bluuebunny/crossref_metadata_2025 huggingface dataset:
Sustainability and Depletion Accounting for Non-Renewable Resources: The Case of Copper in Chile
Authors: D. Green Barry , A. Blatner Keith
Published: October 2015

This research develops a framework for assessing just compensation values for mining projects, where they might contribute toward a responsible, profitable, and sustainable path to economic growth and development. More specifically, it deals with methods to determine a “sustainable” rate of mineral extraction, putting a dollar value on the environmental impacts from various levels of mineral extraction. The project focuses on an emerging political economy (Chile) and uses an interdisciplinary approach. The approach rests on the assumption that the policy objectives of environmental protection and sustainable economic development can be subsumed into the “Hartwick rule” goal of investing mining rents in natural, social, and infrastructure capital. This study aids in policy decisions relating to benefit transfer to local/regional infrastructure investment.
A informação na consulta presencial em Medicina Geral e Familiar: classificações segundo a ICPC-2 e anotações livres para a memória futura no SOAP
Authors: Santiago Luiz Miguel , Carvalho Rosa , Botas Philippe , Miranda Paula , Matias Catarina , Simões Ana Rita , Pereira Carolina , Glória Neto Maria
Published: October 2015

Objetivos: assumindo a obrigatoriedade de classificação ICPC-2 em cada consulta, conhecer a informação, em consultas passadas pelo método de Weed-SOAP segundo o gênero e idade de quem consulta o médico (consulente ou paciente), caracterizando o nível de registro pelo método SOAP em Subjetivo (S) - classificação e anotações - em Objetivo (O) anotações sobre o estado do paciente, em Avaliação (A) da classificação e em Plano (P) da classificação e anotações. Métodos: estudo observacional, transversal em outubro de 2012, em amostra aleatorizada das consultas presenciais de dois médicos orientadores de internato de especialidade, em três meses sorteados do 1º semestre de 2012, e em quatro dias sorteados em cada mês, em amostra representativa com intervalo de confiança de 95% e margem de erro de 6%. Utilizou-se estatística descritiva e inferencial. Resultados: amostra de 318 consultas, n=149 (46,9%) no gênero masculino, n=61 (19,2%) no grupo etário <18 anos e n=194 (61,0%) no ≥18 e <65 anos, ns por grupos etários e gênero. Em S, há classificação em 98,7% e anotação em 47,2% das consultas; Em O, verificamos “As anotações demonstram o estado do paciente” em 66,0% e “As anotações são explícitas e entendíveis” em 79,9%; em A, 97,8% das consultas têm classificação; Em P, há classificação em 96,5% e anotações explicando o plano em 23,0% das consultas. Distribuição sem significado por grupo etário para as variáveis estudadas. É mais frequente haver no gênero feminino em S “As anotações são explícitas e entendíveis” e em P “Há classificação de procedimentos”. Conclusão: há campo para mais completa coleta da informação na consulta, permitindo, assim, melhor conhecimento de cada consulta e caso para o futuro.
Under-13 rugby: What are the issues? A panel discussion
Authors: Durandt Justin , Hendricks Sharief , Marshall Mike , Roux Andries , Hare Eugene
Published: October 2015

There are many questions about youth rugby for whichthere are no immediate answers. At what age shouldthe young players specialise? How often should theypractise? How many matches should they play inseason? Science has lagged behind in providing clearanswers, and in many cases decisions about the development of thegame at this level have to be made based on logic and intuition. As aresult, opinions may differ and controversy may prevail.Recently a panel of experts representing different aspects of youthrugby was asked a series of questions about this sport, the aim beingto examine the answers given from different perspectives. The overallgoal was to identify where agreement does or does not exist.
Economic and epidemiological impact of early antiretroviral therapy initiation in India
Authors: Maddali Manoj V , Dowdy David W , Gupta Amita , Shah Maunank
Published: October 2015

Introduction

Recent WHO guidance advocates for early antiretroviral therapy (ART) initiation at higher CD4 counts to improve survival and reduce HIV transmission. We sought to quantify how the cost‐effectiveness and epidemiological impact of early ART strategies in India are affected by attrition throughout the HIV care continuum.

Methods

We constructed a dynamic compartmental model replicating HIV transmission, disease progression and health system engagement among Indian adults. Our model of the Indian HIV epidemic compared implementation of early ART initiation (i.e. initiation above CD4 ≥350 cells/mm3) with delayed initiation at CD4 ≤350 cells/mm3; primary outcomes were incident cases, deaths, quality‐adjusted‐life‐years (QALYs) and costs over 20 years. We assessed how costs and effects of early ART initiation were impacted by suboptimal engagement at each stage in the HIV care continuum.

Results

Assuming “idealistic” engagement in HIV care, early ART initiation is highly cost‐effective ($442/QALY‐gained) compared to delayed initiation at CD4 ≤350 cells/mm3 and could reduce new HIV infections to <15,000 per year within 20 years. However, when accounting for realistic gaps in care, early ART initiation loses nearly half of potential epidemiological benefits and is less cost‐effective ($530/QALY‐gained). We project 1,285,000 new HIV infections and 973,000 AIDS‐related deaths with deferred ART initiation with current levels of care‐engagement in India. Early ART initiation in this continuum resulted in 1,050,000 new HIV infections and 883,000 AIDS‐related deaths, or 18% and 9% reductions (respectively), compared to current guidelines. Strengthening HIV screening increases benefits of earlier treatment modestly (1,001,000 new infections; 22% reduction), while improving retention in care has a larger modulatory impact (676,000 new infections; 47% reduction).

Conclusions

Early ART initiation is highly cost‐effective in India but only has modest epidemiological benefits at current levels of care‐engagement. Improved retention in care is needed to realize the full potential of earlier treatment.
Formação do professor: a docência universitária em busca de legitimidade
Authors: Regina Soares Sandra , Isabel da Cunha Maria
Published: October 2015

Este estudo aborda a formação do professor universitário em cursos de pós-graduação. Contempla produções de autores e grupos de pesquisa reconhecidos no campo da pedagogia universitária e formula reflexões e proposições que fornecem pistas para reformulação dos projetos político-pedagógicos desses cursos. As autoras increvem-se no grupo de pesquisadores do tema responsáveis por diversas publicações e pela coordenação de eventos nacioanis e internacionais tomando a resposabilidade de difundir os conhecimentos na área.
Evolutionary adaptation after crippling cell polarization follows reproducible trajectories
Authors: Laan Liedewij , Koschwanez John H , Murray Andrew W
Published: October 2015

Cells are organized by functional modules, which typically contain components whose removal severely compromises the module's function. Despite their importance, these components are not absolutely conserved between parts of the tree of life, suggesting that cells can evolve to perform the same biological functions with different proteins. We evolved Saccharomyces cerevisiae for 1000 generations without the important polarity gene BEM1. Initially the bem1∆ lineages rapidly increase in fitness and then slowly reach >90% of the fitness of their BEM1 ancestors at the end of the evolution. Sequencing their genomes and monitoring polarization reveals a common evolutionary trajectory, with a fixed sequence of adaptive mutations, each improving cell polarization by inactivating proteins. Our results show that organisms can be evolutionarily robust to physiologically destructive perturbations and suggest that recovery by gene inactivation can lead to rapid divergence in the parts list for cell biologically important functions.
Oklahoma physician needs
Authors: Lapolla Michael , Phillips Steven , Mitchell Linda
Published: October 2015

State policy makers, healthcare professionals, and advocates have been asking various iterations of the question, Do we have too many or too few physicians? In order to address this question, a relative-needs analysis ~as conducted for the state of Oklahoma. Six projection-needs studies were used for comparison with Oklahoma's supply of practicing physicians. This analysis found that Oklahoma did not have a surplus of primary care physicians. While the national average for primary care physicians per 100,000 was 79, Oklahoma's ratio was 68. This analysis also compares not only the number of physicians in Oklahoma per 100,000 population, it also discusses the proportion of primary care physicians in the physician workforce. Primary care physicians were found to be neither oversupplied nor undersupplied in Oklahoma. Oklahoma was found to be closer to national planning model goals than most states in the United States. Because this study combines both allopathic and osteopathic physicians and includes only those physicians in active practice, it is unique in comparison to many other studies concerning physician workforce needs.
Skin manifestations of food allergies
Authors: Martin Bryan L
Published: October 2015

The role of dietary factors in chronic skin diseases has been a subject of controversy, but several investigators have shown the effectiveness of elimination diets in the management of some patients with atopic dermatitis. Chronic skin diseases are common, complex, and often difficult to treat; therefore, the physician should consider all possible causes. More people consider themselves to have food allergies than can actually be documented to have an immunologic reaction to foods. Six foods--egg, peanut, cow's milk, soy, fish, and wheat-account for most skin reactions to food in children, with egg, peanut, and cow's milk being most common. Elimination of the offending food can be an effective form of treatment, but it must be done with caution, and while ensuring that the patient maintains adequate nutrition.
Effect of shampoo, conditioner and permanent waving on the molecular structure of human hair
Authors: Zhang Yuchen , Alsop Richard J. , Soomro Asfia , Yang Fei-Chi , Rheinstädter Maikel C.
Published: October 2015

The hair is a filamentous biomaterial consisting of thecuticle, thecortexand themedulla, all held together by the cell membrane complex. Thecortexmostly consists of helical keratin proteins that spiral together to form coiled-coil dimers, intermediate filaments, micro-fibrils and macro-fibrils. We used X-ray diffraction to study hair structure on the molecular level, at length scales between ∼3–90 Å, in hopes of developing a diagnostic method for diseases affecting hair structure allowing for fast and noninvasive screening. However, such an approach can only be successful if common hair treatments do not affect molecular hair structure. We found that a single use of shampoo and conditioner has no effect on packing of keratin molecules, structure of the intermediate filaments or internal lipid composition of the membrane complex. Permanent waving treatments are known to break and reform disulfide linkages in the hair. Single application of a perming product was found to deeply penetrate the hair and reduce the number of keratin coiled-coils and change the structure of the intermediate filaments. Signals related to the coiled-coil structure of theα-keratin molecules at 5 and 9.5 Å were found to be decreased while a signal associated with the organization of the intermediate filaments at 47 Å was significantly elevated in permed hair. Both these observations are related to breaking of the bonds between two coiled-coil keratin dimers.
Carbon isotope ratios suggest no additional methane from boreal wetlands during the rapid Greenland Interstadial 21.2
Authors: Sperlich Peter , Schaefer Hinrich , Mikaloff Fletcher Sara E. , Guillevic Myriam , Lassey Keith , Sapart Célia J. , Röckmann Thomas , Blunier Thomas
Published: October 2015

Samples from two Greenland ice cores (NEEM and NGRIP) have been measured for methane carbon isotope ratios (δ13C‐CH4) to investigate the CH4 mixing ratio anomaly during Greenland Interstadial (GI) 21.2 (85,000 years before present). This extraordinarily rapid event occurred within 150 years, comprising a CH4 mixing ratio pulse of 150 ppb (∼25%). Our new measurements disclose a concomitant shift in δ13C‐CH4 of 1‰. Keeling plot analyses reveal the δ13C of the additional CH4 source constituting the CH4 anomaly as −56.8 ± 2.8‰, which we confirm by means of a previously published box model. We propose tropical wetlands as the most probable additional CH4 source during GI‐21.2 and present independent evidence that suggests that tropical wetlands in South America and Asia have played a key role. We find no evidence that boreal CH4 sources, such as permafrost degradation, contributed significantly to the atmospheric CH4 increase, despite the pronounced warming in the Northern Hemisphere during GI‐21.2.
Anisotropic upper crust above the aftershock zone of the 2013 Ms 7.0 Lushan earthquake from the shear wave splitting analysis
Authors: Liu Ying , Zhang Haijiang , Zhang Xin , Pei Shunping , An Meijian , Dong Shuwen
Published: October 2015

We have conducted a systematic shear wave splitting analysis using 1000 selected aftershocks with M > 2 from the 2013 Ms 7.0 Lushan earthquake along the Longmenshan fault system in southwest China. Polarization directions of fast shear waves show a bimodal distribution with one dominant direction approximately parallel to the fault strike and the other close to the regional maximum horizontal compressive stress direction. This indicates that in this area mechanisms causing crustal seismic anisotropy are both stress induced and fault zone structure controlled. Delay times between fast and slow shear waves do not show a clear trend of increase for deeper events, suggesting the anisotropic zone is mostly above the aftershocks, which are generally located below 8 km. We further applied a shear wave splitting tomography method to measured delay times to characterize the spatial distribution of seismic anisotropy. The three‐dimensional anisotropic percentage model shows strong anisotropy above 8 km but low anisotropy below it. The mainshock slip zone and its aftershocks are associated with very low or negligible anisotropy and high velocity, indicating that the zones with high anisotropy and low velocity above 8 km are mechanically weak and it is difficult for stress to accumulate there. The main and back reverse fault zones are associated with high anisotropic anomalies above ∼8 km, likely caused by shear fabric or microfractures aligned parallel to the fault zone.
Analysis of plasmaspheric hiss wave amplitudes inferred from low‐altitude POES electron data: Validation with conjunctive Van Allen Probes observations
Authors: de Soria‐Santacruz M. , Li W. , Thorne R. M. , Ma Q. , Bortnik J. , Ni B. , Kletzing C. A. , Kurth W. S. , Hospodarsky G. B.
Published: October 2015

Plasmaspheric hiss plays an important role in controlling the overall structure and dynamics of the Earth's radiation belts. The interaction of plasmaspheric hiss with radiation belt electrons is commonly evaluated using diffusion codes, which rely on statistical models of wave observations that may not accurately reproduce the instantaneous global wave distribution or the limited in situ satellite wave measurements. This paper evaluates the performance and limitations of a novel technique capable of inferring wave amplitudes from low‐altitude electron flux observations from the Polar Orbiting Environmental Satellites (POES), which provide extensive coverage in shell and magnetic local time (MLT). We found that, within its limitations, this technique could potentially be used to build a dynamic global model of the plasmaspheric hiss wave intensity. The technique is validated by analyzing the conjunctions between the POES spacecraft and the Van Allen Probes from September 2012 to June 2014. The technique performs well for moderate‐to‐strong hiss activity (≥30 pT) with sufficiently high electron fluxes. The main source of these limitations is the number of counts of energetic electrons measured by the POES spacecraft capable of resonating with hiss waves. For moderate‐to‐strong hiss events, the results show that the wave amplitudes from the EMFISIS instruments on board the Van Allen Probes are well reproduced by the POES technique, which provides more consistent estimates than the parameterized statistical hiss wave model based on CRRES data.
Dual radar investigation of E region plasma waves in the southern polar cap
Authors: Forsythe Victoriya V. , Makarevich Roman A.
Published: October 2015

Origins and characteristics of small‐scale plasma irregularities in the polar ionosphere are investigated using a dual radar setup in which the E region is probed from opposite directions by two Super Dual Auroral Radar Network facilities at the McMurdo and Dome Concordia Antarctic stations. In certain time intervals, velocity agreement is observed when velocities are compared at the same physical location in the horizontal plane. Such an agreement is widely expected if velocity at a given location is largely controlled by the convection electric field. In other cases, however, velocity agreement is unexpectedly observed when measurements are considered at the same slant range (distance along the radar beam) for both radars. This implies that it is not the electric field at a given location that is a controlling factor. Raytracing results show that the same range agreement may be explained for certain E region density conditions when echo altitude increases with radar range. Backscatter observations under generally unfavorable conditions for irregularity generation and the critical role of propagation conditions in the polar cap are discussed. The observed E region velocity in the polar cap is demonstrated to depend indirectly on the plasma density distribution, which is important for establishing the fundamental dependence on the convection electric field.
Effects of the interannual variability in chlorophyll concentrations on sea surface temperatures in the east tropical Indian Ocean
Authors: Ma Jinfeng , Liu Hailong , Lin Pengfei , Zhan Haigang
Published: October 2015

The effects of interannual variability in chlorophyll concentrations on sea surface temperatures in the east tropical Indian Ocean (ETIO) during two positive Indian Ocean Dipole (IOD) events (in the boreal fall of 1997 and 2006) are investigated; this is done through two ocean model experiments, one with and one without the interannual variability of chlorophyll concentrations. A comparison of the two chlorophyll perturbation experiments reveals that, in contrast to the cooling effects at the seasonal time scale, increased chlorophyll concentrations during positive IOD events lead to an increase in the sea surface temperatures within the ETIO. Although upward velocity is enhanced (with a cooling effect), this does not counterbalance the increase in solar heating caused by the increased chlorophyll concentrations. This interannual variability of chlorophyll concentrations in the ETIO could reduce the amplitude of the IOD by about 6%.
Positively biased self‐perceptions of peer acceptance and subtypes of aggression in children
Authors: Lynch Rebecca J. , Kistner Janet A. , Stephens Haley F. , David‐Ferdon Corinne
Published: October 2015

There is a growing body of research linking children's positively biased self‐perceptions with higher levels of aggression. This study extended this area of research by examining prospective associations of positively biased self‐perceptions of peer acceptance with overt and relational aggression. In addition, moderating effects of peer rejection were examined to test the “disputed overestimation hypothesis,” which posits that the link between bias and aggression is limited to children who are rejected by their peers. Using a two‐wave longitudinal design, measures of peer‐rated and self‐perceived peer acceptance and peer‐rated overt and relational aggression were obtained for 712 children in 3rd through 5th grades (386 girls and 326 boys). Positively biased perceptions led to increases in relational, but not overt, aggression. This pattern was observed even when the effects of gender, race, peer rejection, and overt aggression on relational aggression were controlled. Contrary to the disputed overestimation hypothesis, the prospective associations between bias and aggression did not vary as a function of children's peer rejection status, thus supporting the view that positive bias predicts future aggressive behavior, regardless of social status. The results are discussed in terms of the comparability with previous findings and practical implications. Aggr. Behav. 42:82–96, 2016. © 2015 Wiley Periodicals, Inc.
Interobserver agreement for neonatal seizure detection using multichannel EEG
Authors: Stevenson Nathan J. , Clancy Robert R. , Vanhatalo Sampsa , Rosén Ingmar , Rennie Janet M. , Boylan Geraldine B.
Published: October 2015

Objective

To determine the interobserver agreement (IOA) of neonatal seizure detection using the gold standard of conventional, multichannel EEG.

Methods

A cohort of full‐term neonates at risk of acute encephalopathy was included in this prospective study. The EEG recordings of these neonates were independently reviewed for seizures by three international experts. The IOA was estimated using statistical measures including Fleiss' kappa and percentage agreement assessed over seizure events (event basis) and seizure duration (temporal basis).

Results

A total of 4066 h of EEG recordings from 70 neonates were reviewed with an average of 2555 seizures detected. The IOA was high with temporal assessment resulting in a kappa of 0.827 (95% CI: 0.769–0.865; n = 70). The median agreement was 83.0% (interquartile range [IQR]: 76.6–89.5%; n = 33) for seizure and 99.7% (IQR: 98.9–99.8%; n = 70) for nonseizure EEG. Analysis of events showed a median agreement of 83.0% (IQR: 72.9–86.6%; n = 33) for seizures with 0.018 disagreements per hour (IQR: 0.000–0.090 per hour; n = 70). Observers were more likely to disagree when a seizure was less than 30 sec. Overall, 33 neonates were diagnosed with seizures and 28 neonates were not, by all three observers. Of the remaining nine neonates with contradictory EEG detections, seven presented with low total seizure burden.

Interpretation

The IOA is high among experts for the detection of neonatal seizures using conventional, multichannel EEG. Agreement is reduced when seizures are rare or have short duration. These findings support EEG‐based decision making in the neonatal intensive care unit, inform EEG interpretation guidelines, and provide benchmarks for seizure detection algorithms.
Synthesis and Photovoltaic Properties of the Novel Dye of Branched Chain Polymeric Metal Complexes with Cyclopentadithiophene Derivatives as a Donor
Authors: Liu Ye , Xie Qiufang , Hu Jiaomei , Peng Dahai , Liao Yanlong , Zhu Chunxiao , Zhong Chaofan
Published: October 2015

Four novel donor‐π‐acceptor dyes (P1–P4) based on branched chain polymeric metal complexes were designed and synthesized, which use cyclopentadithiophene or fluorene derivatives as an electron donor (D), phenanthroline metal complex as an electron acceptor (A), and thiophene as a π‐bridge (π). The photovoltaic performances of dye‐sensitized solar cells (DSSCs) based on the four polymers were investigated. The results show that they all have good thermal stability (Td,P1 313°C, P2 320°C, P3 306°C, P4 340°C), and the dyes with cyclopentadithiophene derivatives as a donor (P1 and P2) show higher power conversion efficiency (P1 2.41%, P2 2.31%) than that with fluorene derivatives (P3 1.65%, P4 1.52%) under standard illumination due to their broader absorptions in the UV–visible region and lower band gaps. It indicates a new way to design stable and highly efficient DSSCs with novel conjugated organic polymers as dyes.
Mesoporous Li3VO4/C Submicron‐Ellipsoids Supported on Reduced Graphene Oxide as Practical Anode for High‐Power Lithium‐Ion Batteries
Authors: Li Qidong , Wei Qiulong , Sheng Jinzhi , Yan Mengyu , Zhou Liang , Luo Wen , Sun Ruimin , Mai Liqiang
Published: October 2015

Despite the enormous efforts devoted to high‐performance lithium‐ion batteries (LIBs), the present state‐of‐the‐art LIBs cannot meet the ever‐increasing demands. With high theoretical capacity, fast ionic conductivity, and suitable charge/discharge plateaus, Li3VO4 shows great potential as the anode material for LIBs. However, it suffers from poor electronic conductivity. In this work, we present a novel composite material with mesoporous Li3VO4/C submicron‐ellipsoids supported on rGO (LVO/C/rGO). The synthesized LVO/C/rGO exhibits a high reversible capacity (410 mAh g−1 at 0.25 C), excellent rate capability (230 mAh g−1 at 125 C), and outstanding long‐cycle performance (82.5% capacity retention for 5000 cycles at 10 C). The impressive electrochemical performance reveals the great potential of the mesoporous LVO/C/rGO as a practical anode for high‐power LIBs.
CuSbSe2 as a Potential Photovoltaic Absorber Material: Studies from Theory to Experiment
Authors: Xue Ding‐Jiang , Yang Bo , Yuan Zhen‐Kun , Wang Gang , Liu Xinsheng , Zhou Ying , Hu Long , Pan Daocheng , Chen Shiyou , Tang Jiang
Published: October 2015

CuSbSe2 appears to be a promising absorber material for thin‐film solar cells due to its attractive optical and electrical properties, as well as earth‐abundant, low‐cost, and low‐toxic constituent elements. However, no systematic study on the fundamental properties of CuSbSe2 has been reported, such as defect physics, material, optical, and electrical properties, which are highly relevant for photovoltaic application. First, using density functional theory calculations, CuSbSe2 is shown to have benign defect properties, i.e., free of recombination‐center defects, and flexible defect and carrier concentration which can be tuned through the control of growth condition. Next, systematic material, optical, and electrical characterizations uncover many unexplored fundamental properties of CuSbSe2 including band position, temperature‐dependent band gap energy, Raman spectrum, and so on, thus providing a solid foundation for further photovoltaic research. Finally, a prototype CuSbSe2‐based thin film solar cell is fabricated by a hydrazine solution process. The systematic theoretical and experimental investigation, combined with the preliminary efficiency, confirms the great potential of CuSbSe2 for thin‐film solar cell applications.
Calculation of the phase envelope of multicomponent mixtures with the bead spring method
Authors: Nikolaidis Ilias K. , Economou Ioannis G. , Boulougouris Georgios C. , Peristeras Loukas D.
Published: October 2015

A robust numerical scheme for the calculation of constant composition (isoplethic) phase diagrams of complex multicomponent mixtures is presented. The scheme refers to the sequential calculation of the phase envelope of a mixture by guiding the estimation for the equilibrium curve via the introduction of a “spring” that sets the slope value of the modified tangent plane distance with respect to either temperature or pressure. A simple variation of the proposed method allows direct estimation of the Cricondentherm and/or Cricondenbar points, thus avoiding the calculation of the entire phase diagram. Extensive tests of the proposed scheme for different types of phase diagrams, using both cubic and higher‐order equations of state are presented. © 2015 American Institute of Chemical Engineers AIChE J, 62: 868–879, 2016
A General Strategy for Synthesis of Heterocyclic Hemiketal‐Containing α,β‐Unsaturated Ketones from Ynediones
Authors: Zhang Zeguang , Dai Zhihong , Jiang Xuefeng
Published: October 2015

A general strategy for synthesis of heterocyclic hemiketal‐containing α,β‐unsaturated ketones has been established. Using the environmentally sound and readily available reagents water and thiourea applied to ynediones, a series of sensitive hemiketals of 3(2 H)‐furanones and 3(2 H)‐thienones were constructed under mild conditions. Both of the reaction conditions are compatible with a diverse range of functional groups. Isotopic labeling, tautomerism, and GC‐MS tracking methods were used to reveal the mechanisms.
Polymeres graphitisches Kohlenstoffnitrid für die nachhaltige Photoredoxkatalyse
Authors: Zheng Yun , Lin Lihua , Wang Bo , Wang Xinchen
Published: October 2015

Graphitisches Kohlenstoffnitrid (g‐C3N4) ist ein vielversprechendes zweidimensionales konjugiertes Polymer, das als kostengünstiger, robuster, metallfreier und im sichtbaren Spektralbereich aktiver Photokatalysator für die Umwandlung von Sonnenenergie verwendet wird. Hauptthema dieses Aufsatzes sind die neuesten Entwicklungen bei g‐C3N4‐Photokatalysatoren für die Wasserspaltung. Anwendungen für CO2‐Umwandlung, organische Synthese und Schadstoffabbau werden ebenfalls diskutiert. Außerdem werden Methoden zur Anpassung der elektronischen Struktur, Nanostruktur, Kristallstruktur und Heterostruktur von g‐C3N4 sowie die entsprechenden Korrelationen zwischen Struktur und Leistung vorgestellt. Es erfolgt ein Ausblick auf die Herausforderungen und Chancen bei der künftigen Erforschung von g‐C3N4‐Photokatalysatoren. Dieser Aufsatz ist als eine Werbung für die Nutzung von g‐C3N4‐Materialien auf den Gebieten der Photokatalyse, der Energieumwandlung, des Schadstoffabbaus und für Sensoren gedacht.
Die Diarylprolinolsilylether: zehn Jahre später
Authors: Donslund Bjarke S. , Johansen Tore Kiilerich , Poulsen Pernille H. , Halskov Kim Søholm , Jørgensen Karl Anker
Published: October 2015

Die asymmetrische Organokatalyse hat seit Beginn dieses Jahrhunderts eine unglaubliche Entwicklung erlebt, die zu einer Vielzahl leistungsfähiger Katalysatortypen führte. Darunter sind die 2005 eingeführten Diarylprolinolsilylether eine der in der Aminokatalyse am häufigsten verwendeten Gruppen. In diesem Kurzaufsatz – zehn Jahre nach Einführung der Diarylprolinolsilylether – wollen wir einen Rückblick wagen. Dabei liegt der Schwerpunkt auf den Möglichkeiten der verschiedenen Aktivierungsmodi, die dieses katalytische System zugänglich macht. Nach einer kurzen Einführung in die Aminokatalyse gehen wir auf die Eigenschaften ein, die Diarylprolinolsilylether zu häufig gewählten Katalysatoren gemacht haben. Des Weiteren werden die Hauptrichtungen der Aktivierung sowie die im Hinblick auf Reaktionsmuster entwickelten Reaktionskonzepte und Kombinationen mit anderen Aktivierungskonzepten beschrieben.
Ein neutrales frustriertes Silicium/Phosphor‐Lewis‐Paar
Authors: Waerder Benedikt , Pieper Martin , Körte Leif A. , Kinder Timo A. , Mix Andreas , Neumann Beate , Stammler Hans‐Georg , Mitzel Norbert W.
Published: October 2015

Frustrierte Lewis‐Paare (FLPs) zeigen großes Potenzial für die Aktivierung kleiner Moleküle. Die meisten bekannten FLP‐Systeme basieren auf Bor‐ oder Aluminiumatomen als saure Funktionen, wenige auf Zink und nur zwei auf zum Bor isoelektronischen Silicenium‐Kation‐Systemen. Hier stellen wir das erste FLP‐System vor, das auf einem neutralen Silan aufbaut, (C2F5)3SiCH2P(tBu)2 (1). Es wurde aus (C2F5)3SiCl mit stark elektronegativen C2F5‐Gruppen durch Umsetzung mit LiCH2P(tBu)2 hergestellt. H/D‐Austauschreaktionen an H2/D2‐Gemischen belegen, dass 1 in der Lage ist, Wasserstoff zu spalten; es kann auch CO2 sowie SO2 addieren. Die Strukturen von 1, seinen CO2‐ und SO2‐Addukten sowie die eines Zersetzungsproduktes mit CO2 wurden durch Röntgenbeugung am Kristall aufgeklärt.
Einzelmolekül‐Spinschalter auf Basis spannungsinduzierter Verzerrung der Koordinationssphäre
Authors: Harzmann Gero D. , Frisenda Riccardo , van der Zant Herre S. J. , Mayor Marcel
Published: October 2015

Wir berichten hier über ein neuartiges Einzelmolekül‐Schaltkonzept, das auf dem Koordinationssphären‐abhängigen Spinzustand von FeII‐Komplexen beruht. Die lotrechte Anordnung zweier Terpyridin(tpy)‐Liganden eines heteroleptischen Komplexes wird durch das angelegte elektrische Feld verzerrt. Während der eine Ligand den Komplex zwischen beiden Elektroden fixiert, erfühlt der zweite Ligand durch ein intrinsisches Dipolmoment das angelegte elektrische Feld, was zur Verzerrung der Koordinationssphäre und dadurch zum Spinübergang führt. Eine Serie von Komplexen mit unterschiedlichen Dipolmomenten wurde hergestellt und auf ihre Transporteigenschaften in mechanisch kontrollierten Bruchkontakten untersucht. Die statistische Auswertung stützt die Hypothese des Schaltmechanismus, bei dem mit zunehmender Stärke des Dipolmomentes des Eisenkomplexes die Anzahl der Einzelmolekülkontakte mit spannungsabhängigen Bistabilitäten zunimmt. Ein konstanter Schwellwert der E‐Feldstärke, die zum Schalten eines Kontaktes erforderlich ist, spricht ebenfalls für den postulierten Schaltmechanismus.
Rapid Determination of the Specificity Constant of Irreversible Inhibitors (kinact/KI) by Means of an Endpoint Competition Assay
Authors: Miyahisa Ikuo , Sameshima Tomoya , Hixon Mark S.
Published: October 2015

Owing to their covalent target occupancy, irreversible inhibitors require low exposures and offer long duration, and their use thus represents a powerful strategy for achieving pharmacological efficacy. Importantly, the potency metric of irreversible inhibitors is kinact/KI not IC50. A simple approach to measuring kinact/KI was developed that makes use of an irreversible probe for competitive assays run to completion against test compounds. In this system, the kinact/KI value of the test compound is equal to (kinact/KI)probe×[probe]/IC50. The advantages of this method include simplicity, high throughput, and application to all target classes, and it only requires an in‐depth kinetic evaluation of the probe.
Remote Control of the Planar Chirality in Peptide‐Bound Metallomacrocycles and Dynamic‐to‐Static Planar Chirality Control Triggered by Solvent‐Induced 310‐to‐α‐Helix Transitions
Authors: Mamiya Fumihiko , Ousaka Naoki , Yashima Eiji
Published: October 2015

The dynamic planar chirality in a peptide‐bound NiII‐salphen‐based macrocycle can be remotely controlled. First, a right‐handed (P)‐310‐helix is induced in the dynamic helical oligopeptides by a chiral amino acid residue far from the macrocyclic framework. The induced planar chirality remains dynamic in chloroform and acetonitrile, but is almost completely locked in fluoroalcohols as a result of the solvent‐induced transition of the peptide chains from a 310‐helix to a wider α‐helix, which freezes the rotation of the pendant peptide units around the macrocycle.
Alexithymia in children with and without autism spectrum disorders
Authors: Griffin Cáit , Lombardo Michael V. , Auyeung Bonnie
Published: October 2015

Alexithymia refers to pronounced difficulty in identifying and describing one's own emotions and is associated with an externally oriented focus of thinking. Alexithymia is known to be much more common in adults with autism spectrum disorders (ASD) compared with the typically developing (TD) adult population. However, we know very little about alexithymia in young children with ASD and advancing our understanding of this topic may be of critical clinical and translational importance. Here, we present the first study to examine alexithymia in children with ASD. We find that alexithymia is substantially elevated in ASD on both self‐ and parent‐report measures. Despite both measures being sensitive to on‐average group differentiation, we find no evidence of correlation between such measures, indicating that children and their parents may be using different sources of information. Parent‐rated alexithymia is also associated with increasing levels of autistic traits. Discrepancy between self and other alexithymia ratings are also associated with autistic traits, but only in ASD. These results underscore the idea that assessing alexithymia in ASD at younger ages may help identify important subgroups that have particular difficulties in the domain of emotion processing. Autism Res 2016, 9: 773–780. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
Toleranzen und Vorhaltemaß der Betondeckung beim Nachweis der Feuerwiderstandsdauer im Massivbau
Authors: Unterbuchberger Claudia , Müller André
Published: October 2015

Bezüglich des konstruktiven Brandschutznachweises von Stahl‐ und Spannbetonbauteilen ist die Betondeckung der Bewehrung eine der entscheidensten Einflussgrößen. Seit Längerem steht immer wieder die Frage im Raum, wie hinsichtlich dieses relevanten Parameters eine Gleichstellung zwischen Neu‐ und Bestandsbauten beim Nachweis der Feuerwiderstandsdauer erzielt werden kann. Während für Neubauten die Verwendung des Nennmaßes normativ eindeutig zugelassen ist, besteht im Bestand nicht selten die Notwendigkeit, den rechnerisch ansetzbaren Wert auf Basis von Betondeckungsmessungen zu definieren.

Mit dem Ziel, künftig ein vergleichbares Sicherheitsniveau zwischen neuen und bestehenden Bauwerken im Brandfall erreichen zu können, werden in diesem Beitrag sowohl Überlegungen zur Durchführung als auch zur statistischen Auswertung von Betondeckungsmessungen angestellt. Besonderes Augenmerk wird dabei auf die bauseitig unvermeidbaren Streuungen der Betondeckung und deren Auswirkungen auf die Feuerwiderstandsdauer verschiedener Bauteilarten gelegt. Beispiele aus der Praxis verdeutlichen die behandelte Thematik. Auf Grundlage der gewonnenen Erkenntnisse wird abschließend eine neue Vorgehensweise zur Festlegung der rechnerisch ansetzbaren Betondeckung für den Nachweis der Feuerwiderstandsdauer im Massivbau formuliert.

Concrete cover tolerances and allowance with regard to the fire resistance design of concrete structures

Regarding the fire resistance design of reinforced and prestressed concrete members the cover of reinforcement is one of the most important parameters. With reference to the chargeable concrete cover, the problem of how to ensure the same standards for new and existing buildings hasn't been solved so far. In contrast to historical buildings the use of the nominal dimension is undoubtedly normatively admitted for new constructions. However, the first‐mentioned often require the interpretation of concrete cover measurements.

To guarantee a comparable safety level in future in case of fire between new and existing structures, this article deals with the realization and probabilistic assessment of the named measurements. Specific attention is given to the unavoidable statistical scattering and its effects on the fire safety of various structural member types. Practical examples visualize the treated subject. Based on the results gained from these investigations, a new approach is established to define the chargeable cover of reinforcement for the fire resistance design.
Addressing the cross‐country applicability of the theory of planned behaviour (TPB): A structured review of multi‐country TPB studies
Authors: Hassan Louise M. , Shiu Edward , Parry Sara
Published: October 2015

The theories of reasoned action and planned behaviour (TRA/TPB) have received substantial research interest from consumer behaviourists. One important area of interest that has not been adequately researched concerns the impact of national culture on the TRA/TPB components and interrelationships. To date, no systematic assessment of the impact of culture on the TRA/TPB model relationships has been undertaken. In order to understand the potential impact of culture on the TRA/TPB model relationships, a structured review of TRA/TPB studies is undertaken. Studies that have quantitatively applied the TRA/TPB across at least two countries within a consumption domain since 2000 are reviewed. The authors propose that two of Hofstede's cultural dimensions, individualism and power distance, may moderate the TRA/TPB relationships. The review highlights that the impact of subjective norm on intention varies most across countries, with the relationship between intention and both attitude and perceived behavioural control operating more similarly across country samples. Further, a systematic assessment of variation in the TRA/TPB model relationships via multilevel modelling shows that only the subjective norm–intention relationship varies across the countries studied. The relationship between subjective norm and intention is found to be influenced by power distance, with a stronger relationship evident in high power distance cultures. This review is the first of its kind and is of significance in addressing the emic versus etic nature of the TRA/TPB. Importantly, the article outlines relevant avenues and recommendations for future cross‐national research utilizing the TRA/TPB. Copyright © 2015 John Wiley & Sons, Ltd.
Interactions between Flavins and Quadruplex Nucleic Acids
Authors: Merkle Tobias , Sinn Malte , Hartig Jörg S.
Published: October 2015

Quadruplex nucleic acids are widespread in genomes. They influence processes such as transcription, translation, replication, recombination, and the regulation of gene expression. Several synthetic ligands have been demonstrated to target quadruplex nucleic acids. However, only very few metabolites have been reported to interact with quadruplexes. In principle, an intracellular metabolite that selectively binds to four‐stranded sequences could modulate quadruplex formation, stability, and thus functions in a riboswitch (or deoxyriboswitch) manner. Here we report quadruplex interactions with flavin derivatives such as FMN and FAD. The affinities were highest with parallel quadruplexes, with low (14–20 μm) dissociation constants. Taking into account combined intracellular flavin concentrations of 243 μm in E. coli, the observed interactions in principle open up the possibility of flavin levels affecting gene expression and other processes by modulating quadruplex formation.
ChemInform Abstract: Tuning Sodium Ion Conductivity in the Layered Honeycomb Oxide Na3‐xSn2‐xSbxNaO6.
Authors: Smaha Rebecca W. , Roudebush John H. , Herb Jake T. , Seibel Elizabeth M. , Krizan Jason W. , Fox Gary M. , Huang Qingzhen , Arnold Craig B. , Cava Robert J.
Published: October 2015

The title compounds are prepared by solid‐state reaction of stoichiometric amounts of Na2CO3, SnO2, and Sb2O5 (1.
ChemInform Abstract: Synthesis of Enantioenriched 1,2‐trans‐Diamines Using the Borono‐Mannich Reaction with N‐Protected α‐Amino Aldehydes.
Authors: Norsikian Stephanie , Beretta Margaux , Cannillo Alexandre , Martin Amelie , Retailleau Pascal , Beau Jean‐Marie
Published: October 2015

1,2‐trans‐diamines are prepared with an enantiomeric excess of up to 98% e.e.
ChemInform Abstract: Regioselectivity Switch in Chiral Amine‐Catalyzed Asymmetric Addition of Aldehydes to Reactive Enals.
Authors: Kano Taichi , Maruyama Hiroki , Sakamoto Ryu , Maruoka Keiji
Published: October 2015

1,2‐ or 1,4‐addition of aldehydes to enals can be controlled by the choice of catalyst.
ChemInform Abstract: An Unsymmetrical Iron Catalyst for the Asymmetric Transfer Hydrogenation of Ketones.
Authors: Smith Samantha A. M. , Morris Robert H.
Published: October 2015

The new iron(II)(Ph2P‐NH‐N‐PCy2) complex possessing a dicyclohexylphosphino group trans to the NH group efficiently catalyzes the asymmetric transfer hydrogenation of prochiral ketones furnishing the corresponding alcohols with high enantioselectivity.
ChemInform Abstract: Uses of 1‐(3‐Cyano‐4,5,6,7‐tetrahydrobenzo [b]‐thiophen‐2‐yl)‐3‐dodecanoylthiourea as a Building Block in the Synthesis of Fused Pyrimidine and Thiazine Systems.
Authors: Hemdan Magdy Mohamed , Abd El‐Mawgoude Heba Kamal
Published: October 2015

The title compound prepared by reaction of lauroyl isothiocyanate with 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]‐thiophene‐3‐carbonitrile, is used to synthesize several condensed pyrimidines via intramolecular exo‐dig annulation reactions.
ChemInform Abstract: Bond‐Weakening Catalysis: Conjugate Aminations Enabled by the Soft Homolysis of Strong N—H Bonds.
Authors: Tarantino Kyle T. , Miller David C. , Callon Ted A. , Knowles Robert R.
Published: October 2015

A catalytic bond‐weakening protocol for the conjugate amination is reported.
ChemInform Abstract: The 4,5‐Methano‐L‐proline as a Chiral Organocatalysts in Direct Asymmetric Aldol Reactions.
Authors: Yu Na , Han Sheng , Yu Han
Published: October 2015

The reaction works well with acyclic and cyclic ketones and arylaldehydes whereas isobutyraldehyde as reaction partner only yields trace amounts of the desired product.
ChemInform Abstract: Rh(I)‐Catalyzed Hydroamidation of Olefins via Selective Activation of N—H Bonds in Aliphatic Amines.
Authors: Dong Kaiwu , Fang Xianjie , Jackstell Ralf , Laurenczy Gabor , Li Yuehui , Beller Matthias
Published: October 2015

In the presence of a ligand‐ and additive‐free Rh(I) catalyst various olefins and aliphatic amines are transformed into N‐alkyl amides in medium to high yields with excellent regioselectivities.
ChemInform Abstract: Scalable Synthesis of the Potent HIV Inhibitor BMS‐986001 by Non‐enzymatic Dynamic Kinetic Asymmetric Transformation (DYKAT).
Authors: Ortiz Adrian , Benkovics Tamas , Beutner Gregory L. , Shi Zhongping , Bultman Michael , Nye Jeffrey , Sfouggatakis Chris , Kronenthal David R.
Published: October 2015

Title compound (IX*) is prepared from racemic lactol (I) using small‐molecule‐mediated dynamic kinetic resolution and a selective pyranose‐to‐furanose ring contraction as the key steps.
ChemInform Abstract: Highly Efficient and Eco‐Friendly Protocol to Functionalized Imidazoles via Ring‐Opening of α‐Nitro Epoxides.
Authors: Guo Xiao , Shao Jiaan , Liu Huan , Chen Binhui , Chen Wenteng , Yu Yongping
Published: October 2015

2‐Alkyl‐3‐aryl disubstituted α‐nitroepoxides are efficiently reacted with aryl, alkyl, and formamidines to form highly substituted imidazoles in high yields.
ChemInform Abstract: Prussian Blue Derived Nanoporous Iron Oxides as Anticancer Drug Carriers for Magnetic‐Guided Chemotherapy.
Authors: Zakaria Mohamed B. , Belik Alexei A. , Liu Chia‐Hung , Hsieh Han‐Yun , Liao Yu‐Te , Malgras Victor , Yamauchi Yusuke , Wu Kevin. C.‐W.
Published: October 2015

Nanoporous iron oxide nanoparticles with superparamagnetic behavior are prepared from Prussian blue nanocubes by thermal aging of an aqueous solution of PVP and K3[Fe(CN)6] in 0.01 M HCl (80 °C, 30 h) followed by thermal decomposition in air (250 and 400 °C,1 h).
ChemInform Abstract: Synthetic Chemistry with Nitrous Oxide
Authors: Severin Kay
Published: October 2015

Review: [use of N2O as O‐atom donor, as N‐atom donor, or as a oxidant in metal‐catalyzed reactions; 116 refs.
ChemInform Abstract: Hypervalent Iodine(III) in Direct Carbon—Hydrogen Bond Functionalization
Authors: Narayan Rishikesh , Manna Srimanta , Antonchick Andrey P.
Published: October 2015

Review: [36 refs.
ChemInform Abstract: A Concise Synthesis of Isatin‐Based Aromatic Compounds in Water as the Reaction Medium Resulting in an Approach to Green Chemistry
Authors: Nikoofar Kobra , Dizgarani Shekoufe Moazzez
Published: October 2015

Review: 141 refs.
ChemInform Abstract: Why You Really Should Consider Using Palladium‐Catalyzed Cross‐Coupling of Silanols and Silanolates
Authors: Denmark Scott E. , Ambrosi Andrea
Published: October 2015

Review: [70 refs.
ChemInform Abstract: Enzymatic Conversion of Carbon Dioxide
Authors: Shi Jiafu , Jiang Yanjun , Jiang Zhongyi , Wang Xueyan , Wang Xiaoli , Zhang Shaohua , Han Pingping , Yang Chen
Published: October 2015

Review: 49 refs.
ChemInform Abstract: Label‐Free DNA Sensors Based on Field‐Effect Transistors with Semiconductor of Carbon Materials
Authors: Zhao Lu , Cao Dapeng , Gao Zhiqiang , Mi Baoxiu , Huang Wei
Published: October 2015

Review: 99 refs.
ChemInform Abstract: High‐Frequency and ‐Field Electron Paramagnetic Resonance of Vanadium(IV, III, and II) Complexes
Authors: Krzystek J. , Ozarowski Andrew , Telser Joshua , Crans Debbie C.
Published: October 2015

Review: 152 refs.