bluuebunny/crossref_metadata_2025 huggingface dataset:
Physical Hardware‐in‐the‐Loop Modeling and Simulation
Authors: Roscoe Andrew , Guillo‐Sansano Efren , Burt Graeme
Published: August 2016

It is too risky to install a newly designed device, component, or controller, directly into a real power system without rigorous testing. To help derisk the system integration, and to assist in the design process, computer simulation is an accepted and widely adopted tool. However, in a simulation‐only environment, many real‐world issues such as noise, randomness of event timings, and hardware design issues are not well explored. In addition, there are limits on the size and fidelity of system, which can be simulated, due to the required computational intensity, and because control systems for devices often contain software that is proprietary and cannot be modeled accurately. Physical hardware‐in‐the‐loop simulation provides an interim stage between purely computer‐based simulation and real device deployment. Part of the power system (or “smart grid”) is simulated, but specific components are implemented in actual hardware. The hardware may consist of instrumentation, relays, or controllers, carrying no primary current. Such testing is termedsecondary hardware‐in‐the‐loop, as the signals exchanged between the simulation and hardware consist only of measurements and control values. A more advanced environment is created where primary power flow is exchanged with the hardware. This is termedprimary hardware‐in‐the‐looporpower hardware‐in‐the‐looptesting. In addition to measurement and control signals being exchanged with the simulation, an interface is required at which primary power is exchanged between the simulation and the hardware, at the voltage and current levels suitable for the hardware under test. Creation of such environments is complex, but allows steady‐state, dynamic, and worst‐case scenarios to be recreated in a controlled environment. Therefore, hardware‐in‐the‐loop testing offers a cheaper, safer, faster, and more comprehensive derisking process than trying the hardware for the first time on a real network. The complexity and interconnected nature of the smart grid means that such hardware‐in‐the‐loop‐based testing is becoming even more critical to understanding the behavior of systems and schemes, and consequently the safe and secure introduction of new technologies.
Industry Practice and Operational Experience of Key Transmission Applications of Smart Grid Technologies
Authors: Martin Kenneth E.
Published: August 2016

Synchrophasor measurement technology is one of the key enablers for the smart grid. This measurement technique supports the growing need for wide‐area situational awareness, advanced system protection, and control. It also supports comprehensive analysis and the development of better power system models. This chapter provides an overview of this technology including the technique, technical requirements, standards, applications, and world‐wide deployments.

A synchrophasor is the complex value of the AC magnitude and phase angle synchronized to coordinated universal time (UTC). A phasor measurement unit (PMU) estimates these values from the AC waveform and synchronizes it to time. These measurements can then be sent over communication networks in real time to control centers to provide a comprehensive report of the power system status. Communication and data storage requirements are high owing to the high volume of data. Data validation techniques have been developed to assure reliable information. Real‐time applications provide situational awareness to operators and alarms for problem conditions. Analysis applications have been developed to verify operation and to validate system models. Controls using synchrophasors for input take advantage of the high accuracy and speed of the measurement. Standards have been developed along with the technology to assure the measurements are high quality and comparable, and data collection systems are compatible. Some examples of synchrophasor‐based systems deployment throughout the world are given.
Operational Experience of Microgrids
Authors: Choi Young‐Jun , Choi In‐Sun , Lee Hak‐Ju , Chae Woo‐Kyu
Published: August 2016

Microgrids are small‐scale grids that can efficiently operate distributed resources, which include renewable energy sources and energy storage system to effectively supply energy to loads in a specific region. They can be operated independently as an island, or interconnected to an existing grid.

As the design of microgrids needs to be optimized according to geographical and environmental conditions, system design engineering technology is one of the most crucial elements. System operation and reliability technology are also important.

Microgrids can be classified as grid‐connected types and isolated (off‐grid) types. The grid‐connected types are generally applied to minimize the operation costs of buildings, factories, and specific regions, but are not economically attractive owing to the low price of electric power from the utility.

Thus, in island regions where a diesel generator is already in use, it is more economically feasible to select an environment‐friendly isolated‐type microgrid system with renewable energy sources and energy storage, some are already in commercial operation.

When the initial investment costs of energy storage and renewable resources are reduced in the near future, the microgrid system will evolve to a future power system, which will replace part of the electric power grid system used by utilities.
Synthesis and Interfacial Properties of Optically‐Active Photonic Nanocomposites with Single Nanoparticle Dispersion at High Solids Loading
Authors: Zhao Xinyu , Sun Yang , He Chaobin , Tan Mei Chee
Published: August 2016

The integration of inorganic rare earth doped nanoparticles in polymer matrices to obtain transparent polymer composites has attracted much attention in optical applications as the polymer‐based systems harness the benefits of both inorganic and polymer materials. To obtain highly emissive nanocomposites, it is highly desirable to maximize the loading of nanoparticles in the polymer matrices while minimizing scattering losses. This work develops a nanocomposite with brightly infrared‐emitting NaYF4:Yb,Er nanoparticles dispersed in hydrolyzed polyhedral oligomeric silsesquioxane‐graft‐poly (methyl methacrylate) (H‐POSS‐PMMA) matrix, which is prepared by spin coating. In this process, H‐POSS‐PMMA acts as both surfactant and polymer matrix. The resulting nanocomposite exhibits mostly single nanoparticle dispersion at a high solid loading of 10 vol%, excellent thermal stability, and superior optical properties. Moreover, the H‐POSS‐PMMA modifies the particle interfacial behavior to improve colloidal stability in anisole for approximately two months. Our modification method can also be extended to other optical inorganic nanoparticles and polymer matrices, leading to significant advancements in various commercial applications such as flexible optoelectronic devices, photovoltaics, and photodetectors.
pH‐Responsive Self‐Organization of Metal‐Binding Protein Motifs from Biomolecular Junctions in Mussel Byssus
Authors: Reinecke Antje , Brezesinski Gerald , Harrington Matthew J.
Published: August 2016

Mussels rapidly fabricate tough and self‐healing biopolymeric fibers called byssal threads that provide an excellent role model for bio‐inspired design. The remarkable tensile properties arise from a collagenous protein family known as preCols, which self‐assemble into a semicrystalline array in the distal thread core. Histidine‐rich domains (HRDs) at the preCol ends are critical both for the self‐healing capacity and for the thread assembly process due to their propensity for coordinating transition metal ions; however, very little is understood about the molecular relationship between HRD sequence, structure, and function. Here, a comprehensive spectroscopic investigation of two model peptides based on conserved repetitive motifs in the HRDs is performed to elucidate molecular level details of their role in thread assembly and function. It is observed that environmental factors relevant to the natural assembly process (e.g., concentration, pH, and metal content) trigger dramatic changes in HRD nanostructure and higher order assembly, leading to the formation of highly defined backbone conformation and metal binding geometry.
Nano‐Au and Ferroelectric Polarization Mediated Si/ITO/BiFeO3 Tandem Photocathode for Efficient H2 Production
Authors: Cheng Xiaorong , Shen Huanyu , Dong Wen , Zheng Fengang , Fang Liang , Su Xiaodong , Shen Mingrong
Published: August 2016

For efficient utilization of solar light during photoelectrochemical (PEC) water splitting, tandem photoelectrodes comprising a wider bandgap top semiconductor stacked above a smaller bandgap one have been proposed in the previous studies. However, the photocurrent is usually limited due to the blocked transfer of photogenerated carriers on the interface between the semiconductors. Here, this study constructs an Si‐pnn+/ITO/Au/BiFeO3 (BFO) hybrid photocathode catalyzed by MoS2/Pt with an intension to fulfill the efficient transfer of photogenerated electrons from Si to electrode surface. This study reveals how the local surface plasmonic resonance effect of Au nanoparticles and the depolarization electric field of BFO enhance the PEC reactivity of the photocathode, and also the catalytic effect of the combined MoS2/Pt catalyst. Remarkably, the photocathode exhibits an onset potential of 1.3 V versus reversible hydrogen electrode (RHE), and the photocurrent at 0 V versus RHE can be up to –9.1 mA cm−2 under 100 mW cm−2 Xe‐lamp illuminations. Such a unique design represents a general strategy to enhance the PEC performance of a tandem photoelectrode where the energy bands are not so matched on the interfaces, and therefore extends the scope of the tandem architectures.
Photoreversible Growth of Micropattern
Authors: Hou Honghao , Ma Xiaodong , Xu Hongjie , Shi Zixing , Yin Jie , Jiang Xuesong
Published: August 2016

Self‐organized surface patterns from the nano‐ to microscale inspired by nature find wide applications in functional intelligent materials in various fields. In particular, complex patterns with the reversible topographies that do not alter the material's intrinsic properties allow for the possibility of on‐demand control of the surface properties. Herein, a facile strategy is presented to fabricate a micro/nanopatterned surface whose morphology can be changed timely and spatially by light. The complex pattern is fabricated on the surface of a photocuring coating through a one‐step, self‐patterned process, in which self‐assembly of fluorinated azobenzene‐containing polymer and photoreversible isomerization lead to the generation of compressive stress, resulting in the formation of a reversible surface pattern. The reversible change of the pattern morphology allows for light control of the adhesion and wettability of the surface. Moreover, the one‐step approach to fabricate the complex pattern possesses characteristics similar to the formation process of the self‐organizing micro/nanopatterns in nature. The feasibility and generality of this approach for obtaining such bioinspired, photoreversible, and self‐organized patterned surfaces will find wide applications in functional intelligent materials with properties that can be tuned on‐demand without altering the material's intrinsic properties.
Simplified Hybrid White Organic Light‐Emitting Diodes with a Mixed Fluorescent Blue Emitting Layer for Exciton Managing and Lifetime Improving
Authors: Liu Yuan , Liang Feng , Cui Lin‐Song , Shi Xiao‐Bo , Wang Zhao‐Kui , Liao Liang‐Sheng
Published: August 2016

The authors demonstrate a simple but effective way to manage the exciton, reduce the efficiency roll‐off, enhance the color stability and improve the lifetime of hybrid white organic light‐emitting diodes simultaneously. Red and green phosphorescent emission layers (EMLs) are connected by a mixed fluorescent blue‐emitting layer (MBL), which is composed of two self‐host fluorescent materials of N,N′‐di‐1‐naphthalenyl‐N,N′‐diphenyl‐[1,1′:4′,1″:4″,1″′‐quaterphenyl]‐4,4′″‐diamine and bis[2‐(2‐hydroxyphenyl)‐pyridine]beryllium. By adjusting the mixture ratio and the thickness of MBL, the intensity of blue and green emissions can be tuned independently. A maximum power efficiency of 41.1 lm W−1 and external quantum efficiency of 15.8% is obtained without any out‐coupling schemes or doping strategies. In addition, the device shows a stable electroluminescence spectrum with Commission International de L'Eclairage coordinates of (0.47, 0.43) in the practical range of 1000–5000 cd m−2. Furthermore, the fuzzy interfaces between MBL and phosphorescent EMLs, and the wide distribution of charges and excitons, result in four times prolonged device lifetime.
Two‐Photon Excitation Temperature Nanosensors Based on a Conjugated Fluorescent Polymer Doped with a Europium Probe
Authors: Wang Xu‐dong , Meier Robert J. , Schäferling Michael , Bange Sebastian , Lupton John M. , Sperber Michaela , Wegener Joachim , Ondrus Vladimir , Beifuss Uwe , Henne Ulrich , Klein Christian , Wolfbeis Otto S.
Published: August 2016

A strongly fluorescent organic semiconducting polymer doped with a highly temperature dependent fluorescent europium(III) complex is converted into a nanosized material that is capable of optically sensing temperature (T) in the range from 0 to 50 °C via two‐photon excitation at 720 nm. The nanosensors are prepared from a blue‐fluorescent polyfluorene that acts as both a light‐harvesting antenna (to capture two‐photon energy) and an energy donor in a fluorescence resonance energy transfer (FRET) system. The photonic energy absorbed by the polymer is transferred to the T‐sensitive red‐luminescent europium complex contained in the nanoparticles. The close spatial proximity of the donor and the acceptor warrants efficient FRET. A poly(ethylene glycol)‐co‐poly(propylene oxide) block copolymer is also added to render the particles biocompatible. It is shown that T can be calculated from a) the intensity of the luminescence of the europium complex, b) the ratio of the intensities of the red and blue luminescence, or c) the T‐dependent luminescence lifetime of the Eu(III) complex.
Encapsulated Cobalt Oxide on Carbon Nanotube Support as Catalyst for Selective Continuous Hydrogenation of the Showcase Substrate 1‐Iodo‐4‐nitrobenzene
Authors: Baramov Todor , Loos Patrick , Hassfeld Jorma , Alex Hannes , Beller Matthias , Stemmler Tobias , Meier Gregor , Gottfried Michael , Roggan Stefan
Published: August 2016

A carbon nanotube supported catalyst containing cobalt/cobalt oxide (Co/Co3O4) nanoparticles encapsulated within a shell of nitrogen‐doped graphene layers (Co3O4/NGr@CNT) was prepared. It shows excellent chemoselectivity in the hydrogenation of 1‐iodo‐4‐nitrobenzene, which contains an iodine substituent highly sensitive against hydrodehalogenation. In contrast to traditional activated charcoal‐supported catalysts such as Pt‐V/C or the closely related Vulcan carbon black supported Co3O4/NGr@C, the advantageous morphological properties of the CNT support allow for the application of the new Co3O4/NGr@CNT as a fixed bed catalyst in a continuous flow reactor. Under optimized conditions, no dehalogenation side products could be detected. This remarkable selectivity in combination with its mechanical stability under operation conditions render Co3O4/NGr@CNT a catalyst particularly relevant for application in continuous processes based on a packed bed reactor.

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Gold(I)‐Catalyzed Intramolecular Carbon‐Oxygen Bond Cleavage Reaction via Gold Carbenes Derived from Vinylidenecyclopropanes
Authors: Li De‐Yao , Wei Yin , Shi Min
Published: August 2016

Under gold(I) catalysis, the in situ generated gold carbene from vinylidenecyclopropanes bearing a methoxymethyl group can undergo an intramolecular nucleophilic attack to give the carbon‐oxygen bond cleavage product in good yield within 15 min. and different phosphine ligands could control both Z‐ and E‐configurations, respectively. The reaction mechanism has been clarified on the basis of deuterium‐ and 18O‐labeling experiments. This method provides a new and efficient approach to stereoselectively synthesize alkylidenecyclobutanones under mild conditions.

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CO2 abatement in oscillating packed‐bed scrubbers: Hydrodynamics and reaction performances for marine applications
Authors: Iliuta Ion , Larachi Faïçal
Published: August 2016

Gas‐liquid flow dynamics and CO2‐monoethanolamine absorption performances of an oscillating countercurrent packed bed were analyzed by means of a transient 3D nonisothermal two‐fluid flow model with a goal to understand the behavior of scrubbing units on‐board floating production, storage and offloading platforms. Gas‐liquid flow deviation from axial symmetry was significant at larger vessel inclinations prompting noticeable liquid accumulation in the column lowermost area. Conversely, in static vertical and slightly inclined columns only a reduced fraction of the liquid was subject to transverse segregation. Externally‐generated column oscillations brought about complex secondary flows in radial and tangential directions resulting in oscillatory patterns with amplitude and propagation frequency affected by the packed bed oscillations. CO2 abatement in inclined and asymmetrically oscillating columns suffered perceptible deviations with respect to vertical configuration while symmetrically oscillating columns gave rise to CO2 performances oscillating around the steady‐state solutions of the vertical column. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1064–1076, 2017
Fecal carbon and nitrogen isotopic analysis as an indicator of diet in Kanyawara chimpanzees, Kibale National Park, Uganda
Authors: Phillips Caroline A. , O'Connell Tamsin C.
Published: August 2016

Objectives

The shorter‐term overview from feces provides scope to investigate dietary fluctuations. We assess the correlation of stable isotopic fecal values with recorded seasonal diet of 10 adult chimpanzees (P. t. schweinfurthii) of the Kanyawara community (Kibale National Park, Uganda) and whether fecal nitrogen levels (%N) indicate a change in crude protein intake.

Materials and Methods

We recorded food eaten by each ape and collected both concurrent fecal samples (N = 115) and plant foods eaten by this community (N = 64). We compared fecal δ13C and δ15N values (also %N) with: (a) plant values; (b) feeding data; and (c) food‐items found macroscopically in the fecal samples. Interspecies and intraspecies differences in plant and fecal isotope values (and %N) as well as seasonality in diet were determined using parametric and nonparametric tests.

Results

No difference in plant δ13C and δ15N values was found at intraspecies or interspecies level. Fecal isotope values reflected a diet of C3 plants from evergreen forest vegetation. Seasonal differences in δ13C and δ15N corresponded with aspects of feeding and fecal macroscopic data, but only at community level. A change in crude protein intake was not indicated from %N content.

Discussion

This study further validates the use of staple isotope analyses of primate feces to provide a dietary overview, revealing seasonal differences at community level; however, conclusive results may be limited for individuals when using short sampling periods. Further study of variables that influence fecal %N content is also suggested to interpret crude protein intake.
A study of the peopling of Greenland using next generation sequencing of complete mitochondrial genomes
Authors: Lopopolo Maria , Børsting Claus , Pereira Vania , Morling Niels
Published: August 2016

Objectives

The Greenlandic population history is characterized by a number of migrations of people of various ethnicities. In this work, the analysis of the complete mtDNA genome aimed to contribute to the ongoing debate on the origin of current Greenlanders and, at the same time, to address the migration patterns in the Greenlandic population from a female inheritance demographic perspective.

Methods

We investigated the maternal genetic variation in the Greenlandic population by sequencing the whole mtDNA genome in 127 Greenlandic individuals using the Illumina MiSeq® platform.

Results

All Greenlandic individuals belonged to the Inuit mtDNA lineages A2a, A2b1, and D4b1a2a1. No European haplogroup was found.

Discussion

The mtDNA lineages seem to support the hypothesis that the Inuit in Greenland are descendants from the Thule migration. The results also reinforce the importance of isolation and genetic drift in shaping the genetic diversity in Greenlanders. Based on the mtDNA sequences, the Greenlandic Inuit are phylogenetically close to Siberian groups and Canadian Inuit.
Preclinical disease activity in multiple sclerosis: A prospective study of cognitive performance prior to first symptom
Authors: Cortese Marianna , Riise Trond , Bjørnevik Kjetil , Bhan Alok , Farbu Elisabeth , Grytten Nina , Hogenesch Ineke , Midgard Rune , Smith Simonsen Cecilia , Telstad Wenche , Ascherio Alberto , Myhr Kjell‐Morten
Published: August 2016

Objective

To prospectively investigate potential signs of preclinical multiple sclerosis (MS) activity and when they are present prior to first symptom using data from a historical cohort.

Methods

We linked the cognitive performance of all Norwegian men born 1950–1995 who underwent conscription examination at age 18 to 19 years to the Norwegian MS registry to identify those later developing MS, and randomly selected controls frequency‐matched on year of birth from the Norwegian Conscript Service database. In this nested case–control study, cognitive test scores were available for 924 male cases and 19,530 male controls. We estimated mean score differences among cases and controls (Student t test) and the risk of developing MS comparing lower to higher scores (Cox regression) in strata of years to clinical onset.

Results

Men developing first clinical MS symptoms up to 2 years after the examination scored significantly lower than controls (Δ = 0.80, p = 0.0095), corresponding to a 6 intelligence quotient (IQ)‐point difference. Those scoring lowest, that is, >1 standard deviation below the controls’ mean, had an increased MS risk during the 2 following years (relative risk = 2.81, 95% confidence interval = 1.52–5.20). Whereas results were similar for relapsing–remitting MS cases (RRMS), those developing primary–progressive MS (PPMS) scored a significant 4.6 to 6.9 IQ points lower than controls up to 20 years prior to first progressive symptoms.

Interpretation

RRMS may start years prior to clinical presentation, and disease processes in PPMS could start decades prior to first apparent progressive symptoms. Cognitive problems could be present in both MS forms before apparent symptoms. Apart from potential implications for clinical practice and research, these findings challenge our thinking about the disease. Ann Neurol 2016;80:616–624
Ultra‐Long Crystalline Red Phosphorus Nanowires from Amorphous Red Phosphorus Thin Films
Authors: Smith Joshua B. , Hagaman Daniel , DiGuiseppi David , Schweitzer‐Stenner Reinhard , Ji Hai‐Feng
Published: August 2016

Heating red phosphorus in sealed ampoules in the presence of a Sn/SnI4 catalyst mixture has provided bulk black phosphorus at much lower pressures than those required for allotropic conversion by anvil cells. Herein we report the growth of ultra‐long 1D red phosphorus nanowires (>1 mm) selectively onto a wafer substrate from red phosphorus powder and a thin film of red phosphorus in the present of a Sn/SnI4 catalyst. Raman spectra and X‐ray diffraction characterization suggested the formation of crystalline red phosphorus nanowires. FET devices constructed with the red phosphorus nanowires displayed a typical I–V curve similar to that of black phosphorus and a similar mobility reaching 300 cm2 V−1 s with an Ion/Ioff ratio approaching 102. A significant response to infrared light was observed from the FET device.
Ladungstransport und Leitfähigkeitsschalten von redoxaktiven Azulen‐Derivaten
Authors: Schwarz Florian , Koch Michael , Kastlunger Georg , Berke Heinz , Stadler Robert , Venkatesan Koushik , Lörtscher Emanuel
Published: August 2016

Azulen (Az) ist ein nicht‐alternierender aromatischer Kohlenwasserstoff, der aus einem elektronenreichen Ring mit fünf und einem elektronenarmen Ring mit sieben Gliedern besteht. Diese Elektronenverteilung führt zu einer intrinsischen Redoxaktivitiät. Durch Variieren der Befestigungspunkte der beiden elektrodenverbindenden Substituenten am Az‐Zentrum wird der Einfluss der Redoxfunktionalität auf den Ladungstransport untersucht. Die Leitfähigkeit des 1,3‐Az‐Derivats ist dabei mindestens eine Größenordnung geringer als die der 2,6‐Az‐ und 4,7‐Az‐Derivate, in Übereinstimmung mit Resultaten der Dichtefunktionaltheorie (DFT). Außerdem weist nur 1,3‐Az eine ausgeprägt nichtlineare Strom‐Spannungs‐Kennlinie mit Hysterese auf, was durch einen spannungsabhängigen Schaltvorgang ausgelöst wird. Die DFT‐Ergebnisse zeigen weiter, dass das LUMO einerseits am nächsten bei der Fermi‐Energie der Elektroden liegt, andererseits aber nur bei den 2,6‐ und 4,7‐Az‐Derivaten den aktiven Ladungskanal darstellt, während das 1,3‐Az‐Derivat bei niedriger Spannung das HOMO und bei hoher Spannung das LUMO+1 verwendet. Im Gegenzug schafft das lokalisierte, nur schwach gekoppelte LUMO des 1,3‐Az einen zusätzlichen, langsamen Transportkanal für Elektronenhopping, das für den spannungsinduzierte Schaltvorgang aufgrund der Besetzung eines einzelnen Molekülorbitals (MO) verantwortlich ist.
Development of Light‐Activated CRISPR Using Guide RNAs with Photocleavable Protectors
Authors: Jain Piyush K. , Ramanan Vyas , Schepers Arnout G. , Dalvie Nisha S. , Panda Apekshya , Fleming Heather E. , Bhatia Sangeeta N.
Published: August 2016

The ability to remotely trigger CRISPR/Cas9 activity would enable new strategies to study cellular events with greater precision and complexity. In this work, we have developed a method to photocage the activity of the guide RNA called “CRISPR‐plus” (CRISPR‐precise light‐mediated unveiling of sgRNAs). The photoactivation capability of our CRISPR‐plus method is compatible with the simultaneous targeting of multiple DNA sequences and supports numerous modifications that can enable guide RNA labeling for use in imaging and mechanistic investigations.
Charge Transport and Conductance Switching of Redox‐Active Azulene Derivatives
Authors: Schwarz Florian , Koch Michael , Kastlunger Georg , Berke Heinz , Stadler Robert , Venkatesan Koushik , Lörtscher Emanuel
Published: August 2016

Azulene (Az) is a non‐alternating, aromatic hydrocarbon composed of a five‐membered, electron‐rich and a seven‐membered, electron‐poor ring; an electron distribution that provides intrinsic redox activity. By varying the attachment points of the two electrode‐bridging substituents to the Az center, the influence of the redox functionality on charge transport is evaluated. The conductance of the 1,3 Az derivative is at least one order of magnitude lower than those of the 2,6 Az and 4,7 Az derivatives, in agreement with density functional theory (DFT) calculations. In addition, only 1,3 Az exhibits pronounced nonlinear current–voltage characteristics with hysteresis, indicating a bias‐dependent conductance switching. DFT identifies the LUMO to be nearest to the Fermi energy of the electrodes, but to be an active transport channel only in the case of the 2,6 and the 4,7 Az derivatives, whereas the 1,3 Az derivative uses the HOMO at low and the LUMO+1 at high bias. In return, the localized, weakly coupled LUMO of 1,3 Az creates a slow electron‐hopping channel responsible for the voltage‐induced switching due to the occupation of a single molecular orbital (MO).
A Simple Primary Amide for the Selective Recovery of Gold from Secondary Resources
Authors: Doidge Euan D. , Carson Innis , Tasker Peter A. , Ellis Ross J. , Morrison Carole A. , Love Jason B.
Published: August 2016

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl4]− ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. The fundamental chemical understanding gained herein should be integral to the development of metal‐recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.
Luminescent Europium(III) Coordination Zippers Linked with Thiophene‐Based Bridges
Authors: Hirai Yuichi , Nakanishi Takayuki , Kitagawa Yuichi , Fushimi Koji , Seki Tomohiro , Ito Hajime , Hasegawa Yasuchika
Published: August 2016

Novel EuIII coordination polymers [Eu(hfa)3(dpt)]n (dpt: 2,5‐bis(diphenylphosphoryl)thiophene) and [Eu(hfa)3(dpedot)]n (dpedot: 2,5‐bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogen‐bonded zipper structures are reported. The coordination polymers are composed of EuIII ions, hexafluoroacetylacetonato ligands, and thiophene‐based phosphine oxide bridges. The zig‐zag orientation of single polymer chains induced the formation of densely packed coordination structures with multiple intermolecular interactions, resulting in thermal stability above 300 °C. They exhibit a high intrinsic emission quantum yield (ca. 80 %) due to their asymmetrical and low‐vibrational coordination structures around EuIII ions. Furthermore, the characteristic alternative orientation of substituents also contributes to the dramatically high ligand‐to‐metal energy transfer efficiencies of up to 80 % in the solid state.
Secondary Structure and Membrane Topology of the Full‐Length Dengue Virus NS4B in Micelles
Authors: Li Yan , Wong Ying Lei , Lee Michelle Yueqi , Li Qingxin , Wang Qing‐Yin , Lescar Julien , Shi Pei‐Yong , Kang CongBao
Published: August 2016

Dengue virus nonstructural protein 4B (NS4B) is a membrane protein consisting of 248 residues with a crucial role in virus replication and interference with the host innate immunity. The dengue virus serotype 3 NS4B was reconstituted into lyso‐myristoyl phosphatidylglycerol (LMPG) micelles. Backbone resonance assignment of NS4B was obtained using conventional solution NMR experiments. Further studies suggested that NS4B contained eleven helices and six of them form five potential transmembrane regions. This study provides atomic level information for an important drug target to control flavivirus infections.
Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation
Authors: Zou Guohong , Lin Chensheng , Jo Hongil , Nam Gnu , You Tae‐Soo , Ok Kang Min
Published: August 2016

A meticulously designed, polar, non‐centrosymmetric lead borate chloride, Pb2BO3Cl, was synthesized using KBe2BO3F2 (KBBF) as a model. Single‐crystal X‐ray diffraction revealed that the structure of Pb2BO3Cl consists of cationic [Pb2(BO3)]+ honeycomb layers and Cl− anions. Powder second harmonic generation (SHG) measurements on graded polycrystalline Pb2BO3Cl indicated that the title compound is phase‐matchable (type I) and exhibits a remarkably strong SHG response, which is approximately nine times stronger than that of potassium dihydrogen phosphate, and the largest efficiency observed in materials with structures similar to KBBF. Further characterization suggested that the compound melts congruently at high temperature and has a wide transparency window from the near‐UV to the mid‐IR region.
Preparation of epoxy‐ended hyperbranched polymers with precisely controllable degree of branching by thiol‐ene Michael addition
Authors: Zhang Daohong , Wang Yimei , Xu Zhicai , Cheng Juan , Chen Sufang , Zhang Junheng , Miao Menghe
Published: August 2016

Epoxy‐ended hyperbranched polymers (EHPs) have a wide range of applications due to their outstanding performances. Because their microstructures are not positively identified, it is very difficult to ascertain the reinforcing and toughening mechanisms of EHPs and their interface interaction with other matrixes. Controllable synthesis of EHPs with precise degree of branching (DB) remains to be a major challenge. Here, a method for preparing novel nitrogen‐phosphor skeleton epoxy‐ended hyperbranched polymers (NPEHP) with controllable DB by a thiol‐ene Michael addition between thiol‐ended hyperbranched polymers (NPHSH) and glycidyl methacrylate have been firstly reported. NPHSH is synthesized by an esterification between hydroxyl‐ended hyperbranched polymers (NPHOH) and 3‐mercaptopropionic acid. NPHOH is prepared by a thiol‐ene Michael addition between methacrylate group of a monomer and thiol group of linear monomer (AB) and/or branched monomer (AB2). The molar ratio between the AB and AB2 monomers controls the DB of the products. The 1H NMR spectra analysis of NPHOH shows that their experimentally determined DBs are very close to their theoretical values, indicating good controllability of their DBs. The narrow molecular weight distributions of NPHOH, NPHSH, and NPEHP suggest high efficiency of the thiol‐ene Michael addition. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44277.
BaTiO3 incorporation effect on the dielectric properties of polymer from aqueous emulsion: An enhanced dispersion technique
Authors: Zyane Adel , Belfkira Ahmed , Brouillette François , Marchet Pascal , Lucas Romain
Published: August 2016

An economic and environment friendly process was adapted to synthesize new dielectric composite materials. Using ethylene vinyl acetate (EVA)/vinyl ester of versatic acid (VeoVa) terpolymer as an aqueous emulsion provides a homogenous dispersion of BaTiO3 (BT) particles, due to the high viscosity and polarity of the vinyl resin (VR). Composites films were obtained from these dispersions by water evaporation. The evolution of the dielectric properties as a function of the BaTiO3 content, was correctly fitted by a Maxwell‐Garnett model. This fitting of the experimental curve shows a good dispersion of filler in the vinyl resin and the particles separation by a layer of resin as expected for the preparation method used in this study. The VR/BT composites show good synergy between the dielectric properties of the different phases of the composites due to the formation of macrodipoles and to the strong interactions between polar EVA/VeoVa groups and the BaTiO3 particles surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44333.
The effects of the concentration‐dependent erythrocyte distribution of TAK‐802, a potent acetylcholinesterase inhibitor, on rat pharmacokinetics
Authors: Kakehi Masaaki , Tagawa Yoshihiko , Goto Akihiko , Kondo Takahiro , Asahi Satoru
Published: August 2016

The purpose of this study was to investigate the effect of the concentration‐dependent erythrocyte distribution of TAK‐802, a potent acetylcholinesterase inhibitor, on rat pharmacokinetics. In an ascending oral dose study, the maximum plasma concentration (Cmax) of TAK‐802 increased in a dose‐dependent manner. The time to reach Cmax decreased as the dose increased, whereas the total clearance was independent of the tested dose range. In this intravenous (i.v.) ascending dose study in rats, the apparent distribution volumes at steady state decreased, and the apparent terminal elimination rate constants increased with TAK‐802 dose escalation. A marked concentration dependency was observed in an associated in vitro erythrocyte distribution study. The in vitro erythrocyte distribution study results and a relationship analysis between the plasma and blood concentrations of TAK‐802 after i.v. dosing revealed that the characteristics of the erythrocyte distribution could be expressed by Langmuir's adsorption formula. The concentration–time profiles of TAK‐802 in plasma and whole blood calculated using a nonlinear pharmacokinetic model incorporating the concentration‐dependent erythrocyte distribution with optimized parameters fit well to the observed plasma and blood concentration profiles obtained from the i.v. ascending dose study. These results indicate that the concentration‐dependent erythrocyte distribution plays a major role in the nonlinear pharmacokinetics of TAK‐802 in rats. Copyright © 2016 John Wiley & Sons, Ltd.
A new validated HPLC method for the determination of quercetin: Application to study pharmacokinetics in rats
Authors: Abdelkawy Khaled S. , Balyshev Mark E. , Elbarbry Fawzy
Published: August 2016

A simple, accurate, and reproducible high‐performance liquid chromatography (HPLC) method has been developed and validated for the quantification of quercetin (QR) in rat plasma. The method involves a simple protein precipitation procedure to extract both QR and thymoquinone (TQ), the internal standard. The chromatographic analysis was achieved on a Shimadzu LC 20 A HPLC system equipped with a Supelcosil LC‐18 T C18 column and an isocratic mobile phase consisting of 0.3% trichloroacetic acid in water and acetonitrile HPLC‐grade (50:50, v/v) run at a flow rate of 0.9 mL/min for 13 min. The UV detection wavelength was set at 254 nm. The method exhibited good linearity (R2 > 0.994) over the assayed concentration range (0.10–25 μg/mL) and demonstrated good intra‐day and inter‐day precision and accuracy (relative standard deviations and the deviation from predicted values were <20%). This method was also successfully applied for studying the pharmacokinetics of QR in rats following a single oral dose of QR to evaluate its pharmacokinetic parameters in rats.
Development and validation of an LC–MS/MS quantitative method for endogenous deoxynucleoside triphosphates in cellular lysate
Authors: Chen Xinhui , McAllister Kevin J. , Klein Brandon , Bushman Lane R. , Anderson Peter L.
Published: August 2016

The endogenous deoxynucleoside triphosphate (dNTP) pool includes deoxyadenosine triphosphate (dATP), deoxycytidine triphosphate (dCTP), deoxyguanosine triphosphate (dGTP) and thymidine triphosphate (TTP). The endogenous dNTP pool is regulated by complex enzymatic pathways that can be targeted by drugs, such as antimetabolites. In addition, these components compete with antiviral nucleos(t)ide analog triphosphates, contributing to the mechanism of pharmacologic action. This communication describes the development and validation of a sensitive method to quantify the intracellular dNTP pool in cellular lysates. The extraction process was optimized for dNTPs using an indirect strategy – the separation of mono‐, di‐ and triphosphate moieties by strong anion exchange, dephosphorylation of target fractions to molar equivalent nucleosides – followed by sensitive quantitation using liquid chromatography–tandem mass spectrometry. The validated analytical range was 50–2500 fmol/sample for each dNTP. The assay was used to quantify dNTPs in peripheral blood mononuclear cells from 40 clinical research participants (n = 279 samples). Median (interquartile range) concentrations were 143 (116, 169) for dATP, 737 (605, 887) for dCTP, 237 (200, 290) for dGTP and 315 (220, 456) for TTP, in femtomoles per million cells. This method allows for future studies of endogenous dNTP disposition in subjects receiving antimetabolites or nucleos(t)ide analogs, or for other clinical scenarios.
A fast and sensitive UHPLC–MS/MS method for the determination ofN‐butylscopolamine in human plasma: application in a bioequivalence study
Authors: Suenaga Eunice Mayumi , Val Ligia de Cássia , Tominaga Mineko , Souza Filho José Homero , Soares Gidel , Vioto Monalisa , Nakaie Clovis Ryuichi
Published: August 2016

We have developed and validated a fast and sensitive ultra high‐performance liquid chromatography with positive ion electrospray ionization tandem mass spectrometry method for determining N‐butylscopolamine levels in human plasma using propranolol as an internal standard. The acquisition was set up in the multiple reaction monitoring mode with the transitions m/z 360.3 → 138.0 for N‐butylscopolamine and m/z 260.2 → 116.1 for IS. This method uses a liquid–liquid extraction process with dichloromethane. The analyte and IS were chromatographed on a C18, 50 × 2.1 mm, 1.7 μm column through isocratic elution with acetonitrile–5 mm ammonium acetate (adjusted to pH 3.0 with formic acid). The method was linear in the 1–1000 pg/mL range for N‐butylscopolamine and was selective, precise, accurate and robust. The validated method was successfully applied to perform a bioequivalence study of the reference (Buscopan®, from Boehringer Ingelheim) and the test sample coated‐tablet formulations (from Foundation for Popular Remedy), both containing 10 mg of N‐butylscopolamine bromide administered as a single dose. Using 58 healthy volunteers and accounting for the high intra‐individual variability confirmed by statistical calculations (38%), the two formulations were considered bioequivalent because the rate and extent of absorption (within 80–125% interval), satisfying international requirements.
Process‐relevant concentrations of the leachable bDtBPP impact negatively on CHO cell production characteristics
Authors: Kelly Paul S. , McSweeney Shane , Coleman Orla , Carillo Sara , Henry Michael , Chandran Deepak , Kellett Andrew , Bones Jonathan , Clynes Martin , Meleady Paula , Barron Niall
Published: August 2016

The biopharmaceutical industry has invested considerably in the implementation of single‐use disposable bioreactors in place of or in addition to their stainless steel‐counterparts. This new wave of construction materials for disposable bioprocess containers encompass a plethora of uncharacterized secondary compounds that, when in contact with the culture media, can leach, contaminating the bioprocess. One such cytotoxic leachable already receiving attention is bis(2,4‐di‐tert‐butylphenyl)‐phosphate (bDtBPP), a breakdown product of the secondary antioxidant Irgafos 168 in polyethylene‐film based bags. This compound has been demonstrated to inhibit cell growth at concentrations ranging from 0.12 to 0.73 mg/L across an array of cell lines. Here we demonstrate that a further two CHO cell lines exhibit sensitivity to bDtBPP exposure at concentrations lower than that previously reported (0.035–0.1 mg/L). Furthermore, these inhibitory concentrations reflect bDtBPP levels found to leach early into the bioprocess, exposing reactor inoculums to serious risk. Quantitative label‐free LC‐MS/MS revealed that irrespective of cell line or concentration of bDtBPP, 8 proteins were found to be commonly differentially expressed in response to exposure to the compound highlighting biological processes related to cellular stress. Although the glycoprofile of the recombinant antibody remains primarily unchanged, we demonstrate that this compound when spiked at meaningful concentrations 72 h into culture considerably reduces the maximum cell density achieved. Studies like this reinforce the requirement for the complete characterization of all potential leachable compounds from disposable materials to assess their risk not only to the patient but also to the production pipeline itself. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1547–1558, 2016
Paleodysmorphology and paleoteratology: Diagnosing and interpreting congenital conditions of the skeleton in anthropological contexts
Authors: Oostra Roelof‐Jan , Boer Lucas , van der Merwe Alie E.
Published: August 2016

Most congenital conditions have low prevalence, but collectively they occur in a few percent of all live births. Congenital conditions are rarely encountered in anthropological studies, not least because many of them have no obvious effect on the skeleton. Here, we discuss two groups of congenital conditions that specifically affect the skeleton, either qualitatively or quantitatively. Skeletal dysplasias (osteochondrodysplasias) interfere with the histological formation, growth and maturation of skeletal tissues leading to diminished postural length, but the building plan of the body is unaffected. Well‐ known skeletal dysplasias represented in the archeological record include osteogenesis imperfecta and achondroplasia. Dysostoses, in contrast, interfere with the building plan of the body, leading to e.g. missing or extraskeletal elements, but the histology of the skeletal tissues is unaffected. Dysostoses can concern the extremities (e.g., oligodactyly and polydactyly), the vertebral column (e.g., homeotic and meristic anomalies), or the craniofacial region. Conditions pertaining to the cranial sutures, i.e., craniosynostoses, can be either skeletal dysplasias or dysostoses. Congenital conditions that are not harmful to the individual are known as anatomical variations, several of which have a high and population‐specific prevalence that could potentially make them useful for determining ethnic origins. In individual cases, specific congenital conditions could be determinative in establishing identity, provided that ante‐mortem registration of those conditions was ensured. Clin. Anat. 29:878–891, 2016. © 2016 The Authors Clinical Anatomy published by Wiley Periodicals, Inc. on behalf of American Association of Clinical Anatomists
Mutation and prognostic analyses of PIK3CA in patients with completely resected lung adenocarcinoma
Authors: Song Zhengbo , Yu Xinmin , Zhang Yiping
Published: August 2016

PIK3CA mutation represents a clinical subset of diverse carcinomas. We explored the status of PIK3CA mutation and evaluated its genetic variability, treatment, and prognosis in patients with lung adenocarcinoma. A total of 810 patients with completely resected lung adenocarcinoma were recruited between 2008 and 2013. The status of PIK3CA mutation and other three genes, that is, EGFR mutation, KRAS mutation and ALK fusion were examined by reverse transcription‐polymerase chain reaction (RT‐PCR). Survival curves were plotted with the Kaplan–Meier method and log‐rank for comparison. Cox proportional hazard model was performed for multivariate analysis. Among the 810 patients, 23 cases of PIK3CA mutation were identified with a frequency of 2.8%. There were 14 men and 9 women with a median age of 61 years. Seventeen tumors revealed concurrent gene abnormalities of EGFR mutation (n = 12), KRAS mutation (n = 3), and ALK fusion (n = 2). Seven patients with EGFR & PIK3CA mutations recurred and administrated of EGFR‐TKIs yielded a median progression free‐survival of 6.0 months. Among four eviromous‐treated patients, stable disease was observed in three patients with a median Progression‐free survival (PFS) of 3.5 months. Patients with and without PIK3CA mutation had different overall survivals (32.2 vs. 49.6 months, P = 0.003). Multivariate analysis revealed that PIK3CA mutation was an independent predictor of poor overall survival (HR = 2.37, P = 0.017). The frequency of PIK3CA mutation was around 2.8% in the Chinese patients of lung adenocarcinoma. PIK3CA mutation was associated with reduced PFS of EGFR‐TKIs treatment and shorter overall survival.
Idiopathic sclerosing orbital inflammation mimicking a malignant spindle cell tumor in a dog
Authors: Marie Rzechorzek Nina , Smith Colin , Schwarz Tobias , Liuti Tiziana , Elders Richard , Woods Samantha , Lawrence Jessica , Marioni‐Henry Katia
Published: August 2016

Key Clinical Message

A dog presented with a retrobulbar mass, diagnosed histopathologically as malignant spindle cell neoplasia. Emergence of analogous findings in the contralateral orbit prompted extended immunohistochemistry of the original mass and reassignment to idiopathic sclerosing orbital inflammation. Early incisional biopsy with extended immunohistochemical analysis should be considered for canine orbital tumors.