bluuebunny/crossref_metadata_2025_split huggingface dataset:
Radiative‐convective instability
Authors: Emanuel Kerry , Wing Allison A. , Vincent Emmanuel M. 
Published: November 2013

AbstractRadiative‐moist‐convective equilibrium (RCE) is a simple paradigm for the statistical equilibrium the earth's climate would exhibit in the absence of lateral energy transport. It has generally been assumed that for a given solar forcing and long‐lived greenhouse gas concentration, such a state would be unique, but recent work suggests that more than one stable equilibrium may be possible. Here we show that above a critical specified sea surface temperature, the ordinary RCE state becomes linearly unstable to large‐scale overturning circulations. The instability migrates the RCE state toward one of the two stable equilibria first found by Raymond and Zeng (2000). It occurs when the clear‐sky infrared opacity of the lower troposphere becomes so large, owing to high water vapor concentration, that variations of the radiative cooling of the lower troposphere are governed principally by variations in upper tropospheric water vapor. We show that the instability represents a subcritical bifurcation of the ordinary RCE state, leading to either a dry state with large‐scale descent, or to a moist state with mean ascent; these states may be accessed by finite amplitude perturbations to ordinary RCE in the subcritical state, or spontaneously in the supercritical state. As first suggested by Raymond (2000) and Sobel et al. (2007), the latter corresponds to the phenomenon of self‐aggregation of moist convection, taking the form of cloud clusters or tropical cyclones. We argue that the nonrobustness of self‐aggregation in cloud system resolving models may be an artifact of running such models close to the critical temperature for instability.
Aortic aneurysm and craniosynostosis in a family with Cantu syndrome
Authors: Hiraki Yoko , Miyatake Satoko , Hayashidani Michiko , Nishimura Yutaka , Matsuura Hiroo , Kamada Masahiro , Kawagoe Takuji , Yunoki Keiji , Okamoto Nobuhiko , Yofune Hiroko , Nakashima Mitsuko , Tsurusaki Yoshinori , Satisu Hirotomo , Murakami Akira , Miyake Noriko , Nishimura Gen , Matsumoto Naomichi 
Published: November 2013

AbstractCantu syndrome is an autosomal dominant overgrowth syndrome associated with facial dysmorphism, congenital hypertrichosis, and cardiomegaly. Some affected individuals show bone undermodeling of variable severity. Recent investigations revealed that the disorder is caused by a mutation in ABCC9, encoding a regulatory SUR2 subunit of an ATP‐sensitive potassium channel mainly expressed in cardiac and skeletal muscle as well as vascular smooth muscle. We report here on a Japanese family with this syndrome. An affected boy and his father had a novel missense mutation in ABCC9. Each patient had a coarse face and hypertrichosis. However, cardiomegaly was seen only in the boy, and macrosomia only in the father. Skeletal changes were not evident in either patient. Craniosynostosis in the boy and the development of aortic aneurysm in the father are previously undescribed associations with Cantu syndrome. © 2013 Wiley Periodicals, Inc.
NLRP3 inflammasome contributes to inflammation after intracerebral hemorrhage
Authors: Ma Qingyi , Chen Sheng , Hu Qin , Feng Hua , Zhang John H. , Tang Jiping 
Published: November 2013

ObjectiveThe NLRP3 (NALP3, cryopyrin) inflammasome, a key component of the innate immune system, facilitates caspase‐1 and interleukin (IL)−1β processing, which amplifies the inflammatory response. Here, we investigated whether NLRP3 knockdown decreases neutrophil infiltration, reduces brain edema, and improves neurological function in an intracerebral hemorrhage (ICH) mouse model. We also determined whether mitochondrial reactive oxygen species (ROS) governed by mitochondrial permeability transition pores (mPTPs) would trigger NLRP3 inflammasome activation following ICH.MethodsICH was induced by injecting autologous arterial blood (30μl) into a mouse brain. NLRP3 small interfering RNAs were administered 24 hours before ICH. A mPTP inhibitor (TRO‐19622) or a specific mitochondria ROS scavenger (Mito‐TEMPO) was coinjected with the blood. In naive animals, rotenone, which is a respiration chain complex I inhibitor, was applied to induce mitochondrial ROS production, and followed by TRO‐19622 or Mito‐TEMPO treatment. Neurological deficits, brain edema, enzyme‐linked immunosorbent assay, Western blot, in vivo chemical cross‐linking, ROS assay, and immunofluorescence were evaluated.ResultsICH activated the NLRP3 inflammasome. NLRP3 knockdown reduced brain edema and decreased myeloperoxidase (MPO) levels at 24 hours, and improved neurological functions from 24 to 72 hours following ICH. TRO‐19622 or Mito‐TEMPO reduced ROS, NLRP3 inflammasome components, and MPO levels following ICH. In naive animals, rotenone administration induced mPTP formation, ROS generation, and NLRP3 inflammasome activation, which were then reduced by TRO‐19622 or Mito‐TEMPO.InterpretationThe NLRP3 inflammasome amplified the inflammatory response by releasing IL‐1β and promoting neutrophil infiltration following ICH. Mitochondria ROS may be a major trigger of NLRP3 inflammasome activation. The results of our study suggest that the inhibition of the NLRP3 inflammasome may effectively reduce the inflammatory response following ICH.ANN NEUROL 2014;75:209–219
Organische Elektronendonoren als leistungsfähige Ein‐Elektronen‐Reduktionsmittel in der organischen Synthese
Authors: Broggi Julie , Terme Thierry , Vanelle Patrice 
Published: November 2013

AbstractIn der organischen Chemie wird die Ein‐Elektronen‐Reduktion häufig verwendet, um eine Radikalbildung durch den schrittweisen Transfer von einem oder zwei Elektronen von einem Donor auf ein organisches Substrat zu realisieren. Neben den metallischen Reagentien haben sich Reduktionsmittel auf der Basis neutraler organischer Moleküle, die einen Ein‐Elektronen‐Transfer ermöglichen, als eine attraktive neue Quelle für reduzierende Elektronen erwiesen. In den letzten zwanzig Jahren ist eine besondere Klasse organischer Reduktionsmittel, die elektronenreichen Olefine, zunehmend in Erscheinung getreten, und ihre Anwendung in der organischen Synthese hat sich vervielfacht. In diesem Aufsatz werden die verschiedenen Arten von organischen Donoren und ihre spezifischen Besonderheiten in organischen Umwandlungen zusammengefasst und diskutiert.
Zur Metallierung von Benzol und Toluol durch die Schlosser‐Base: ein superbasischer Li2K4‐Cluster unter Beteiligung von PhK, PhLi und tBuOLi
Authors: Unkelbach Christian , O'Shea Donal F. , Strohmann Carsten 
Published: November 2013

AbstractDie Metallierung von Benzol durch die Schlosser‐Base (nBuLi/tBuOK) läuft in THF glatt bei niedrigen Temperaturen unter Bildung eines diskreten, gemischtmetallischen Li2K4‐Clusters ab, der neben tert‐Butoxid auch Phenylanionen enthält (siehe Bild). Das Aggregat selbst weist mit der Metallierung von Toluol superbasische Reaktivität auf. Das auf diesem Weg erhaltene Benzylanion zeigt π‐Wechselwirkungen zum Kaliumgegenion, unter Bildung eines 2D‐Koordinationspolymers.
Diaryl Sulfoxides from Aryl Benzyl Sulfoxides: A Single Palladium‐Catalyzed Triple Relay Process
Authors: Jia Tiezheng , Bellomo Ana , Montel Sonia , Zhang Mengnan , EL Baina Kawtar , Zheng Bing , Walsh Patrick J. 
Published: November 2013

AbstractA novel approach to produce diaryl sulfoxides from aryl benzyl sulfoxides is reported. Optimization of the reaction conditions was performed using high‐throughput experimentation techniques. The [Pd(dba)2]/NiXantPhos catalyst system successfully promotes a triple relay process involving sulfoxide α‐arylation, CS bond cleavage, and CS bond formation. The byproduct benzophenone is formed by an additional palladium‐catalyzed process. It is noteworthy that palladium‐catalyzed benzylative CS bond cleavage of sulfoxides is unprecedented. A wide range of aryl benzyl sulfoxides, as well as alkyl benzyl sulfoxides with various (hetero)aryl bromides were employed in the triple relay process in good to excellent yields (85–99 %). Moreover, aryl methyl sulfoxides, dibenzyl sulfoxides, and dimethylsulfoxide could be utilized to generate diaryl sulfoxides involving multiple catalytic cycles by a single catalyst.
Catalytic Enantioselective Oxidative Cross‐Coupling of Benzylic Ethers with Aldehydes
Authors: Meng Zhilin , Sun Shutao , Yuan Huiqing , Lou Hongxiang , Liu Lei 
Published: November 2013

AbstractThe first one‐pot enantioselective oxidative coupling of cyclic benzylic ethers with aldehydes has been developed. A variety of benzylic ethers were transformed into the corresponding oxygen heterocycles with high enantioselectivity. Mechanistic experiments were conducted to determine the nature of the reaction intermediates. The application of this strategy to coupling reactions with other nucleophiles besides aldehydes was also explored.
Organic Electron Donors as Powerful Single‐Electron Reducing Agents in Organic Synthesis
Authors: Broggi Julie , Terme Thierry , Vanelle Patrice 
Published: November 2013

AbstractOne‐electron reduction is commonly used in organic chemistry for the formation of radicals by the stepwise transfer of one or two electrons from a donor to an organic substrate. Besides metallic reagents, single‐electron reducers based on neutral organic molecules have emerged as an attractive novel source of reducing electrons. The past 20 years have seen the blossoming of a particular class of organic reducing agents, the electron‐rich olefins, and their application in organic synthesis. This Review gives an overview of the different types of organic donors and their specific characteristics in organic transformations.
Synthesis, film morphology, and performance on cotton substrates of dodecyl/piperazine functional polysiloxane
Authors: Min Caina , Pu Qun , Yang Liu , Fan Hong 
Published: November 2013

ABSTRACTA novel polysiloxane bearing dodecyl and epoxy side groups (DESO) was synthesized as an intermediate through hydrosilylation of polymethylhydrosiloxane with allyl glycidyl ether and 1‐dodecene. Then, dodecyl/piperazine functional polysiloxane (DPSO) was prepared through the reaction of N‐aminoethylpiperazine with DESO. The chemical structure of DPSO was characterized with FTIR and 1H‐NMR spectroscopy and its application performance on cotton fabrics was studied. DPSO with dodecyl side groups gifted the treated fabrics with good wettability and whiteness compared with piperazine functional polysiloxane, while with a slightly reduced softness as well as thickening handle. Film morphology, orientation, and performance on cotton substrates of DPSO were investigated by scanning electron microscope, atomic force microscopy, X‐ray photoelectron microscope, and so on. Affected by the dodecyl side groups, DPSO formed relatively hydrophilic, macroscopically smooth but actually uneven films with many dodecyl side chain pillars on the treated substrate surfaces. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40186.
The impact of volcanic eruptions in the period 2000–2013 on global mean temperature trends evaluated in the HadGEM2‐ES climate model
Authors: Haywood Jim M. , Jones Andy , Jones Gareth S. 
Published: November 2013

AbstractThe slow‐down in global warming over the last decade has lead to significant debate about whether the causes are of natural or anthropogenic origin. Using an ensemble of HadGEM2‐ES coupled climate model simulations we investigate the impact of overlooked modest volcanic eruptions. We deduce a global mean cooling of around −0.02 to −0.03 K over the period 2008–2012. Thus while these eruptions do cause a cooling of the Earth and may therefore contribute to the slow‐down in global warming, they do not appear to be the sole or primary cause.
Regional response of annual‐mean tropical rainfall to global warming
Authors: Huang Ping 
Published: November 2013

AbstractRegional response of annual‐mean tropical rainfall to global warming is investigated based on 18 models from the Coupled Model Intercomparison Project 5. With surface warming, the climatological ascending circulation pumps up increased surface moisture and leads to a rainfall increase over the convergence zone, while the change in ascending flow induces a rainfall increase over the region with sea surface temperature (SST) increase exceeding the tropical mean, with a concomitant modification of background surface moisture and SST. These two effects form a hook‐like pattern of rainfall change over the tropical Pacific and an elliptic pattern over the northern Indian Ocean.
Does the “C3 effect” offset the Δ2 effect, as regards the solution flexibility of aldoses?
Authors: Morris Mallory J. , Striegel André M. 
Published: November 2013

ABSTRACTThe solution flexibility of carbohydrates influences a variety of molecular recognition and regulatory processes. For aldoses and other monosaccharides, this flexibility is dictated by the orientations of the various hydroxyl (OH) groups present, which influences conformer and anomer ratios, interactions among these OH groups, and interactions between them and the surrounding solvent. Depending on the number and position of axial OH groups, a variety of structures can coexist in solutions at equilibrium. In 1950, as part of his pioneering studies on the shape of pyranoside rings, Reeves described the Δ2 effect, the greater destabilization of the pyranose ring conformation when the OH group on carbon 2 (C2) is in the axial position. It was later proposed by Angyal that the Δ2 effect could be cancelled by the presence of an axial OH on C3, termed here the “C3 effect.” Employing size‐exclusion chromatography, an entropically‐controlled separation technique, we have investigated whether or not the C3 and Δ2 effects indeed do compensate for one another with respect to their influence on the solution flexibility of select aldohexoses and aldopentoses. As will be seen, while qualitatively and semiquantitatively this mutual cancellation of effects does occur in aldohexoses, it does not appear to do so in aldopentoses. An explanation for the latter appears to lie in the variety of anomers and conformers present in equilibrium solutions of those aldopentoses studied and in the relative entropic contribution of individual conformers or anomers to the total solution flexibility. © 2013 Wiley Periodicals, Inc. Biopolymers 101: 703–711, 2014.
Interactive learning management system to develop spatial visualization abilities
Authors: Melgosa Pedrosa Carlos , Ramos Barbero Basilio , Baños García M. Esther 
Published: November 2013

ABSTRACTAn Interactive Learning Management System (ILMS) is presented, which functions as a web‐based Spatial Visualization Ability (SVA) learning support tool for students of engineering graphics and as a management tool for teachers to track student learning. This software is designed to fill the gaps in student knowledge, giving them more uniform spatial visualization abilities when enrolling on University Engineering degrees. The ILMS_SVA consists of: (1) a Content Management System (CMS); (2) a preliminary level assessment test; (3) a web‐based tool for exercise management and self‐assessment incorporating a 3D viewer that functions as an interactive tutorial (IT), allowing the manipulation of 3D objects in every exercise; (4) a database. It is designed for three types of users (student, teacher, and administrator), and has been validated with engineering graphics students at the University of Burgos (Spain) by means of experimental trials in the classroom and a user satisfaction survey, over two academic years. The results indicate that use of this tool improved SVA among students generally and was even of greater effectiveness for those students that accessed engineering courses with no prior knowledge of Technical Drawing. © 2013 Wiley Periodicals, Inc. Comput Appl Eng Educ 23:203–216, 2015; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21590
Biosynthesis of Hygrocins, Antitumor Naphthoquinone Ansamycins Produced by Streptomyces sp. LZ35
Authors: Li Shanren , Wang Haoxin , Li Yaoyao , Deng Jingjing , Lu Chunhua , Shen Yan , Shen Yuemao 
Published: November 2013

AbstractHygrocins are naphthoquinone ansamycins with significant antitumor activities. Here, we report the identification and characterization of the hygrocin biosynthetic gene cluster (hgc) in Streptomyces sp. LZ35. A biosynthetic pathway is proposed based on bioinformatics analysis of the hgc genes and intermediates accumulated in selected gene disruption mutants. One of the steps during the biosynthesis of hygrocins is a Baeyer–Villiger oxidation between C5 and C6, catalyzed by luciferase‐like monooxygenase homologue Hgc3. Hgc3 represents the founding member of a previously uncharacterized family of enzymes acting as Baeyer–Villiger monooxygenases.
High dose statin loading prior to percutaneous coronary intervention decreases cardiovascular events: A meta‐analysis of randomized controlled trials
Authors: Benjo Alexandre M. , El‐Hayek Georges E. , Messerli Franz , DiNicolantonio James J. , Hong Mun K. , Aziz Emad F. , Herzog Eyal , Tamis‐Holland Jacqueline E. 
Published: November 2013

ObjectiveWe performed a meta‐analysis of randomized controlled trials of statin loading prior to percutaneous coronary intervention (PCI).BackgroundStatin loading prior to PCI has been shown to decrease peri‐procedural myocardial infarction (pMI) but less is known regarding the clinical benefit of pre‐procedural statin loading.MethodsWe searched for trials of statin naïve patients presenting with stable angina or NSTE‐ACS and treated with statins prior to PCI. We evaluated the incidence of pMI and major cardiac events including spontaneous myocardial infarction, death, and target vessel revascularization.ResultsOut of 1,210 articles, 14 randomized controlled trials were included in this meta‐analysis. Among 3,146 patients, 1,591 patients were randomized to a loading dose of statin before PCI and 1,555 patients were given statin therapy initiated only after the PCI. Statin loading prior to PCI was associated with a 56% relative reduction in pMI (OR: 0.44, 95% CI: 0.35–0.56; P < 0.00001). There was a 41% reduction in clinical events in follow‐up in the group of patients treated with statin loading prior to PCI (OR: 0.59, 95% CI: 0.38–0.92, P = 0.02). When stratified according to the clinical presentation, the results were only significant for those patients with NSTE‐ACS (OR: 0.18, 95% CI: 0.07–0.47; P = 0.0005) and was not noted in the group of patients who underwent PCI for stable angina (OR: 0.92, 95% CI: 0.53–1.61; P = 0.78).ConclusionsHigh dose statin therapy given prior to PCI in patients with NSTE‐ACS is associated with a reduction in pMI and short‐term clinical events. © 2013 Wiley Periodicals, Inc.
Study of Homologous Elements: Fe, Co, and Ni Dopant Effects on the Photoreactivity of TiO2 Nanosheets
Authors: Sun Lei , Zhai Jiali , Li Haiyan , Zhao Yan , Yang Hongjun , Yu Hongwen 
Published: November 2013

AbstractDespite sustained effort over the years, additional investigations into the relationship between doping elements and the photocatalytic properties of TiO2 are needed. In this work, Fe‐group(Fe, Co, Ni)‐doped anatase TiO2 nanosheets with exposed {0 0 1} facets are prepared by using a facile solvothermal synthetic route. A change in the type and concentration of the doping element consequently leads to a change in the size and percentage of {0 0 1} facets in the TiO2 nanosheets, and finally causes a significant difference in the photocatalytic activities of the as‐prepared TiO2 samples. In this case, the performance of doped TiO2, which serves as the photocatalyst, is investigated by directly assessing its effect on the photodegradation of azo dyes (methylene blue) under UV and visible light irradiation, respectively. Importantly, for the first time these studies reveal that the order of the activities of the doped TiO2 is Ni>Co>Fe, and the optimal value of the percentage of the doping ions to Ti ions is 0.75 %. Electrochemical impedance spectra, photocurrent, and photoluminescence measurements indicate that the charge separation and transportation rate is mainly influenced by the type and concentration of doping ions, which determines the photodegradation activities of the TiO2 host.
Towards the Core Structure of Strychnos Alkaloids Using Samarium Diiodide‐Induced Reactions of Indole Derivatives
Authors: Beemelmanns Christine , Gross Steffen , Reissig Hans‐Ulrich 
Published: November 2013

AbstractThis report describes the development of a first and second generation approach towards the synthesis of the ABCEG pentacyclic core structure of Strychnos alkaloids. First, we discuss a sequential approach applying a series of functional group transformations to prepare suitable precursors for cyclization reactions. These include attempts of samarium diiodide‐induced cyclizations or a Barbier‐type reaction of a transient lithium organyl, which successfully led to a tetracyclic key building block earlier used for the synthesis of strychnine. Secondly, we account our first steps towards the development of an atom‐economical samarium diiodide‐induced cascade reaction using “dimeric” indolyl ketones as cyclization precursors. In this context, we discuss plausible mechanisms for the samarium diiodide‐induced cascade reaction as well as transformations of the obtained tetracyclic dihydroindoline derivatives.
Increased Halide Recognition Strength by Enhanced Intercomponent Preorganisation in Triazolium Containing [2]Rotaxanes
Authors: White Nicholas G. , Costa Paulo J. , Carvalho Sílvia , Félix Vítor , Beer Paul D. 
Published: November 2013

AbstractThree triazolium‐based [2]rotaxanes containing different sized axle and macrocycle components were synthesised in good yields (40–57 %) through chloride anion templation. The anion recognition properties of the interlocked receptor systems were investigated using 1H NMR titration experiments: all three rotaxanes display impressive selectivities for halide anions over the more basic oxoanion acetate. The rotaxanes incorporating shorter, more rigid axle components with aryl‐substituted triazolium groups display substantially higher anion binding affinities than those with longer, bis‐alkyl‐substituted heterocycles, which is attributed to the increased intercomponent preorganisation afforded by the smaller axle component. Computational DFT and molecular dynamics simulations composed of unconstrained and umbrella sampling simulations corroborate the experimental observations.