bluuebunny/crossref_metadata_2025 huggingface dataset:
Television production, Funding Models and Exploitation of Content
Authors: Doyle Gillian
Published: July 2016

El creciente aumento de las plataformas digitales está transformando las estrategias de financiación de los medios de comunicación para la producción y la explotación del valor económico de los contenidos creativos. En la industria de la televisión, los cambios que se han producido en las tecnologías de distribución y la aparición de servicios VOD (video bajo demanda) como Netflix están cambiando gradualmente tanto al público como el poder financiero de los radiodifusores, al tiempo que está generando oportunidades sin precedentes para los realizadores de programas. A partir de los resultados de un reciente investigación financiada por la RCUK (Research Councils UK), este artículo examina cómo estos cambios están afectando a la financiación de la producción de contenidos para televisión. En particular se centra en evaluar los cambios en las dinámicas de los mercados de derechos así como los nuevos enfoques estratégicos para la financiación
de la producción de la televisión con el fin de comprender el valor que tienen para los mercados, las industrias y las políticas destinadas a apoyar la sostenibilidad económica de las empresas de producción de contenidos televisivos independientes.
The New International Division of Cultural Labor Revisited
Authors: Miller Toby
Published: July 2016

La economía política radical dió lugar al concepto de la Nueva División Internacional del Trabajo Cultural (NICL). Este parte de comprender las situaciones de desigualdad que se producen a diario tanto en el trabajo como en la vida doméstica. Aunque los trabajadores generan valor, rara vez se benefician proporcionalmente de este debido al poder del capital. Mientras que la economía neoclásica o burguesa asume que la oferta y demanda determinan el precio de los productos básicos, la economía política examina el papel del Estado y el capital en el control de mano de obra y la ideologización de consumidores y ciudadanos. En otras palabras, la economía ortodoxa se concentra en los mercados, considerándolos como las joyas de la conducta humana; el enfoque heterodoxo desafía este enfoque sobre el consumo, haciendo hincapié en la producción como una fuente de valor y un espacio de control. En este trabajo se analiza como el NICL se ha convertido en un modelo para la explotación en todos los territorios, las industrias y ocupaciones, por lo que ejercer un pensamiento crítico sigue siendo vital. Analíticamente, tenemos que centrarnos en la división del trabajo como una herramienta teórica, empírica, y de organización si queremos entender el trabajo diario de una manera que pueda enriquecerlo y liberarlo de acuerdo con las experiencias y las necesidades tanto de los trabajadores como ecológicas.
Economía Digital y su Impacto en los Medios. Presentación.
Authors: Álvarez Monzoncillo José María , De Haro Rodríguez Guillermo , López Villanueva Javier
Published: July 2016

La economía digital está impactando en todas las industrias, con especial énfasis en aquellas intensivas en información o en las que la información es el producto. Los medios de comunicación se han visto afectados por estos cambios de forma abrupta. Aspectos como el talento y el empleo, las nuevas audiencias, la adaptación al medio digital de diferentes sectores o la evolución ante los retos a los que se enfrentan son, entre otros, revisitados en este monográfico para obtener una visión de la posible evolución futura mediante un repaso de aquellos aspectos importantes del pasado.
Spanish media in a new digital world: The great bonfire of the vanities
Authors: Álvarez Monzoncillo José María , De Haro Guillermo , López-Villanueva Javier
Published: July 2016

Los medios de comunicación de masas en España han realizado un ajuste importante en los últimos años para adaptarse a la Gran Recesión y a una tecnología disruptiva como ha sido, en muchos casos, Internet. Esto se ha traducido en la caída de los ingresos publicitarios y de las subvenciones públicas, más una bajada de ventas y suscripciones. En los años de bonanza, las promesas de Internet y el fácil acceso a los mercados financieros internacionales a intereses bajos por debajo de la inflación hicieron posible que los grupos diseñaran estrategias de expansión verticales y horizontales para tomar posición en el mercado nacional y expandirse hacia los mercados internacionales, fundamentalmente hacia América Latina y Europa. Además, los consumidores han podido acceder más fácilmente y a un menor precio a los contenidos a través de la red y con multitud de dispositivos. La mala situación económica de los medios clásicos (provocada, sobre todo, por su alto endeudamiento) no permite afrontar los nuevos retos que exige el cambio mientras que las nuevas empresas digitales subsisten bajo una elevada precariedad económica.
Influence of output power of a spin torque oscillator on phase locked loop operation
Authors: Tamaru Shingo , Kubota Hitoshi , Yakushiji Kay , Fukushima Akio , Yuasa Shinji
Published: August 2016

This work investigates the influence of the output power of a spin torque oscillator (STO) on the operation of a phase locked loop (PLL) circuit. Timing jitter and minimum output power for stable PLL operation determined by Johnson noise and shot noise are first theoretically calculated, and compared with experimental results. The theory and experiment show a reasonably good agreement, indicating that smaller than −50 dBm (10 nW), or −60 dBm (1 nW) when a low pass filter is used, of output power is sufficient for stable PLL operation if a large timing jitter is acceptable. However, it is also shown that a large output power is needed to suppress timing jitter down to the level comparable to state-of-the-art commercial PLL circuits. The estimate of minimum output power for stable PLL operation is verified by intentionally attenuating the STO output signal down to −55 dBm (3.2 nW) and demonstrating a stable phase locked oscillation.
The ammonium sulfate inhibition of human angiogenin
Authors: Chatzileontiadou Demetra S. M. , Tsirkone Vicky G. , Dossi Kyriaki , Kassouni Aikaterini G. , Liggri Panagiota G. V. , Kantsadi Anastassia L. , Stravodimos George A. , Balatsos Nikolaos A. A. , Skamnaki Vassiliki T. , Leonidas Demetres D.
Published: August 2016

In this study, we investigate the inhibition of human angiogenin by ammonium sulfate. The inhibitory potency of ammonium sulfate for human angiogenin (IC50 = 123.5 ± 14.9 mm) is comparable to that previously reported for RNase A (119.0 ± 6.5 mm) and RNase 2 (95.7 ± 9.3 mm). However, analysis of two X‐ray crystal structures of human angiogenin in complex with sulfate anions (in acidic and basic pH environments, respectively) indicates an entirely distinct mechanism of inhibition. While ammonium sulfate inhibits the ribonucleolytic activity of RNase A and RNase 2 by binding to the active site of these enzymes, sulfate anions bind only to peripheral substrate anion‐binding subsites of human angiogenin, and not to the active site.
A physically based analytical model of flood frequency curves
Authors: Basso S. , Schirmer M. , Botter G.
Published: August 2016

Predicting magnitude and frequency of floods is a key issue in hydrology, with implications in many fields ranging from river science and geomorphology to the insurance industry. In this paper, a novel physically based approach is proposed to estimate the recurrence intervals of seasonal flow maxima. The method links the extremal distribution of streamflows to the stochastic dynamics of daily discharge, providing an analytical expression of the seasonal flood frequency curve. The parameters involved in the formulation embody climate and landscape attributes of the contributing catchment and can be estimated from daily rainfall and streamflow data. Only one parameter, which is linked to the antecedent wetness condition in the watershed, needs to be calibrated on the observed maxima. The performance of the method is discussed through a set of applications in four rivers featuring heterogeneous daily flow regimes. The model provides reliable estimates of seasonal maximum flows in different climatic settings and is able to capture diverse shapes of flood frequency curves emerging in erratic and persistent flow regimes. The proposed method exploits experimental information on the full range of discharges experienced by rivers. As a consequence, model performances do not deteriorate when the magnitude of events with return times longer than the available sample size is estimated. The approach provides a framework for the prediction of floods based on short data series of rainfall and daily streamflows that may be especially valuable in data scarce regions of the world.
Multifrequency seismic detectability of seasonal thermoclines assessed from ARGO data
Authors: Ker S. , Le Gonidec Y. , Marié L.
Published: August 2016

Seismic oceanography is a developing research topic where new acoustic methods allow high‐resolution teledetection of the thermohaline structure of the ocean. First implementations to study the Ocean Surface Boundary Layer have recently been achieved but remain very challenging due to the weakness and shallowness of such seismic reflectors. In this article, we develop a multifrequency seismic analysis of hydrographic data sets collected in a seasonally stratified midlatitude shelf by ARGO network floats to assess the detectability issue of shallow thermoclines. This analysis, for which sensitivity to the data reduction scheme used by ARGO floats for the transmission of the profiles is discussed, allows characterizing both the depth location and the frequency dependency of the dominant reflective feature of such complex structures. This approach provides the first statistical distribution of the range of variability of the frequency‐dependent seismic reflection amplitude of the midlatitude seasonal thermoclines. We introduce a new parameter to quantify the overall capability of a multichannel seismic setup, including the source strength, the fold, and the ambient noise level, to detect shallow thermoclines. Seismic source signals are approximated by Ricker wavelets, providing quantitative guidelines to help in the design of seismic experiments targeting such oceanic reflectors. For shallow midlatitude seasonal thermoclines, we show that the detectability is optimal for seismic peak frequencies between 200 and 400 Hz: this means that airgun and Sparker sources are not well suited and that significant improvements of source devices will be necessary before seismic imaging of OSBL structures can be reliably attempted.
Investigating Predictors of Superior Face Recognition Ability in Police Super‐recognisers
Authors: Davis Josh P. , Lander Karen , Evans Ray , Jansari Ashok
Published: August 2016

There are large individual differences in the ability to recognise faces. Super‐recognisers are exceptionally good at face memory tasks. In London, a small specialist pool of police officers (also labelled ‘super‐recognisers’ by the Metropolitan Police Service) annually makes 1000's of suspect identifications from closed‐circuit television footage. Some suspects are disguised, have not been encountered recently or are depicted in poor quality images. Across tests measuring familiar face recognition, unfamiliar face memory and unfamiliar face matching, the accuracy of members of this specialist police pool was approximately equal to a group of non‐police super‐recognisers. Both groups were more accurate than matched control members of the public. No reliable relationships were found between the face processing tests and object recognition. Within each group, however, there were large performance variations across tests, and this research has implications for the deployment of police worldwide in operations requiring officers with superior face processing ability. Copyright © 2016 John Wiley & Sons, Ltd.
Patterns and Consequences of Multimorbidity in the General Population: There is No Chronic Disease Management Without Rheumatic Disease Management
Authors: Simões Daniela , Araújo Fábio A. , Severo Milton , Monjardino Teresa , Cruz Ivo , Carmona Loreto , Lucas Raquel
Published: August 2016

Objective

To identify empirical model‐based patterns of multimorbidity from chronic noncommunicable diseases in the general population, with a focus on the contribution of rheumatic and musculoskeletal diseases (RMDs), and to quantify their association with adverse health outcomes.

Methods

Cross‐sectional data from the Portuguese Fourth National Health Survey were analyzed (n = 23,754). Latent class analysis was used to identify patterns of coexistence of 11 chronic noncommunicable diseases (RMDs, diabetes mellitus, hypertension, chronic obstructive pulmonary disease, stroke, depression, myocardial infarction, cancer, osteoporosis, asthma, and renal failure). Based on the Outcome Measures in Rheumatology, filter 2.0, health outcomes included life impact, pathophysiologic manifestations, and resource use. We assessed the association between patterns and adverse health outcomes, through sex‐, age‐, and body mass index–adjusted prevalence ratios with 95% confidence intervals, obtained using Poisson regression.

Results

Four patterns of chronic noncommunicable diseases co‐occurrence were identified and labeled as low disease probability, cardiometabolic conditions, respiratory conditions, and RMDs and depression. RMDs were highly prevalent in patients with chronic diseases (from 38.6% in cardiometabolic conditions to 66.7% in RMDs and depression). While negative self‐rated health, short‐term disability, and chronic pain were more strongly associated with cardiometabolic conditions and respiratory conditions, all multimorbidity patterns were similarly associated with long‐term disability, frequent health care utilization, and out‐of‐pocket health care expenses.

Conclusion

Our study emphasizes RMDs as a major presence in multimorbidity in the general population. All multimorbidity patterns were associated with a wide set of adverse health outcomes. Management strategies for the patient with chronic cardiometabolic, respiratory, or depressive conditions should also target RMDs.
Impact of Rheumatoid Arthritis on the Mortality of Elderly Patients Who Develop Cancer: A Population‐Based Study
Authors: Nayak Pratibha , Luo Ruili , Elting Linda , Zhao Hui , Suarez‐Almazor Maria E.
Published: August 2016

Objective

Comorbidity among cancer patients poses additional risks for mortality. The possible impact of rheumatoid arthritis (RA) on cancer patient survival is unclear. Our objective was to examine survival among elderly patients with RA who develop cancer.

Methods

Patients diagnosed with breast, prostate, colorectal, or lung cancer between 2001 and 2010 were identified from the Texas Cancer Registry and Medicare–linked databases. The cohort was categorized into 3 groups according to the number of claims patients had with a diagnosis of RA in the year prior to the cancer diagnosis: 2‐RA (patients with ≥2 claims), 1‐RA (1 claim), and no claims. Overall survival was estimated for these groups and for each cancer, using Cox proportional hazards models adjusting for covariates.

Results

The cohort included 139,097 patients with cancer (35,026 breast, 43,181 prostate, 31,103 colorectal, and 29,787 lung); 1.7% had 1 RA claim, and 1.1% had 2 or more. Adjusted hazard ratios for patients in the 2‐RA group were 1.41 (95% confidence interval [95% CI] 1.21–1.65) for breast and 1.53 (95% CI 1.26–1.85) for prostate. No significant differences were observed for those with colorectal or lung cancer.

Conclusion

Mortality was increased by 40% and 50%, respectively, in elderly patients with RA who developed breast or prostate cancer, after controlling for other comorbidities. This association was not seen in cancers with shorter survival time (colorectal or lung). Research is needed to determine whether the increased risk is related to comorbid burden or to differential utilization of cancer or rheumatoid therapies in patients with both diseases.
Is the Site of Back Pain Related to the Location of Magnetic Resonance Imaging Lesions in Patients With Chronic Back Pain? Results From the Spondyloarthritis Caught Early Cohort
Authors: de Hooge Manouk , de Bruin Freek , de Beer Lieke , Bakker Pauline , van den Berg Rosaline , Ramiro Sofia , van Gaalen Floris , Fagerli Karen , Landewé Robert , van Oosterhout Maikel , Ramonda Roberta , Huizinga Tom , Bloem Hans , Reijnierse Monique , van der Heijde Désirée
Published: August 2016

Objective

To determine associations between magnetic resonance imaging (MRI) lesions originating from either axial spondyloarthritis (SpA) or from degeneration and pain in patients with chronic back pain of <2 years duration.

Methods

Patients from the Spondyloarthritis Caught Early (SPACE) cohort identified the sites of pain (thoracic, lumbar, buttock). The average MRI scores from 2 readers for axial SpA lesions and from 2 different readers for degenerative lesions were used. Associations between sacroiliac (SI) joint lesions and buttock pain were investigated by logistic regression analysis, and associations between axial SpA or degenerative lesions and pain in the spine (thoracic and lumbar) were investigated using generalized estimating equations. Interactions with sex, age, HLA–B27, and fulfillment of Assessment of SpondyloArthritis international Society (ASAS) criteria were tested.

Results

In 348 patients (126 males, 127 fulfilling ASAS criteria, mean age 29.4 years), spinal MRI (and SI joint images in 342) were available. Pain was localized in the thoracic spine (35.9%), the lumbar spine (82.5%), or in the buttock(s) (57.8%). Inflammatory lesions of the SI joint (odds ratio [OR] 1.06; P = 0.04) and erosions of the SI joint in patients <25 years (OR 1.16; P = 0.04) were associated with buttock pain. Axial SpA spinal lesions were not associated with pain. Modic type 1 lesions in patients >35 years (OR 5.19; P = 0.001), high‐intensity zone lesions in females not fulfilling ASAS criteria (OR 5.09; P = 0.001), and herniation in various subgroups (OR range 2.07–4.66) were associated with pain.

Conclusion

Specific degenerative lesions, but not typical axial SpA lesions, of the spine are associated with pain at the same location in some subgroups. Inflammatory lesions in the SI joint are associated with buttock pain.
Process Development for Innovative Iron Alloy Metallic Glass Coatings
Authors: Bobzin Kirsten , Öte Mehmet , Linke Thomas Frederik , Königstein Tim
Published: August 2016

Bulk metallic glasses exhibit high corrosive resistance, good tribological behavior, and low thermal conductivity. The production of metallic glass using Thermal Spray technology is a novel approach. In this study, the manufacturing of iron‐based metallic glass coatings by high velocity oxygen fuel spraying is investigated. For this purpose individually designed, amorphous feedstock materials are used. By means of X‐Ray‐Diffraction and Differential Scanning Calorimetry amorphous structures are identified. Subsequently, the thermal diffusivities are determined by means of Laser‐Flash method. The low thermal diffusivity measured proves the potential of metallic glasses as thermal barrier coatings for low temperature applications, such as combustion engines.
Mechanistic Insights on Ternary Ni2−xCoxP for Hydrogen Evolution and Their Hybrids with Graphene as Highly Efficient and Robust Catalysts for Overall Water Splitting
Authors: Li Jiayuan , Yan Ming , Zhou Xuemei , Huang Zheng‐Qing , Xia Zhaoming , Chang Chun‐Ran , Ma Yuanyuan , Qu Yongquan
Published: August 2016

Searching the high‐efficient, stable, and earth‐abundant electrocatalysts to replace the precious noble metals holds the promise for practical utilizations of hydrogen and oxygen evolution reactions (HER and OER). Here, a series of highly active and robust Co‐doped nickel phosphides (Ni2−xCoxP) catalysts and their hybrids with reduced graphene oxide (rGO) are developed as bifunctional catalysts for both HER and OER. The Co‐doping in Ni2P and their hybridization with rGO effectively regulate the catalytic activity of the surface active sites, accelerate the charge transfer, and boost their superior catalytic activity. Density functional theory calculations show that the Co‐doped catalysts deliver the moderate trapping of atomic hydrogen and facile desorption of the generated H2 due to the H‐poisoned surface active sites of Ni2−xCoxP under the real catalytic process. Electrochemical measurements reveal the high HER efficiency and durability of the NiCoP/rGO hybrids in electrolytes with pH 0–14. Coupled with the remarkable and robust OER activity of the NiCoP/rGO hybrids, the practical utilization of the NiCoP/rGO‖NiCoP/rGO for overall water splitting yields a catalytic current density of 10 mA cm−2 at 1.59 V over 75 h without an obvious degradation and Faradic efficiency of ≈100% in a two‐electrode configuration and 1.0 m KOH.
Constraining Si Particles within Graphene Foam Monolith: Interfacial Modification for High‐Performance Li+ Storage and Flexible Integrated Configuration
Authors: Ma Yue , Younesi Reza , Pan Ruijun , Liu Chenjuan , Zhu Jiefang , Wei Bingqing , Edström Kristina
Published: August 2016

Pulverization of electrode materials and loss of electrical contact have been identified as the major causes for the performance deterioration of alloy anodes in Li‐ion batteries. This study presents the hierarchical arrangement of spatially confining silicon nanoparticles (Si NPs) within graphene foam (GF) for alleviating these issues. Through a freeze‐drying method, the highly oriented GF monolith is engineered to fully encapsulate the Si NPs, serving not only as a robust framework with the well‐accessible thoroughfares for electrolyte percolation but also a physical blocking layer to restrain Si from direct exposure to the electrolyte. In return, the pillar effect of Si NPs prevents the graphene sheets from restacking while preserving the highly efficient electron/Li+ transport channels. When evaluated as a binder‐free anode, impressive cycle performance is realized in both half‐cell and full‐cell configurations. Operando X‐ray diffraction and in‐house X‐ray photoelectron spectroscopy confirm the pivotal protection of GF to sheathe the most volume‐expanded lithiated phase (Li15Si4) at room temperature. Furthermore, a free‐standing composite film is developed through readjusting the pore size in GF/Si monolith and directly integrated with nanocellulose membrane (NCM) separator. Because of the good electrical conductivity and structural integrity of the GF monolith as well as the flexibility of the NCM separator, the as‐developed GF/Si‐NCM electrode showcases the potential use in the flexible electronic devices.
Channeled β‐TCP Scaffolds Promoted Vascularization and Bone Augmentation in Mandible of Beagle Dogs
Authors: Yu Tao , Liu Qing , Jiang Ting , Wang Xuesong , Yang Yunzhi , Kang Yunqing
Published: August 2016

A major hindrance to successful alveolar bone augmentation and ridge preservation using synthetic scaffolds is insufficient vascularization in the implanted bone grafts. The slow ingrowth of host vasculature from the bone bed of alveolar bone to the top of the implanted bone grafts leads to limited bone formation in the upper layers of the implanted grafts, which hinders the subsequent implantation of titanium dental implants. In this study, macroporous beta‐tricalcium phosphate (β‐TCP) scaffolds with multiple vertical hollow channels are fabricated that play a similar role as blood vessels for nutrient diffusion and cell migration. The results show that the hollow channels accelerate the degradation rate of the β‐TCP scaffolds and the in vitro release of a bone forming peptide‐1, which significantly promote proliferation and osteogenesis of human bone mesenchymal stem cells on the channeled scaffolds, compared to nonchanneled scaffolds in vitro. More volume of newly formed bone tissues with more blood vessels are augmented in the channeled scaffolds when implanted in mandibular bone defects of beagle dogs. Channeled scaffolds significantly promote new bone formation and augment the height of the mandible. These findings indicate channeled scaffolds facilitate vascularization and bone formation and have great potential for vascularized bone augmentation.
Plasmonically Induced Potential in Metal–Semiconductor Composites
Authors: Shahin Shiva , Gangopadhyay Palash , Norwood Robert A.
Published: August 2016

Techniques such as conductive atomic force microscopy and electrostatic force microscopy are applied to the study of photoexcited arrays of gold nanoparticles decorating an indium tin oxide coated glass substrate. The nanoparticles are partially covered by a thin semiconducting polymer. The change in the current and potential profiles of the composite metal‐semiconductor sample after excitation at the plasmonic resonance frequency of the metallic nanoparticles is analyzed.
Diastereo‐ and Enantioselective Construction of Dihydroisocoumarin‐Based Spirooxindole Frameworks via Organocatalytic Tandem Reactions
Authors: Wu Jia‐Le , Du Bai‐Xiang , Zhang Yu‐Chen , He Ying‐Ying , Wang Jing‐Yi , Wu Ping , Shi Feng
Published: August 2016

An organocatalytic asymmetric approach has been developed for the ennantioselective construction of dihydroisocoumarin‐based spirooxindole frameworks in high yields, excellent diastereo‐ and enantioselectivities (up to 99%, all >95:5 dr, up to 99% ee). This approach takes advantage of chiral thiourea‐tertiaryamine catalyzed tandem reaction of isatins with enolizable homophthalic anhydride, which has wide substrate scope and can be performed with low catalyst loading. This reaction not only provides an efficient and useful method for constructing enantioenriched dihydroisocoumarin‐based spirooxindole scaffold, but also will enrich the research contents of catalytic asymmetric tandem reactions and enantioselective synthesis of biologically important spirooxindoles.

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Ruthenium‐Mediated Dual Catalytic Reactions of Isoquinoline via C−H Activation and Dearomatization for Isoquinolone
Authors: Wang Ting‐Hsuan , Lee Wei‐Chih , Ong Tiow‐Gan
Published: August 2016

We have unraveled the ruthenium‐promoted prototype reaction based on C(sp2)−C(sp3) bond formation through the reigoselective C−H activation of isoquinoline and pyridine derivatives with various alkyl halides, leading to 1‐substituted isoquinoline products in good yield. This C−H catalytic reaction did not rely on chelation assistance of the directing group of the substrates. The dimer [RuCl2(p‐cymene)]2 in combination with an N‐heterocyclic carbene ligand, adamantanecarboxylic acid and K2CO3 base in N‐methyl‐2‐pyrrolidone solution at 150 °C are the best conditions. Simultaneously, we are also able to chemically tune the reaction mode to dearomatization by adding water, leading to isoquinolone products. This reaction methodology is not suitable for other nitrogen‐containing heteroarenes such as pyridazines and pyrimidines.

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Cobalt‐Catalyzed Twofold Direct C(sp2)−C(sp3) Bond Coupling: Regioselective C‐3 Alkylation of Coumarins with (Cyclo)alkyl Ethers
Authors: Dian Longyang , Zhao Hui , Zhang‐Negrerie Daisy , Du Yunfei
Published: August 2016

A cobalt‐catalyzed regioselective C‐3 alkylation of coumarins was realized under mild reaction conditions, during which a variety of substituted coumarins including those containing sensitive functional groups could smoothly undergo the selective C(sp2)−C(sp3) bond formation with a series of cyclic or straight‐chain alkyl ethers.

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Selective Synthesis of Enantiomeric η6‐Arene Chromium Tricarbonyl Complexes with Epimeric Pyrroloimidazolones
Authors: Wilson‐Konderka Cody , Doxtator Kathleen , Metallinos Costa
Published: August 2016

A pair of epimeric l‐proline derived chiral auxiliaries have been developed for the diastereoselective lithiation–substitution of η6‐arene chromium tricarbonyl complexes. Lithiation of the anti epimer affords planar chiral imidazolones in >95:5 dr upon electrophile quench. Application of the same reaction sequence to the syn epimer provides products with opposite planar chirality in equally high levels of diastereomeric purity. The ortho‐substituted epimeric imidazolones give rise to planar chiral enantiomers upon acid‐induced elimination, thus precluding the need to prepare a d‐proline‐derived starting material.

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Enantioselective Copper‐Catalyzed Intramolecular N−H Bond Insertion: Synthesis of Chiral 2‐Carboxytetrahydroquinolines
Authors: Song Xiao‐Guang , Ren Yuan‐Yuan , Zhu Shou‐Fei , Zhou Qi‐Lin
Published: August 2016

The first highly enantioselective intramolecular N−H bond insertion was realized by using copper catalysts modified with chiral spirobisoxazoline ligands, which provides a novel strategy for the synthesis of chiral 2‐carboxytetrahydroquinolines. This reaction features fast reaction rate, high yield, high enantioselectivity, and mild reaction conditions.

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Sodium Iodide/Hydrogen Peroxide‐Mediated Oxidation/Lactonization for the Construction of Spirocyclic Oxindole‐Lactones
Authors: Li Guofeng , Huang Liwu , Xu Jiecheng , Sun Wangsheng , Xie Junqiu , Hong Liang , Wang Rui
Published: August 2016

The sodium iodide/hydrogen peroxide‐mediated oxidation/lactonization of indolepropionic acids was achieved, affording the corresponding spirocyclic oxindole‐lactones in moderate to high yields. This metal‐free procedure features mild reaction conditions, non‐toxicity and easy handling, with hydrogen peroxide (H2O2) as a clean oxidant.

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FGFR‐associated craniosynostosis syndromes and gastrointestinal defects
Authors: Hibberd Christine E. , Bowdin Sarah , Arudchelvan Yamini , Forrest Christopher R. , Brakora Katherine A. , Marcucio Ralph S. , Gong Siew‐Ging
Published: August 2016

Craniosynostosis is a relatively common birth defect characterized by the premature fusion of one or more cranial sutures. Examples of craniosynostosis syndromes include Crouzon (CS), Pfeiffer (PS), and Apert (AS) syndrome, with clinical characteristics such as midface hypoplasia, hypertelorism, and in some cases, limb defects. Mutations in Fibroblast Growth Factor Receptor‐2 comprise the majority of known mutations in syndromic forms of craniosynostosis. A number of clinical reports of FGFR‐associated craniosynostosis patients and mouse mutants have been linked to gastrointestinal tract (GIT) disorders, leading to the hypothesis of a direct link between FGFR‐associated craniosynostosis syndromes and GIT malformations. We conducted an investigation to determine GIT symptoms in a sample of FGFR‐associated craniosynostosis syndrome patients and a mouse model of CS containing a mutation (W290R) in Fgfr2. We found that, compared to the general population, the incidence of intestinal/bowel malrotation (IM) was present at a higher level in our sample population of patients with FGFR‐associated craniosynostosis syndromes. We also showed that the mouse model of CS had an increased incidence of cecal displacement, suggestive of IM. These findings suggest a direct relationship between FGFR‐related craniosynostosis syndromes and GIT malformations. Our study may shed further light on the potential widespread impact FGFR mutations on different developmental systems. Based on reports of GIT malformations in children with craniosynostosis syndromes and substantiation with our animal model, GIT malformations should be considered in any child with an FGFR2‐associated craniosynostosis syndrome. © 2016 Wiley Periodicals, Inc.
A current snapshot of common genomic variants contribution in psychiatric disorders
Authors: Santoro Marcos L. , Moretti Patricia N. , Pellegrino Renata , Gadelha Ary , Abílio Vanessa C. , Hayashi Mirian A.F. , Belangero Sintia I. , Hakonarson Hakon
Published: August 2016

In the past decade, numerous advances were achieved in psychiatric genetics. Particularly, the genome wide association studies (GWAS) have contributed to uncovering new genes and pathways associated to psychiatric disorders (PDs). At the same time, with increasing sample sizes in the GWAS, the polygenic risk score (PRS) promoted an additional tool for identification and evaluation the genetic risk quantitatively in PDs. This concept review presents the state of the art GWAS analysis and PRS focusing on the genetic underpinnings of PDs. © 2016 Wiley Periodicals, Inc.
Investigating shared aetiology between type 2 diabetes and major depressive disorder in a population based cohort
Authors: Clarke Toni‐Kim , Obsteter Jana , Hall Lynsey S. , Hayward Caroline , Thomson Pippa A. , Smith Blair H. , Padmanabhan Sandosh , Hocking Lynne J. , Deary Ian J. , Porteous David J. , McIntosh Andrew M.
Published: August 2016

Type II diabetes (T2D) and major depressive disorder (MDD) are often co‐morbid. The reasons for this co‐morbidity are unclear. Some studies have highlighted the importance of environmental factors and a causal relationship between T2D and MDD has also been postulated. In the present study we set out to investigate the shared aetiology between T2D and MDD using Mendelian randomization in a population based sample, Generation Scotland: the Scottish Family Health Study (N = 21,516). Eleven SNPs found to be associated with T2D were tested for association with MDD and psychological distress (General Health Questionnaire scores). We also assessed causality and genetic overlap between T2D and MDD using polygenic risk scores (PRS) assembled from the largest available GWAS summary statistics to date. No single T2D risk SNP was associated with MDD in the MR analyses and we did not find consistent evidence of genetic overlap between MDD and T2D in the PRS analyses. Linkage disequilibrium score regression analyses supported these findings as no genetic correlation was observed between T2D and MDD (rG = 0.0278 (S.E. 0.11), P‐value = 0.79). As suggested by previous studies, T2D and MDD covariance may be better explained by environmental factors. Future studies would benefit from analyses in larger cohorts where stratifying by sex and looking more closely at MDD cases demonstrating metabolic dysregulation is possible. © 2016 The Authors. American Journal of Medical Genetics Part B: Neuropsychiatric Genetics Published by Wiley Periodicals, Inc.
Femtosecond Hydrogen Bond Dynamics of Bulk‐like and Bound Water at Positively and Negatively Charged Lipid Interfaces Revealed by 2D HD‐VSFG Spectroscopy
Authors: Singh Prashant Chandra , Inoue Ken‐ichi , Nihonyanagi Satoshi , Yamaguchi Shoichi , Tahara Tahei
Published: August 2016

Interfacial water in the vicinity of lipids plays an important role in many biological processes, such as drug delivery, ion transportation, and lipid fusion. Hence, molecular‐level elucidation of the properties of water at lipid interfaces is of the utmost importance. We report the two‐dimensional heterodyne‐detected vibrational sum frequency generation (2D HD‐VSFG) study of the OH stretch of HOD at charged lipid interfaces, which shows that the hydrogen bond dynamics of interfacial water differ drastically, depending on the lipids. The data indicate that the spectral diffusion of the OH stretch at a positively charged lipid interface is dominated by the ultrafast (<∼100 fs) component, followed by the minor sub‐picosecond slow dynamics, while the dynamics at a negatively charged lipid interface exhibit sub‐picosecond dynamics almost exclusively, implying that fast hydrogen bond fluctuation is prohibited. These results reveal that the ultrafast hydrogen bond dynamics at the positively charged lipid–water interface are attributable to the bulk‐like property of interfacial water, whereas the slow dynamics at the negatively charged lipid interface are due to bound water, which is hydrogen‐bonded to the hydrophilic head group.
Direct Monitoring of γ‐Glutamyl Transpeptidase Activity In Vivo Using a Hyperpolarized 13C‐Labeled Molecular Probe
Authors: Nishihara Tatsuya , Yoshihara Hikari A. I. , Nonaka Hiroshi , Takakusagi Yoichi , Hyodo Fuminori , Ichikawa Kazuhiro , Can Emine , Bastiaansen Jessica A. M. , Takado Yuhei , Comment Arnaud , Sando Shinsuke
Published: August 2016

The γ‐glutamyl transpeptidase (GGT) enzyme plays a central role in glutathione homeostasis. Direct detection of GGT activity could provide critical information for the diagnosis of several pathologies. We propose a new molecular probe, γ‐Glu‐[1‐13C]Gly, for monitoring GGT activity in vivo by hyperpolarized (HP) 13C magnetic resonance (MR). The properties of γ‐Glu‐[1‐13C]Gly are suitable for in vivo HP 13C metabolic analysis since the chemical shift between γ‐Glu‐[1‐13C]Gly and its metabolic product, [1‐13C]Gly, is large (4.3 ppm) and the T1 of both compounds is relatively long (30 s and 45 s, respectively, in H2O at 9.4 T). We also demonstrate that γ‐Glu‐[1‐13C]Gly is highly sensitive to in vivo modulation of GGT activity induced by the inhibitor acivicin.
Struktureller Nachweis des ersten Polychloriddianions: Untersuchung von [Cl8]2−
Authors: Brückner Robin , Pröhm Patrick , Wiesner Anja , Steinhauer Simon , Müller Carsten , Riedel Sebastian
Published: August 2016

Das Polychloridsalz [CCl(NMe2)2]+2[Cl8]2− wurde in der ionischen Flüssigkeit [BMP]OTf synthetisiert und kristallisiert. Die Verbindung wurde mittels Raman‐Spektroskopie und Einkristallröntgenstrukturanalyse vollständig charakterisiert und enthält das erste literaturbekannte Polychloriddianion. Des Weiteren wurden detaillierte Gasphasen‐ und Festkörperrechnungen bezüglich der Bindungssituation durchgeführt.
Direct Catalytic Asymmetric Mannich Reaction with Dithiomalonates as Excellent Mannich Donors: Organocatalytic Synthesis of (R)‐Sitagliptin
Authors: Bae Han Yong , Kim Mun Jong , Sim Jae Hun , Song Choong Eui
Published: August 2016

In this study, dithiomalonates (DTMs) were demonstrated to be exceptionally efficient Mannich donors in terms of reactivity and stereoselectivity in cinchona‐based‐squaramide‐catalyzed enantioselective Mannich reactions of diverse imines or α‐amidosulfones as imine surrogates. Owing to the superior reactivity of DTMs as compared to conventional malonates, the catalyst loading could be reduced to 0.1 mol % without the erosion of enantioselectivity (up to 99 % ee). Furthermore, by the use of a DTM, even some highly challenging primary alkyl α‐amidosulfones were smoothly converted into the desired adducts with excellent enantioselectivity (up to 97 % ee), whereas the use of a malonate or monothiomalonate resulted in no reaction under identical conditions. The synthetic utility of the chiral Mannich adducts obtained from primary alkyl substrates was highlighted by the organocatalytic, coupling‐reagent‐free synthesis of the antidiabetic drug (−)‐(R)‐sitagliptin.
A Multinuclear Metal Complex Based DNase‐Mimetic Artificial Enzyme: Matrix Cleavage for Combating Bacterial Biofilms
Authors: Chen Zhaowei , Ji Haiwei , Liu Chaoqun , Bing Wei , Wang Zhenzhen , Qu Xiaogang
Published: August 2016

Extracellular DNA (eDNA) is an essential structural component during biofilm formation, including initial bacterial adhesion, subsequent development, and final maturation. Herein, the construction of a DNase‐mimetic artificial enzyme (DMAE) for anti‐biofilm applications is described. By confining passivated gold nanoparticles with multiple cerium(IV) complexes on the surface of colloidal magnetic Fe3O4 /SiO2 core/shell particles, a robust and recoverable artificial enzyme with DNase‐like activity was obtained, which exhibited high cleavage ability towards both model substrates and eDNA. Compared to the high environmental sensitivity of natural DNase in anti‐biofilm applications, DMAE exhibited a much better operational stability and easier recoverability. When DMAE was coated on substratum surfaces, biofilm formation was inhibited for prolonged periods of time, and the DMAE excelled in the dispersion of established biofilms of various ages. Finally, the presence of DMAE remarkably potentiated the efficiency of traditional antibiotics to kill biofilm‐encased bacteria and eradiate biofilms.
Stabilization of a Chiral Dirhodium Carbene by Encapsulation and a Discussion of the Stereochemical Implications
Authors: Werlé Christophe , Goddard Richard , Philipps Petra , Farès Christophe , Fürstner Alois
Published: August 2016

For the first time, the stereochemical course of an asymmetric cyclopropanation can be discussed on the basis of experimental structural information on a pertinent chiral dirhodium carbene intermediate. Key to success was the formation of racemic single crystals of a heterochiral [Rh2{(S*)‐PTTL}4{=C(Ar)COOMe}][Rh2{(R*)‐PTTL}4] (Ar=MeOC6H4; PTTL=N‐phthaloyl‐tert‐leucinate) capsule, which has been characterized by X‐ray diffraction. NMR spectroscopic data confirm that the obtained structural portrait is also relevant in solution and provide additional information about the dynamics of this species. The chiral binding pocket is primarily defined by the conformational preferences of the N‐phthaloyl‐protected amino acid ligands and reinforced by a network of weak interligand interactions that get stronger when chlorinated phthalimide residues are used.
Coke Formation in a Zeolite Crystal During the Methanol‐to‐Hydrocarbons Reaction as Studied with Atom Probe Tomography
Authors: Schmidt Joel E. , Poplawsky Jonathan D. , Mazumder Baishakhi , Attila Özgün , Fu Donglong , de Winter D. A. Matthijs , Meirer Florian , Bare Simon R. , Weckhuysen Bert M.
Published: August 2016

Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub‐nm length scale in a single zeolite ZSM‐5 crystal, which has been partially deactivated by the methanol‐to‐hydrocarbons reaction using 13C‐labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–60 13C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.
Structural Proof for the First Dianion of a Polychloride: Investigation of [Cl8]2−
Authors: Brückner Robin , Pröhm Patrick , Wiesner Anja , Steinhauer Simon , Müller Carsten , Riedel Sebastian
Published: August 2016

The polychloride salt [CCl(NMe2)2]+2[Cl8]2− was synthesized and crystallized in the ionic liquid [BMP]OTf. The compound was fully characterized by Raman spectroscopy as well as X‐ray single‐crystal structure determination, and represents the first example of a polychloride dianion to be described. Detailed gas‐phase and solid‐state calculations concerning the nature of the bonding situation were also performed.
Coke Formation in a Zeolite Crystal During the Methanol‐to‐Hydrocarbons Reaction as Studied with Atom Probe Tomography
Authors: Schmidt Joel E. , Poplawsky Jonathan D. , Mazumder Baishakhi , Attila Özgün , Fu Donglong , de Winter D. A. Matthijs , Meirer Florian , Bare Simon R. , Weckhuysen Bert M.
Published: August 2016

Understanding the formation of carbon deposits in zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, atom probe tomography (APT) has been used to spatially resolve the 3D compositional changes at the sub‐nm length scale in a single zeolite ZSM‐5 crystal, which has been partially deactivated by the methanol‐to‐hydrocarbons reaction using13C‐labeled methanol. The results reveal the formation of coke in agglomerates that span length scales from tens of nanometers to atomic clusters with a median size of 30–6013C atoms. These clusters correlate with local increases in Brønsted acid site density, demonstrating that the formation of the first deactivating coke precursor molecules occurs in nanoscopic regions enriched in aluminum. This nanoscale correlation underscores the importance of carefully engineering materials to suppress detrimental coke formation.
Influence of dynamic crosslinking on the morphology, crystallization, and dynamic mechanical properties of PA6,12/EVA blends
Authors: Bondan Fabrício , Ernzen Juliano Roberto , Amalvy Javier , Machado Ana Vera , Nardi Martins Johnny De , Bianchi Otávio
Published: August 2016

This study investigated the effect of dynamic crosslinking of polyamide 6,12 and random copolymers of ethylene and vinyl acetate blends (PA6,12/EVA) on the morphology, crystallinity, and dynamic mechanical properties. The crosslinking agent was dicumyl peroxide (DCP), and the blends were processed in a torque rheometer. The morphology depended on the DCP content, and all blends exhibited the same crystallinity index. However, with increasing crosslinking degree, the interfacial tackiness (E) values increased from 1.8 to 2.7 nm. The lamellar structures of all blends started forming at approximately 160 °C, close to the temperature of pure polyamide. The crosslinked phase enhanced the pseudo‐elastic behavior of the blends and increased their molecular mobility activation energy. Samples with higher crosslinking degree exhibited smaller permanent deformation (0.01%) than those with low crosslinking. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44206.
Large‐scale integration of flexible materials into rolled and corrugated thermoelectric modules
Authors: Fang Haiyu , Popere Bhooshan C. , Thomas Elayne M. , Mai Cheng‐Kang , Chang William B. , Bazan Guillermo C. , Chabinyc Michael L. , Segalman Rachel A.
Published: August 2016

Organic materials are promising candidates for thermoelectric applications owing to their tunable structure and therefore, properties, low cost, earth abundance, and solution processability. Conventional thermoelectric module architecture that relies on relatively thick (∼ mm) “legs” has limited the incorporation of organics into scalable modules. Herein, we report the fabrication of thermoelectric modules based on organic thermoelectric materials consisting of 100 or more p‐ and n‐legs. This approach utilizes an innovative rolled module design that is shown to easily maintain a temperature gradient above 50 K in the axial direction. Rolled modules comprising PEDOT:PSS (p‐type) and nickel (n‐type) material system with 288 legs were shown to produce an open circuit voltage and a power output of 260 mV and 46 μW, respectively at a temperature difference of 65 K. We note that the thermoelectric power generated by such modules is sufficient to simultaneously light up nine blue LEDs after boosting the output voltage with a voltage step up converter. We also demonstrate the versatility of this approach by fabricating corrugated modules, which enables facile module assembly onto rigid (polylactic acid, PLA) or flexible (polydimethylsiloxane, PDMS) substrates, without significant loss in the power output compared to the rolled modules. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44208.