bluuebunny/crossref_metadata_2025 huggingface dataset:
Bertrand Russell e a cura dos provincialismos por meio do ensino da história
Authors: Valle Júlio César Augusto do
Published: August 2016

O propósito deste artigo consiste em oferecer ao historiador e também ao professor de história elementos que orientaram a perspectiva de Bertrand Russell, matemático e filósofo reconhecido no século XX, sobre estas áreas de estudos. Assim, no cerne do debate está a “cura dos provincialismos” – expressão muito utilizada por Russell – que o ensino da história pode proporcionar aos educandos. Para isto, há também a elucidação de um possível diálogo entre Russell e Freire no que tange aos receios freireanos com o fatalismo que corrompe o senso histórico dos homens, tornando-os deterministas e implicando, mais gravemente, a redução do futuro ao presente.
As possibilidades da literatura infantil/juvenil no processo de aprendizagem histórica
Authors: Thomson Ana Beatriz Accorsi
Published: August 2016

Essa pesquisa tem como objetivo geral estabelecer considerações acerca da utilização dos paradidáticos no ensino de história e analisar como os professores se relacionam e entendem tais materiais. Nesse sentido, buscamos inicialmente nesse artigo investigar o contexto de surgimento da literatura infantil/juvenil e dos materiais paradidáticos voltados ao ensino de história. Buscamos analisar também as tendências mais atuais dos materiais literários voltados ao público jovem, verificando as possibilidades de articulação com um ensino de história mais significativo e preocupado com a alteridade. Consideramos importante verificar a hipótese de que a utilização desse tipo de material possa expandir os conteúdos que normalmente são abordados pelos professores no ensino de história, podendo representar também um incentivo à formação do aluno-leitor. Assim, concordamos com as propostas teórico-metodológicas do campo da Educação Histórica, que têm buscado analisar e compreender as diversas práticas em sala aula, as relações entre professores e alunos, a construção do conhecimento histórico, das narrativas e, também, como os materiais didáticos e paradidáticos se articulam ao processo de aprendizagem.
As publicações do projeto Jovens e a História (2007–2014): Metodologia, conceitos, temáticas, abordagens e algumas conclusões
Authors: Barom Wilian Carlos Cipriani
Published: August 2016

Coordenado pelo prof. Dr. Luis Fernando Cerri, o projeto de pesquisa “Jovens e a História”, financiado pelo CNPq (2010 - 2012) e pela Fundação Araucária (2014- 2016), é um levantamento sobre a consciência histórica, cultura política e percepções da aprendizagem escolar de História de jovens entre 15 e 16 anos na América do Sul (Brasil, Argentina, Paraguai, Chile, Uruguai). Esta coleta de dados foi feita por meio de questionários impressos, para professores e alunos, em uma sala de aula por escola, em sete tipos de escolas (Pública de excelência, pública de periferia, pública rural, pública central, privada laica empresarial, privada laica comunitária e privada confessional). O que resultou num montante de 3246 questionários aplicados à alunos e 267 a professores. Com esta aplicação concluída em 2013, pesquisadores iniciaram um processo de análise destes dados, o que resultou em inúmeras publicações científicas. O presente artigo busca realizar uma breve análise destas publicações na intenção apontar os principais conceitos e teorias que envolvem o Projeto Jovens e a História, sua metodologia de pesquisa, limites estruturais e possibilidades, além de temáticas e abordagens que estão sendo preferidas por estes pesquisadores. Contou com uma amostra de doze artigos publicados em periódicos, um trabalho dissertativo e oito publicações de comunicação oral, num recorte de 2007 a 2014.

 
Response Patterns of Art Based Intervention for Self-Regulation among Athletes
Authors: Roy Jolly , Kuan Garry , Chy Tneh Khai
Published: August 2016

Competition outcome often shows a player’s ability to self-regulate and be in control. This study examined the response patterns of Clay Button Method (CBM), an adapted art approach, in a sport context, among Paralympics, footballers and injured athletes for self-regulation. The article enlists the steps involved in CBM and the percentage of change is noted across six sessions among the participants. CBM focuses on teaching self-regulation by identifying individual areas of strengths and areas of concern, to build personal resources and weed out possible deficits. The participants engaged in CBM using playing clay, making their own self-image and exploring any unresolved emotional issues and bringing in desired changes. The response patterns revealed a trend where the players were able to self-regulate by reducing unproductive thoughts and strengthening personal resources. The study provides preliminary findings for introducing innovative approach in a sport context.
Assessing Four Quality Indicators for Multiple Sclerosis Management Through Patient-Reported Data
Authors: Shoemaker Sarah J. , Pozniak Alyssa , Hadden Louise
Published: August 2016

Background: Although hundreds of quality indicators (QIs) have been developed for various chronic conditions, QIs specific to multiple sclerosis (MS) care have only recently been developed. We sought to examine the extent to which the self-reported care of individuals with MS meets four recently developed MS QIs related to treatment of depression, spasticity, and fatigue and timely initiation of disease-modifying agents (DMAs) for relapsing MS.

Methods: Using the Sonya Slifka Study data, we examined the proportion of the MS population meeting four QIs (based on patient-reported data) in a sample of individuals with MS in 2007–2009. For the three diagnoses, meeting the QI was defined as receiving appropriate medication or seeing a provider for treatment of the diagnosis; for timely initiation, it was defined as receiving a DMA within 3 months of a relapsing MS diagnosis. We also examined differences in characteristics between respondents who met the QI versus those who did not.

Results: Approximately two-thirds of people with MS in this sample, per the predefined criteria, met the QIs for treatment of depression, management of spasticity, and DMA initiation within 3 months of a relapsing diagnosis, and approximately one-fifth met the QI for management of fatigue. There were some significant differences in characteristics between respondents who met the QIs and those who did not.

Conclusions: This study examined a subset of MS QIs based on patient-reported data. Additional data sources are needed to fully assess compliance with MS QIs.
Preliminary conceptual model of an Alpine carbonate aquifer (Pale di San Martino, Dolomites, Italy)
Authors: Lucianetti Giorgia , Mastrorillo Lucia , Mazza Roberto
Published: August 2016

A hydrogeological and hydrochemical monitoring was conducted in the Pale di San Martino mountain ridge (Trento and Belluno Provinces, Italy) to build a preliminary conceptual model of the groundwater system. The model derives from a combination of new fieldwork and preexisting data provided by various public authorities. New data include geological and hydrogeological surveys, such as in situ measurements of the physical and chemical parameters, geochemical sampling and streamflow measurements. The lithologies outcropping in the area were grouped into seven hydrogeological complexes, each playing a different role in groundwater circulation. The dolomitic body of the ridges forms the main aquifer complex and is located above a terrigenous and evaporitic aquiclude. Due to this geometrical relationship, the site can be considered an isolated hydrostructure with well-defined no-flow boundaries. The main springs outcome near the aquifer-aquiclude boundary and in particular where the elevation of the contact is low and the tectonic pattern favors the drainage. Most of them have a calciumbicarbonate water composition, low temperature and low electrical conductivity, supporting the hypothesis of a fast flowing circulation in carbonate rocks and a high-altitude recharge. Seasonal streamflow measurements allowed the identification of linear springs and provided the first cumulative discharge data at the scale of the entire mountain group. The resulting model highlights a great spatial and temporal variability of the groundwater resources. Considering the geometry of the aquifer and the great seasonal variability of the discharge, it is possible to infer the absence of significant groundwater reserves at a regional scale. Thus, the hydrostructure shows a great capacity to supply water resources (mean discharge of 6 m3/s), but a low selfregulation capacity. It is necessary to consider this aspect when planning a long-term exploitation of the water resources that are used in the area for drinking purposes and hydropower generation.
Water conflicts
Authors: La Vigna Francesco
Published: August 2016

Not available.
Trains of large Kelvin‐Helmholtz billows observed in the Kuroshio above a seamount
Authors: Chang Ming‐Huei , Jheng Sin‐Ya , Lien Ren‐Chieh
Published: August 2016

Trains of large Kelvin‐Helmholtz (KH) billows within the Kuroshio current at ~230 m depth off southeastern Taiwan and above a seamount were observed by shipboard instruments. The trains of large KH billows were present in a strong shear band along the 0.55 m s−1 isotach within the Kuroshio core; they are presumably produced by flow interactions with the rapidly changing topography. Each individual billow, resembling a cat's eye, had a horizontal length scale of 200 m, a vertical scale of 100 m, and a timescale of 7 min, near the local buoyancy frequency. Overturns were observed frequently in the billow cores and the upper eyelids. The turbulent kinetic energy dissipation rates estimated using the Thorpe scale had an average value of O(10−4) W kg−1 and a maximum value of O(10−3) W kg−1. The turbulence mixing induced by the KH billows may exchange Kuroshio water with the surrounding water masses.
Was Venus the first habitable world of our solar system?
Authors: Way M. J. , Del Genio Anthony D. , Kiang Nancy Y. , Sohl Linda E. , Grinspoon David H. , Aleinov Igor , Kelley Maxwell , Clune Thomas
Published: August 2016

Present‐day Venus is an inhospitable place with surface temperatures approaching 750 K and an atmosphere 90 times as thick as Earth's. Billions of years ago the picture may have been very different. We have created a suite of 3‐D climate simulations using topographic data from the Magellan mission, solar spectral irradiance estimates for 2.9 and 0.715 Gya, present‐day Venus orbital parameters, an ocean volume consistent with current theory, and an atmospheric composition estimated for early Venus. Using these parameters we find that such a world could have had moderate temperatures if Venus had a prograde rotation period slower than ~16 Earth days, despite an incident solar flux 46–70% higher than Earth receives. At its current rotation period, Venus's climate could have remained habitable until at least 0.715 Gya. These results demonstrate the role rotation and topography play in understanding the climatic history of Venus‐like exoplanets discovered in the present epoch.
On the relationship between atmospheric rivers and high sea water levels along the U.S. West Coast
Authors: Khouakhi A. , Villarini G.
Published: August 2016

Atmospheric rivers (ARs) are narrow filaments of high moisture transported within extratropical systems. The role of ARs as drivers of heavy precipitation and flooding has been well documented; however, little is known about the contribution of landfalling ARs to high sea water levels, which are the leading cause of coastal flooding. Here we assess the relationship between ARs and extreme hourly sea level time series at 15 tide gauges along the continental U.S. Pacific Coast. Results indicate that ARs are associated with 15% to 50% of the annual sea level maxima before (and 22% to 65% after) removing tidal oscillations. Strong associations are also found when using other high sea level metrics. From a climatic perspective, the frequency of extreme hourly sea levels tends to increase during the negative phase of the Arctic Oscillation and during the positive phases of the Pacific‐North American pattern and the El Niño–Southern Oscillation.
Method for estimating the stress field from seismic moment tensor data based on the flow rule in plasticity theory
Authors: Matsumoto S.
Published: August 2016

The stress field is a key factor controlling earthquake occurrence and crustal evolution. In this study, we propose an approach for determining the stress field in a region using seismic moment tensors, based on the classical equation in plasticity theory. Seismic activity is a phenomenon that relaxes crustal stress and creates plastic strain in a medium because of faulting, which suggests that the medium could behave as a plastic body. Using the constitutive relation in plastic theory, the increment of the plastic strain tensor is proportional to the deviatoric stress tensor. Simple mathematical manipulation enables the development of an inversion method for estimating the stress field in a region. The method is tested on shallow earthquakes occurring on Kyushu Island, Japan.
Monte Carlo simulation of the neutron monitor yield function
Authors: Mangeard P.‐S. , Ruffolo D. , Sáiz A. , Madlee S. , Nutaro T.
Published: August 2016

Neutron monitors (NMs) are ground‐based detectors that measure variations of the Galactic cosmic ray flux at GV range rigidities. Differences in configuration, electronics, surroundings, and location induce systematic effects on the calculation of the yield functions of NMs worldwide. Different estimates of NM yield functions can differ by a factor of 2 or more. In this work, we present new Monte Carlo simulations to calculate NM yield functions and perform an absolute (not relative) comparison with the count rate of the Princess Sirindhorn Neutron Monitor (PSNM) at Doi Inthanon, Thailand, both for the entire monitor and for individual counter tubes. We model the atmosphere using profiles from the Global Data Assimilation System database and the Naval Research Laboratory Mass Spectrometer, Incoherent Scatter Radar Extended model. Using FLUKA software and the detailed geometry of PSNM, we calculated the PSNM yield functions for protons and alpha particles. An agreement better than 9% was achieved between the PSNM observations and the simulated count rate during the solar minimum of December 2009. The systematic effect from the electronic dead time was studied as a function of primary cosmic ray rigidity at the top of the atmosphere up to 1 TV. We show that the effect is not negligible and can reach 35% at high rigidity for a dead time >1 ms. We analyzed the response function of each counter tube at PSNM using its actual dead time, and we provide normalization coefficients between count rates for various tube configurations in the standard NM64 design that are valid to within ∼1% for such stations worldwide.
Relative importance of horizontal and vertical transports to the formation of ionospheric storm‐enhanced density and polar tongue of ionization
Authors: Liu Jing , Wang Wenbin , Burns Alan , Solomon Stanley C. , Zhang Shunrong , Zhang Yongliang , Huang Chaosong
Published: August 2016

There are still uncertainties regarding the formation mechanisms for storm‐enhanced density (SED) in the high and subauroral latitude ionosphere. In this work, we deploy the Thermosphere Ionosphere Electrodynamic General Circulation Model (TIEGCM) and GPS total electron content (TEC) observations to identify the principle mechanisms for SED and the tongue of ionization (TOI) through term‐by‐term analysis of the ion continuity equation and also identify the advantages and deficiencies of the TIEGCM in capturing high‐latitude and subauroral latitude ionospheric fine structures for the two geomagnetic storm events occurring on 17 March 2013 and 2015. Our results show that in the topside ionosphere, upward E × B ion drifts are most important in SED formation and are offset by antisunward neutral winds and downward ambipolar diffusion effects. In the bottomside F region ionosphere, neutral winds play a major role in generating SEDs. SED signature in TEC is mainly caused by upward E × B ion drifts that lift the ionosphere to higher altitudes where chemical recombination is slower. Horizontal E × B ion drifts play an essential role in transporting plasma from the dayside convection throat region to the polar cap to form TOIs. Inconsistencies between model results and GPS TEC data were found: (1) GPS relative TEC difference between storm time and quiet time has “holes” in the dayside ion convection entrance region, which do not appear in the model results. (2) The model tends to overestimate electron density enhancements in the polar region. Possible causes for these inconsistencies are discussed in this article.
An east‐west contrast of upper ocean heat content variation south of the subpolar front in the East/Japan Sea
Authors: Yoon Seung‐Tae , Chang Kyung‐Il , Na Hanna , Minobe Shoshiro
Published: August 2016

Long‐term variability of nonseasonal ocean heat content (OHC) in the upper 500 m in the East/Japan Sea (EJS) exhibits a distinct east‐west contrast during the recent 30 years. The contrasting OHC variations are revisited and investigated more in detail by analyzing two observational data sets, the gridded data from 1976 to 2007 and in situ data from 1976 to 2011 in the southwestern EJS that covers the zone of western boundary current. The OHC variability shows in‐phase and predominant decadal variation in both east and west regions before 1995, but uncorrelated and predominant interannual variations after 1995. Heaving effects due to major branches of warm currents in the EJS, the East Korea Warm Current (EKWC) in the western part and other two branches in the eastern part, mainly contribute to the OHC variations. The heaving effect in the western EJS is shown to be associated with changes in winter wind‐stress curl field in the northern EJS. Weakening of the subpolar gyre due to weakening of positive wind‐stress curl in the Japan Basin related with wintertime Western Pacific teleconnection pattern and Siberian High appears to enhance the northward penetration of the EKWC resulting in an increase of OHC in the western EJS. The heaving effect in the eastern EJS is significantly correlated with the Siberian High, but the causative mechanism is inconclusive. This study also demonstrates the importance of using highly resolved data sets for areas affected by strong and narrow boundary currents in computing and understanding the OHC variability.
Interactions between complex craters and the lunar crust: Analysis using GRAIL data
Authors: Bierson C. J. , Phillips Roger J. , Nimmo Francis , Besserer Jonathan , Milbury Colleen , Keane James T. , Soderblom Jason M. , Zuber Maria T.
Published: August 2016

A high‐resolution gravity map over the entire lunar surface has been derived from data acquired by the Gravity Recovery and Interior Laboratory (GRAIL) mission. Soderblom et al. (2015) showed that crater Bouguer gravity anomalies scale with crater diameter and porosity for craters in the lunar highlands. Here we extend this study globally, examining complex craters in each of the three lunar terranes: highlands, maria, and the South Pole‐Aitken basin. We find that craters within South Pole‐Aitken basin and in the lunar maria have statistically different Bouguer anomalies from those in the lunar highlands. These differences are best explained by differences in crustal porosity among the three terranes. Though there is still much unresolved scatter in the data, we find that no other lunar material properties (crustal thickness, density gradient, etc.) are able to improve our model fit to the data.
Microbial consortia controlling biogenic gas formation in the Qaidam Basin of western China
Authors: Shuai Yanhua , Zhang Shuichang , Grasby Stephen E. , Hou Weiguo , Chen Zhuoheng , Huang Ling , Kui Mingqing , Xu Yirui , Wang Yang
Published: August 2016

Knowledge of what controls the activity of subsurface microbial communities is critical for assessing and managing biogenic methane resources. In this study, 19 formation waters and five gas samples were collected at depths of 800 to 1900 m from Quaternary biogenic gas fields of the Qaidam Basin, China. The formation waters were brines with chloride (Cl) concentrations from 1200 to 2700 mM. Bacterial 16S rRNA gene copies ranged from 3.75 × 104 to 2.23 × 106 copies mL−1 of water, and those of archaea ranged from 2.44 × 103 to 4.66 × 107 copies mL−1 of water. Both bacterial and archaea 16 s rRNA gene copies were negatively correlated with Cl concentration. The microbial community structure differed significantly depending on Cl concentrations. At high Cl waters (>1800 mM), the microbial community showed a halophilic signature made up of several abundant taxonomic groups within Firmicules, γ‐Proteobacteria, and methylotrophic Methanosarcinales. At low Cl, Firmicules and hydrogenotrophic methanogens were dominant members. The proportion of inferred hydrogenotrophic methanogens decreased from 89% to 14% of total archaeal reads with increasing Cl concentration; in contrast, methylotrophic species increased from 11% to 85%. Given that the proportion of hydrogenotrophic species was positively correlated with the archaeal gene abundances, we suggest that Cl concentrations primarily constrain the activity of archaea catalyzing H2 reduction of CO2. Our results show that dilution of formation waters is critical in the process of biogenic gas formation, suggesting that an engineered decrease in Cl concentrations may induce methanogenesis as a potential method to increase gas reserves in such areas in the future.
Toward Tailored Film Morphologies: The Origin of Crystal Orientation in Hybrid Perovskite Thin Films
Authors: Oesinghaus Lukas , Schlipf Johannes , Giesbrecht Nadja , Song Lin , Hu Yinghong , Bein Thomas , Docampo Pablo , Müller‐Buschbaum Peter
Published: August 2016

Efficient perovskite solar cells can be produced by a wide variety of different methods. Previous results show that controlling the film morphology is critical to enhance the efficiency of the prepared devices. Here, grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) is used to study the morphology and especially the orientation distribution of CH3NH3PbI3 (MAPI) perovskite films prepared by five typical methods. We find that the investigated one‐step methods produce non‐oriented films, while the two‐step deposition methods produce varying degrees of orientation depending on the method chosen to convert the highly oriented PbI2 precursor, providing direct evidence for different perovskite conversion mechanisms. In particular, we show that the morphology and crystal orientation of MAPI films is tunable by varying the spin‐coating temperature and by adding chloride to the conversion solution. By relating the precursor morphology to the resulting MAPI film morphology, we link the observed preferential orientations to specific conversion mechanisms, thereby establishing GIWAXS as an important tool toward a rational development of new synthesis methods.
20‐mm‐Large Single‐Crystalline Formamidinium‐Perovskite Wafer for Mass Production of Integrated Photodetectors
Authors: Liu Yucheng , Sun Jiankun , Yang Zhou , Yang Dong , Ren Xiaodong , Xu Hua , Yang Zupei , Liu Shengzhong (Frank)
Published: August 2016

CH3NH3PbX3 (MAPbX3)‐based perovskite has attracted tremendous research efforts in the last few years. With the discovery that the HC(NH2)2PbI3 (FAPbI3) perovskite offers even higher solar cell efficiency, better thermal stability, and broader optical absorption, it is expected that it will provide more excitement in optoelectronic applications including laser, LED, photodetector, etc. The development in preparing large Single‐Crystalline Formamidinium‐Perovskite FAPbI3 using the inverse‐temperature reactive crystallization process, and associated wafer‐slicing process is presented. The availability of the large Single‐Crystalline Formamidinium‐Perovskite Wafer makes it possible to fabricate integrated circuits. An array of 153 photodetectors on a piece of thin wafer, demonstrating feasibility of mass production of integrated circuits on the perovskite wafer is designed and prepared. It is found that the wafer‐based photodetector shows much superior performance, with 90 times higher photoresponse and broader optical absorption than its thin‐film perovskite counterpart.
Hirschsprung disease as a yet undescribed phenotype in a patient with ARID1B mutation
Authors: Takenouchi Toshiki , Yoshihashi Hiroshi , Sakaguchi Yuri , Uehara Tomoko , Honda Masataka , Takahashi Takao , Kosaki Kenjiro , Miyama Sahoko
Published: August 2016

Mutations in the BAF complex (mammalian SWI/SNF complex) are responsible for Coffin‐Siris syndrome, which is characterized by developmental delay, distinctive facial features, hirsutism, and hypoplasia/aplasia of the fifth finger/fingernails. Hirschsprung disease is characterized by defective stem cells in the enteric neural system, and the involvement of multiple signaling cascades has been implicated. So far, the roles of the BAF complex in the genesis of Hirschsprung disease have remained unknown. Here, we document a patient with coarse facial features, postnatal growth failure, developmental delay, epilepsy, and hypoplasia of the corpus callosum and cerebellum but without a hypoplastic fifth finger/fingernail. In addition, he had Hirschsprung disease. Exome sequencing with a gene set representing a total of 4,813 genes with known relationships to human diseases revealed a heterozygous frameshift mutation in ARID1B (c.5789delC p.Pro1930Leufs*44). The presence of a congenital cataract and Hirschsprung disease in the presently reported patient further expands the phenotypic spectrum of patients with ARID1B mutations and may suggest the potential role of the BAF complex in the pathogenesis of the enteric neural system. The present observation is in agreement with a recent study of Drosophila neuroblasts showing that the dysregulated BAF complex leads to an abnormal lineage progression of neural stem cell lineages and that Hirschsprung disease is caused by abnormal stem cell lineages in the peripheral neural tissues. © 2016 Wiley Periodicals, Inc.
Resection of the ethmoidal crest in sphenopalatine artery surgery
Authors: Saraceni Neto Paulo , Nunes Leonardo Mendes Acatauassu , Caparroz Fabio de Azevedo , Gregorio Luciano Lobato , de Souza Rafael de Paula e Silva Felice , Simões Juliana Caminha , Kosugi Eduardo Macoto
Published: August 2016

Background

In severe cases of epistaxis, in spite of several procedures described in the literature for its management, surgical treatment has been recognized by most authors as 1 of the most effective, especially when it includes ligation and/or electrocoagulation of the nasal branches of the sphenopalatine artery. The objective of this study is to determine the importance of ethmoid crest resection during sphenopalatine artery surgery, in the management of severe epistaxis.

Methods

We report a double‐blinded randomized clinical trial, in which intervention was the ethmoid crest resection during electrocoagulation of the sphenopalatine artery. The study participants consisted of 42 patients with severe epistaxis and indication for surgical treatment, treated at the Otorhinolaryngology Emergency Room (ORL ER) of Hospital Sao Paulo, the teaching hospital of the Federal University of Sao Paulo.

Results

There was significant greater exposure of the arterial branch after removal of the ethmoidal crest (p = 0.009). The rate of bleeding within 48 hours of the procedure was significantly lower in the crest removal group.

Conclusion

Resection of the ethmoid crest during sphenopalatine surgery proved to be feasible without additional risks, including promoting decrease in the overall surgical time. It provided better exposure of arterial branches of the sphenopalatine foramen, leading to a lower rebleeding rate within 48 hours.
A Description of Vibrational Modes in Hexaphyrins: Understanding the Aromaticity Reversal in the Lowest Triplet State
Authors: Sung Young Mo , Oh Juwon , Naoda Koji , Lee Taegon , Kim Woojae , Lim Manho , Osuka Atsuhiro , Kim Dongho
Published: August 2016

Aromaticity reversal in the lowest triplet state, or Baird's rule, has been postulated for the past few decades. Despite numerous theoretical works on aromaticity reversal, experimental study is still at a rudimentary stage. Herein, we investigate the aromaticity reversal in the lowest excited triplet state using a comparable set of [26]‐ and [28]hexaphyrins by femtosecond time‐resolved infrared (IR) spectroscopy. Compared to the relatively simple IR spectra of [26]bis(rhodium) hexaphyrin (R26H), those of [28]bis(rhodium) hexaphyrin (R28H) show complex IR spectra the region for the stretching modes of conjugated rings. Whereas time‐resolved IR spectra of R26H in the excited triplet state are dominated by excited state IR absorption peaks, while those of R28H largely show ground state IR bleaching peaks, reflecting the aromaticity reversal in the lowest triplet state. These contrasting IR spectral features serve as new experimental aromaticity indices for Baird's rule.
Total Synthesis of 11‐Saxitoxinethanoic Acid and Evaluation of its Inhibitory Activity on Voltage‐Gated Sodium Channels
Authors: Wang Chao , Oki Mana , Nishikawa Toru , Harada Daisuke , Yotsu‐Yamashita Mari , Nagasawa Kazuo
Published: August 2016

11‐Saxitoxinethanoic acid (SEA) is a member of the saxitoxin (STX) family of paralytic shellfish poisons, and contains an unusual C−C bond at the C11 position. Reported herein is a total synthesis of SEA. The key to our synthesis lies in a Mukaiyama aldol condensation reaction of silyl enol ether with glyoxylate in the presence of an anhydrous fluoride reagent, [Bu4N][Ph3SnF2], which directly constructs the crucial C−C bond at the C11 position in SEA. The NaVCh‐inhibitory activities of SEA and its derivatives were evaluated by means of cell‐based assay. SEA showed an IC50 value of (47±12) nm, which is approximately twice as potent as decarbamoyl‐STX (dcSTX).
Photoswitchable NIR‐Emitting Gold Nanoparticles
Authors: Bonacchi Sara , Cantelli Andrea , Battistelli Giulia , Guidetti Gloria , Calvaresi Matteo , Manzi Jeannette , Gabrielli Luca , Ramadori Federico , Gambarin Alessandro , Mancin Fabrizio , Montalti Marco
Published: August 2016

Photo‐switching of the NIR emission of gold nanoparticles (GNP) upon photo‐isomerization of azobenzene ligands, bound to the surface, is demonstrated. Photophysical results confirm the occurrence of an excitation energy transfer process from the ligands to the GNP that produces sensitized NIR emission. Because of this process, the excitation efficiency of the gold core, upon excitation of the ligands, is much higher for the trans form than for the cis one, and t→c photo‐isomerization causes a relevant decrease of the GNP NIR emission. As a consequence, photo‐isomerization can be monitored by ratiometric detection of the NIR emission upon dual excitation. The photo‐isomerization process was followed in real‐time through the simultaneous detection of absorbance and luminescence changes using a dedicated setup. Surprisingly, the photo‐isomerization rate of the ligands, bound to the GNP surface, was the same as measured for the chromophores in solution. This outcome demonstrated that excitation energy transfer to gold assists photo‐isomerization, rather than competing with it. These results pave the road to the development of new, NIR‐emitting, stimuli‐responsive nanomaterials for theranostics.
Amyloid Aggregates Arise from Amino Acid Condensations under Prebiotic Conditions
Authors: Greenwald Jason , Friedmann Michael P. , Riek Roland
Published: August 2016

Current theories on the origin of life reveal significant gaps in our understanding of the mechanisms that allowed simple chemical precursors to coalesce into the complex polymers that are needed to sustain life. The volcanic gas carbonyl sulfide (COS) is known to catalyze the condensation of amino acids under aqueous conditions, but the reported di‐, tri‐, and tetra‐peptides are too short to support a regular tertiary structure. Here, we demonstrate that alanine and valine, two of the proteinogenic amino acids believed to have been among the most abundant on a prebiotic earth, can polymerize into peptides and subsequently assemble into ordered amyloid fibers comprising a cross‐β‐sheet quaternary structure following COS‐activated continuous polymerization of as little as 1 mm amino acid. Furthermore, this spontaneous assembly is not limited to pure amino acids, since mixtures of glycine, alanine, aspartate, and valine yield similar structures.
Cold Sintering: A Paradigm Shift for Processing and Integration of Ceramics
Authors: Guo Jing , Guo Hanzheng , Baker Amanda L. , Lanagan Michael T. , Kupp Elizabeth R. , Messing Gary L. , Randall Clive A.
Published: August 2016

This paper describes a sintering technique for ceramics and ceramic‐based composites, using water as a transient solvent to effect densification (i.e. sintering) at temperatures between room temperature and 200 °C. To emphasize the incredible reduction in sintering temperature relative to conventional thermal sintering this new approach is named the “Cold Sintering Process” (CSP). Basically CSP uses a transient aqueous environment to effect densification by a mediated dissolution–precipitation process. CSP of NaCl, alkali molybdates and V2O5 with small concentrations of water are described in detail, but the process is extended and demonstrated for a diverse range of chemistries (oxides, carbonates, bromides, fluorides, chlorides and phosphates), multiple crystal structures, and multimaterial applications. Furthermore, the properties of selected CSP samples are demonstrated to be essentially equivalent as samples made by conventional thermal sintering.
Bicontinuous Nanoporous Frameworks: Caged Longevity for Enzymes
Authors: Bae Jae‐Sung , Jeon Eunkyung , Moon Su‐Young , Oh Wangsuk , Han Sun‐Young , Lee Jeong Hun , Yang Sung Yun , Kim Dong‐Myung , Park Ji‐Woong
Published: August 2016

The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three‐ dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme‐loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts.
Palladium‐Catalyzed Defluorinative Coupling of 1‐Aryl‐2,2‐Difluoroalkenes and Boronic Acids: Stereoselective Synthesis of Monofluorostilbenes
Authors: Thornbury Richard T. , Toste F. Dean
Published: August 2016

The palladium‐catalyzed defluorinative coupling of 1‐aryl‐2,2‐difluoroalkenes with boronic acids is described. Broad functional‐group tolerance arises from a redox‐neutral process by a palladium(II) active species which is proposed to undergo a β‐fluoride elimination to afford the products. The monofluorostilbene products were formed with excellent diastereoselectivity (≥50:1) in all cases, and it is critical, as traditional chromatographic techniques often fail to separate monofluoroalkene isomers. As a demonstration of this method's unique combination of reactivity and functional‐group tolerance, a Gleevec® analogue, using a monofluorostilbene as an amide isostere, was synthesized.
Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium–Sulfur Batteries
Authors: Peng Hong‐Jie , Zhang Ge , Chen Xiang , Zhang Ze‐Wen , Xu Wen‐Tao , Huang Jia‐Qi , Zhang Qiang
Published: August 2016

Lithium–sulfur (Li–S) batteries have been recognized as promising substitutes for current energy‐storage technologies owing to their exceptional advantage in energy density. The main challenge in developing highly efficient and long‐life Li–S batteries is simultaneously suppressing the shuttle effect and improving the redox kinetics. Polar host materials have desirable chemisorptive properties to localize the mobile polysulfide intermediates; however, the role of their electrical conductivity in the redox kinetics of subsequent electrochemical reactions is not fully understood. Conductive polar titanium carbides (TiC) are shown to increase the intrinsic activity towards liquid–liquid polysulfide interconversion and liquid–solid precipitation of lithium sulfides more than non‐polar carbon and semiconducting titanium dioxides. The enhanced electrochemical kinetics on a polar conductor guided the design of novel hybrid host materials of TiC nanoparticles grown within a porous graphene framework (TiC@G). With a high sulfur loading of 3.5 mg cm−2, the TiC@G/sulfur composite cathode exhibited a substantially enhanced electrochemical performance.
Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N‐Donor SBA15 Surface Ligands: A Solid‐State NMR and DFT Study
Authors: Bendjeriou‐Sedjerari Anissa , Sofack‐Kreutzer Julien , Minenkov Yury , Abou‐Hamad Edy , Hamzaoui Bilel , Werghi Baraa , Anjum Dalaver H. , Cavallo Luigi , Huang Kuo‐Wei , Basset Jean‐Marie
Published: August 2016

Designing supported well‐defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(≡CtBu)(CH2tBu)3 with amine‐modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(≡SiOH)(≡SiNH2)], leads to [(≡SiNH2−)(≡SiO−)W(≡CHtBu)(CH2tBu)2] and [(≡SiNH2−)(≡SiO−)W(=CHtBu)2(CH2tBu). Variable temperature, 1H–1H 2D double‐quantum, 1H–13C HETCOR, and HETCOR with spin diffusion solid‐state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(≡Si−OH)(≡Si−NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface–complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 °C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl‐supported catalysts.
Direct Observation of Aggregation‐Induced Backbone Conformational Changes in Tau Peptides
Authors: Jiji A. C. , Shine A. , Vijayan Vinesh
Published: August 2016

In tau proteins, the hexapeptides in the R2 and R3 repeats are known to initiate tau fibril formation, which causes a class of neurodegenerative diseases called the taupathies. We show that in R3, in addition to the presence of the hexapeptides, the correct turn conformation upstream to it is also essential for producing prion‐like fibrils that are capable of propagation. A time‐dependent NMR aggregation assay of a slow fibril forming R3‐S316P peptide revealed a trans to cis equilibrium shift in the peptide‐bond conformation preceding P316 during the growth phase of the aggregation process. S316 was identified as the key residue in the turn that confers templating capacity on R3 fibrils to accelerate the aggregation of the R3‐S316P peptide. These results on the specific interactions and conformational changes responsible for tau aggregation could prove useful for developing an efficient therapeutic intervention in Alzheimer's disease.
Gold‐Induced Fibril Growth: The Mechanism of Surface‐Facilitated Amyloid Aggregation
Authors: Gladytz Anika , Abel Bernd , Risselada Herre Jelger
Published: August 2016

The question of how amyloid fibril formation is influenced by surfaces is crucial for a detailed understanding of the process in vivo. We applied a combination of kinetic experiments and molecular dynamics simulations to elucidate how (model) surfaces influence fibril formation of the amyloid‐forming sequences of prion protein SUP35 and human islet amyloid polypeptide. The kinetic data suggest that structural reorganization of the initial peptide corona around colloidal gold nanoparticles is the rate‐limiting step. The molecular dynamics simulations reveal that partial physisorption to the surface results in the formation of aligned monolayers, which stimulate the formation of parallel, critical oligomers. The general mechanism implies that the competition between the underlying peptide–peptide and peptide–surface interactions must strike a balance to accelerate fibril formation.
Two‐Dimensional Skyrmion Lattice Formation in a Nematic Liquid Crystal Consisting of Highly Bent Banana Molecules
Authors: Kang Sungmin , Lee Eun‐Woo , Li Tianqi , Liang Xiaobin , Tokita Masatoshi , Nakajima Ken , Watanabe Junji
Published: August 2016

We synthesized a novel banana‐shaped molecule based on a 1,7‐naphthalene central core that exhibits a distinct mesomorphism of the nematic‐to‐nematic phase transition. Both the X‐ray profile and direct imaging of atomic force microscopy (AFM) investigations clearly indicates the formation of an anomalous nematic phase possessing a two‐dimensional (2D) tetragonal lattice with a large edge (ca. 59 Å) directed perpendicular to the director in the low‐temperature nematic phase. One plausible model is proposed by an analogy of skyrmion lattice in which two types of cylinders formed from left‐ and right‐handed twist‐bend helices stack into a 2D tetragonal lattice, diminishing the inversion domain wall.
Dermal Fibroblasts from Different Layers of Pig Skin Exhibit Different Profibrotic and Morphological Characteristics
Authors: Zuo Yanhai , Yu Xiaoping , Lu Shuliang
Published: August 2016

In vitro studies of human dermal fibroblast (DF) heterogeneity have long been reported, yet in vivo studies and related research on animals are rare. The objectives of the study were to determine whether the DFs of pigs exhibit heterogeneity and to identify an animal model for the in vivo study of DF heterogeneity. The skin of three female red Duroc pigs (FRDPs) was separated into six layers, and the second and fifth layers (i.e., the superficial and deep dermis) were used in the establishment of wound models and cell cultures. To create the wound models, 54 tongue‐shaped flaps were created on one side of the dorsum, and the underlying dermis was then fully replaced with the superficial or deep dermis (the superficial and deep groups, respectively). Skin samples were harvested at postoperative weeks 1, 2, and 3 for measurements of the normal and wounded skin thicknesses. Cells cultured from the superficial and deep dermis (i.e., superficial and deep DFs) were subjected to quantitative estimation of collagen and electron microscopy. The wounded skin thickness in the deep group was significantly greater than that in the superficial group. In contrast with the long deep DFs, the superficial DFs were short and exhibited microvilli‐like cell surface projections. Compared with the superficial DFs, the deep DFs exhibited a greater density of rough endoplasmic reticulum and produced significantly more collagen. Similar to humans, FRDPs exhibit DF heterogeneity and should thus be a good animal model for in vivo studies of DF heterogeneity. Anat Rec, 299:1585–1599, 2016. © 2016 Wiley Periodicals, Inc.
Cultural acceptability and personal willingness of Iranian students toward cadaveric donation
Authors: Abbasi Asl Jamal , Nikzad Hossein , Taherian Aliakbar , Atlasi Mohammad Ali , Naderian Homayoun , Mousavi Gholamabbas , Kashani Milad Motalebi , Omidi Abdollah
Published: August 2016

Cadaver dissection stands as a crucial component in medical curricula around the world, although computer‐based multimedia programs have been introduced in order to replace the need for cadaver donations. Due to a decrease in the number of unclaimed bodies and rather few donations, there is an insufficient number of cadavers for anatomical studies in Iran. This study was carried out to evaluate medical students' awareness and willingness regarding body donation in Kashan University of Medical Sciences, Iran. In this study, a questionnaire was designed to focus on the cultural acceptability and personal willingness to donate one's body after death. Students from the university's anatomy classes (n = 331) participated in this study. Seventy‐seven percent of the students expressed their agreement toward the idea of utilizing body donation services, though only 25.4% of participants were willing to donate their own bodies. None of the demographic factors were associated with cultural acceptability or personal willingness towards body donation. These findings indicated that besides “payment”, other factors were associated with students' willingness to become donors. All factors of awareness except “previous awareness of organization” were associated with cultural acceptability. In this study, students suggested that encouraging people to register for body donation using mass media (25.6%) and teaching students to respect cadavers in the dissection environment (24.8%) were the best solutions for addressing the lack of cadavers. These findings indicated that a lack of awareness about body donation might be the main factor responsible for unwillingness towards body donation; therefore, improving the public's awareness and addressing the willingness of students regarding body donation may help overcome the current lack of donated cadavers. Anat Sci Educ 10: 120–126. © 2016 American Association of Anatomists.
Tailoring Size and Coverage Density of Silver Nanoparticles on Monodispersed Polymer Spheres as Highly Sensitive SERS Substrates
Authors: Hu Yougen , Zhao Tao , Zhu Pengli , Zhu Yu , Liang Xianwen , Sun Rong , Wong Ching‐Ping
Published: August 2016

Silver nanoparticles (AgNPs) were deposited onto the monodispersed carboxylic polystyrene (CPS) spheres by an improved in situ reduction method. The size and coverage density of the AgNPs on the surface of CPS spheres could be easily tailored by tuning the concentrations of carboxylic functional groups and silver precursor. The morphologies and structures of the resulting CPS/Ag hybrid particles were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), UV‐Vis‐NIR spectrometer and X‐ray photoelectron spectroscopy (XPS), etc. The surface enhanced Raman scattering (SERS) performances of the resulting uniform CPS/Ag hybrid particles were investigated using 4‐aminobenzenethiol (4‐ABT) as the probe molecule. The optimized CPS/Ag hybrid particles show high enhancement factor (EF) of 2.71×107, low limit of detection (LOD) of 10−10 m and good reproducibility with relative standard deviation (RSD) of 9.64 %. The good SERS improvement properties demonstrate these hybrid particles could be employed as simple and effective substrates in the SERS spectroscopy.
Stability of Local On‐Ramp Metering Control Laws
Authors: Alvarez‐Icaza Luis , Rosas‐Jaimes Oscar , Lárraga María Elena
Published: August 2016

A framework for stability analysis of local on‐ramp metering control strategies based on the cell transmission model is presented. Within this framework, it is possible to formulate Lyapunov and input‐state stability results for on‐ramp metering control strategies in an open section of highway with on‐ramps. Using this analysis, recommendations for the design of on‐ramp metering control laws set points are derived. Two examples on the use of such analysis are presented. One deals with the stability analysis of a local on‐ramp metering control law and the other with the design of a disturbance observer that, used in combination with the local on‐ramp metering control law, provides a more robust response to traffic regulation. Simulation results are included that confirm the possibility of using this framework to test the impact of local on‐ramp metering control strategies.