergoes more complex phase transitions at high pressure than other polymorphs of calcium carbonate, calcite, and aragonite. These phase transitions of vaterite will open a window to understanding phase transitions of metastable minerals at high pressure. Copyright © 2017 John Wiley & Sons, Ltd.
Graphite‐bearing mineral assemblages in the mantle beneath Central Aldan superterrane of North Asian craton: combined confocal micro‐Raman and electron microprobe characterization
Authors: Nikolenko Evgeny I. , Sharygin Igor S. , Alifirova Taisia A. , Korsakov Andrey V. , Zelenovskiy Pavel S. , Shur V. Ya.
Published: May 2017

Mantle‐derived lherzolitic and harzburgitic Cr‐pyropes from lamprophyres of the Chompolo field (Central Aldan superterrane, North Asian Craton) were studied using micro‐Raman spectroscopy and electron microprobe microanalysis. These garnets enclose graphite coexisting with forsterite, diopside, Ba‐Cl‐phlogopite, tschermakite, rutile, magnesiochromite, Mg‐ilmenite, apatite, chalcopyrite, dolomite, magnesite and lindsleyite inclusions. The PT conditions of residence of graphite‐bearing assemblage in the mantle were estimated, using a combination of mineral thermometers and barometers, to be as high as 2.87–3.55 GPa and 710–770 °C. Generally, graphite within inclusions is well ordered; D1 and D2 disordered bands in its spectra are restricted to inclusion edges. The residual pressure up to 2.1 GPa was inferred for graphite assuming pressure dependence of the G‐band upshift (1580 cm−1 at ambient conditions vs 1588.6 cm−1 at 2.1 GPa). Disordered graphite most likely appears due to the stress‐induced distortion of the fully ordered graphite crystal structure. The distortion results from difference in the thermoelastic properties of graphite inclusions and their garnet hosts exposed to decompression during ascent to the surface with lamprophyre magma. The mineralogy of inclusions in the studied garnets strongly suggests an episode(s) of metasomatism by carbon‐rich agent(s) (COH‐fluid or carbonatitic melt) in the lithospheric mantle of the Central Aldan superterrane, which was coeval with the formation of graphite inclusions and the host pyropes. Copyright © 2017 John Wiley & Sons, Ltd.
Nipple aspirate fluid—A liquid biopsy for diagnosing breast health
Authors: Shaheed Sadr‐ul , Tait Catherine , Kyriacou Kyriacos , Mullarkey Joanne , Burrill Wayne , Patterson Laurence H. , Linforth Richard , Salhab Mohamed , Sutton Chris W.
Published: May 2017

Purpose

Nipple secretions are protein‐rich and a potential source of breast cancer biomarkers for breast cancer screening. Previous studies of specific proteins have shown limited correlation with clinicopathological features. Our aim, in this pilot study, was to investigate the intra‐ and interpatient protein composition of nipple secretions and the implications for their use as liquid biopsies.

Experimental design

Matched pairs of nipple discharge/nipple aspirate fluid (NAF, n = 15) were characterized for physicochemical properties and SDS‐PAGE. Four pairs were selected for semiquantitative proteomic profiling and trypsin‐digested peptides analyzed using 2D‐LC Orbitrap Fusion MS. The resulting data were subject to bioinformatics analysis and statistical evaluation for functional significance.

Results

A total of 1990 unique proteins were identified many of which are established cancer‐associated markers. Matched pairs shared the greatest similarity (average Pearson correlation coefficient of 0.94), but significant variations between individuals were observed.

Conclusions and clinical relevance

This was the most complete proteomic study of nipple discharge/nipple aspirate fluid to date providing a valuable source for biomarker discovery. The high level of milk proteins in healthy volunteer samples compared to the cancer patients was associated with galactorrhoea. Using matched pairs increased confidence in patient‐specific protein levels but changes relating to cancer stage require investigation of a larger cohort.
Taking the Settlements to the ICC? Substantive Issues
Authors: Ronen Yaël
Published: May 2017

Interest in the criminal aspects of the Israeli settlement project in the West
Bank is hardly new; it informed the drafting of Additional Protocol I (AP I) and
of the Statute of
the International Criminal Court (ICC), and motivated Israel's
rejection of both instruments. The 2009 Palestinian attempt to establish ICCjurisdictionpromptedextensivescholarly
debate
on the preconditions for jurisdiction and on its territorial and temporal
aspects, as well as on specific admissibility questions, primarily gravity.
(Complementarity is not an issue with regard to the establishment of West Bank
settlements, since Israeli law and jurisprudence do not prohibit it, although
they regulate some aspects related thereto).
From Marxan to management: ocean zoning with stakeholders for Tun Mustapha Park in Sabah, Malaysia
Authors: Jumin Robecca , Binson Augustine , McGowan Jennifer , Magupin Sikula , Beger Maria , Brown Christopher J. , Possingham Hugh P. , Klein Carissa
Published: May 2017

Tun Mustapha Park, in Sabah, Malaysia, was gazetted in May 2016 and is the first multiple-use park in Malaysia where conservation, sustainable resource use and development co-occur within one management framework. We applied a systematic conservation planning tool, Marxan with Zones, and stakeholder consultation to design and revise the draft zoning plan. This process was facilitated by Sabah Parks, a government agency, and WWF-Malaysia, under the guidance of the Tun Mustapha Park steering committee and with support from the University of Queensland. Four conservation and fishing zones, including no-take areas, were developed, each with representation and replication targets for key marine habitats, and a range of socio-economic and community objectives. Here we report on how decision-support tools informed the reserve design process in three planning stages: prioritization, government review, and community consultation. Using marine habitat and species representation as a reporting metric, we describe how the zoning plan changed at each stage of the design process. We found that the changes made to the zoning plan by the government and stakeholders resulted in plans that compromised the achievement of conservation targets because no-take areas were moved away from villages and the coastline, where unique habitats are located. The design process highlights a number of lessons learned for future conservation zoning, which we believe will be useful as many other places embark on similar zoning processes on land and in the sea.
Host-specific serological response to Angiostrongylus vasorum infection in red foxes (Vulpes vulpes): implications for parasite epidemiology
Authors: GILLIS-GERMITSCH N. , KAPEL C. M. O. , THAMSBORG S. M. , DEPLAZES P. , SCHNYDER M.
Published: May 2017

Angiostrongylus vasorum is a cardiovascular nematode increasingly found in dogs and foxes in endemic foci throughout Europe. The present study evaluates ELISAs for detection of circulating antigens and specific antibodies against A. vasorum in foxes. Blood and worm burdens (WBs) from carcasses of 215 Swiss wild red foxes (Vulpes vulpes) and from 75 farmed foxes of different age groups experimentally inoculated once or repeatedly with infective doses of 50, 100 or 200 third-stage larvae were obtained. Antigen detection in the naturally infected Swiss foxes had 91·2% sensitivity and 89·4% specificity, whereas the corresponding figures for antibody detection were 42·2 and 92·0%. The experimentally infected foxes became positive for circulating antigens 5–10 weeks post-inoculation (wpi) and remained highly positive up to 22 wpi, irrespectively of further challenge inoculation. The antibody responses in the same foxes were highly variable: high optical density (OD) values were reached 5–7 wpi in all animals, followed by a decrease in over half of the animals despite accumulating and consequently high WBs resulting in persistent infections. After each challenge, a slight increase of OD values was observed 7 weeks later. We hypothesize that infected foxes develop a variable and non-protective immunity. Such parasite tolerance allows long-term survival of A. vasorum in the animals, and may explain why the parasite appears to spread rapidly within a fox population, an epidemiological dynamic that is evident in many parts of Europe where A. vasorum has been found over the last decades.
Experimental mixed infection ofLeishmania(Leishmania)amazonensisandLeishmania(L.)infantumin hamsters (Mesocricetus auratus)
Authors: DE LIMA CELESTE JORDANNA LUÍZA , VENUTO MOURA ANA PAULA , FRANÇA-SILVA JOÃO CARLOS , MATOS DE SOUSA GABRIELA , OLIVEIRA SILVA SORAIA , NORMA MELO MARIA , LUIZ TAFURI WAGNER , CARVALHO SOUZA CAROLINA , MONTEIRO DE ANDRADE HÉLIDA
Published: May 2017

In South America, visceral leishmaniasis is frequently caused byLeishmania infantumand, at an unknown frequency, byLeishmania amazonensis. Therefore, mixed infections with these organisms are possible. Mixed infections might affect the clinical course, immune response, diagnosis, treatment and epidemiology of the disease. Here we describe the clinical course of mixed infections withL. amazonensisandL. infantumin a hamster model. We show that mixed infections are associated with more severe clinical disease than infection withL. amazonensisorL. infantumalone. In spleens with mixed infections,L. infantumoutcompetedL. amazonensisin the tissue, but not in culture from tissue. We found increased levels of IgG in animals infected withL. infantum.Although more than 30 bands were revealed in a Western blot, the highest immunogenicity was observed with proteins having molecular masses of 95 and 90 kDa, whereas proteins with molecular masses of lower than 50 kDa were reactive frequently with serum from hamsters infected withL. amazonensis, and proteins with molecular masses of 80 and 70 kDa were reactive only with serum from hamsters infected withL. infantum. This finding has important implications regarding the biology ofLeishmaniaand humoral immune responses to infections with these organisms.