bluuebunny/crossref_metadata_2025 huggingface dataset:
CIENCIA UNIVERSITARIA PARA DINAMIZAR LA ECONOMÍA LOCAL
Authors: Soulary Carracedo Victor , González Ortiz Marianela , Pacheco Feria Ulises
Published: May 2018

Resumen. La ciencia universitaria tiene un papel prioritario en la dinamización económica, ya que repercute en la productividad y competitividad de las empresas, y en su destreza para generar riqueza. Las universidades son las instituciones con mayor concentración de recursos avanzados para crear conocimiento; por tanto, se constituyen en uno de los fundamentos del crecimiento económico de las sociedades avanzadas. El artículo reflexiona sobre los antecedentes teóricos y prácticos que avalan la necesidad de evaluar la contribución de la ciencia universitaria a la dinamización económica local. A partir de la revisión crítica del estado del arte se demuestra que evaluar la articulación de los resultados científicos universitarios con el desempeño de los agentes económicos es una herramienta clave en la mejora de la relación simbiótica entre empresas y academias.
 
Palabras clave: ciencia, universidad, dinamización, economía, desarrollo local, evaluación.
 
Abstract. The university science has a priority role in economic revitalizing, since it impact in the productivity and competitiveness of enterprises, and in their skill to generate richness. Universities are the institutions with more advanced resources to create knowledge; therefore they constitute one of the fundaments of economics’ growth of advanced societies. This paper intends about the theoretical and practical antecedents that justify the necessity of evaluate the contribution of the university’s science to the local economic revitalizing. From the critical revision of the state of the art, we argue that assets the articulation of the universities scientific results with the performance of the economic agents is a key tool to improve the symbiotic relationship between enterprises and academies.
 
Key words: science, university, revitalizing, economy, local development, assets.
IMPLICACIONES DE LA IMPLANTACIÓN DE LA LEY DE RACIONALIDAD Y SOSTENIBILIDAD DE LAS ADMINISTRACIONES LOCALES (LEY 27/2013) EN LAS ADMINISTRACIONES LOCALES DE LA COMUNITAT VALENCIANA
Authors: Noguera Tur Joan , Scardaccione Giuseppe , Gascó Martínez Estefanía , Riera Spiegehalder Mar , Del Alcálzar Indarte Héctor
Published: May 2018

Resumen. En menos de un cuarto de siglo el texto de la Ley Reguladora de las Bases del Régimen Local (LRBRL) ha sido modificado doce veces, con cambios que afectan a 41 de los 120 artículos, al tiempo que se han añadido 37 nuevos artículos y disposiciones adicionales. La última de estas modificaciones, con profundas implicaciones en la forma de operar de las administraciones locales, ha levantado suspicacias e incertidumbres sobre el papel de los gobiernos locales. Tras su publicación en el BOE, la Ley 27/2013 del 27 de diciembre de racionalización y sostenibilidad de la administración local (LRSAL), ha generado numerosas controversias entre los profesionales del municipalismo. Es desde este sentir que se ha emprendido la realización de un trabajo de análisis que permita conocer, a partir del análisis documental y de la evidencia empírica, las opiniones dominantes y emergentes sobre esta nueva reforma y la situación en la que queda la gobernanza de las administraciones locales como consecuencia de la implantación de la LRSAL..
 
Palabras clave: sector público, localismo, gobernanza, competencias impropias, duplicidades, racionalidad y sostenibilidad financiera.
 
Abstract. In less than a quarter century, the text of the Law regulating local administrations (LRBRL) has been amended a dozen times, introducing changes in 41 of the 120 articles, while 37 new articles and additional provisions have been added. The last of these changes, with profound implications for the way local government operates, has raised suspicions and doubts regarding the immediate future role of local governments. After its publication in the Official State Gazette (BOE), the Law 27/2013 of December 27th of Rationalization and Sustainability of Local Administrations (LRSAL) has generated much controversy among municipal professionals. It is in this sense that the authors have undertaken the realization of an analysis to find out, from relevant documents and empirical evidence, the emerging views on the reform and the situation of the governance of local administrations as a result of the implementation of the LRSAL.
 
Key words: public sector, localism, governance, improper powers, duplicities, financial rationality and sustainability.
Ecocardiografia no diagnóstico de reticulopericardite traumática bovina
Authors: De Freitas Bárbara Barbi , Dos Santos Julio Pereira , Perotta João Henrique , Marcom Nicoly Nayana , Cocco Mariana , Da Silva Thais Gislon , Brum Juliana Sperotto , Sousa Marlos Gonçalves , De Barros Filho Ivan Roque
Published: May 2018

A reticulopericardite traumática bovina é uma doença caracterizada pelo processo inflamatório resultante da perfuração do retículo e do pericárdio por objeto pontiagudo ingerido. O animal tem sinais de dor como abatimento, odontoprise, arqueamento e respiração predominantemente abdominal. Outros sinais podem ocorrer de acordo com as estruturas envolvidas. No caso do pericárdio, pode haver sinais de insuficiência cardíaca congestiva, taquicardia, abafamento das bulhas cardíacas, dispneia, edema e distensão da veia jugular. O objetivo deste trabalho é relatar um caso de reticulopericardite traumática bovina, atendido no Hospital Veterinário da UFPR, com enfoque nos achados ecocardiográficos. Por meio dos sinais clínicos e exames complementares, foi possível conduzir a suspeita diagnóstica para reticulopericardite traumática. Para confirmação desta suspeita foi realizado exame ecocardiográfico, onde foi possível visualizar espessamento pericárdico, bem como efusão pleural e pericárdica, confirmando o diagnóstico. Apesar de a ecocardiografia ser um método não invasivo, ela ainda não é amplamente utilizada na clínica de bovinos, e no presente trabalho mostrou-se eficaz e de grande importância para definição do diagnóstico e prognóstico do animal.
The impact on global warming potential of converting from disposable to reusable sharps containers in a large US hospital geographically distant from polymer and container manufacturer
Authors: McPherson Brett , Sharip Mihray , Grimmond Terry
Published: May 2018

Background. Sustainable purchasing can reduce greenhouse gas (GHG) emissions at healthcare facilities (HCF). A previous study found that converting from disposable to reusable sharps containers (DSC, RSC) reduced sharps waste stream GHG by 84% but, in finding transport distances impacted significantly on GHG outcomes, recommended further studies where transport distances are large. This case-study examines the impact on GHG of nation-wide transport distances when a large US health system converted from DSC to RSC.

Methods. The study examined the alternate use of DSC and RSC at a large US university hospital where: the source of polymer was distant from the RSC manufacturing plant; both manufacturing plants were over 3,000 km from the HCF; and the RSC disposal plant was considerably further from the HCF than was the DSC disposal plant. Using a “cradle to grave” life cycle assessment (LCA) tool we calculated annual GHG emissions (CO2, CH4, N2O) in metric tonnes of carbon dioxide equivalents (MTCO2eq) to assess the impact on global warming potential (GWP) of each container system. Primary energy input data was used wherever possible and region-specific impact conversions used to calculate GWP of each activity over a 12-month period. Unit process GHG were collated into Manufacture, Transport, Washing, and Treatment & disposal. Emission totals were workload-normalized and analysed using CHI2 test with P ≤0.05 and rate ratios at 95% CL.

Results. The hospital reduced its annual GWP by 168 MTCO2eq (-64.5%; p < 0.001), and annually eliminated 50.2 tonnes of plastic DSC and 8.1 tonnes of cardboard from the sharps waste stream. Of the plastic eliminated, 31.8 tonnes were diverted from landfill and 18.4 from incineration.

Discussion. Unlike GHG reduction strategies dependent on changes in staff behaviour (waste segregation, recycling, turning off lights, car-pooling, etc), purchasing strategies can enable immediate, sustainable and institution-wide GHG reductions to be achieved. Medical waste containers contribute significantly to the supply chain carbon footprint and, although non-sharp medical waste volumes have decreased significantly with avid segregation, sharps wastes have increased, and can account for 50% of total medical waste volume. Thus converting from DSC to RSC can assist reduce the GWP footprint of the medical waste stream. This study confirmed that large transport distances between polymer manufacturer and container manufacturer; container manufacturer and user; and/or between user and processing facilities, can significantly impact the GWP of sharps containment systems. However, even with large transport distances, we found that a large university health system significantly reduced the GWP of their sharps waste stream by converting from DSC to RSC.
Supervised Mover's Distance: A simple model for sentence comparison
Authors: Srivastava Muktabh Mayank
Published: May 2018

We propose a simple neural network model which can learn relation between sentences by passing their representations obtained from Long Short Term Memory(LSTM) through a Relation Network. The Relation Network module tries to extract similarity between multiple contextual representations obtained from LSTM. Our model is simple to implement, light in terms of parameters and works across multiple supervised sentence comparison tasks. We show good results for the model on two sentence comparison datasets.
Conflict in the Colorado Delta - A response to Brusca (2018)
Authors: Jacobs David K. , Lau Clive L. F.
Published: May 2018

In his enthusiasm to highlight the impacts of fisheries in the Gulf of California, Richard Brusca (Brusca 2018) attacks our paper which is about a largely separate issue, makes false claims, does a disservice to his own cause, and undermines science. Brusca sets out to defame our work because, as he states, he fears that third parties will misuse work of this type in fisheries management. This is unfortunate. Brusca’s effort to manipulate and suppress scientific work because he fears managers will use it inappropriately is overt and chilling. We respond to Brusca’s numerous and varied criticisms in as much detail and in as measured a way as we can muster.
Effect of Reactive Black 5 azo dye on soil processes related to C and N cycling
Authors: Rehman Khadeeja , Shahzad Tanvir , Sahar Amna , Hussain Sabir , Mahmood Faisal , Siddique Muhammad H. , Siddique Muhammad A. , Rashid Muhammad I.
Published: May 2018

Azo dyes are one of the largest classes of synthetic dyes being used in textile industries. It has been reported that 15–50% of these dyes find their way into wastewater that is often used for irrigation purpose in developing countries. The effect of azo dyes contamination on soil nitrogen (N) has been studied previously. However, how does the azo dye contamination affect soil carbon (C) cycling is unknown. Therefore, we assessed the effect of azo dye contamination (Reactive Black 5, 30 mg kg−1dry soil), bacteria that decolorize this dye and dye + bacteria in the presence or absence of maize leaf litter on soil respiration, soil inorganic N and microbial biomass. We found that dye contamination did not induce any change in soil respiration, soil microbial biomass or soil inorganic N availability (P > 0.05). Litter evidently increased soil respiration. Our study concludes that the Reactive Black 5 azo dye (applied in low amount, i.e., 30 mg kg−1dry soil) contamination did not modify organic matter decomposition, N mineralization and microbial biomass in a silty loam soil.
An improved primer set and amplification protocol with increased specificity and sensitivity targeting the Symbiodinium ITS2 region
Authors: Hume Benjamin C.C. , Ziegler Maren , Poulain Julie , Pochon Xavier , Romac Sarah , Boissin Emilie , de Vargas Colomban , Planes Serge , Wincker Patrick , Voolstra Christian R.
Published: May 2018

The Internal Transcribed Spacer 2 (ITS2) rRNA gene is a commonly targeted genetic marker to assess diversity of Symbiodinium, a dinoflagellate genus of algal endosymbionts that is pervasively associated with marine invertebrates, and notably reef-building corals. Here we tested three commonly used ITS2 primer pairs (SYM_VAR_5.8S2/SYM_VAR_REV, ITSintfor2/ITSReverse, and ITS-DINO/ITS2Rev2) with regard to amplification specificity and sensitivity towards Symbiodinium, as well as sub-genera taxonomic bias. We tested these primers over a range of sample types including three coral species, coral surrounding water, reef surface water, and open ocean water to assess their suitability for use in large-scale next generation sequencing projects and to develop a standardised PCR protocol. We found the SYM_VAR_5.8S2/SYM_VAR_REV primers to perform superior to the other tested ITS2 primers. We therefore used this primer pair to develop a standardised PCR protocol. To do this, we tested the effect of PCR-to-PCR variation, annealing temperature, cycle number, and different polymerase systems on the PCR efficacy. The Symbiodinium ITS2 PCR protocol developed here delivers improved specificity and sensitivity towards Symbiodinium with apparent minimal sub-genera taxonomic bias across all sample types. In particular, the protocol’s ability to amplify Symbiodinium from a range of environmental sources will facilitate the study of Symbiodinium populations across biomes.
Comprometimento da integridade intestinal na fibromialgia e sindrome dolorosa miofascial: uma revisão
Authors: Barros Neto João Araújo , Machado Adelmir Souza , Kraychete Durval Campos , Jesus Rosângela Passos de
Published: May 2018

Fibromialgia e dor crônica miofascial são condições muito frequentes na clínica da dor e podem representar uma das maiores causas de sofrimento humano. A fisiopatologia dessas doenças vem sendo relacionada com a presença de substâncias proinflamatórias produzidas em resposta a mecanismos estressores. Diversos fatores têm sido comumente encontrados em associação a presença dessas síndromes dolorosas, entre eles, alterações e comprometimento da integridade intestinal tem sido frequentemente relatados. O presente estudo teve como meta revisar artigos publicados em periódicos nacionais e internacionais de 2001 a 2011, cujos objetivos foram avaliar o comprometimento da integridade intestinal e as dores crônicas musculoesqueléticas do tipo fibromialgia e dor crônica miofascial, enfatizando a síntese e liberação das citocinas proinflamatórias nessas situações clínicas.
Reações adversas às estatinas: mecanismo de ação e evidências clínicas
Authors: Santos Leonardo Nascimento , Silva Fabiano Vinagre da
Published: May 2018

As doenças cardiovasculares são as maiores causadoras de óbitos no mundo, e o aumento do LDL (lipoproteína de baixa

densidade) é apontado como um dos fatores de risco mais importantes para essas doenças. Hoje em dia, as estatinas são

os fármacos mais potentes e eficazes na diminuição do LDL, mas apesar de seus efeitos potencialmente benéficos, elas

devem ser administradas com precaução, já que também apresentam efeitos colaterais. O objetivo deste trabalho foi fazer

uma revisão de literatura que buscasse elucidar os mecanismos dos efeitos adversos causados pelas estatinas e as

evidências clínicas destes efeitos. Os mecanismos bioquímicos e celulares da toxicidade muscular, hepática e neuronal

estão abordados. Em suma, os efeitos terapêuticos das estatinas, assim como os efeitos adversos, ocorrem devido à

inibição da síntese de moléculas dependentes da enzima HMG-CoA-redutase, tais como o mevalonato e isoprenóides. O

real panorama de ocorrência das reações adversas e uma breve comparação entre as estatinas utilizadas terapeuticamente

também são apresentados.
Optimization of a secondary VOI protocol for lung imaging in a clinical CT scanner
Authors: Larsen Thomas C. , Gopalakrishnan Vissagan , Yao Jianhua , Nguyen Catherine P. , Chen Marcus Y. , Moss Joel , Wen Han
Published: May 2018

We present a solution to meet an unmet clinical need of an in‐situ “close look” at a pulmonary nodule or at the margins of a pulmonary cyst revealed by a primary (screening) chest CT while the patient is still in the scanner. We first evaluated options available on current whole‐body CT scanners for high resolution screening scans, including ROI reconstruction of the primary scan data and HRCT, but found them to have insufficient SNR in lung tissue or discontinuous slice coverage. Within the capabilities of current clinical CT systems, we opted for the solution of a secondary, volume‐of‐interest (VOI) protocol where the radiation dose is focused into a short‐beam axial scan at the z position of interest, combined with a small‐FOV reconstruction at the xy position of interest. The objective of this work was to design a VOI protocol that is optimized for targeted lung imaging in a clinical whole‐body CT system. Using a chest phantom containing a lung‐mimicking foam insert with a simulated cyst, we identified the appropriate scan mode and optimized both the scan and recon parameters. The VOI protocol yielded 3.2 times the texture amplitude‐to‐noise ratio in the lung‐mimicking foam when compared to the standard chest CT, and 8.4 times the texture difference between the lung mimicking and reference foams. It improved details of the wall of the simulated cyst and better resolution in a line‐pair insert. The Effective Dose of the secondary VOI protocol was 42% on average and up to 100% in the worst‐case scenario of VOI positioning relative to the standard chest CT. The optimized protocol will be used to obtain detailed CT textures of pulmonary lesions, which are biomarkers for the type and stage of lung diseases.
Mechanical Properties of an Fe‐Based SAM2×5‐630 Metallic Glass Matrix Composite with Tungsten Particle Additions
Authors: Cheng I‐Chung , Kelly James P. , Novitskaya Ekaterina , Eliasson Veronica , Hodge Andrea M. , Graeve Olivia A.
Published: May 2018

We present the role of tungsten additions on the mechanical properties of a Fe‐based structural amorphous metal (SAM2×5‐630) containing crystalline tungsten. Matrix cracking by microindentation is inhibited by the addition of tungsten and indicates that tungsten improves the fracture toughness. Response surfaces from nanoindentation arrays indicate that the hardness and modulus of the matrix phase are increased by tungsten additions. Bulk composites with 30 vol% tungsten subjected to 4‐point flexure exhibited brittle fracture behavior and the characteristic strength and Weibull modulus were 165 and 8.7 MPa, respectively. The addition of tungsten did not cause devitrification of the matrix phase.
Perovskite Solar Cells with Inorganic Electron‐ and Hole‐Transport Layers Exhibiting Long‐Term (≈500 h) Stability at 85 °C under Continuous 1 Sun Illumination in Ambient Air
Authors: Seo Seongrok , Jeong Seonghwa , Bae Changdeuck , Park Nam‐Gyu , Shin Hyunjung
Published: May 2018

Despite the high power conversion efficiency (PCE) of perovskite solar cells (PSCs), poor long‐term stability is one of the main obstacles preventing their commercialization. Several approaches to enhance the stability of PSCs have been proposed. However, an accelerating stability test of PSCs at high temperature under the operating conditions in ambient air remains still to be demonstrated. Herein, interface‐engineered stable PSCs with inorganic charge‐transport layers are shown. The highly conductive Al‐doped ZnO films act as efficient electron‐transporting layers as well as dense passivation layers. This layer prevents underneath perovskite from moisture contact, evaporation of components, and reaction with a metal electrode. Finally, inverted‐type PSCs with inorganic charge‐transport layers exhibit a PCE of 18.45% and retain 86.7% of the initial efficiency for 500 h under continuous 1 Sun illumination at 85 °C in ambient air with electrical biases (at maximum power point tracking).
Automated Buildup of Biomimetic Films in Cell Culture Microplates for High‐Throughput Screening of Cellular Behaviors
Authors: Machillot Paul , Quintal Catarina , Dalonneau Fabien , Hermant Loic , Monnot Pauline , Matthews Kelsey , Fitzpatrick Vincent , Liu Jie , Pignot‐Paintrand Isabelle , Picart Catherine
Published: May 2018

An automatic method is established for layer‐by‐layer (LbL) assembly of biomimetic coatings in cell culture microplates using a commercial liquid‐handling robot. Highly homogeneous thin films are formed at the bottom of each microwell. The LbL film‐coated microplates are compatible with common cellular assays, using microplate readers and automated microscopes. Cellular adhesion is screened on crosslinked and peptide‐functionalized LbL films and stem cell differentiation in response to increasing doses of bone morphogenetic proteins (2, 4, 7, 9). This method paves the way for future applications of LbL films in cell‐based assays for regenerative medicine and high‐throughput drug screening.
Boosting Carrier Mobility of Synthetic Few Layer Graphene on SiO2 by Interlayer Rotation and Decoupling
Authors: Wu Xiangyu , Chuang Yaoteng , Contino Antonino , Sorée Bart , Brems Steven , Tokei Zsolt , Heyns Marc , Huyghebaert Cedric , Asselberghs Inge
Published: May 2018

The role of interlayer rotation on the electrical transport of few layer graphene (FLG) is rarely considered. In this paper, the impact of twisting angle on physical and electrical properties of synthetic single crystal bilayer and few layer graphene deposited on thermal SiO2 substrate is systematically studied. Bernal AB‐stacked graphene layers show low carrier mobility due to strong interlayer coupling and substrate scattering. A dramatic increase in carrier mobility and conductivity is observed when the graphene layers are twisted. A field effect mobility up to 15000 cm2 V−1 s−1 and 460 nm mean free path is measured on a twisted three‐layer graphene at room temperature is among the highest for graphene transferred to SiO2. In average, twisted graphene shows a fivefold improvement compared to AB stacked graphene in terms of mobility and conductivity, regardless of twist angles.
Fundamental Carrier Lifetime Exceeding 1 µs in Cs2AgBiBr6 Double Perovskite
Authors: Hoye Robert L. Z. , Eyre Lissa , Wei Fengxia , Brivio Federico , Sadhanala Aditya , Sun Shijing , Li Weiwei , Zhang Kelvin H. L. , MacManus‐Driscoll Judith L. , Bristowe Paul D. , Friend Richard H. , Cheetham Anthony K. , Deschler Felix
Published: May 2018

There is current interest in finding nontoxic alternatives to lead‐halide perovskites for optoelectronic applications. Silver–bismuth double perovskites have recently gained attention, but evaluating their carrier lifetime and recombination mechanisms from photoluminescence measurements is challenging due to their indirect bandgap. In this work, transient absorption spectroscopy is used to directly track the photocarrier population in Cs2AgBiBr6 by measuring the ground state bleach dynamics. A small initial drop is resolved in the ground state bleach on a picosecond timescale, after which the remaining photocarriers decay monoexponentially with a lifetime of 1.4 µs. The majority of the early‐time decay is attributed to hot‐carrier thermalization from the direct transition to the indirect bandgap, and the 1.4 µs lifetime represents the recombination of most photocarriers. From this lifetime, a steady‐state excess carrier density of 2.2 × 1016 cm−3 under 1 sun is calculated, which is an order of magnitude larger than that for methylammonium lead iodide, suggesting that charge transport and extraction can be efficient in Cs2AgBiBr6 solar cells.
Mass Spectrometry Imaging with Isomeric Resolution Enabled by Ozone‐Induced Dissociation
Authors: Paine Martin R. L. , Poad Berwyck L. J. , Eijkel Gert B. , Marshall David L. , Blanksby Stephen J. , Heeren Ron M. A. , Ellis Shane R.
Published: May 2018

Mass spectrometry imaging (MSI) enables the spatial distributions of molecules possessing different mass‐to‐charge ratios to be mapped within complex environments revealing regional changes at the molecular level. Even at high mass resolving power, however, these images often reflect the summed distribution of multiple isomeric molecules, each potentially possessing a unique distribution coinciding with distinct biological function(s) and metabolic origin. Herein, this chemical ambiguity is addressed through an innovative combination of ozone‐induced dissociation reactions with MSI, enabling the differential imaging of isomeric lipid molecules directly from biological tissues. For the first time, we demonstrate both double bond‐ and sn‐positional isomeric lipids exhibit distinct spatial locations within tissue. This MSI approach enables researchers to unravel local lipid molecular complexity based on both exact elemental composition and isomeric structure directly from tissues.
Glykoinformatik: Brücken zwischen isolierten Inseln im Datenmeer
Authors: Egorova Ksenia S. , Toukach Philip V.
Published: May 2018

Glykoinformatik ist eine sich aktiv entwickelnde wissenschaftliche Disziplin, die Wissenschaftlern den Zugang zu den Daten über natürliche Glykane und zu verschiedenen Datenverarbeitungswerkzeugen ermöglicht. Die Informatisierung der Glykomik hat jedoch noch einen langen Weg vor sich, bevor sie zur Genomik und Proteomik aufschließen wird. In diesem Standpunkt wird die aktuelle in Situation der Glykoinformatik betrachtet und ihre Errungenschaften und Mängel diskutiert, wobei die größten Nachteile hervorgehoben werden: das Fehlen anerkannter Standards, Protokolle, Datenindizes und ‐werkzeuge sowie die informationstechnologische Isoliertheit der bestehenden Projekte. Wir reiterieren mögliche Lösungen der anhaltenden Probleme und beschreiben unsere Vision eines idealen Glykoinformatik‐Projekts.
Ursache der Photolumineszenzverstärkung in Gold‐dotierten Silber‐Nanoclustern: Beiträge relativistischer Effekte und heteronuklearer Gold‐Silber‐Bindungen
Authors: Xie Xiao‐Ying , Xiao Pin , Cao Xiaoyan , Fang Wei‐Hai , Cui Ganglong , Dolg Michael
Published: May 2018

Die schwache Photolumineszenz von Silber‐Nanoclustern verhindert ihre breite Anwendung als lumineszenter Nanowerkstoff. In jüngerer Zeit haben Experimente jedoch gezeigt, dass eine Au‐Dotierung die Intensität der Photolumineszenz von Ag29‐Nanoclustern signifikant verstärken kann, wobei die molekularen und physikalischen Ursachen dieses Effekts noch unverstanden sind. Daher haben wir rechnerisch die Geometrien und die Elektronenstrukturen von Ag29 und seinen Au‐dotierten Ag29−xAux (mit x=1–5) Nanoclustern im S0‐ und S1‐Zustand untersucht. Dabei ergab sich, dass (1) relativistische Effekte, die hauptsächlich von den Au‐Atomen herrühren, bei der Verstärkung der Fluoreszenzintensität eine wichtige Rolle spielen, insbesondere für stark dotiertes Ag26Au3, Ag25Au4 und Ag24Au5; (2) heteronukleare Au‐Ag‐Bindungen die Stabilität bei Isomeren dieser Au‐dotierten Nanocluster erhöhen und ihre Fluoreszenzintensität regulieren können. Diese neuen Ergebnisse könnten dabei helfen, dotierte Silber‐Nanocluster mit hervorragenden Lumineszenzeigenschaften zu entwickeln.
Enolkatalyse ermöglicht eine unerwartete α‐Oxidation zyklischer Ketone mit 1,4‐Benzochinonen
Authors: Shevchenko Grigory A. , Oppelaar Barry , List Benjamin
Published: May 2018

In der vorliegenden Zuschrift berichten wir nun über eine, durch die Enolkatalyse ermöglichte, direkte und asymmetrische α‐Aryloxylierung zyklischer Ketone mit Chinonen als Reaktionspartnern. Ausgehend von α‐verzweigten Ketonen können unter zur Hilfenahme katalytischer Mengen einer Phosphorsäure die entsprechenden α,α‐disubstituierten Ketone in guten Ausbeuten und Enantioselektivitäten (bis zu 96.5:3.5 er) erhalten werden. Vorläufige mechanistische Experimente deuten darauf hin, dass die Reaktion über einen protonengekoppelten Elektronentransfer (PCET) mit anschließender Radikalrekombination abläuft.
Bandgap‐Tunable Preparation of Smooth and Large Two‐Dimensional Antimonene
Authors: Wang Xin , He Junjie , Zhou Benqing , Zhang Youming , Wu Jiatao , Hu Rui , Liu Liwei , Song Jun , Qu Junle
Published: May 2018

As a highly stable band gap semiconductor, antimonene is an intriguing two‐dimensional (2D) material in optoelectronics. However, its short layer distance and strong binding energy make it challenging to prepare high‐quality large 2D antimonene; therefore, its predicted tunable band gap has not been experimentally confirmed. Now, an approach to prepare smooth and large 2D antimonene with uniform layers that uses a pregrinding and subsequent sonication‐assisted liquid‐phase exfoliation process has been established. Mortar pregrinding provides a shear force along the layer surfaces, forming large, thin antimony plates, which can then easily be exfoliated into smooth, large antimonene, avoiding long sonication times and antimonene destruction. The resulting antimonene also enabled verification of the tunable band gap from 0.8 eV to 1.44 eV. Hole extraction and current enhancement by about 30 % occurred when the antimonene was used as a hole transport layer in perovskite solar cells.
Room‐Temperature Ferroelectricity in an Organic Cocrystal
Authors: Wiscons Ren A. , Goud N. Rajesh , Damron Joshua T. , Matzger Adam J.
Published: May 2018

Ferroelectric materials exhibit switchable remanent polarization due to reversible symmetry breaking under an applied electric field. Previous research has leveraged temperature‐induced neutral‐ionic transitions in charge‐transfer (CT) cocrystals to access ferroelectrics that operate through displacement of molecules under an applied field. However, displacive ferroelectric behavior is rare in organic CT cocrystals and achieving a Curie temperature (TC) above ambient has been elusive. Here a cocrystal between acenaphthene and 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane is presented that shows switchable remanent polarization at room temperature (TC=68 °C). Raman spectroscopy, X‐ray diffraction, and solid‐state NMR spectroscopy indicate the ferroelectric behavior is facilitated by acenaphthene (AN) rotation, deviating from conventional design strategies for CT ferroelectrics. These findings highlight the relevance of non‐CT interactions in the design of displacive ferroelectric cocrystals.
A General Synthesis of Phosphorus‐ and Arsenic‐Containing Analogues of the Thio‐ and Seleno‐cyanate Anions
Authors: Tambornino Frank , Hinz Alexander , Köppe Ralf , Goicoechea Jose M.
Published: May 2018

A general synthetic protocol for the synthesis of phosphorus‐ and arsenic‐containing analogues of the thio‐ and seleno‐cyanate anions is reported. This procedure allows for the isolation of three unprecedented species: the phosphaethynselenolate, PCSe− (1), the arsaethynthiolate, AsCS− (2), and the arsaethynselenolate, AsCSe− (3), anions. The structures, electronic properties, and spectroscopic signatures of these species are reported.
An Objective Alternative to IUPAC's Approach To Assign Oxidation States
Authors: Postils Verònica , Delgado‐Alonso Carlos , Luis Josep M. , Salvador Pedro
Published: May 2018

The IUPAC has recently clarified the term oxidation state (OS), and provided algorithms for its determination based on the ionic approximation (IA) of the bonds supported by atomic electronegativities (EN). Unfortunately, there are a number of exceptions and ambiguities in IUPAC's algorithms when it comes to practical applications. Our comprehensive study reveals the critical role of the chemical environment on establishing the OS, which cannot always be properly predicted using fix atomic EN values. By identifying what we define here as subsystems of enhanced stability within the molecular system, the OS can be safely assigned in many cases without invoking exceptions. New insights about the effect of local aromaticity upon OS are revealed. Moreover, we prove that there are intrinsic limitations of the IA that cannot be overcome. In this context, the effective oxidation state (EOS) analysis arises as a robust and general scheme to derive an OS without any external guidance.
The Origin of the Photoluminescence Enhancement of Gold‐Doped Silver Nanoclusters: The Importance of Relativistic Effects and Heteronuclear Gold–Silver Bonds
Authors: Xie Xiao‐Ying , Xiao Pin , Cao Xiaoyan , Fang Wei‐Hai , Cui Ganglong , Dolg Michael
Published: May 2018

The weak photoluminescence of silver nanoclusters prevents their broad application as luminescent nanomaterials. Recent experiments, however, have shown that gold doping can significantly enhance the photoluminescence intensity of Ag29 nanoclusters but the molecular and physical origins of this effect remain unknown. Therefore, we have computationally explored the geometric and electronic structures of Ag29 and gold‐doped Ag29−xAux (x=1–5) nanoclusters in the S0 and S1 states. We found that 1) relativistic effects that are mainly due to the Au atoms play an important role in enhancing the fluorescence intensity, especially for highly doped Ag26Au3, Ag25Au4, and Ag24Au5, and that 2) heteronuclear Au−Ag bonds can increase the stability and regulate the fluorescence intensity of isomers of these gold‐doped nanoclusters. These novel findings could help design doped silver nanoclusters with excellent luminescence properties.
Electrochemical Reduction of Carbon Dioxide to Methanol on Hierarchical Pd/SnO2 Nanosheets with Abundant Pd–O–Sn Interfaces
Authors: Zhang Wuyong , Qin Qing , Dai Lei , Qin Ruixuan , Zhao Xiaojing , Chen Xumao , Ou Daohui , Chen Jie , Chuong Tracy T , Wu Binghui , Zheng Nanfeng
Published: May 2018

Electrochemical conversion of CO2 into fuels using electricity generated from renewable sources helps to create an artificial carbon cycle. However, the low efficiency and poor stability hinder the practical use of most conventional electrocatalysts. In this work, a 2D hierarchical Pd/SnO2 structure, ultrathin Pd nanosheets partially capped by SnO2 nanoparticles, is designed to enable multi‐electron transfer for selective electroreduction of CO2 into CH3OH. Such a structure design not only enhances the adsorption of CO2 on SnO2, but also weakens the binding strength of CO on Pd due to the as‐built Pd–O–Sn interfaces, which is demonstrated to be critical to improve the electrocatalytic selectivity and stability of Pd catalysts. This work provides a new strategy to improve electrochemical performance of metal‐based catalysts by creating metal oxide interfaces for selective electroreduction of CO2.
Thorpe–Ingold Effect in Branch‐Selective Alkylation of Unactivated Aryl Fluorides
Authors: O'Neill Matthew J. , Riesebeck Tim , Cornella Josep
Published: May 2018

Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe–Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C−C coupling event. This protocol is characterized by mild reaction conditions, robustness, and simplicity. Both electron‐rich and electron‐deficient aryl fluorides are suitable candidates in this transformation. Equally amenable are a variety of heterocycles, permitting the coupling without over alkylation at the electrophilic sites.
Design, synthesis, in vitro and in silico evaluation of new pyrrole derivatives as monoamine oxidase inhibitors
Authors: Altintop Mehlika D. , Sever Belgin , Osmaniye Derya , Sağlık Begüm N. , Özdemir Ahmet
Published: May 2018

In an effort to develop potent monoamine oxidase (MAO) inhibitors, new pyrrole derivatives were obtained via the selective reduction of the CC bonds of 1‐(1‐methyl‐1H‐pyrrol‐2‐yl)‐3‐[5‐(aryl)furan‐2‐yl]prop‐2‐en‐1‐ones through palladium catalyzed hydrogenation in ethanol. The synthesized compounds were screened for their inhibitory effects on MAO‐A and MAO‐B by an in vitro fluorometric method. The selectivity index (SI) value was given as the ratio of IC50 (MAO‐A)/IC50 (MAO‐B) for each compound. 3‐(5‐(4‐Chlorophenyl)furan‐2‐yl)‐1‐(1‐methyl‐1H‐pyrrol‐2‐yl)propan‐1‐one (6) was identified as the most selective MAO‐A inhibitor in this series, with an IC50 value of 0.162 µM and a SI value of 0.002. Kinetic studies were also carried out to assess the nature of MAO‐A inhibition by compound 6. According to Lineweaver–Burk plots, compound 6 was found to be a competitive MAO‐A inhibitor and the Ki value of compound 6 was determined as 0.1221 μM. Docking studies were performed for compound 6 and clorgyline using the human MAO‐A crystal structure (PDB ID: 2Z5Y). The docking results showed that compound 6 presented similar interactions as clorgyline in the active center cavity of the enzyme. Molinspiration software was used to determine the physicochemical parameters of all compounds for an evaluation of their compliance to Lipinski's rule of five. Compound 6 did not violate Lipinski's rule, making it a potential orally bioavailable therapeutic agent.
Analytical Correlation Rules between States in the United Atom and Separated Atom Limits for Diatomic Screened Orbitals
Authors: Lee Chun‐Woo
Published: May 2018

The analytic correlation rule of Gershtein and Krivchenkov between states in the united atom and separated atom limits for one‐electron diatomic molecule is extended to diatomic molecules with more than one electron for diabatic screened molecular orbitals, which are solutions of the Hartree‐like Schrödinger equation that is separable in prolate spheroidal coordinates. The rule is interpreted with the WKB method.
Pregnancies complicated by maternal osteogenesis imperfecta type III: a case report and review of literature
Authors: Kawakita Tetsuya , Fries Melissa , Singh Jasbir , Al‐Kouatly Huda B.
Published: May 2018

Key Clinical Message

The restrictive lung disease can be exacerbated by growing fundus in women with osteogenesis imperfecta type III. Regional anesthesia can be performed in these women. Mode of delivery for women with osteogenesis imperfecta type III is generally cesarean delivery. Neonatal outcomes are complicated due to indicated preterm deliveries.
Reversible Oxidative Addition/Reductive Elimination of a Si−H Bond with Base‐Stabilized Silylenes: A Theoretical Insight
Authors: Nakagaki Masayuku , Baceiredo Antoine , Kato Tsuyoshi , Sakaki Shigeyoshi
Published: May 2018

Although oxidative addition (OA) and reductive elimination (RE) are exceedingly important processes in organometallic chemistry, such processes are still extremely rare for main‐group element species. Herein, we report a theoretical study on the reaction of phosphine‐stabilized silylenes with silanes that proceeds through reversible OA/RE at room temperature. Of particular interest is that this theoretical approach highlights the important role of the ligand, which can greatly affect the kinetics and energy balance of the reaction. Indeed, in contrast to the case of free aminosilylenes, the reaction of ligand‐supported silylenes proceeds in an unsynchronized manner and starts with the silylene→silane charge transfer (CT). Suitably electron‐donating ligands, such as phosphines or N‐heterocyclic carbenes, enhancing the CT at the transition state (TS), significantly decrease the Gibbs activation energy and the exergonic nature of the reaction, which promote the OA/RE processes. In the same way, silanes with electron‐withdrawing groups also favor the CT and thus stabilize the TS. It was also computationally predicted that phosphine‐stabilized silylenes should be able to activate the C−Si bond of trimethoxy(ethynyl)silane (HC≡C−Si(OMe)3) and that the reaction should proceed in a reversible manner under mild conditions.
New Insights into the Anion Transport Selectivity and Mechanism of Tren‐based Tris‐(thio)ureas
Authors: Jowett Laura A. , Howe Ethan N. W. , Wu Xin , Busschaert Nathalie , Gale Philip A.
Published: May 2018

The anion transport properties of a series of previously reported tren‐based anionophores have been revisited using new assays designed to measure anion uniport. This study provides new insights into the transport mechanism and selectivity of this important class of transporters. Specifically, we report the chloride and nitrate transport selectivity of these systems and quantify sulfate transport to determine EC50 values for sulfate transport for the first time. Two new assays were developed to study bicarbonate transport allowing accurate quantification of chloride/bicarbonate exchange.
Organotin Selenide Clusters and Hybrid Capsules
Authors: Hanau Katharina , Rinn Niklas , Argentari Mario , Dehnen Stefanie
Published: May 2018

Several compounds with unique structural motifs that have already been known from organotin sulfide chemistry, but remained unprecedented in organotin selenide chemistry so far, have been synthesized. The reaction of [(R1Sn)4Se6] (R1=CMe2CH2C(O)Me) with N2H4⋅H2O/(SiMe3)2Se and PhN2H3/(SiMe3)2Se led to the formation of [{(R2Sn)2SnSe4}2(μ‐Se)2] (1; R2=CMe2CH2C(Me)NNH2) and [{(R3Sn)2SnSe4}2(μ‐Se)2] (2; R3=CMe2CH2C(Me)NNPhH)). The addition of ortho‐phthalaldehyde to [(R2Sn)4Se6] yielded a cluster with intramolecular bridging of the organic groups, namely, [(R4Sn2)2Se6] (3; R4=(CMe2CH2C(Me)NNCH)2C6H4). The introduction of organic ligands with longer chains finally allowed the isolation of inorganic–organic capsules of the type [(μ‐R)3(Sn3Se4)2]X2, with R=(CMe2CH2C(Me)NNHC(O))2(CH2)4 and X=[SnC3], Cl (4 a, b) or R=CMe2CH2C(Me)NNH)2 and X=[SnCl3] (5). The capsules enclose solvent molecules and/or anions as guests. All compounds were characterized by means of single‐crystal X‐ray diffraction studies, NMR spectroscopy, and mass spectrometry.
ESIPT‐Modulated Emission of Lanthanide Complexes: Different Energy‐Transfer Pathways and Multiple Responses
Authors: Sun Si‐Si , Wang Zheng , Wu Xiang Wen , Zhang Jian‐Hua , Li Chao‐Jie , Yin Shao‐Yun , Chen Ling , Pan Mei , Su Cheng‐Yong
Published: May 2018

Two series of isostructural lanthanide coordination complexes, namely, LIFM‐42(Ln) (Ln=Eu, Tb, Gd, in which LIFM stands for the Lehn Institute of Functional Materials) and LIFM‐43(Ln) (Ln=Er, Yb), were synthesized through the self‐assembly of an excited‐state intramolecular proton transfer (ESIPT) ligand, 5‐[2‐(5‐fluoro‐2‐hydroxyphenyl)‐4,5‐bis(4‐fluorophenyl)‐1H‐imidazol‐1‐yl]isophthalic acid (H2hpi2cf), with different lanthanide ions. In the coordination structures linked by the ligands and oxo‐bridged LnIII2 clusters (for LIFM‐42(Ln) series) or isolated LnIII ions (for LIFM‐43(Ln) series), the ESIPT ligand can serve as both the host and antenna for protecting and sensitizing the photoluminescence (PL) of LnIII ions. Meanwhile, the −OH⋅⋅⋅N active sites on the ligands are vacant, which provides availability to systematically explore the PL behavior of Ln complexes with ESIPT interference. Based on the accepting levels of different lanthanide ions, energy transfer can occur from the T1(K*) or T1(E*) (K*=excited keto form, E*=excited enol form) excited states of the ligand. Furthermore, the sensitized lanthanide luminescence in both visible and near‐infrared regions, as well as the remaining K* emission of the ligand, can be modulated by the ESIPT responsiveness to different solvents, anions, and temperature.
Annual Report to the Nation on the Status of Cancer, part II: Recent changes in prostate cancer trends and disease characteristics
Authors: Negoita Serban , Feuer Eric J. , Mariotto Angela , Cronin Kathleen A. , Petkov Valentina I. , Hussey Sarah K. , Benard Vicki , Henley S. Jane , Anderson Robert N. , Fedewa Stacey , Sherman Recinda L. , Kohler Betsy A. , Dearmon Barbara J. , Lake Andrew J. , Ma Jiemin , Richardson Lisa C. , Jemal Ahmedin , Penberthy Lynne
Published: May 2018

BACKGROUND

Temporal trends in prostate cancer incidence and death rates have been attributed to changing patterns of screening and improved treatment (mortality only), among other factors. This study evaluated contemporary national‐level trends and their relations with prostate‐specific antigen (PSA) testing prevalence and explored trends in incidence according to disease characteristics with stage‐specific, delay‐adjusted rates.

METHODS

Joinpoint regression was used to examine changes in delay‐adjusted prostate cancer incidence rates from population‐based US cancer registries from 2000 to 2014 by age categories, race, and disease characteristics, including stage, PSA, Gleason score, and clinical extension. In addition, the analysis included trends for prostate cancer mortality between 1975 and 2015 by race and the estimation of PSA testing prevalence between 1987 and 2005. The annual percent change was calculated for periods defined by significant trend change points.

RESULTS

For all age groups, overall prostate cancer incidence rates declined approximately 6.5% per year from 2007. However, the incidence of distant‐stage disease increased from 2010 to 2014. The incidence of disease according to higher PSA levels or Gleason scores at diagnosis did not increase. After years of significant decline (from 1993 to 2013), the overall prostate cancer mortality trend stabilized from 2013 to 2015.

CONCLUSIONS

After a decline in PSA test usage, there has been an increased burden of late‐stage disease, and the decline in prostate cancer mortality has leveled off. Cancer 2018;124:2801‐2814. © 2018 American Cancer Society
Design and Fabrication of Printed Paper‐Based Hybrid Micro‐Supercapacitor by using Graphene and Redox‐Active Electrolyte
Authors: Nagar Bhawna , Dubal Deepak P. , Pires Luis , Merkoçi Arben , Gómez‐Romero Pedro
Published: May 2018

Inspired by future needs of flexible, simple, and low‐cost energy storage devices, smart graphene‐based micro‐supercapacitors on conventional Xerox paper substrates were developed. The use of redox‐active species (iodine redox couple) was explored to further improve the paper device's performance. The device based on printed graphene paper itself already had a remarkable maximum volumetric capacitance of 29.6 mF cm−3 (volume of whole device) at 6.5 mA cm−3. The performance of the hybrid electrode with redox‐active potassium iodide at the graphene surface was tested. Remarkably, the hybrid device showed improved volumetric capacitance of 130 mF cm−3. The maximum energy density for a graphene+KI device in H2SO4 electrolyte was estimated to be 0.026 mWh cm−3. Thus, this work offers a new simple, and lightweight micro‐supercapacitor based on low‐cost printed graphene paper, which will have great applications in portable electronics.
Two‐Step Synthesis of Cobalt Iron Alloy Nanoparticles Embedded in Nitrogen‐Doped Carbon Nanosheets/Carbon Nanotubes for the Oxygen Evolution Reaction
Authors: Liu Yang , Li Feng , Yang Haidong , Li Jing , Ma Ping , Zhu Yan , Ma Jiantai
Published: May 2018

There is a vital need to explore highly efficient and stable non‐precious‐metal catalysts for the oxygen evolution reaction (OER) to reduce the overpotential and further improve the energy‐conversion efficiency. Herein, we report a unique and cost‐effective lyophilization and thermal treatment two‐step procedure to synthesize a high‐performance hybrid consisting of CoFe alloy nanoparticles embedded in N‐doped carbon nanosheets interspersed with carbon nanotubes (CoFe‐N‐CN/CNTs) hybrid. The lyophilization step during the catalyst preparation leads to a uniform dispersion of carbon‐like precursors and avoids the agglomeration of metal particles. In addition, the inserted CNTs and doped N in this hybrid provide a good electrical conductivity, an abundance of chemically active sites, good mass transport capability, and effective gas adsorption/release channels. All these lead to a high specific surface area of 240.67 m2 g−1, favorable stability, and remarkable OER activities with an overpotential of only 285 mV at a current density of 10 mA cm−2 and a Tafel slope of 51.09 mV dec−1 in 1.0 m KOH electrolyte, which is even superior to commercial IrO2 catalysts. The CoFe‐N‐CN/CNTs hybrid thus exhibits great potential as a highly efficient and earth‐abundant anode OER electrocatalyst.