bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ultra‐Tuning of the Rare‐Earth fcu‐MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins
Authors: Assen Ayalew H. , Belmabkhout Youssef , Adil Karim , Bhatt Prashant M. , Xue Dong‐Xu , Jiang Hao , Eddaoudi Mohamed 
Published: October 2015

AbstractUsing isoreticular chemistry allows the design and construction of a new rare‐earth metal (RE) fcu‐MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12‐connected RE hexanuclear clusters has afforded the contraction of the well‐defined RE‐fcu‐MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y3+ and Tb3+) fcu‐MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate‐size cut‐off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies.
Stable Co‐Catalyst‐Free Photocatalytic H2 Evolution From Oxidized Titanium Nitride Nanopowders
Authors: Zhou Xuemei , Zolnhofer Eva M. , Nguyen Nhat Truong , Liu Ning , Meyer Karsten , Schmuki Patrik 
Published: October 2015

AbstractA simple strategy is used to thermally oxidize TiN nanopowder (∼20 nm) to an anatase phase of a TiO2:Ti3+:N compound. In contrast to the rutile phase of such a compound, this photocatalyst provides activity for hydrogen evolution under AM1.5 conditions, without the use of any noble metal co‐catalyst. Moreover the photocatalyst is active and stable over extended periods of time (tested for 4 months). Importantly, to achieve successful conversion to the active anatase polymorph, sufficiently small starting particles of TiN are needed. The key factor for catalysis is the stabilization of the co‐catalytically active Ti3+ species against oxidation by nitrogen present in the starting material.
Stereodivergent Dual Catalytic α‐Allylation of Protected α‐Amino‐ and α‐Hydroxyacetaldehydes
Authors: Sandmeier Tobias , Krautwald Simon , Zipfel Hannes F. , Carreira Erick M. 
Published: October 2015

AbstractFully stereodivergent dual‐catalytic α‐allylation of protected α‐amino‐ and α‐hydroxyacetaldehydes is achieved through iridium‐ and amine‐catalyzed substitution of racemic allylic alcohols with chiral enamines generated in situ. The operationally simple method furnishes useful aldehyde building blocks in good yields, more than 99 % ee, and with d.r. values greater than 20:1 in some cases. Additionally, the γ,δ‐unsaturated products can be further functionalized in a stereodivergent fashion with high selectivity and with preservation of stereochemical integrity at the Cα position.
Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H]+: Experimental and Computational Studies of their Hydricities, Interaction with CO2, and Photochemistry
Authors: Garg Komal , Matsubara Yasuo , Ertem Mehmed Z. , Lewandowska‐Andralojc Anna , Sato Shunsuke , Szalda David J. , Muckerman James T. , Fujita Etsuko 
Published: October 2015

AbstractWe prepared two geometric isomers of [Ir(tpy)(ppy)H]+, previously proposed as a key intermediate in the photochemical reduction of CO2 to CO, and characterized their notably different ground‐ and excited‐state interactions with CO2 and their hydricities using experimental and computational methods. Only one isomer, C‐trans‐[Ir(tpy)(ppy)H]+, reacts with CO2 to generate the formato complex in the ground state, consistent with its calculated hydricity. Under photocatalytic conditions in CH3CN/TEOA, a common reactive C‐trans‐[Ir(tpy)(ppy)]0 species, irrespective of the starting isomer or monodentate ligand (such as hydride or Cl), reacts with CO2 and produces CO with the same catalytic efficiency.
Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells
Authors: Xu Jia‐Quan , Liu Yan‐Ling , Wang Qian , Duo Huan‐Huan , Zhang Xin‐Wei , Li Yu‐Tao , Huang Wei‐Hua 
Published: October 2015

AbstractElectrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO2 to form a sandwiching RGO@TiO2 structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO2 ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing.
Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes
Authors: Buslov Ivan , Becouse Jeanne , Mazza Simona , Montandon‐Clerc Mickael , Hu Xile 
Published: October 2015

AbstractChemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base‐metal catalysts. Reported herein is that well‐defined bis(amino)amide nickel pincer complexes are efficient catalysts for anti‐Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83 000 per hour and turnover numbers of up to 10 000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts.
Polyfluorides and Neat Fluorine as Host Material in Matrix‐Isolation Experiments
Authors: Brosi Felix , Vent‐Schmidt Thomas , Kieninger Stefanie , Schlöder Tobias , Beckers Helmut , Riedel Sebastian 
Published: October 2015

AbstractThe use of neat fluorine in matrix isolation is reported, as well as the formation of polyfluoride monoanions under cryogenic conditions. Purification procedures and spectroscopic data of fluorine are described, and matrix shifts of selected molecules and impurities in solid fluorine are compared to those of common matrix gases (Ar, Kr, N2, Ne). The reaction of neat fluorine and IR‐laser ablated metal atoms to yield fluorides of chromium (CrF5), palladium (PdF2), gold (AuF5), and praseodymium (PrF4) has been investigated. The fluorides have been characterized in solid fluorine by IR spectroscopy at 5 K. Also the fluorination of Kr and the photo‐dismutation of XeO4 have been studied by using IR spectroscopy in neat fluorine. Formation of the [F5]− ion was obtained by IR‐laser ablation of platinum in the presence of fluorine and proven in a Ne matrix at 5 K by two characteristic vibrational bands of [F5]− at =850.7 and 1805.0 cm−1 and its photo‐behavior.
Total Synthesis of Codeine
Authors: Li Qilin , Zhang Hongbin 
Published: October 2015

AbstractIn this paper, a new strategy towards the synthesis of codeine and morphine is reported. This new approach features a cascade cyclization to construct the dihydrofuran ring, and an intramolecular palladium catalyzed CH olefination of unactivated aliphatic alkene to install the morphinan ring system.
Design, Synthesis and in vitro Evaluation of Indolotacrine Analogues as Multitarget‐Directed Ligands for the Treatment of Alzheimer's Disease
Authors: Benek Ondrej , Soukup Ondrej , Pasdiorova Marketa , Hroch Lukas , Sepsova Vendula , Jost Petr , Hrabinova Martina , Jun Daniel , Kuca Kamil , Zala Dominykas , Ramsay Rona R. , Marco‐Contelles José , Musilek Kamil 
Published: October 2015

AbstractNovel indolotacrine analogues were designed, synthesized, and evaluated as potential drugs for the treatment of Alzheimer's disease. By using a multitarget‐directed ligand approach, compounds were designed to act simultaneously as cholinesterase (ChE) and monoamine oxidase (MAO) inhibitors. The compounds were also evaluated for antioxidant, cytotoxic, hepatotoxic, and blood–brain barrier (BBB) permeability properties. Indolotacrine 9 b (9‐methoxy‐2,3,4,6‐tetrahydro‐1H‐indolo[2,3‐b]quinolin‐11‐amine) showed the most promising results in the in vitro assessment; it is a potent inhibitor of acetylcholinesterase (AChE IC50: 1.5 μm), butyrylcholinesterase (BChE IC50: 2.4 μm) and MAO A (IC50: 0.49 μm), and it is also a weak inhibitor of MAO B (IC50: 53.9 μm). Although its cytotoxic (IC50: 5.5±0.4 μm) and hepatotoxic (IC50: 1.22±0.11 μm) profiles are not as good as those of the standard 7‐methoxytacrine (IC50: 63±4 and 11.50±0.77 μm, respectively), the overall improvement in the inhibitory activities and potential to cross the BBB make indolotacrine 9 b a promising lead compound for further development and investigation.
Two‐tiered subdivision of atypia on urine cytology can improve patient follow‐up and optimize the utility of UroVysion
Authors: Glass Ryan E. , Coutsouvelis Constantinos , Sheikh‐Fayyaz Silvat , Chau Karen , Rosen Lisa , Brenkert Ryan , Slim Farah , Epelbaum Fanya , Das Kasturi , Cocker Rubina S. 
Published: October 2015

BACKGROUNDThe annual incidence of urothelial carcinoma continues to increase, and it is projected that greater than 70,000 new cases will occur in the year 2015. However, as much as 23% of cytologic specimens will demonstrate some degree of atypia without meeting the criteria for urothelial carcinoma and thus will be reported as atypical.METHODSThe authors conducted 2 laboratory information searches and 1 survey. In total, 311 patients who had atypical cytology‐biopsy pairs available were identified from the initial data search. The second data search identified 942 patients who had fluorescence in situ hybridization (FISH) results available.RESULTSThere was fair agreement between FISH results and cytology results (κ = 0.34; 95% confidence interval, 0.27‐0.41). The analysis did not reveal any benefits of using additional atypical subcategories beyond the 2 suggested in the literature. It was determined that 2 strategies would provide an optimal balance: standardizing patient management and facilitating the adoption of universally recognized templates.CONCLUSIONSWhen combining cytology and the 2‐tiered atypical classification system with FISH testing, a marked increase in sensitivity and an accompanying decrease in specificity were observed compared with either test individually. Thus, highly sensitive FISH testing may help to identify high‐risk patients among those in the group with uncertain atypical findings. Cancer Cytopathol 2016;124:188–195. © 2015 American Cancer Society.
Insulin receptor isoforms: an integrated view focused on gestational diabetes mellitus
Authors: Westermeier F. , Sáez T. , Arroyo P. , Toledo F. , Gutiérrez J. , Sanhueza C. , Pardo F. , Leiva A. , Sobrevia L. 
Published: October 2015

SummaryThe human insulin receptor (IR) exists in two isoforms that differ by the absence (IR‐A) or the presence (IR‐B) of a 12‐amino acid segment encoded by exon 11. Both isoforms are functionally distinct regarding their binding affinities and intracellular signalling. However, the underlying mechanisms related to their cellular functions in several tissues are only partially understood. In this review, we summarize the current knowledge in this field regarding the alternative splicing of IR isoform, tissue‐specific distribution and signalling both in physiology and disease, with an emphasis on the human placenta in gestational diabetes mellitus (GDM). Furthermore, we discuss the clinical relevance of IR isoforms highlighted by findings that show altered insulin signalling due to differential IR‐A and IR‐B expression in human placental endothelium in GDM pregnancies. Future research and clinical studies focused on the role of IR isoform signalling might provide novel therapeutic targets for treating GDM to improve the adverse maternal and neonatal outcomes. Copyright © 2015 John Wiley & Sons, Ltd.
Interpreting behaviors from accelerometry: a method combining simplicity and objectivity
Authors: Collins Philip M. , Green Jonathan A. , Warwick‐Evans Victoria , Dodd Stephen , Shaw Peter J. A. , Arnould John P. Y. , Halsey Lewis G. 
Published: October 2015

AbstractQuantifying the behavior of motile, free‐ranging animals is difficult. The accelerometry technique offers a method for recording behaviors but interpretation of the data is not straightforward. To date, analysis of such data has either involved subjective, study‐specific assignments of behavior to acceleration data or the use of complex analyses based on machine learning. Here, we present a method for automatically classifying acceleration data to represent discrete, coarse‐scale behaviors. The method centers on examining the shape of histograms of basic metrics readily derived from acceleration data to objectively determine threshold values by which to separate behaviors. Through application of this method to data collected on two distinct species with greatly differing behavioral repertoires, kittiwakes, and humans, the accuracy of this approach is demonstrated to be very high, comparable to that reported for other automated approaches already published. The method presented offers an alternative to existing methods as it uses biologically grounded arguments to distinguish behaviors, it is objective in determining values by which to separate these behaviors, and it is simple to implement, thus making it potentially widely applicable. The R script coding the method is provided.
CD70 and IFN‐1 selectively induce eomesodermin or T‐bet and synergize to promote CD8+ T‐cell responses
Authors: Dong Han , Franklin Nathan A. , Ritchea Shane B. , Yagita Hideo , Glennie Martin J. , Bullock Timothy N. J. 
Published: October 2015

CD70‐mediated stimulation of CD27 is an important cofactor of CD4+ T‐cell licensed dendritic cells (DCs). However, it is unclear how CD70‐mediated stimulation of T cells is integrated with signals that emanate from signal 3 pathways, such as type‐1 interferon (IFN‐1) and IL‐12. We find that while stimulation of CD27 in isolation drives weak EomesoderminhiT‐betlo CD8+ T‐cell responses to OVA immunization, profound synergistic expansion is achieved by cotargeting TLR. This cooperativity can substantially boost antiviral CD8+ T‐cell responses during acute infection. Concomitant stimulation of TLR significantly increases per cell IFN‐γ production and the proportion of the population with characteristics of short‐lived effector cells, yet also promotes the ability to form long‐lived memory. Notably, while IFN‐1 contributes to the expression of CD70 on DCs, the synergy between CD27 and TLR stimulation is dependent upon IFN‐1's effect directly on CD8+ T cells, and is associated with the increased expression of T‐bet in T cells. Surprisingly, we find that IL‐12 fails to synergize with CD27 stimulation to promote CD8+ T‐cell expansion, despite its capacity to drive effector CD8+ T‐cell differentiation. Together, these data identify complex interactions between signal 3 and costimulatory pathways, and identify opportunities to influence the differentiation of CD8+ T‐cell responses.
Linear and V‐Shaped Alkynyl‐1,3,5‐tri­azines
Authors: Gao Peisen , Wang Zhenhua , Wang Xiu , Zhang Weiqiang , Gao Ziwei 
Published: October 2015

AbstractA concise route for the synthesis of linear and V‐shaped alkynyl‐1,3,5‐triazines has been developed by starting from 2,4‐dichloro‐1,3,5‐triazine derivatives. The sequential substitution of the 2‐ and 4‐chloro groups by a regioselective Sonogashira coupling reaction afforded symmetric and unsymmetric V‐shaped alkynyl‐1,3,5‐triazines. A modulated copper‐free Pd/1,10‐phenanthroline catalyst system showed good compatibility with the –OCH3, –NPh2, and p‐CH3OC6H4– substitutents and furnished the targeted linear alkynyl‐1,3,5‐triazines in good yields. A Pd/Ag bimetallic system afforded the desired symmetric and unsymmetric V‐shaped alkynyl‐1,3,5‐triazines in moderate to good yields. The photophysical properties of the new alkynyl‐1,3,5‐triazine compounds were characterized experimentally. The X‐ray diffraction analysis of 2a confirmed a coplanar position between the phenyl group and the 1,3,5‐triazinal moiety. Intermolecular π–π interactions were observed between two of the TZ units, and the shortest atomic contact distance between the phenyl moieties of two adjacent molecules is 3.655 Å.
Liebe geht durch den Daumen
Authors: Walter Anna‐Maria 
Published: October 2015

AbstractWie die Handy‐Kultur das Leben verändert, zeigt sich selbst im abgelegenen Hochgebirge Nordpakistans. In einer strikt geschlechtergetrennten Gesellschaft schafft es für die Frauen neue Räume der Kommunikation. Eine ethnologische Studie gewinnt neue Einblicke durch teilnehmende Beobachtung.
Space mapping surrogate‐based microwave circuit design centering using a new statistical technique
Authors: Hassan Abdel‐Karim S.O. , Abdel‐Malek Hany L. , Mohamed Ahmed S.A. , Elqenawy Ahmed E. 
Published: October 2015

AbstractDesign centering is an optimal design process that seeks for the values of system parameters which maximize the probability of satisfying the design specifications (yield function). In this article, a derivative‐free trust region (TR) optimization approach is combined with the generalized space mapping technique to develop a new space mapping (SM) surrogate‐based statistical technique for design centering of computationally expensive microwave circuits. The TR optimization approach is well suited for expensive objective functions that have some uncertainty in their values or subject to statistical variations. The principal operation relies on building and successively updating quadratic surrogate models to be optimized instead of the objective function over TRs employing the truncated conjugate gradients. The approach constructs the initial quadratic surrogate model using fewer data points, then updates the surrogate model using a weighted least squares fitting that gives more emphasis to points close to the current center point. Integrating the TR optimization approach with the generalized space mapping technique results in a novel statistical design centering technique for the microwave circuits with a great reduction in computations and simulations needed for the yield optimization process. Design of practical microwave circuits is presented to indicate the effectiveness of the new design centering technique. Copyright © 2015 John Wiley & Sons, Ltd.
Causes of uncertainty in China's net primary production over the 21st century projected by theCMIP5Earth system models
Authors: Wang Tao , Lin Xin , Liu Yongwen , Dantec‐Nédélec Sarah , Ottlé Catherine 
Published: October 2015

ABSTRACTNet primary production is the initial step of the carbon cycle in which atmosphericCO2is fixed by plants. The responses of net primary production (NPP) to climate change andCO2are key processes that have the potential to significantly affect the climate–carbon feedback and future atmosphericCO2levels. Understanding futureNPPchanges is important for China that became the world's largestCO2emitter since 2006. Here, we analysedNPPchanges in China under the four emission scenarios from 11 Earth system models participating in the Coupled Model Intercomparison Project Phase 5. We find a general increase ofNPPover the 21st century under the four emission scenarios, with the large percentage increase in northwestern China and Qinghai–Tibetan Plateau. However, there is a large model spread in the increase ofNPPat both country and local scales. We present a statistical approach to assess various processes to explain this large spread, and find that the large spread at the country level is predominantly attributed to inter‐model difference in parameterization ofCO2fertilization effect within each emission scenario. But the parameterization ofCO2fertilization effect not always dominates over the model spread across China. When it comes to the local scale, the model spread can be significantly contributed by inter‐model difference in parameterization ofNPPresponses to precipitation along with precipitation projection in northwestern China. Our findings provide the reasons for divergent responses of futureNPPthrough process decomposition and are the first to pinpoint that the model process dominating over the uncertainty exhibits regional dependence.
Trends in extreme temperature over Nigeria from percentile‐based threshold indices
Authors: Abatan Abayomi A. , Abiodun Babatunde J. , Lawal Kamoru A. , Gutowski William J. 
Published: October 2015

ABSTRACTThis study analyses spatial and temporal trends in extreme temperature indices over Nigeria. The percentile indices were calculated from newly homogenized daily minimum and maximum temperature data for the period 1971–2012 for 21 stations in Nigeria. Indices describing the characteristics of hot extremes and cold extremes are calculated with the RClimDex software. The annual and seasonal trends in these indices are obtained using the ordinary least square fit and the statistical significance tested using the R‐based modified Mann–Kendall test. We examine characteristics of these indices for the entire country and separately for the three geographical zones in Nigeria: Guinea, Savanna, and Sahel. The spatial and temporal patterns of trends in the indices indicate that Nigeria has experienced statistically significant increase in the frequency of hot extreme and decrease in cold extreme events. Although majority of the stations have significant trends in warm days and warm nights, the annual trend is greatest in warm nights. In addition, the rate of warming in minimum temperature (‘warm nights’) is stronger in June, July, August (JJA) and September, October, November (SON) compare with December, January, February (DJF) and March, April, May (MAM). As for the trends in cold days and cold nights, the trends in cold nights are larger than for cold days at both the annual and seasonal scales. The regional analysis indicates that trends in warm nights and cold nights are most pronounced in Guinea and Sahel regions.
Observed trend of diurnal temperature range in the Tibetan Plateau in recent decades
Authors: You Qinglong , Min Jinzhong , Jiao Yang , Sillanpää Mika , Kang Shichang 
Published: October 2015

ABSTRACTSpatial and temporal variabilities of long‐term (1961–2013) diurnal temperature range (DTR) are examined in the Tibetan Plateau (TP) based on the 71 observational stations. The relative regional contributions to DTR in the TP are studied among maximum temperature, minimum temperature, total cloud cover (TCC), and atmospheric teleconnections. The regional annual mean DTR (average of the 71 stations) is 14.17 °C, with a clear maximum in winter (16.35 °C) and minimum in summer (12.62 °C). During 1961–2013, the DTR in the TP declines before the 1980s and shows mute change afterwards, with an annual rate of −0.20 °C decade−1 calculated by the Mann–Kendall method. The trend in DTR is primarily a consequence of greater warming in minimum temperature than maximum temperature. In summer, there are significant negative correlations between the TCC and DTR in the TP, suggesting that the decreases in the DTR are associated with variations of TCC in the region. The atmospheric circulation composite analysis between strongly positive and negative DTR in summer in the TP reveals that during the low DTR period the TP has more water vapour flux, stronger temperature advection, and strengthened southerly wind. This suggests that the atmospheric circulations have contributed to the trends in the DTR, but it is difficult to account for the specific contributions. Further investigations of the impact of global warming on the DTR in the TP are still required.