bluuebunny/crossref_metadata_2025 huggingface dataset:
An analytical thermohydraulic model for discretely fractured geothermal reservoirs
Authors: Fox Don B. , Koch Donald L. , Tester Jefferson W.
Published: August 2016

In discretely fractured reservoirs such as those found in Enhanced/Engineered Geothermal Systems (EGS), knowledge of the fracture network is important in understanding the thermal hydraulics, i.e., how the fluid flows and the resulting temporal evolution of the subsurface temperature. The purpose of this study was to develop an analytical model of the fluid flow and heat transport in a discretely fractured network that can be used for a wide range of modeling applications and serve as an alternative analysis tool to more computationally intensive numerical codes. Given the connectivity and structure of a fracture network, the flow in the system was solved using a linear system of algebraic equations for the pressure at the nodes of the network. With the flow determined, the temperature in the fracture was solved by coupling convective heat transport in the fracture with one‐dimensional heat conduction perpendicular to the fracture, employing the Green's function derived solution for a single discrete fracture. The predicted temperatures along the fracture surfaces from the analytical solution were compared to numerical simulations using the TOUGH2 reservoir code. Through two case studies, we showed the capabilities of the analytical model and explored the effect of uncertainty in the fracture apertures and network structure on thermal performance. While both sources of uncertainty independently produce large variations in production temperature, uncertainty in the network structure, whenever present, had a predominant influence on thermal performance.
Joint inversion of hydraulic head and self‐potential data associated with harmonic pumping tests
Authors: Soueid Ahmed A. , Jardani A. , Revil A. , Dupont J. P.
Published: August 2016

Harmonic pumping tests consist in stimulating an aquifer by the means of hydraulic stimulations at some discrete frequencies. The inverse problem consisting in retrieving the hydraulic properties is inherently ill posed and is usually underdetermined when considering the number of well head data available in field conditions. To better constrain this inverse problem, we add self‐potential data recorded at the ground surface to the head data. The self‐potential method is a passive geophysical method. Its signals are generated by the groundwater flow through an electrokinetic coupling. We showed using a 3‐D saturated unconfined synthetic aquifer that the self‐potential method significantly improves the results of the harmonic hydraulic tomography. The hydroelectric forward problem is obtained by solving first the Richards equation, describing the groundwater flow, and then using the result in an electrical Poisson equation describing the self‐potential problem. The joint inversion problem is solved using a reduction model based on the principal component geostatistical approach. In this method, the large prior covariance matrix is truncated and replaced by its low‐rank approximation, allowing thus for notable computational time and storage savings. Three test cases are studied, to assess the validity of our approach. In the first test, we show that when the number of harmonic stimulations is low, combining the harmonic hydraulic and self‐potential data does not improve the inversion results. In the second test where enough harmonic stimulations are performed, a significant improvement of the hydraulic parameters is observed. In the last synthetic test, we show that the electrical conductivity field required to invert the self‐potential data can be determined with enough accuracy using an electrical resistivity tomography survey using the same electrodes configuration as used for the self‐potential investigation.
Demand Response at Distribution Grids: Exploiting Flexible Power Electronics Interfaces
Authors: Taylor Zach , Mohsenian‐Rad Hamed , Davoudi Ali
Published: August 2016

We explore the unique opportunities and challenges that arise in developing demand response programs that are intended for power distribution systems. The key is to understand the characteristics of the underlying physical power system, such as whether the distribution system is of type AC or DC. The role of power electronics interfaces are of particular interest in this context. Looking at controllability as a resource for power electronics interfaces, new design potentials are explored and case studies are presented to achieve optimal demand response operation in power distribution systems.
The Socio‐Economics of the Smart Grid – An Introduction
Authors: Pollitt Michael G.
Published: August 2016

This chapter aims to discuss the main socio‐economic issues raised by smart grid developments, drawing on the subsequent chapters in this section. These start with cyber‐security and privacy concerns. The economic benefits of smart grids are examined, focussing on business‐to‐business transactions within the electricity system, the system benefits of dynamic pricing, and the behavioural change opportunities of smart meters. We go on to introduce possible developments in the design of future markets made possible by increased transaction resolution. We then consider possible changes to the future organisation of the electricity distribution sector and the implications of increased smartness for electricity regulation.
Smart Grid Interoperability Standards
Authors: Gunther Erich W.
Published: August 2016

The Smart Grid must necessarily integrate numerous systems and devices that have historically operated autonomously and in silos of automation. These systems and devices generally come from multiple vendors and are deployed independently over long periods of time. The integration of these siloed systems results in a larger system that is more capable than the individual parts. Cost effective, maintainable, and secure integration of these systems requires identifying points of interoperability between these devices and systems where the rules of information exchange are well defined. The rules at the well‐defined points of interoperability are governed by Smart Grid interoperability standards. This chapter explores what is meant by a standard and how that term is often loosely applied to refer to a wide range of interoperability agreements.
Load Modeling
Authors: Terzija Vladimir , Regulski Pawel
Published: August 2016

Load modeling is an important aspect of power system studies and simulations and its role will become even more critical in future smart grids. This chapter summarizes some of the main opportunities and challenges of load modeling in the context of modern power systems and smart grids. Traditional static and dynamic load models are presented as well as power electronics load models to account for harmonic emission of loads. Deterministic and evolutionary computation methods for load model parameters identification are explained and online load modeling with the use of phasor measurement units is presented. The chapter also provides an introduction to the identification of active distribution network equivalents with the use of black box and gray box models. Such equivalents will become crucial in efficient power system simulations. Finally, the chapter discusses the potential of remote load control achieved through local voltage control. This mechanism may play an important role in helping to integrate the highly variable and often unpredictable intermittent renewable generation.
Dynamic‐State Estimation
Authors: Abur Ali
Published: August 2016

Static state estimators have been in use in control centres for over four decades now. Recent availability of synchronized phasor measurements for bus voltages and line currents allows development of dynamic state estimators which can track the frequency and synchronous machine state variables and complement the information provided by static state estimators on the network states. This chapter provides a brief overview of the static state estimation problem followed by an introduction to dynamic state estimation. The problem of dynamic state estimation is formulated and a dynamic state estimator whose implementation lends itself to large size power grids is described. The chapter also contains a discussion of observability analysis for dynamic state estimators which presents additional challenges due to the time varying and nonlinear nature of the system and measurement equations.
FACTS
,
HVDC
, and Supergrid
Authors: Wang Fred , Li Yalong , Shi Xiaojie
Published: August 2016

This chapter presents an overview of flexible AC transmission systems (FACTS), high‐voltage DC (HVDC) transmission, and the supergrid concept. All these technologies and concepts are based on power electronics. Their basic working principles, technology status and limitations, benefits, and applications in electric power grids are introduced. Some of the recent developments including distributed FACTS, partial FACTS, hybrid AC/DC, and DC grids are also discussed.
Grid Monitoring and State Estimation
Authors: McDermott Thomas E.
Published: August 2016

State estimation is a “big data” enabler for any number of “smart grid” applications on the distribution system; these include reactive power management, outage management, loss reduction, demand response, adaptable overcurrent protection, condition‐based maintenance, distributed generation dispatch, integration with transmission system operations, and more. While fully developed on transmission systems, it has been more difficult to apply on distribution because there are not enough redundant sensors and communication capability. Algorithmic developments are also needed. When fully enabled, even more applications are likely to arise. The potential future use of microgrids would increase the value and opportunity for state estimation. In order to enable the full value of state estimation, the requirements and use cases need to be included up front in planning smart grid projects. Otherwise, post‐deployment sensor and communication channel upgrades are likely to be prohibitively expensive. Research continues to develop algorithms and software suited to the special problems of distribution system state estimation, but these are readily deployed when they become available. The real expense lies in the sensor and communication hardware.
Characterization of liquid‐liquid flows in horizontal pipes
Authors: Shi Jing , Yeung Hoi
Published: August 2016

Diverse flow regimes have been encountered in liquid‐liquid flows. Some degree of consistency in the observed flow patterns is shown in reported studies, while inconsistency exits when physical properties of the two phases concerned are wide enough. An attempt was made in this study to investigate the mechanisms behind flow patterns of liquid‐liquid flows in horizontal pipes. A literature review on flow patterns of liquid‐liquid flows in horizontal pipes was conducted. The ratio of the gravitational force to viscous force was proposed to characterize liquid‐liquid flows in horizontal pipes into gravitational force dominant, viscous force dominant, and gravitational force and viscous force comparable flow featured with different basic flow regimes. Comparisons of the proposed characterization criterion with the literature data show good agreement. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1132–1143, 2017
Multimetal‐Substituted Epsilon‐Iron Oxide ϵ‐Ga0.31Ti0.05Co0.05Fe1.59O3 for Next‐Generation Magnetic Recording Tape in the Big‐Data Era
Authors: Ohkoshi Shin‐ichi , Namai Asuka , Yoshikiyo Marie , Imoto Kenta , Tamazaki Kazunori , Matsuno Koji , Inoue Osamu , Ide Tsutomu , Masada Kenji , Goto Masahiro , Goto Takashi , Yoshida Takayuki , Miyazaki Tatsuro
Published: August 2016

From the viewpoints of large capacity, long‐term guarantee, and low cost, interest in magnetic recording tapes has undergone a revival as an archive storage media for big data. Herein, we prepared a new series of metal‐substituted ϵ‐Fe2O3, ϵ‐GaIII0.31TiIV0.05CoII0.05FeIII1.59O3, nanoparticles with an average size of 18 nm. Ga, Ti, and Co cations tune the magnetic properties of ϵ‐Fe2O3 to the specifications demanded for a magnetic recording tape. The coercive field was tuned to 2.7 kOe by introduction of single‐ion anisotropy on CoII (S=3/2) along the c‐axis. The saturation magnetization was increased by 44 % with GaIII (S=0) and TiIV (S=0) substitution through the enhancement of positive sublattice magnetizations. The magnetic tape media was fabricated using an actual production line and showed a very sharp signal response and a remarkably high signal‐to‐noise ratio compared to the currently used magnetic tape.
Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3SiCF2H
Authors: Chen Dingben , Ni Chuanfa , Zhao Yanchuan , Cai Xian , Li Xinjin , Xiao Pan , Hu Jinbo
Published: August 2016

A pentacoordinate bis(difluoromethyl)silicate anion, [Me3Si(CF2H)2]−, is observed for the first time by the activation of Me3SiCF2H with a nucleophilic alkali‐metal salt and 18‐crown‐6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3SiCF2H by using a combination of CsF and 18‐crown‐6 as the initiation system. Mechanistic investigations demonstrate that [(18‐crown‐6)Cs]+[Me3Si(CF2H)2]− is a key intermediate in this catalytic reaction.
Reciprocal Self‐Assembly of Peptide–DNA Conjugates into a Programmable Sub‐10‐nm Supramolecular Deoxyribonucleoprotein
Authors: Kye Mahnseok , Lim Yong‐beom
Published: August 2016

To overcome the limitations of molecular assemblies, the development of novel supramolecular building blocks and self‐assembly modes is essential to create more sophisticated, complex, and controllable aggregates. The self‐assembly of peptide–DNA conjugates (PDCs), in which two orthogonal self‐assembly modes, that is, β‐sheet formation and Watson–Crick base pairing, are covalently combined in one supramolecular system, is reported. Despite extensive research, most self‐assembly studies have focused on using only one type of building block, which restricts structural and functional diversity compared to multicomponent systems. Multicomponent systems, however, suffer from poor control of self‐assembly behaviors. Covalently conjugated PDC building blocks are shown to assemble into well‐defined and controllable nanostructures. This controllability likely results from the decrease in entropy associated with the restriction of the molecular degrees of freedom by the covalent constraints. Using this strategy, the possibility to thermodynamically program nano‐assemblies to exert gene regulation activity with low cytotoxicity is demonstrated.
Paper‐Origami‐Based Multiplexed Malaria Diagnostics from Whole Blood
Authors: Xu Gaolian , Nolder Debbie , Reboud Julien , Oguike Mary C. , van Schalkwyk Donelly A. , Sutherland Colin J. , Cooper Jonathan M.
Published: August 2016

We demonstrate, for the first time, the multiplexed determination of microbial species from whole blood using the paper‐folding technique of origami to enable the sequential steps of DNA extraction, loop‐mediated isothermal amplification (LAMP), and array‐based fluorescence detection. A low‐cost handheld flashlight reveals the presence of the final DNA amplicon to the naked eye, providing a “sample‐to‐answer” diagnosis from a finger‐prick volume of human blood, within 45 min, with minimal user intervention. To demonstrate the method, we showed the identification of three species of Plasmodium, analyzing 80 patient samples benchmarked against the gold‐standard polymerase chain reaction (PCR) assay in an operator‐blinded study. We also show that the test retains its diagnostic accuracy when using stored or fixed reference samples.
Event‐Based Semiglobal Consensus of Homogenous Linear Multi‐Agent Systems Subject to Input Saturation
Authors: Zhou Bo , Liao Xiaofeng , Huang Tingwen , Li Huaqing , Chen Guo
Published: August 2016

In this paper, we consider the semiglobal leader‐following consensus of general linear multi‐agent systems subject to input saturation. First, an event‐triggered control protocol is provided to ensure semiglobal consensus of the multi‐agent systems, in which the agents should continuously monitor the information of their neighbors. Second, a self‐triggered control protocol is proposed to guarantee the semiglobal consensus of the multi‐agent systems, in which the agents only have access to the information of their neighbors in discrete time instants. Moreover, both event‐triggered control protocol and self‐triggered control protocol are proved to be Zeno‐free, that is, the inter‐event times for such two protocols have positive lower bounds. Finally, two numerical examples are provided to illustrate the effectiveness of the proposed event‐based semiglobal consensus protocols.
Cloning and characterization of novel cyclotides genes from South American plants
Authors: Cunha Nicolau Brito da , Barbosa Aulus Estevão Anjos de Deus , de Almeida Renato Goulart , Porto William Farias , Maximiano Mariana Rocha , Álvares Luana Cristina Silva , Munhoz Cassia Beatriz Rodrigues , Eugênio Chesterton Ulysses Orlando , Viana Antônio Américo Barbosa , Franco Octavio Luiz , Dias Simoni Campos
Published: August 2016

Cyclotides are multifunctional plant cyclic peptides containing 28‐37 amino acid residues and a pattern of three disulfide bridges, forming a motif known as the cyclic cystine knot. Due to their high biotechnological potential, the sequencing and characterization of cyclotide genes are crucial not only for cloning and establishing heterologous expression strategies, but also to understand local plant evolution in the context of host‐pathogen relationships. Here, two species from the Brazilian Cerrado, Palicourea rigida (Rubiaceae) and Pombalia lanata (A.St.‐Hil.) Paula‐Souza (Violaceae), were used for cloning and characterizing novel cyclotide genes. Using 3′ and 5′ RACE PCR and sequencing, two full cDNAs, named parigidin‐br2 (P. rigida) and hyla‐br1 (P. lanata), were isolated and shown to have similar genetic structures to other cyclotides. Both contained the conserved ER‐signal domain, N‐terminal prodomain, mature cyclotide domain and a C‐terminal region. Genomic sequencing of parigidin‐br2 revealed two different gene copies: one intronless allele and one presenting a rare 131‐bp intron. In contrast, genomic sequencing of hyla‐br1 revealed an intronless gene—a common characteristic of members of the Violaceae family. Parigidin‐br2 5′ and 3′ UTRs showed the presence of 12 putative candidate sites for binding of regulatory proteins, suggesting that the flanking and intronic regions of the parigidin‐br2 gene must play important roles in transcriptional rates and in the regulation of temporal and spatial gene expression. The high degree of genetic similarity and structural organization among the cyclotide genes isolated in the present study from the Brazilian Cerrado and other well‐characterized plant cyclotides may contribute to a better understanding of cyclotide evolution.
Accounting for host cell protein behavior in anion‐exchange chromatography
Authors: Swanson Ryan K. , Xu Ruo , Nettleton Daniel S. , Glatz Charles E.
Published: August 2016

Host cell proteins (HCP) are a problematic set of impurities in downstream processing (DSP) as they behave most similarly to the target protein during separation. Approaching DSP with the knowledge of HCP separation behavior would be beneficial for the production of high purity recombinant biologics. Therefore, this work was aimed at characterizing the separation behavior of complex mixtures of HCP during a commonly used method: anion‐exchange chromatography (AEX). An additional goal was to evaluate the performance of a statistical methodology, based on the characterization data, as a tool for predicting protein separation behavior. Aqueous two‐phase partitioning followed by two‐dimensional electrophoresis provided data on the three physicochemical properties most commonly exploited during DSP for each HCP: pI (isoelectric point), molecular weight, and surface hydrophobicity. The protein separation behaviors of two alternative expression host extracts (corn germ and E. coli) were characterized. A multivariate random forest (MVRF) statistical methodology was then applied to the database of characterized proteins creating a tool for predicting the AEX behavior of a mixture of proteins. The accuracy of the MVRF method was determined by calculating a root mean squared error value for each database. This measure never exceeded a value of 0.045 (fraction of protein populating each of the multiple separation fractions) for AEX. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1453–1463, 2016
Highly Active Carbon/α‐MnO2 Hybrid Oxygen Reduction Reaction Electrocatalysts
Authors: Chen Gao , Sunarso Jaka , Zhu Yanping , Yu Jie , Zhong Yijun , Zhou Wei , Shao Zongping
Published: August 2016

Manganese oxides are attractive catalyst candidates for the oxygen reduction reaction (ORR) given their natural abundance and low toxicity. α‐MnO2, in particular, exhibits high ORR activity in an alkaline medium. The hybrid concept provides a way to obtain enhanced ORR performance and long‐term durability through an optimized metal oxide–support interaction. Herein, we synthesized a carbon nanotube (CNT)–graphene–α‐MnO2 hybrid in a hydrothermal reaction in which the MnO2 nanosheets were deposited on the interior and exterior surfaces of the CNT channels. The resultant hybrid displayed very high ORR activity that is only marginally less than the performance of a commercial 20 wt % Pt/C catalyst and showed even better stability. The excellent ORR activity was attributed to two main factors, that is, the mesoporous architecture of the catalyst and the strong electron coupling between the encapsulated metal oxide and the support. We also showed that the preferential deposition of MnO2 nanosheets within the CNT channels provides enhanced ORR performance relative to deposition on the exterior surfaces of the channels only. This in turn demonstrates unequivocally the confinement effect that the CNT exerts on the encapsulated metal oxide component, which can be exploited as a route to enhanced ORR activity.
Photoluminescence in Carborane–Stilbene Triads: A Structural, Spectroscopic, and Computational Study
Authors: Cabrera‐González Justo , Viñas Clara , Haukka Matti , Bhattacharyya Santanu , Gierschner Johannes , Núñez Rosario
Published: August 2016

A set of triads in which o‐ and m‐carborane clusters are bonded to two stilbene units through Ccluster−CH2 bonds was synthesized, and their structures were confirmed by X‐ray diffraction. A study on the influence of the o‐ and m‐ isomers on the absorption and photoluminescence properties of the stilbene units in solution revealed no charge‐transfer contributions in the lowest excited state, as confirmed by (TD)DFT calculations. The presence of one or two B−I groups in m‐carborane derivatives does not affect the emission properties of the stilbenes in solution, probably due to the rather large distance between the iodo substituents and the fluorophore. Nevertheless, a significant redshift of the photoluminescence (PL) emission maximum in the solid state (thin films and powder samples) compared to solution was observed; this can be traced back to PL sensitization, most probably due to more densely packed stilbene moieties. Remarkably, the PL absolute quantum yields of powder samples are significantly higher than those in solution, and this was attributed to the restricted environment and the aforementioned sensitization. Thus, the bonding of the carborane clusters to two stilbene units preserves their PL behavior in solution, but produces significant changes in the solid state. Furthermore, iodinated species can be considered to be promising precursors for theranostic agents in which both imaging and therapeutic functions could possibly be combined.
Effect of Inter‐Porphyrin Distance on Spin‐State in Diiron(III) μ‐Hydroxo Bisporphyrins
Authors: Sil Debangsu , Khan Firoz Shah Tuglak , Rath Sankar Prasad
Published: August 2016

The synthesis, structure, and properties of bischloro, μ‐oxo, and a family of μ‐hydroxo complexes (with BF4−, SbF6−, and PF6− counteranions) of diethylpyrrole‐bridged diiron(III) bisporphyrins are reported. Spectroscopic characterization has revealed that the iron centers of the bischloro and μ‐oxo complexes are in the high‐spin state (S=5/2). However, the two iron centers in the diiron(III) μ‐hydroxo complexes are equivalent with high spin (S=5/2) in the solid state and an intermediate‐spin state (S=3/2) in solution. The molecules have been compared with previously known diiron(III) μ‐hydroxo complexes of ethane‐bridged bisporphyrin, in which two different spin states of iron were stabilized under the influence of counteranions. The dimanganese(III) analogues were also synthesized and spectroscopically characterized. A comparison of the X‐ray structural parameters between diethylpyrrole and ethane‐bridged μ‐hydroxo bisporphyrins suggest an increased separation, and hence, less interactions between the two heme units of the former. As a result, unlike the ethane‐bridged μ‐hydroxo complex, both iron centers become equivalent in the diethylpyrrole‐bridged complex and their spin state remains unresponsive to the change in counteranion. The iron(III) centers of the diethylpyrrole‐bridged diiron(III) μ‐oxo bisporphyrin undergo very strong antiferromagnetic interactions (J=−137.7 cm−1), although the coupling constant is reduced to only a weak value in the μ‐hydroxo complexes (J=−42.2, −44.1, and −42.4 cm−1 for the BF4, SbF6, and PF6 complexes, respectively).
Photoisomerization Mechanism of Ruthenium Sulfoxide Complexes: Role of the Metal‐Centered Excited State in the Bond Rupture and Bond Construction Processes
Authors: Li Huifang , Zhang Lisheng , Zheng lvyin , Li Xun , Fan Xiaolin , Zhao Yi
Published: August 2016

Phototriggered intramolecular isomerization in a series of ruthenium sulfoxide complexes, [Ru(L)(tpy)(DMSO)]n+ (where tpy=2,2’:6’,2’’‐terpyridine; DMSO=dimethyl sulfoxide; L=2,2’‐bipyridine (bpy), n=2; N,N,N’,N’‐tetramethylethylenediamine (tmen) n=2; picolinate (pic), n=1; acetylacetonate (acac), n=1; oxalate (ox), n=0; malonate (mal), n=0), was investigated theoretically. It is observed that the metal‐centered ligand field (3MC) state plays an important role in the excited state S→O isomerization of the coordinated DMSO ligand. If the population of 3MCS state is thermally accessible and no 3MCO can be populated from this state, photoisomerization will be turned off because the 3MCS excited state is expected to lead to fast radiationless decay back to the original 1GSS ground state or photodecomposition along the Ru2+−S stretching coordinate. On the contrary, if the population of 3MCS (or 3MCO) state is inaccessible, photoinduced S→O isomerization can proceed adiabatically on the potential energy surface of the metal‐to‐ligand charge transfer excited states (3MLCTS→3MLCTO). It is hoped that these results can provide valuable information for the excited state isomerization in photochromic d6 transition‐metal complexes, which is both experimentally and intellectually challenging as a field of study.
Cyclobuteno[60]fullerenes as Efficient n‐Type Organic Semiconductors
Authors: Reboredo Silvia , Girón Rosa M. , Filippone Salvatore , Mikie Tsubasa , Sakurai Tsuneaki , Seki Shu , Martín Nazario
Published: August 2016

Cyclobuteno[3,4:1,2][60]fullerenes have been prepared in a straightforward manner by a simple reaction between [60]fullerene and readily available allenoates or alkynoates as organic reagents under basic and mild conditions. The chemical structure of the new modified fullerenes has been determined by standard spectroscopic techniques and confirmed by X‐ray diffraction analysis. Some of these new fullerene derivatives exhibit a remarkable intrinsic electron mobility (determined by using flash‐photolysis time‐resolved microwave conductivity (FP‐TRMC) measurements), which surpasses that of the well‐known phenyl‐C61‐butyric acid methyl ester, thus behaving as promising n‐type organic semiconductors.
Atomic and Ionic Radii of Elements 1–96
Authors: Rahm Martin , Hoffmann Roald , Ashcroft N. W.
Published: August 2016

Atomic and cationic radii have been calculated for the first 96 elements, together with selected anionic radii. The metric adopted is the average distance from the nucleus where the electron density falls to 0.001 electrons per bohr3, following earlier work by Boyd. Our radii are derived using relativistic all‐electron density functional theory calculations, close to the basis set limit. They offer a systematic quantitative measure of the sizes of non‐interacting atoms, commonly invoked in the rationalization of chemical bonding, structure, and different properties. Remarkably, the atomic radii as defined in this way correlate well with van der Waals radii derived from crystal structures. A rationalization for trends and exceptions in those correlations is provided.
Photo‐induced Carboiodination: A Simple Way to Synthesize Functionalized Dihydrobenzofurans and Indolines
Authors: Yang Xiaobo , Liu Wenbo , Li Lu , Wei Wei , Li Chao‐Jun
Published: August 2016

Herein, we report a simple, redox‐neutral and pH‐neutral photo‐induced carboiodination reaction under very mild conditions. This protocol employs readily available and cheap aryl bromides and sodium iodide as the starting materials to synthesize valuable functionalized dihydrobenzofurans and indolines in good to excellent yields with broad functional‐group compatibility. As examples to demonstrate the utility of this protocol, gram‐scale reactions and further transformations of the products were accomplished towards the synthesis of bioactive drug candidates. Most significantly, to the best of our knowledge, this reaction represents the first example of a cascade atom‐radical‐transfer addition involving the cleavage of aromatic C−Br bond.
Catalyst‐Guided C=Het Hydroarylations by Manganese‐Catalyzed Additive‐Free C−H Activation
Authors: Liang Yu‐Feng , Massignan Leonardo , Liu Weiping , Ackermann Lutz
Published: August 2016

Expedient hydroarylations of C=Het bonds (Het=heteroatom) were accomplished by user‐friendly organometallic C−H activation in a positional‐selective manner. The broadly applicable C−H functionalization platform enabled the step‐economical transformation of aldehydes, ketones, and imines under additive‐free reaction conditions. In contrast to palladium, rhodium, ruthenium, rhenium, iridium, nickel, and cobalt catalysis, solely manganese(I) complexes outcompeted the innate substrate control, clearly highlighting the unique power of manganese(I) C−H activation catalysis.
Synthesis of Fluorine‐Doped Hydrophilic Carbon Nanoparticles from Hexafluorobenzene by Femtosecond Laser Pulses
Authors: Okamoto Takuya , Mitamura Koji , Hamaguchi Tomoyuki , Matsukawa Kimihiro , Yatsuhashi Tomoyuki
Published: August 2016

We report on the preparation and characterization of fluorine‐doped hydrophilic carbon nanoparticles by the exposure of hexafluorobenzene or a water/hexafluorobenzene bilayer solution to femtosecond laser pulses. Uniform atom distributions are achieved not only on the particle surface but also inside the particles. The semi‐ionic character of C−F bonds and the non‐aggregating feature of the nanoparticles play key roles in the water‐dispersible character of fluorine‐doped carbon nanoparticles. We suggest the following building‐up process of carbon nanoparticles: the fragmentation of hexafluorobenzene initiated by the electrons generated in laser‐induced plasma followed by the reconstruction of a carbon framework of nanoparticles.
Self‐Assembled 1D‐Nanowire Lasers of Perylenediimides
Authors: Yu Zhenyi , Wu Yishi , Zhang Haihua , Wang Xuedong , Chen Jianwei , Yao Jiannian , Fu Hongbing
Published: August 2016

The 1D nanostructures of perylenediimides (PDIs) have been readily obtained owing to strong cofacial π–π stacking interactions, which, however, subsequently render PDIs weakly emissive in the solid state. Therefore, organic solid‐state lasers based on 1D nanostructures of PDIs have not been achieved yet. Herein, we prepared 1D‐nanowires of N,N’‐bis(1‐ethylpropyl)‐2,5,8,11‐tetrakis(o‐methylphenyl)‐perylene‐3,4:9,10‐tetracarboxylic acid diimide (mp‐PDI), which stack into a loosely J‐type arrangement. J‐aggregation leads to a solid‐state photoluminescence (PL) efficiency φ>18 % and the nanowires of mp‐PDI exhibit excellent Fabry–Perot (FP) mode laser action.
Identifying clinically relevant sources of variability: The clopidogrel challenge
Authors: Samant S , Jiang XL , Peletier LA , Shuldiner AR , Horenstein RB , Lewis JP , Lesko LJ , Schmidt S
Published: August 2016

High interindividual variability in clinical outcomes following clopidogrel's standard dosing regimen continues to be a challenge even two decades after its approval. CYP2C19 polymorphisms, obesity, older age, diabetes, and drug–drug interactions have been identified as risk factors for adverse events and treatment failure. We conducted a mechanism‐based pharmacokinetic/pharmacodynamic analysis, where we integrated knowledge on in vitro enzyme kinetic, physiological, genetic, and demographic information to characterize changes in platelet reactivity from baseline following clopidogrel antiplatelet therapy. When considering the combined impact of these covariates, our analysis results indicate that higher maintenance doses are required for CYP2C19 intermediate metabolizers and poor metabolizers compared to extensive metabolizers and that respective maintenance doses have to be further increased for obese subjects for each of these CYP2C19 phenotypes. In addition, interindividual differences in the fraction absorbed and the CES1 activity were identified as sources of interindividual differences in clopidogrel's active metabolite concentrations and, thus, platelet reactivity.
Electron Transport Layer‐Free Solar Cells Based on Perovskite–Fullerene Blend Films with Enhanced Performance and Stability
Authors: Pascual Jorge , Kosta Ivet , Tuyen Ngo T. , Chuvilin Andrey , Cabanero German , Grande Hans J. , Barea Eva M. , Mora‐Seró Iván , Delgado Juan Luis , Tena‐Zaera Ramon
Published: August 2016

The solution processing of pinhole‐free methylammonium lead triiodide perovskite–C70 fullerene (MAPbI3:C70) blend films on fluorine‐doped tin oxide (FTO)‐coated glass substrates is presented. Based on this approach, a simplified and robust protocol for the preparation of efficient electron‐transport layer (ETL)‐free perovskite solar cells is described. Power conversion efficiency (PCE) of 13.6 % under AM 1.5 G simulated sunlight is demonstrated for these devices. Comparative impedance spectroscopy and photostability analysis of the MAPbI3:C70 and single MAPbI3 films compared with conventional compact TiO2 ETL‐based devices are shown. The beneficial impact of using MAPbI3:C70 blend films is emphasized.
Extending the Lifetime of Perovskite Solar Cells using a Perfluorinated Dopant
Authors: Salado Manuel , Ramos F. Javier , Manzanares Valentin M. , Gao Peng , Nazeeruddin Mohammad Khaja , Dyson Paul J. , Ahmad Shahzada
Published: August 2016

The principle limitation of perovskite solar cells is related to their instability and, hence, their limited lifetime. Herein, we employ an imidazolium iodide dopant, 1‐methyl‐3‐(1H,1H,2H,2H‐nonafluorohexyl)‐imidazolium iodide, containing a perfluorous appendage, which leads to prolonged (unencapsulated, under Ar atmosphere) device activities exceeding 100 days without compromising the power conversion efficiency and other photovoltaic parameters. The extended lifetime of the device can be attributed, at least in part, to the hydrophobic nature of the imidazolium iodide salt. The functionalization of the perovskite material was found to have negligible influence on the perovskite crystal structure.
Take care reclassifying employee status per updates to FLSA regs
Authors: Porter Michael
Published: August 2016

The U.S. Department of Labor published much‐anticipated regulations concerning overtime eligibility under the Fair Labor Standards Act on May 23.
Role of fine needle aspiration biopsy cytology in the diagnosis of infections
Authors: Field Andrew S. , Geddie William R.
Published: August 2016

The role of fine needle aspiration biopsy (FNAB) cytology in diagnosing infections has expanded due to the increase in the number of immune compromised patients and the increasing role of FNAB in the developing world where infection is a major cause of illness. FNAB has become the first procedural test in cases where the clinical and imaging findings suggest an infectious lesion or where there is a differential diagnosis of infection or metastatic or primary tumor. This applies to FNAB of palpable or image directed or deep seated lesions accessed by EUS and EBUS. This article details a recommended approach and technique for FNAB of infectious lesions, and discusses the role of rapid on site evaluation and the application of ancillary testing including the rapidly expanding array of molecular tests based on FNAB material. The utility of recognizing suppurative and granulomatous infectious patterns in FNAB direct smears, and the specific cytomorphological features on routine Papanicolaou and Giemsa stains and on special stains of FNAB smears is described for a large number of bacterial, fungal, viral, parasitic, and protozoan infections. The role of cytopathologists is to now train cytopathologists in sufficient numbers to provide FNAB services, teach trainee cytopathologists and cytotechnologists, and to encourage our clinical colleagues to use FNAB in the diagnosis of infections and other lesions to the benefit of patients and the medical system. Diagn. Cytopathol. 2016;44:1024–1038. © 2016 Wiley Periodicals, Inc.
Effect of acute stressor on reproductive behavior differs between urban and rural birds
Authors: Abolins‐Abols Mikus , Hope Sydney F. , Ketterson Ellen D.
Published: August 2016

The life‐history trade‐off between self‐maintenance and reproduction posits that investment in one function decreases investment in the other. Manipulating the costs and benefits of functions involved in a trade‐off may alter this interaction. Here we ask whether investment in self‐maintenance during a stress response alters territorial behavior in wild Dark‐eyed Juncos and whether rural and urban birds, which are known to differ in the magnitude of the stress response (greater in rural), also differ in the degree to which stress reduces territorial behavior. In rural and urban habitats, we measured territorial behavior using song playback, followed by either an acute stressor (capture and collection of a blood sample) or a nonstressful control situation. The following day, we again measured territorial behavior, predicting greater reduction in territorial behavior in individuals exposed to the stressor but a lesser reduction in territorial behavior in the urban as compared to the rural environment. We further assessed individual and population differences in response to stressors by measuring flight initiation distance, breath rate, and corticosterone levels in the blood. The rural population had a higher physiological and behavioral stress response than the urban population, and acute capture stress had a lasting (24 h) negative effect on territorial behavior, but only in the rural habitat. However, individual‐level differences in measures of the stress response did not explain variation in the impact of stress on territorial behavior. Our findings show that stressors can have a negative effect on territorial behavior, but that this effect may differ between populations that vary in their stress ecology.
Transition‐Metal Complexes with Ferrocene‐Bridged Bis(imidazolin‐2‐imine) and Bis(diaminocyclopropenimine) Ligands
Authors: Jess Kristof , Baabe Dirk , Freytag Matthias , Jones Peter G. , Tamm Matthias
Published: August 2016

The reaction of the ferrocene‐bridged bis(imidazolin‐2‐imine) ligandN,N′‐bis(1,3‐diisopropyl‐4,5‐dimethylimidazolin‐2‐ylidene)‐1,1′‐ferrocenediamine [fc(NIm)2] with MCl2salts furnished the complexes [{fc(NIm)2}MCl2] (M = Mn, Fe, Co, Ni, Cu, Zn), which were structurally and spectroscopically characterized. The iron complex was oxidized by reaction with ferrocenium hexafluoroantimonate, and both compounds, [{fc(NIm)2}FeCl2] and [{fc(NIm)2}FeCl2]SbF6, were further studied by means of Mössbauer spectroscopy, SQUID magnetometry, and single‐crystal X‐ray diffraction, revealing that oxidation occurred at the tetrahedral FeN2Cl2moiety. The CuX (X = Cl, Br, I) complexes of fc(NIm)2were synthesized, affording dimeric (X = Cl, Br) or polymeric (X = I) structures. In addition, the ligand bis(N,N,N′,N′‐tetraisopropyl‐2,3‐diaminocyclopropen‐1‐ylidene)‐1,1′‐ferrocenediamine [fc(NCyp)2], was prepared and the trimetallic complex [{fc(NCyp)2}Pd2Cl4] was synthesized and structurally characterized. The attempted synthesis of the corresponding nickel complex furnished single crystals of the composition [{fc(NHCyp)2}Cl(NiCl3)]; X‐ray diffraction analysis afforded the first crystal structure of the [Ni2Cl6]2–anion.
Fatty acid composition in the fillets of rainbow trout grown in different conditions
Authors: Krstić Milena P. , Mitrović Radmila R. , Marković Radmila V. , Ivanović Jelena S. , Ćirković Miroslav A. , Djordjević Vesna Ž. , Baltić Milan Ž.
Published: August 2016

The aim of this study was to determine the influence of different feed composition and cultivation on the composition of fatty acids, their relationships, and the cholesterol content in the tissue of rainbow trout (Oncorhynchus mykiss). Trout were reared in ponds at two different altitudes and raised on different feeds. The total amount of monounsaturated fatty acids in fillets of both groups showed no statistically significant difference. However, higher levels of n‐6 fatty acids were found in Pond I trout fillets than in Pond II fillets, while Pond II fillets contained almost even amounts of n‐3 and n‐6 fatty acids. Total cholesterol content in Pond I trout fillets was significantly lower (p < 0.05) than in Pond II fillets. The results indicate that the final composition of the trout fillets was mostly dependent on the feed the live fish had consumed; the altitude of the ponds had less effect. Also, both groups of trout could be used in the human diet as biologically valuable foods.

Practical application: Our results show influence of altitude, feed, and fatty acid composition of feed on trout fillets. The average fatty acid level in the trout fillets increased in the order SFA <MUFA <PUFA. Trout fillets contain low levels of cholesterol but high levels of EPA, DPA, and DHA. These facts are important for fish industries and aquaculture producers to design a healthy food.

The trout, although grown at two different altitudes, showed differences in their basic chemical composition and in their fatty acid composition which more tended to be related to the composition of their feed. Low cholesterol levels and high levels of EPA, DPA, and DHA, as well as reasonably favorable ratios of n‐3 and n‐6 fatty acids indicate that the trout from both groups could be suitable for use in the human diet as biologically valuable foods.
2‐Oxo‐Driven Coupling Reactions of 2‐Oxo Aldehydes/2‐Oxo Iminium Ions and Hydroperoxides at Room Temperature
Authors: Khan Shahnawaz , Ahmed Qazi Naveed
Published: August 2016

An efficient 2‐oxo‐group‐promoted direct coupling reaction between 2‐oxo aldehydes and hydroperoxides has been developed. The method has been used successfully for the generation of different 2‐oxo esters and acids. This reaction harnesses the hydrogen‐bonding‐induced self‐decomposition tendency of hydroperoxides; the intermediates produced by this process then attack the aldehyde or iminium ion to generate cross‐coupled products either by direct coupling or by an amine‐catalysed pathway. No external oxidants or metal catalysts are required for our method, and the reaction takes place at room temperature.
Understanding the Scope of Feist–Bénary Furan Synthesis: Chemoselectivity and Diastereoselectivity of the Reaction Between α‐Halo Ketones and β‐Dicarbonyl Compounds
Authors: Peng Yi , Luo Juan , Feng Qiang , Tang Qiang
Published: August 2016

Feist–Bénary furan synthesis, the reaction between α‐halocarbonyl and β‐dicarbonyl compounds, has been known as an efficient method for generating many different types of furans containing a carbonyl group at C‐3. However, it has also been reported that, under similar reaction conditions, intermediate tricarbonyl species could be further converted to alternative furan isomers through the application of a Paal–Knorr synthesis. In this manuscript, we investigate the chemoselectivity and diastereoselectivity of furan synthesis from α‐halo ketones and β‐dicarbonyl compounds, by carrying out the separation and characterization of the intermediates involved in the reaction. Additionally, a one‐pot Feist–Bénary furan synthesis from α‐halo ketones and β‐dicarbonyl compounds without any base or solvent has also been developed.
Radical Cascade Cyclization: Reaction of 1,6‐Enynes with Aryl Radicals by Electron Catalysis
Authors: Xuan Jun , Gonzalez‐Abradelo Dario , Strassert Cristian Alejandro , Daniliuc Constantin‐Gabriel , Studer Armido
Published: August 2016

The radical cascade cyclization of various 1,6‐enynes with aryl radicals by electron catalysis under metal‐free reaction conditions was explored. Readily available anilines were used as radical precursors, and the reactions proceeded in the absence of any transition metal. These cascades comprise three C–C bond formations, which provide polycyclic structures with extended π‐systems. The photophysical properties of some of these novel compounds were investigated, and a plausible reaction mechanism is proposed.
Low Temperature Complete Combustion of Lean Methane over Cobalt–Nickel Mixed‐Oxide Catalysts
Authors: Shao Chunyu , Li Wenzhi , Lin Qizhao , Huang Qifu , Pi Dong
Published: August 2016

Cobalt–nickel mixed oxides with different Co/Ni molar ratios were prepared by co‐precipitation and used for the catalytic combustion of lean methane. The catalytic performances for methane combustion were evaluated at steady‐state conditions at temperatures ranging from 250 to 500 °C, which were increased in step sizes of 25 °C. Among the catalysts, the cobalt–nickel mixed‐oxide catalysts with an appropriate Co/Ni ratio exhibit a high catalytic performance for the lean methane combustion, with the catalyst having a Co/Ni molar ratio of 1:4 showing the highest catalytic activity (methane conversion reached 100 % at 425 °C). On the basis of TEM and XRD results, the nanoparticles of the catalysts have a suitable interparticle spacing and more crystal defects. X‐ray photoelectron spectroscopy (XPS) results reveal a high number of surface‐active oxygen species and appropriate aliovalent cobalt ion numbers in the catalysts for high catalytic activity. All these effects contribute to the outstanding performance of these catalysts in the combustion of lean methane at low temperatures.