bluuebunny/crossref_metadata_2025 huggingface dataset:
A Study on Social Competence and Temperament of Pre-School Children’s
Authors: Pekdogan Serpil , Kanak Mehmet
Published: September 2016

The purpose of this research is to explore the social competence and temperament of 4-6 age group children attending pre-school education institutions, to identify whether their social competence levels vary by gender, and to show the relationship between the sub-dimensions of social competence and those of temperament. The study group consists of n=148 female children and n=180 male children in 4-6 age group receiving pre-school education. The data were collected via the Social Competence and Behavior Evaluation Scale-SCBE 30 and the Short Temperament Scale for Children. The data were analyzed via independent-samples t-test and Pearson’s correlation coefficient. The findings were evaluated at .05-.001 significance level. The research findings indicated that children’s social competence levels significantly vary by gender (p<05), and there are positive and negative significant relationships between the sub-dimensions of social competence and those of temperament (p<.05, p<.001). The findings of the research were discussed in the light of some research and literature, some suggestions have been made.
An Integration of GIS and Simulation Models for a Cost Benefit Analysis of Irrigation Development
Authors: Ghimire Monika , Stoecker Art , Boyer Tracy A. , Bhavsar Hiren , Vitale Jeffrey
Published: September 2016

This study incorporates spatially explicit geographic information system and simulation models to develop an optimal irrigation system. The purpose of the optimized irrigation system was to save depleted ground water supplies. ArcGIS was used to calculate the area of potential irrigable soils, and EPANET (a hydrological simulation program) was used to calculate energy costs. Crop yield response functions were used to estimate the yield of cotton to the amount of irrigation and the accumulation of soil salinity over a 50-year period. Four irrigation designs (A, B, C, and D) were analyzed with different irrigation schedules.

Design A allowed all producers to irrigate simultaneously at 600 gallons per minute (gpm) or 2,271 liters per minute (lpm) while designs B and C divided the irrigable areas into two parts. Design D divided the areas into four parts to allow producers to irrigate one part at a time at 800 gpm (3,028 lpm). Irrigation scheduling not only lessened the water use and cost, but also amplified the profitability of the irrigation system. In design A, if all producers adopted 600 gpm (2,271 lpm) pivots and operated simultaneously, the cost of the 360,000 gpm (1363,000 lpm) pipeline would be prohibitive. In contrast, designs B, C, and D increased net benefits and lowered the breakeven price of cotton. The 50-year net present value for designs A, B, C, and D was profitable over 75, 70, 70, and 65 cents of cotton price per pound (454 g), respectively. Thus, this study endorses irrigation scheduling as a tool for efficient irrigation development and management, and increases water conservation.
Feitelijk leidinggeven
Authors: Hornman M.J.
Published: September 2016

Feitelijk leidinggeven

In diens recente overzichtsarrest blijft de Hoge Raad in weerwil van tegengeluiden vanuit de lagere rechtspraak en de literatuur vasthouden aan het opzetvereiste voor feitelijk leidinggeven. Daarmee wordt het deelnemingskarakter van deze aansprakelijkheidsfiguur nogmaals bevestigd. Die bevestiging is geheel terecht, maar het (waarschijnlijk onbedoelde neven)gevolg van de huidige benadering van dat opzetvereiste is wel dat de ondermaats presterende leidinggevende beter af is dan zijn normconform of bovenmaats presterende collega. Dit specifieke punt vergt nog redressering door de Hoge Raad en zou verholpen kunnen worden door een meer zorgplichtgerichte benadering van voorwaardelijk opzet.
Het nemo-teneturbeginsel en de verhouding met de Wet herziening strafbaarstelling faillissementsfraude
Authors: van Gelder E.M. , van Toor D.A.G.
Published: September 2016

Het nemo-teneturbeginsel en de verhouding met de Wet herziening strafbaarstelling faillissementsfraude.Een analyse naar de verhouding tussen het nemo-teneturbeginsel en nieuwe strafbaarstellingen van de meld- en inlichtingenplicht uit de Wet herziening strafbaarstelling faillissementsfraude

In dit artikel worden de nieuwe strafbaarstellingen uit de Wet herziening strafbaarstelling faillissementsfraude, inhoudende een inlichtingen- en administratieplicht, in het licht van het nemo-teneturbeginsel geanalyseerd. Deze strafbaarstellingen verplichten de failliet inlichtingen en administratie over te dragen aan de curator op straffe van een gevangenisstraf. De vraag is of deze strafbaarstellingen de Straatsburgse toets kunnen doorstaan.
Witwassen, ontneming & fiscale delicten anno 2016
Authors: Huygen van Dyck-Jagersma V.S.
Published: September 2016

Witwassen, ontneming & fiscale delicten anno 2016. De complicaties bij witwassen & ontneming van voordelen uit belastingfraude

Ontneming van voordelen uit belastingfraude leidt niet zelden tot complicaties. Niet-betaalde belasting levert een voordeel uit misdrijf op dat kan worden witgewassen. Waar de onbetaalde belasting zich in het vermogen bevindt, kan niet exact worden aangewezen. Het gehele vermogen wordt zodoende ‘besmet’, maar dat betekent nog niet dat het gehele (groten)deels legale vermogen ook als ‘uit misdrijf afkomstig’ kan worden ontnomen. Voor de reikwijdte van de ontnemingsmaatregel is ook de specifieke kwalificatie als opbrengsten uit fiscale delicten van belang, aangezien die niet via de strafrechtelijke route maar alleen via belastingheffing mogen worden ‘ontnomen’. Tot slot betoogt de auteur dat legaliteit en rechtszekerheid aan de ontneming voor verjaarde (fiscale) delicten in de weg zou moeten staan.
Aldomà, Ignasi (dir.) (2015). L’actualitat del món rural: Els anys de la gran crisi a la Catalunya rural, 2008-2015
Authors: Garcia i González Mireia
Published: September 2016

Aldomà, Ignasi (dir.) (2015)L’actualitat del món rural: Els anys de la gran crisi a la Catalunya rural, 2008-2015Lleida: Fundació del Món Rural, 106 p.ISBN 978-84-608-2204-2
Nova ruralitat a Catalunya a les últimes dècades: diversificació, emprenedoria i ocupació
Authors: Viladomiu Lourdes , Rosell Jordi
Published: September 2016

L’objectiu de l’article és caracteritzar alguns vectors de la nova ruralitat i assenyalar com això s’ha concretat en la diversificació, l’emprenedoria i les oportunitats laborals de la Catalunya rural a les últimes tres dècades. Per a la realització de l’article hem utilitzat els resultats de diversos projectes de recerca (Canvi rural a Europa, Ideas, Ruremplo, Emprenedoria rural, Rudona, etc.) que, si bé no s’orientaven directament al tema, sí que contenien elements rellevants per a l’anàlisi.A la nova ruralitat catalana, el sector agrari i el model de modernització tradicional agrària han perdut protagonisme en benefici d’una economia més diversificada. Aquesta diversificació s’ha basat molt sovint en les explotacions agràries que han incorporat noves activitats en proporcionar llocs de treball per a les dones i facilitar la seva continuïtat. En paral·lel, nous emprenedors rurals han contribuït a un canvi incorporant activitats que han trobat en les noves tecnologies de la informació i la comunicació (TIC) un aliat important. Però, a més a més, en aquestes ultimes dècades les polítiques de reequilibri territorial, les polítiques de desenvolupament rural impulsades des d’Europa i l’estat del benestar han proporcionat llocs de treball que avui són un element fonamental de la nova ruralitat catalana.
Kull, Michael (2014). European integration and rural development. Actors, institutions and power
Authors: Ricart Casadevall Sandra
Published: September 2016

Kull, Michael (2014)European integration and rural development. Actors, institutions and powerFarnham (England): Ashgate Publishing Limited, 188 p.ISBN 978-14-094-6854-7
López García, Daniel (2015). Producir alimentos, reproducir comunidad. Redes alimentarias alternativas como formas económicas para la transformación social y ecológica
Authors: Espluga Trenc Josep
Published: September 2016

López García, Daniel (2015)Producir alimentos, reproducir comunidad. Redes alimentarias alternativas como formas económicas para la transformación social y ecológicaMadrid: Libros en Acción, 198 p.ISBN 978-84-944051-3-6
Analytical Dependence Relations of Converting Geodetic Coordinates Into UTM Coordinates Recommended in Hydrographic Work
Authors: Morgaś Wacław , Kopacz Zdzisław
Published: September 2016

This article presents mathematical dependence relations used for direct conversion of geodetic coordinates into UTM (Universal Transverse Mercator) and inverse conversion recommended by military standards. It mainly focuses on some formulas taken from the National Geospatial- -Intelligence Agency publication NGA.SIG.0012_2.0.0_UTMUPS - March25, 2014 and additionally from IHO Manual of Hydrography published by the International Hydrographic Office. In order to illustrate application of the presented formulas the article includes some relevant calculation examples on the reference ellipsoid WGS 84 (World Geodetic System of 1984).
The Influence of Parameters of Biomimetic Underwater Vehicle Control System on the Ability of the Vehicle to Avoid Obstacles
Authors: Praczyk Tomasz
Published: September 2016

Autonomous underwater vehicles are vehicles that are entirely or partly independent of human decisions. In order to obtain operational independence, the vehicles have to be equipped with a specialized software that usually has many different parameters. The parameters decide about effectiveness of the software and in consequence the vehicle. The paper reports experiments performed in simulation, whose goal was to analyze the influence of selected parameters of High- -level Control System of Biomimetic Underwater Vehicle on the vehicle ability to avoid obstacles.
Mexico’s Telesecundaria Program and Equitable Access to Resources
Authors: Craig Dana , Etcheverry Jose , Ferris Stefan
Published: September 2016

This Note provides an analysis of Mexico’s Telesecundaria program within the context of Mexico’s new education reform framework offering a succinct background of the project, as well as key policy lessons that can be useful for other jurisdictions interested in the development of distance education programs. This Note uses a literature and data analysis review approach, as well as qualitative analysis of interview data collected recently in Mexico by the authors. The Note positions pedagogical approaches to distance education within the context of developments in communication, internet access and renewable energy technologies, as well as within the challenges of the digital divide as means of powering digital access to information and education to remote, rural and marginalized communities.
Principles of Neural Design
Authors: Sterling Peter , Laughlin Simon
Published: September 2016

Two distinguished neuroscientists distil general principles from more than a century of scientific study, “reverse engineering” the brain to understand its design.

Neuroscience research has exploded, with more than fifty thousand neuroscientists applying increasingly advanced methods. A mountain of new facts and mechanisms has emerged. And yet a principled framework to organize this knowledge has been missing. In this book, Peter Sterling and Simon Laughlin, two leading neuroscientists, strive to fill this gap, outlining a set of organizing principles to explain the whys of neural design that allow the brain to compute so efficiently.

Setting out to “reverse engineer” the brain—disassembling it to understand it—Sterling and Laughlin first consider why an animal should need a brain, tracing computational abilities from bacterium to protozoan to worm. They examine bigger brains and the advantages of “anticipatory regulation”; identify constraints on neural design and the need to “nanofy”; and demonstrate the routes to efficiency in an integrated molecular system, phototransduction. They show that the principles of neural design at finer scales and lower levels apply at larger scales and higher levels; describe neural wiring efficiency; and discuss learning as a principle of biological design that includes “save only what is needed.”

Sterling and Laughlin avoid speculation about how the brain might work and endeavor to make sense of what is already known. Their distinctive contribution is to gather a coherent set of basic rules and exemplify them across spatial and functional scales.
Sharing Cities
Authors: McLaren Duncan , Agyeman Julian
Published: September 2016

How cities can build on the “sharing economy” and smart technology to deliver a “sharing paradigm” that supports justice, solidarity, and sustainability.

The future of humanity is urban, and the nature of urban space enables, and necessitates, sharing—of resources, goods and services, experiences. Yet traditional forms of sharing have been undermined in modern cities by social fragmentation and commercialization of the public realm. In Sharing Cities, Duncan McLaren and Julian Agyeman argue that the intersection of cities' highly networked physical space with new digital technologies and new mediated forms of sharing offers cities the opportunity to connect smart technology to justice, solidarity, and sustainability. McLaren and Agyeman explore the opportunities and risks for sustainability, solidarity, and justice in the changing nature of sharing.

McLaren and Agyeman propose a new “sharing paradigm,” which goes beyond the faddish “sharing economy”—seen in such ventures as Uber and TaskRabbit—to envision models of sharing that are not always commercial but also communal, encouraging trust and collaboration. Detailed case studies of San Francisco, Seoul, Copenhagen, Medellín, Amsterdam, and Bengaluru (formerly Bangalore) contextualize the authors' discussions of collaborative consumption and production; the shared public realm, both physical and virtual; the design of sharing to enhance equity and justice; and the prospects for scaling up the sharing paradigm though city governance. They show how sharing could shift values and norms, enable civic engagement and political activism, and rebuild a shared urban commons. Their case for sharing and solidarity offers a powerful alternative for urban futures to conventional “race-to-the-bottom” narratives of competition, enclosure, and division.
Local atomic structure analysis of SiC interface with oxide using chemical-state-selective X-ray absorption spectroscopy
Authors: Isomura Noritake , Murai Takaaki , Oji Hiroshi , Nomoto Toyokazu , Watanabe Yukihiko , Kimoto Yasuji
Published: September 2016

A local atomic structure analysis of the interface between chemical vapor-deposited SiO2 and 4H-SiC was achieved via a combination of chemical-state-selective X-ray absorption spectroscopy and the use of a sample with a very thin oxide film. The Si K-edge spectrum, which monitors the SiC-assigned Auger peak, allows the SiC side of the SiO2/SiC interface to be selectively measured through the SiO2 film. We estimate the coordination number of the first nearest neighbor to be reduced by 17% with respect to the SiC bulk. This suggests that C vacancy defects exist at the SiC side of the interface.
Fabrication of (110)-one-axis-oriented perovskite-type oxide thin films and their application to buffer layer
Authors: Sato Tomoya , Ichinose Daichi , Kimura Junichi , Inoue Takaaki , Mimura Takanori , Funakubo Hiroshi , Uchiyama Kiyoshi
Published: September 2016

BaCe0.9Y0.1O3−δ (BCYO) and SrZr0.8Y0.2O3−δ (SZYO) thin films of perovskite-type oxides were deposited on (111)Pt/TiO
x
/SiO2/(100)Si substrates. X-ray diffraction patterns showed that the (110)-oriented BCYO and SZYO thin films were grown on (111)Pt/Si substrates directly without using any buffer layers. Thin films of SrRuO3 (SRO), a conductive perovskite-type oxide, were also deposited on those films and highly (110)-oriented SRO thin films were obtained. We believe that this (110)-oriented SRO works as a buffer layer to deposit (110)-oriented perovskite-type ferroelectric oxide thin films as well as a bottom electrode and can modify the ferroelectric properties of the oxide thin films by controlling their crystallographic orientations.
Electrocaloric properties of potassium tantalate niobate crystals
Authors: Maiwa Hiroshi
Published: September 2016

The electrocaloric properties of potassium tantalate niobate (KTN) crystals were investigated by indirect estimation and direct measurement of temperature–electric field (T–E) hysteresis loops. The measured T–E loops showed a similar shape to strain–electric field (s–E) loops. The adiabatic temperature change ΔT due to the electrocaloric effect was estimated from the polarization change of this sample to be 0.49 K under a field of 20 kV/cm. The measured temperature change ΔT in these samples upon the release of the electric field from 20 kV/cm to zero was 0.42 K. The temperature dependences of the electromechanical and electrocaloric properties were measured. The maximum performance appeared at approximately the phase transition temperature of KTN crystal and the properties were relatively moderate-temperature-dependent.
Identification of 11p14.1‐p15.3 deletion probably associated with short stature, relative macrocephaly, and delayed closure of the fontanelles
Authors: Dateki Sumito , Watanabe Satoshi , Kinoshita Fumiko , Yoshiura Koh‐ichiro , Moriuchi Hiroyuki
Published: September 2016

We herein report a de novo hemizygous 9.2‐Mb interstitial deletion of chromosome 11p14.1‐15.3 in a 3‐year‐old Japanese girl with short stature, relative macrocephaly, and delayed closure of cranial fontanelles and sutures. She did not show either any motor or mental development delay. This deletion involves 25 genes including NELL1. The loss of the Nell1 function leads to skeletal defects in the cranial vault and vertebral column, and overexpression of Nell1 causes craniosynostosis in mice. These results imply that short stature and an abnormality of membranous ossification could be explained by haploinsufficiency of NELL1 on 11p14.1‐p15.3. Further studies are needed to clarify the phenotype in patients with an 11p14.1‐15.3 deletion and the pathogenesis of NELL1. © 2016 Wiley Periodicals, Inc.
Expeditious and Divergent Total Syntheses of Aspidosperma Alkaloids Exploiting Iridium(I)‐Catalyzed Generation of Reactive Enamine Intermediates
Authors: Tan Peng Wen , Seayad Jayasree , Dixon Darren J.
Published: September 2016

A new approach for the divergent total syntheses of (±)‐vincaminorine, (±)‐N‐methylquebrachamine, (±)‐quebrachamine, (±)‐minovine and (±)‐vincadifformine, each in less than 10 linear steps starting from a single δ‐lactam building block, is reported. Key to our route design is the late‐stage generation of reactive enamine functionality from stable indole‐linked δ‐lactams via a highly chemoselective iridium(I)‐catalyzed reduction. The efficiently formed secodine intermediates subsequently undergo either a formal Diels–Alder cycloaddition or a competitive Michael addition/reduction to access aspidosperma‐type alkaloids in excellent diastereoselectivities. Product selectivity could be controlled by changing the indole N‐protecting group in the reductive cyclization precursors. An asymmetric variant of this synthetic strategy for the synthesis of (+)‐20‐epi‐ibophyllidine is also described.
Sequestration of Proteins by Fatty Acid Coacervates for Their Encapsulation within Vesicles
Authors: Garenne David , Beven Laure , Navailles Laurence , Nallet Frédéric , Dufourc Erick J. , Douliez Jean‐Paul
Published: September 2016

Encapsulating biological materials in lipid vesicles is of interest for mimicking cells; however, except in some particular cases, such processes do not occur spontaneously. Herein, we developed a simple and robust method for encapsulating proteins in fatty acid vesicles in high yields. Fatty acid based, membrane‐free coacervates spontaneously sequester proteins and can reversibly form membranous vesicles upon varying the pH value, the precrowding feature in coacervates allowing for protein encapsulation within vesicles. We then produced enzyme‐enriched vesicles and show that enzymatic reactions can occur in these micrometric capsules. This work could be of interest in the field of synthetic biology for building microreactors.
Observability and Controllability Analysis for Micro‐Positioning Stage Described by Sandwich Model with Hysteresis
Authors: Luo Na , Tan Yonghong , Dong Ruili
Published: September 2016

In this paper, an approach for analyzing the observability and controllability of micro‐positioning stage with piezoelectric actuator described by sandwich model with hysteresis is proposed. As hysteresis inherent in piezoelectric actuator is a non‐smooth nonlinear function with multi‐valued mapping, the positioning system is also a non‐smooth dynamic system. The Prandtl‐Ishlinksii (PI) submodel is employed to describe the characteristic of hysteresis embedded in the sandwich system. A linearization method based on non‐smooth optimization is proposed to derive a generalized linearized state‐space function to approximate the non‐smooth sandwich systems within a bounded region around the equilibrium points the system works at. Then, both observability and controllability matrices are constructed and the methods to analyze the observability as well as the controllability of sandwich system with hysteresis are derived. Finally, a simulation example and an application of the proposed method to a micro‐positioning stage with piezoactuator are presented to validate the proposed method.
Environmental decision‐making using Bayesian networks: creating an environmental report card
Authors: Johnson Sandra , Logan Murray , Fox David , Kirkwood John , Pinto Uthpala , Mengersen Kerrie
Published: September 2016

Environmental report cards are popular mechanisms for summarising the overall status of an environmental system of interest. This paper describes the development of such a report card in the context of a study for Gladstone Harbour in Queensland, Australia. The harbour is within the World Heritage‐protected Great Barrier Reef and is the location of major industrial development, hence the interest in developing a way of reporting its health in a statistically valid, transparent and sustainable manner. A Bayesian network (BN) approach was used because of its ability to aggregate and integrate different sources of information, provide probabilistic estimates of interest and update these estimates in a natural manner as new information becomes available.

BN modelling is an iterative process, and in the context of environmental reporting, this is appealing as model development can be initiated while quantitative knowledge is still under development, and subsequently refined as more knowledge becomes available. Moreover, the BN model helps build the maturity of the quantitative information needed and helps target investment in monitoring and/or process modelling activities to inform the approach taken. The model is able to incorporate spatial and temporal information and may be structured in such a way that new indicators of relevance to the underlying environmental gradient being monitored may replace less informative indicators or be added to the model with minimal effort.

The model described here focuses on the environmental component, but has the capacity to also incorporate social, cultural and economic components of the Gladstone Harbour Report Card. Copyright © 2016 John Wiley & Sons, Ltd.
Scrutinizing the Emotional Nature of Intuitive Coherence Judgments
Authors: Zander Thea , Fernandez Cruz Ana L. , Winkelmann Martin P. , Volz Kirsten G.
Published: September 2016

Dual‐system models propose that cognitive processing can occur either intuitively or deliberately. Unlike deliberate decision strategies, intuitive ones are assumed to have an emotional component attached to the decision process. We tested if intuitive decisions are indeed accompanied by an emotional response while deliberate decisions are not. Specifically, we conducted a psychophysiological study in which participants were instructed to decide either intuitively or deliberately if three simultaneously presented words were semantically coherent or incoherent (triad task). The degree of emotionality of these two decision strategies (intuitive vs. deliberate) was compared using changes in electrodermal activity (EDA) and the reaction time (RT) effect of an affective priming paradigm as primary measurements. Based on a valence‐arousal model, our results revealed that intuitive and deliberate judgments do not differ as to their emotionalvalencebut that they do differ in emotionalarousal. Most notably, sympathetic activation during intuitive judgments was significantly lower compared to sympathetic activation during deliberate judgments. Our results reflect that a relaxed state of mind—manifested in low sympathetic activity—could underlie the holistic processing that is assumed to facilitate the proliferation of semantic associations during coherence judgments. This suggests that coherence judgments made under an (instructed) intuitive decision mode have a specific psychophysiological signature and that arousal is the differentiating component between intuitive and deliberate decision strategies. © 2016 The Authors Journal of Behavioral Decision Making Published by John Wiley & Sons Ltd.
English Value‐Added Measures: Examining the Limitations of School Performance Measurement
Authors: Perry Thomas
Published: September 2016

Value‐added ‘Progress’ measures are to be introduced for all English schools in 2016 as ‘headline’ measures of school performance. This move comes despite research highlighting high levels of instability in value‐added measures and concerns about the omission of contextual variables in the planned measure. This article studies the impact of disregarding contextual factors, the stability of school scores across time and the consistency of value‐added performance for different cohorts within schools at a given point in time. The first two analyses replicate and extend previous studies using current data, confirming concerns about intake biases and showing that both secondary and primary level value‐added measures exhibit worrying levels of instability. The third analysis goes further by examining whether instability across time is likely to stem from differences between cohorts and whether measures based on a single cohort reflect school performance more generally. Combined, these analyses suggest a general problem of imprecision within value‐added estimates and that current policy use of value‐added is unjustified. Published school performance measures are likely to be profoundly misleading, in particular for those unfamiliar with the level of uncertainty in the estimates. The article closes by considering whether value‐added measures could and should be used by policy‐makers as measures of school performance.
Simple Synthesis of Multi‐Halogen Pyrazino[1,2‐a]indole‐1,8(2H,5aH)‐diones
Authors: Yang Rui‐Xia , Zhao Yu‐Cheng , Kong Ling‐Bin , Yan Sheng‐Jiao , Lin Jun
Published: September 2016

A concise and efficient one‐pot synthesis of multi‐halogen pyrazino[1,2‐a]indole‐1,8(2H,5aH)‐dione (MHPID) derivatives by the reaction of an enamino ester with multi‐halogen benzoquinone derivatives is described. MHPIDs 3a–3d were obtained with good yields (78–83%) by refluxing enamino esters 1a and 1b and tetrahalogen‐1,4‐benzoquinones 2a and 2b for 24 h without the use of catalysts. Compounds 3e–3p were also obtained with excellent yields (69–92%) via the reaction of the phenyl‐substituted enamino esters 1c–1h with tetrahalogen‐1,4‐benzoquinones 2a and 2b in CH3CN catalyzed by Cs2CO3. These two protocols are efficient and effective for the synthesis of MHPIDs.
Transcatheter aortic valve replacement in unicuspid aortic valve stenosis
Authors: Acharji Subasit , Agnihotri Arvind , Carrozza Joseph
Published: September 2016

Unicuspid aortic valve (UAV) offers unique challenges to transcatheter aortic valve replacement (TAVR), due to asymmetric expansion and apposition of the prosthesis during implantation. Although TAVR in bicuspid is now a well described experience, TAVR in unicuspid valve has not yet been described. A challenging case is described with TAVR in UAV using a Edwards Sapiens prosthesis via transapical approach. © 2016 Wiley Periodicals, Inc.
Biogas Reforming for Hydrogen Production: A New Path to High‐Performance Nickel Catalysts Supported on Magnesium Aluminate Spinel
Authors: Habibi Narges , Wang Yuan , Arandiyan Hamidreza , Rezaei Mehran
Published: September 2016

Highly dispersed Ni nanoparticles supported on high‐surface‐area mesoporous nanocrystalline MgAl2O4 powder was generated by a facile and simple propylene oxide assisted gelation agent route. The mesoporous spinel materials exhibited enhanced catalytic performance for hydrogen production in biogas dry reforming. The obtained spinel catalysts with different Ni loadings after calcination at 700 °C possessed high BET surface areas (236–224 m2 g−1). A narrow pore size distribution in the mesopore range was observed in the samples, and all the samples except 2.5 wt % Ni showed a mesoporous–macroporous structure. The 5 wt % Ni/MgAl2O4 sample showed the highest activity for the biogas dry reforming reaction because of the high dispersion of Ni on the mesoporous surface of the spinel support. X‐ray photoelectron spectroscopy revealed that the catalysts with a low Ni loading undergo the exchange of Mg2+ by Ni2+, whereas catalysts with a higher Ni loading undergo the substitution of Al3+ by Ni3+. Thus, appropriate partial Ni substitution in the MgAl2O4 support may play a role in the elevated catalytic performance.
Titanium cis‐1,2‐Diaminocyclohexane Salalen Catalysts of Outstanding Activity and Enantioselectivity for the Asymmetric Epoxidation of Nonconjugated Terminal Olefins with Hydrogen Peroxide
Authors: Lansing Markus , Engler Hauke , Leuther Tobias M. , Neudörfl Jörg‐M. , Berkessel Albrecht
Published: September 2016

We report a new and readily accessible class of titanium salalen complexes derived from cis‐1,2‐diaminocyclohexane (cis‐DACH) and fluorinated salicylic aldehyde derivatives. With aqueous hydrogen peroxide as the oxidant, these complexes catalyze the epoxidation of terminal, nonconjugated olefins in high yields with high enantioselectivities. We furthermore discovered that the addition of certain acidic or basic co‐catalysts significantly accelerated the epoxidation. For example, in the presence of 1 mol % Ti catalyst and 1 mol % pentafluorobenzoic acid, 1‐octene epoxidation (95 % ee) was completed at room temperature within 8 h. The catalytic process was compatible with many functional groups (e.g., ethers, esters, halides, nitriles, and nitro groups), whereas free hydroxy groups appeared to slow down the reaction to some extent. Catalyst recycling was possible.
Ethanol Oxidation on Sn‐modified Pt Single‐Crystal Electrodes: New Mechanistic Insights from On‐line Electrochemical Mass Spectrometry
Authors: Rizo Ruben , Lázaro M. Jesús , Pastor Elena , Koper Marc T. M.
Published: September 2016

The modification of low‐index Pt single crystals with a submonolayer coverage of Sn enhances the electroactivity of the electrode for the ethanol oxidation process in perchloric acid solution. The optimum Sn coverage for ethanol oxidation depends on the Pt crystallography, found to be approximately 0.26, 0.48, and 0.58 for Pt(100), Pt(111), and Pt(110), respectively; the Sn/Pt(110) system being the surface that exhibits the highest activity. On‐line electrochemical mass spectrometry experiments show that both on Pt(111) and Pt(110), the presence of Sn enhances the oxidation of ethanol to acetaldehyde. The further oxidation of acetaldehyde is sensitive to the Pt surface structure: on Pt(110) there are sites able to break the C−C bond in acetaldehyde to form CO2, whereas on Pt(111) such sites are not available and acetaldehyde is oxidized further to acetic acid.
Advances in Transition‐Metal Phosphide Applications in Electrochemical Energy Storage and Catalysis
Authors: Feng Ligang , Xue Huaiguo
Published: September 2016

Transition‐metal phosphides (TMPs) have emerged as robust and efficient catalyst materials recently due to their excellent catalytic properties. This review summarizes the recent advances in TMP applications in electrochemical energy storage and catalysis. Some representative works are highlighted to give a scientific concept and understanding of the versatile applications of TMPS in water splitting, fuel cells, batteries, and supercapacitors. An outstanding catalytic activity/promotion effect was achieved in catalyst systems due to the synergistic effects between the various components. Problems and challenges are also discussed to inspire the development of novel nanoscaled TMPs as efficient and robust catalysts for commercial applications in real energy technologies.
Tuning Proton Conductivity by Interstitial Guest Change in Size‐Adjustable Nanopores of a CuI‐MOF: A Potential Platform for Versatile Proton Carriers
Authors: Khatua Sajal , Kumar Bar Arun , Konar Sanjit
Published: September 2016

By exploiting the breathing behavior of nanopores, we have studied for the first time the dependency of the guest‐induced proton conductivity of an interpenetrated CuI metal–organic framework (CuI‐MOF, [1]) on various guest molecules. Proton conductivities of over 10−3 S cm−1 under humid conditions were induced by a series of guest molecules, namely N,N‐dimethylformamide, dimethyl sulfoxide, diethylamine, 1,4‐dinitrobenzene, nitrobenzene, pyridine, and 1H‐1,2,4‐triazole. A detailed investigation of the guest‐incorporated complexes revealed that low‐energy proton conduction occurs under humid conditions through the Grotthuss mechanism in [1⊃NB] and through the vehicle mechanism in the rest of the complexes. Single‐point energy computations revealed considerable stabilization upon guest encapsulation. To the best of our knowledge, [1] represents the first example in which considerably high protonic conductivity is triggered upon the facile incorporation of small molecules of such a variety. The investigation portrayed herein may be a stepping stone towards the rational design of proton‐conducting materials for practical applications.
Protic N‐Heterocyclic Carbene Versus Pyrazole: Rigorous Comparison of Proton‐ and Electron‐Donating Abilities in a Pincer‐Type Framework
Authors: Toda Tatsuro , Yoshinari Akihiro , Ikariya Takao , Kuwata Shigeki
Published: September 2016

Evaluation of the acidity of proton‐responsive ligands such as protic N‐heterocyclic carbenes (NHCs) bearing an NH‐wingtip provides a key to understanding the metal–ligand cooperation in enzymatic and artificial catalysis. Here, we design a CNN pincer‐type ruthenium complex 2 bearing protic NHC and isoelectronic pyrazole units in a symmetrical skeleton, to compare their acidities and electron‐donating abilities. The synthesis is achieved by direct C−H metalation of 2‐(imidazol‐1‐yl)‐6‐(pyrazol‐3‐yl)pyridine with [RuCl2(PPh3)3]. 15N‐Labeling experiments confirm that deprotonation of 2 occurs first at the pyrazole side, indicating clearly that the protic pyrazole is more acidic than the NHC group. The electrochemical measurements as well as derivatization to carbonyl complexes demonstrate that the protic NHC is more electron‐donating than pyrazole in both protonated and deprotonated forms.
Circularly Polarized Luminescence from Axially Chiral BODIPY DYEmers: An Experimental and Computational Study
Authors: Zinna Francesco , Bruhn Torsten , Guido Ciro A. , Ahrens Johannes , Bröring Martin , Di Bari Lorenzo , Pescitelli Gennaro
Published: September 2016

With our new home‐built circularly polarized luminescence (CPL) instrument, we measured fluorescence and CPL spectra of the enantiomeric pairs of two quasi‐isomeric BODIPY DYEmers 1 and 2, endowed with axial chirality. The electronic circular dichroism (ECD) and CPL spectra of these atropisomeric dimers are dominated by the exciton coupling between the main π–π* transitions (550–560 nm) of the two BODIPY rings. Compound 1 has strong ECD and CPL spectra (glum=4×10−3) well reproduced by TD‐DFT and SCS‐CC2 (spin‐component scaled second‐order approximate coupled‐cluster) calculations using DFT‐optimized ground‐ and excited‐state structures. Compound 2 has weaker ECD and CPL spectra (glum=4×10−4), partly due to the mutual cancellation of electric–electric and electric–magnetic exciton couplings, and partly to its conformational freedom. This compound is computationally very challenging. Starting from the optimized excited‐state geometries, we predicted the wrong sign for the CPL band of 2 using TD‐DFT with the most recommended hybrid and range‐separated functionals, whereas SCS‐CC2 or a DFT functional with full exact exchange provided the correct sign.
Three Short Stories about Hexaarylbenzene–Porphyrin Scaffolds
Authors: Lungerich Dominik , Hitzenberger Jakob F. , Donaubauer Wolfgang , Drewello Thomas , Jux Norbert
Published: September 2016

A feasible two‐step synthesis and characterization of a full series of hexaarylbenzene (HAB) substituted porphyrins and tetrabenzoporphyrins is presented. Key steps represent the microwave‐assisted porphyrin condensation and the statistical Diels–Alder reaction to the desired HAB‐porphyrins. Regarding their applications, they proved to be easily accessible and effective high molecular mass calibrants for (MA)LDI mass spectrometry. The free‐base and zinc(II) porphyrin systems, as well as the respective tetrabenzoporphyrins, demonstrate in solid state experiments strong red‐ and near‐infrared‐light emission and are potentially interesting for the application in “truly organic” light‐emitting devices. Lastly, they represent facile precursors to large polycyclic aromatic hydrocarbon (PAH) substituted porphyrins. We prepared the first tetra‐hexa‐peri‐hexabenzocoronene substituted porphyrin, which represents the largest prepared PAH‐porphyrin conjugate to date.
Multiplicity Regions in a Moving‐Bed Reactor: Bifurcation Analysis, Model Extension, and Application for the High‐Temperature Pyrolysis of Methane
Authors: Munera Parra Alejandro A. , Platte Frank , Agar David W.
Published: September 2016

This paper reports studies on the bifurcation analysis and the generation of regions of multiplicity in the operation of moving‐bed reactors. The studies were first carried out for a generalized model, which allows the investigation of the effect of various scenarios, such as changes in heat capacity or the number of moles with reaction, as well as the previously unstudied equilibrium and allothermic reactions. The insights gained from this extension were then applied to an actual reaction, namely the high temperature pyrolysis of methane.
Reduced feeding tube duration with intensity‐modulated radiation therapy for head and neck cancer: A Surveillance, Epidemiology, and End Results‐Medicare Analysis
Authors: Beadle Beth M. , Liao Kai‐Ping , Giordano Sharon H. , Garden Adam S. , Hutcheson Katherine A. , Lai Stephen Y. , Guadagnolo B. Ashleigh
Published: September 2016

BACKGROUND

Intensity‐modulated radiation therapy (IMRT) is a technologically advanced and resource‐intensive method of delivering radiation therapy (RT) and is used to minimize toxicity for patients with head and neck cancer (HNC). Dependence on feeding tubes is a significant marker of toxicity of RT. The objective of this analysis was to compare the placement and duration of feeding tube use among patients with HNC from 1999 through 2011.

METHODS

The cohort, demographics, and cancer‐related variables were determined using the linked Surveillance, Epidemiology, and End Results (SEER)‐Medicare database, and claims data were used to analyze treatment details.

RESULTS

In total, 2993 patients were identified. At a median follow‐up of 47 months, 54.4% of patients had ever had a feeding tube placed. The median duration from feeding tube placement to removal was 277 days. On zero‐inflated negative binomial regression, patients who received IMRT and 3‐dimensional RT (3DRT) (non‐IMRT) had similar rates of feeding tube placement (odds ratio, 1.10; P = .35); however, patients who received 3DRT had a feeding tube in place 1.18 times longer than those who received IMRT (P = .03). The difference was only observed among patients who received definitive RT; patients who underwent surgery and also received adjuvant RT had no statistically significant difference in feeding tube placement or duration.

CONCLUSIONS

Patients with HNC who received definitive IMRT had a significantly shorter duration of feeding tube placement than those who received 3DRT. These data suggest that there may be significant quality‐of‐life benefits to IMRT with respect to long‐term swallowing function in patients with HNC. Cancer 2017;123:283–293. © 2016 American Cancer Society.
Precise capture of colors in cultural heritage digitization
Authors: Korytkowski Przemyslaw , Olejnik‐Krugly Agnieszka
Published: September 2016

A workflow for the color reproduction of digital still images for the purpose of cultural heritage digitization is presented. An analysis was performed to determine the effect of RAW to TIFF transformation; RGB to CIE L*a*b* transformation; white balancing; use of standard color spaces: sRGB, AdobeRGB (1998), ProPhoto RGB, eciRGBv2; custom DCP, and ICC profiles assigning. For the analysis, Color Checker Classic and Digital Color Checker SG targets were used. The precision of the color reproduction was checked against FADGI and Metamorfoze standards. We demonstrate that to obtain high color fidelity reproduction, white balancing and a custom ICC profile are necessary, while DCP profiling could be omitted. © 2016 Wiley Periodicals, Inc. Col Res Appl, 42, 333–336, 2017
Density Functional Theory Analysis of Anthraquinone Derivative Hydrogenation over Palladium Catalyst
Authors: Yuan Enxian , Wang Li , Zhang Xiangwen , Feng Ren , Wu Chan , Li Guozhu
Published: September 2016

A density functional theory (DFT) analysis was conducted on the hydrogenation of 2‐alkyl‐anthraquinone (AQ), including 2‐ethyl‐9,10‐anthraquinone (eAQ) and 2‐ethyl‐5,6,7,8‐tetrahydro‐9,10‐anthraquinone (H4eAQ), to the corresponding anthrahydroquinone (AQH2) over a Pd6H2 cluster. Hydrogenation of H4eAQ is suggested to be more favorable than that of eAQ owing to a higher adsorption energy of the reactant (H4eAQ), lower barrier of activation energy, and smaller desorption energy of the target product (2‐ethyl‐5,6,7,8‐tetrahydro‐9,10‐anthrahydroquinone, H4eAQH2). For the most probable reaction routes, the energy barrier of the second hydrogenation step of AQ is circa 8 kcal mol−1 higher than that of the first step. Electron transfer of these processes were systematically investigated. Facile electron transfer from Pd6H2 cluster to AQ/AQH intermediate favors the hydrogenation of C=O. The electron delocalization over the boundary aromatic ring of AQ/AQH intermediate and the electron‐withdrawing effect of C=O are responsible for the electron transfer. In addition, a pathway of the electron transfer is proposed for the adsorption and subsequent hydrogenation of AQ on the surface of Pd6H2 cluster. The electron transfers from the abstracted H atom (reactive H) to a neighbor Pd atom (PdH), and finally goes to the carbonyl group through the C4 atom of AQ aromatic ring (C4).
Supramolecular Hemicage Cobalt Mediators for Dye‐Sensitized Solar Cells
Authors: Freitag Marina , Yang Wenxing , Fredin Lisa A. , D'Amario Luca , Karlsson K. Martin , Hagfeldt Anders , Boschloo Gerrit
Published: September 2016

A new class of dye‐sensitized solar cells (DSSCs) using the hemicage cobalt‐based mediator [Co(ttb)]2+/3+ with the highly preorganized hexadentate ligand 5,5′′,5′′′′‐((2,4,6‐triethyl benzene‐1,3,5‐triyl)tris(ethane‐2,1‐diyl))tri‐2,2′‐bipyridine (ttb) has been fully investigated. The performances of DSSCs sensitized with organic D–π–A dyes utilizing either [Co(ttb)]2+/3+ or the conventional [Co(bpy)3]2+/3+ (bpy=2,2′‐bipyridine) redox mediator are comparable under 1000 W m−2 AM 1.5 G illumination. However, the hemicage complexes exhibit exceptional stability under thermal and light stress. In particular, a 120‐hour continuous light illumination stability test for DSSCs using [Co(ttb)]2+/3+ resulted in a 10 % increase in the performance, whereas a 40 % decrease in performance was found for [Co(bpy)3]2+/3+ electrolyte‐based DSSCs under the same conditions. These results demonstrate the great promise of [Co(ttb)]2+/3+ complexes as redox mediators for efficient, cost‐effective, large‐scale DSSC devices.
Rhodium Dopants on Zn2GeO4 Surfaces as Active Sites for Photocatalytic Water Splitting
Authors: Wang Yu Lei , Li Yu Hang , Wang Xue Lu , Chen Ai Ping , Yang Hua Gui
Published: September 2016

Doping has been widely used to engineer efficient photocatalysts for the water‐splitting process in energy conversion and storage systems. Although composition tuning through heteroatom doping is one of the strategies to enhance photoactivity, the origin of the increased activity by doping remains unclear and most illustrations of its role fall in the band engineering area. Herein, it is reported that the rhodium dopants on the surface of Zn2GeO4, which affect the band structure negligibly, can act as active sites for water splitting. As a result, the Rhδ+/Zn2GeO4 photocatalyst demonstrates excellent stability for up to 460 days and significant enhancement of the photocatalytic activity to that of the undoped photocatalyst. The findings in this work may open the door for a rethink of the detailed principles of dopants in photocatalysis, and highlight a feasible route to fabricating efficient photocatalysts.
Stereochemical Control of Enzymatic Carbon–Carbon Bond‐Forming Michael‐Type Additions by “Substrate Engineering”
Authors: Miao Yufeng , Tepper Pieter G. , Geertsema Edzard M. , Poelarends Gerrit J.
Published: September 2016

The enzyme 4‐oxalocrotonate tautomerase (4‐OT) promiscuously catalyzes the Michael‐type addition of acetaldehyde to β‐nitrostyrene derivatives to yield chiral γ‐nitroaldehydes, which are important precursors for pharmaceutically active γ‐aminobutyric acids. In this study, we investigated the effect of different substituents at the aromatic ring of the Michael acceptor on the catalytic efficiency and stereoselectivity of the 4‐OT‐catalyzed acetaldehyde addition reactions. Highly enantioenriched (R)‐ and (S)‐γ‐nitroaldehydes and 4‐substituted chroman‐2‐ol could be obtained in good to excellent yields by applying different substituents at appropriate positions of the aromatic substrate. Stereochemical control of these enzymatic Michael‐type additions by “substrate engineering” allowed the enantioselective synthesis of valuable γ‐aminobutyric acid precursors. In addition, the results suggest a novel enzymatic synthesis route towards precursors for chromans and derivatives, which are valuable scaffolds for preparing biologically active natural products.