bluuebunny/crossref_metadata_2025_split huggingface dataset:
Comparison of the SAWNUC model with CLOUD measurements of sulphuric acid‐water nucleation
Authors: Ehrhart Sebastian , Ickes Luisa , Almeida Joao , Amorim Antonio , Barmet Peter , Bianchi Federico , Dommen Josef , Dunne Eimear M. , Duplissy Jonathan , Franchin Alessandro , Kangasluoma Juha , Kirkby Jasper , Kürten Andreas , Kupc Agnieszka , Lehtipalo Katrianne , Nieminen Tuomo , Riccobono Francesco , Rondo Linda , Schobesberger Siegfried , Steiner Gerhard , Tomé António , Wimmer Daniela , Baltensperger Urs , Wagner Paul E. , Curtius Joachim 
Published: October 2016

AbstractBinary nucleation of sulphuric acid‐water particles is expected to be an important process in the free troposphere at low temperatures. SAWNUC (Sulphuric Acid Water Nucleation) is a model of binary nucleation that is based on laboratory measurements of the binding energies of sulphuric acid and water in charged and neutral clusters. Predictions of SAWNUC are compared for the first time comprehensively with experimental binary nucleation data from the CLOUD chamber at European Organization for Nuclear Research. The experimental measurements span a temperature range of 208–292 K, sulphuric acid concentrations from 1·106 to 1·109 cm−3, and distinguish between ion‐induced and neutral nucleation. Good agreement, within a factor of 5, is found between the experimental and modeled formation rates for ion‐induced nucleation at 278 K and below and for neutral nucleation at 208 and 223 K. Differences at warm temperatures are attributed to ammonia contamination which was indicated by the presence of ammonia‐sulphuric acid clusters, detected by an Atmospheric Pressure Interface Time of Flight (APi‐TOF) mass spectrometer. APi‐TOF measurements of the sulphuric acid ion cluster distributions (
with i = 0, 1, ..., 10) show qualitative agreement with the SAWNUC ion cluster distributions. Remaining differences between the measured and modeled distributions are most likely due to fragmentation in the APi‐TOF. The CLOUD results are in good agreement with previously measured cluster binding energies and show the SAWNUC model to be a good representation of ion‐induced and neutral binary nucleation of sulphuric acid‐water clusters in the middle and upper troposphere.
Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures
Authors: Kürten Andreas , Bianchi Federico , Almeida Joao , Kupiainen‐Määttä Oona , Dunne Eimear M. , Duplissy Jonathan , Williamson Christina , Barmet Peter , Breitenlechner Martin , Dommen Josef , Donahue Neil M. , Flagan Richard C. , Franchin Alessandro , Gordon Hamish , Hakala Jani , Hansel Armin , Heinritzi Martin , Ickes Luisa , Jokinen Tuija , Kangasluoma Juha , Kim Jaeseok , Kirkby Jasper , Kupc Agnieszka , Lehtipalo Katrianne , Leiminger Markus , Makhmutov Vladimir , Onnela Antti , Ortega Ismael K. , Petäjä Tuukka , Praplan Arnaud P. , Riccobono Francesco , Rissanen Matti P. , Rondo Linda , Schnitzhofer Ralf , Schobesberger Siegfried , Smith James N. , Steiner Gerhard , Stozhkov Yuri , Tomé António , Tröstl Jasmin , Tsagkogeorgas Georgios , Wagner Paul E. , Wimmer Daniela , Ye Penglin , Baltensperger Urs , Carslaw Ken , Kulmala Markku , Curtius Joachim 
Published: October 2016

AbstractBinary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 105 and 1 × 109 cm−3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximum of ~1400 parts per trillion by volume (pptv). We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm−3 s−1 to study neutral and ion‐induced nucleation. We found that the contribution from ion‐induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH3 levels. We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.
An attempt to deconstruct recent climate change in the Baltic Sea basin
Authors: Barkhordarian A. , von Storch H. , Zorita E. , Gómez‐Navarro J. J. 
Published: October 2016

AbstractWe investigate whether the recently observed temperature and precipitation trends over the Baltic Sea Basin are consistent with state‐of‐the‐art regional climate model projections. To address this question we use several data sources: (1) multidecadal trends derived from various observational data sets, (2) estimates of natural variability provided by a 2000 year paleoclimatic model simulation, and (3) response to greenhouse gas forcing derived from regional climate simulations driven by the A1B and RCP4.5 scenarios (from ENSEMBLES and CORDEX projects). Results indicate that, over the past decades, the climate in the Baltic Sea Basin has undergone a change that is beyond the estimated range of natural variability. We test the hypothesis that this change may be understood as a manifestation of global warming due to increasing concentrations of greenhouse gases (GHGs). We find that changes in near‐surface temperature support our hypothesis that the effect of GHG is needed to simulate the observed changes. The pattern correlation and regression results clearly illustrate the concerted emergence of an anthropogenic signal consistent with the GHG signal in summer and autumn in the 21st century. However, none of the 19 regional climate simulations used in this study reproduce the observed warming. The observed trends in precipitation and surface solar radiation are also partially inconsistent with the expected changes due to GHG forcing. We conclude that, besides the regional response to GHG forcing, other human‐made drivers have had an imprint. Regional emission of industrial aerosols has been strongly reduced in this region, and we suggest that this reduction may be the missing driver.
Potential negative consequences of geoengineering on crop production: A study of Indian groundnut
Authors: Yang Huiyi , Dobbie Steven , Ramirez‐Villegas Julian , Feng Kuishuang , Challinor Andrew J. , Chen Bing , Gao Yao , Lee Lindsay , Yin Yan , Sun Laixiang , Watson James , Koehler Ann‐Kristin , Fan Tingting , Ghosh Sat 
Published: October 2016

AbstractGeoengineering has been proposed to stabilize global temperature, but its impacts on crop production and stability are not fully understood. A few case studies suggest that certain crops are likely to benefit from solar dimming geoengineering, yet we show that geoengineering is projected to have detrimental effects for groundnut. Using an ensemble of crop‐climate model simulations, we illustrate that groundnut yields in India undergo a statistically significant decrease of up to 20% as a result of solar dimming geoengineering relative to RCP4.5. It is somewhat reassuring, however, to find that after a sustained period of 50 years of geoengineering crop yields return to the nongeoengineered values within a few years once the intervention is ceased.
Particle‐in‐cell modeling of spacecraft‐plasma interaction effects on double‐probe electric field measurements
Authors: Miyake Y. , Usui H. 
Published: October 2016

AbstractThe double‐probe technique, commonly used for electric field measurements in magnetospheric plasmas, is susceptible to environmental perturbations caused by spacecraft‐plasma interactions. To better model the interactions, we have extended the existing particle‐in‐cell simulation technique so that it accepts very small spacecraft structures, such as thin wire booms, by incorporating an accurate potential field solution calculated based on the boundary element method. This immersed boundary element approach is effective for quantifying the impact of geometrically small but electrically large spacecraft elements on the formation of sheaths or wakes. The developed model is applied to the wake environment near a Cluster satellite for three distinctive plasma conditions: the solar wind, the tail lobe, and just outside the plasmapause. The simulations predict the magnitudes and waveforms of wake‐derived spurious electric fields, and these are in good agreement with in situ observations. The results also reveal the detailed structure of potential around the double probes. It shows that any probes hardly experience a negative wake potential in their orbit, and instead, they experience an unbalanced drop rate of a large potential hill that is created by the spacecraft and boom bodies. As a by‐product of the simulations, we also found a photoelectron short‐circuiting effect that is analogous to the well‐known short‐circuiting effect due to the booms of a double‐probe instrument. The effect is sustained by asymmetric photoelectron distributions that cancel out the external electric field.
Synthetic Method for the Preparation of Quinazolines by the Oxidation of Amines Using Singlet Oxygen
Authors: Yamaguchi Tomoaki , Sugiura Yukina , Yamaguchi Eiji , Tada Norihiro , Itoh Akichika 
Published: October 2016

AbstractAn economical method for the preparation of quinazolines by using singlet oxygen as the sole oxidant has been developed. The oxidation of primary amines, such as benzylamine, by singlet oxygen has previously been shown to give products that arise from the rapid nucleophilic addition of amines to imines. To suppress this undesired oxidative coupling reaction, we employed aldehydes as the coupling partners in the preparation of quinazolines. Because of their pharmacological properties such as their sedative, anticonvulsant, and antitussive effects, many different methods have been developed for the efficient synthesis of quinazoline. These include the use of a stoichiometric or excess amount of the oxidant or the use of a transition‐metal catalyst under severe reaction conditions. In contrast, our approach employs visible light, molecular oxygen, and a commercially available photocatalyst, all of which are environmentally friendly.
Manganese‐Catalyzed Hydrogen‐Autotransfer C−C Bond Formation: α‐Alkylation of Ketones with Primary Alcohols
Authors: Peña‐López Miguel , Piehl Patrick , Elangovan Saravanakumar , Neumann Helfried , Beller Matthias 
Published: October 2016

AbstractA novel catalytic hydrogen‐autotransfer protocol for the atom‐efficient α‐alkylation of ketones with readily available alcohols is presented. The use of manganese complexes bearing non‐innocent PNP pincer ligands enabled the functionalization of a broad range of valuable ketones, including 2‐oxindole, estrone 3‐methyl ether, and testosterone. Mechanistic investigations suggest the participation of an intramolecular amidate‐assisted alcohol‐dehydrogenation process.
Novel compound heterozygous mutation in SACS gene leads to a milder autosomal recessive spastic ataxia of Charlevoix‐Saguenay, ARSACS, in a Finnish family
Authors: Palmio Johanna , Kärppä Mikko , Baumann Peter , Penttilä Sini , Moilanen Jukka , Udd Bjarne 
Published: October 2016

Key Clinical MessageAutosomal recessive spastic ataxia of Charlevoix‐Saguenay is a rare disorder outside Quebec causing childhood‐onset cerebellar ataxia, peripheral neuropathy, and pyramidal tract signs. A Finnish family with milder form of ARSACS was found to harbor three mutations, p.E1100K, p.N1489S, and p.M1359T, in SACS gene. The mutations segregated with the disease.
Controlling Hydrodeoxygenation of Stearic Acid to n‐Heptadecane and n‐Octadecane by Adjusting the Chemical Properties of Ni/SiO2–ZrO2 Catalyst
Authors: Foraita Sebastian , Liu Yue , Haller Gary L. , Baráth Eszter , Zhao Chen , Lercher Johannes A. 
Published: October 2016

AbstractA series of SiO2–ZrO2 mixed oxides with varying SiO2 concentrations were hydrothermally synthesized and used as support for Ni in the hydrodeoxygenation of stearic acid. ZrO2 provides a relatively low surface area and only Lewis acid sites, and Ni supported on ZrO2 produces n‐heptadecane from stearic acid through hydrogenation and decarbonylation. The SiO2–ZrO2 mixed oxides have a higher specific surface area than ZrO2 as well as an unprecedented spherical and nanolayered morphology. Brønsted acid sites were created by the incorporation of SiO2 into ZrO2, promoting the hydrodeoxygenation activity of Ni and specifically opening a new reaction route to n‐octadecane through the dehydration of 1‐octadecanol intermediate into 1‐octadecene with subsequent hydrogenation.
Structural and Mechanistic Insights into s‐Block Bimetallic Catalysis: Sodium Magnesiate‐Catalyzed Guanylation of Amines
Authors: De Tullio Marco , Hernán‐Gómez Alberto , Livingstone Zoe , Clegg William , Kennedy Alan R. , Harrington Ross W. , Antiñolo Antonio , Martínez Antonio , Carrillo‐Hermosilla Fernando , Hevia Eva 
Published: October 2016

AbstractTo advance the catalytic applications of s‐block mixed‐metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed‐metal system is much greater than that of its homometallic components [NaCH2SiMe3] and [Mg(CH2SiMe3)2]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N′‐diisopropylcarbodiimide with 4‐tert‐butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine‐assisted rate‐determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.
A Highly Emissive Water‐Soluble Phosphorus Corrole
Authors: Naitana Mario L. , Nardis Sara , Pomarico Giuseppe , Raggio Michele , Caroleo Fabrizio , Cicero Daniel O. , Lentini Sara , Prodi Luca , Genovese Damiano , Mitta Saisameera , Sgarlata Anna , Fanfoni Massimo , Persichetti Luca , Paolesse Roberto 
Published: October 2016

AbstractThe synthesis, spectroscopic, and optical properties of the water‐soluble phosphorus complex of a 2‐sulfonato‐10‐(4‐sulfonatophenyl)‐5,15‐dimesitylcorrole have been investigated. The compound was prepared by adopting a novel strategy for the corrole sulfonation, leading to the regioselective isomer in an almost quantitative yield. The phosphorus coordination has a key role in determining the corrole substitution pattern, limiting the formation of poly‐substituted species, which affected the reaction of the corrole free base. The resulting complex shows excellent optical properties in terms of emission quantum yield, also in polar protic solvents, including water. 31P NMR spectroscopy in CD3OD indicates that the P sulfonate complex has been isolated in a hexacoordinated geometry with two different ligands (L1=‐OH, L2=‐OCH3), and it is prone to axial ligand exchange with methanol, with no evidence of intermediate pentacoordinated species. The morphological characterization of thin layers of the P corrole deposited onto an Au(111) surface showed that the addition of an intermediate layer of reduced graphene oxide allows for a better control of corrole aggregation, inducing also transformation of the Au(111) reconstructed surface.
A Fully Charge‐Delocalized Two‐Dimensional Porphyrin System with Two Different Class III States
Authors: Mishiba Kentaro , Ono Masanori , Tanaka Yuya , Akita Munetaka 
Published: October 2016

AbstractUnderstanding of charge‐delocalization over two‐dimensional (2D) frameworks is a further step in the path towards the development of molecular nanodevices and nanomaterials. Here, we report a porphyrin–nickel complex with four peripheral redox‐active ruthenium pendants (1). A cyclic voltammogram of compound 1 displays reversible five‐electron, four redox waves with large potential separations, suggesting that one‐electron‐ (1+) and two‐electron‐oxidized species (12+) are thermodynamically stable with respect to disproportionation. The paramagnetic one‐electron‐oxidized species 1+ prepared by a comproportionation reaction of compounds 1 and 12+, turns out to be a highly charge‐delocalized two‐dimensional class III compound as clearly indicated by its characteristic intervalence charge‐transfer (IVCT) band as is further supported by IR and ESR spectroscopy as well as DFT and time‐dependent (TD) DFT calculations. Furthermore, the diamagnetic dicationic species 12+ has a spin‐paired electronic structure with a fully charge‐averaged class III character. The substantial contribution of the cumulenic structures to compound 12+ is confirmed by 13C NMR and IR spectroscopy as well as X‐ray structure analyses. Such unique electronic features of the 2D systems provide a clue to development of nanoscale molecular devices.
Synergistic Heterobimetallic Manifold for Expedient Manganese(I)‐Catalyzed C−H Cyanation
Authors: Liu Weiping , Richter Sven C. , Mei Ruhuai , Feldt Milica , Ackermann Lutz 
Published: October 2016

AbstractThe manganese‐catalyzed cyanation of inert C−H bonds was achieved within a heterobimetallic catalysis regime. The manganese(I) catalysis proved widely applicable and enabled C−H cyanations on indoles, pyrroles and thiophenes by facile C−H manganesation. The robustness of the manganese catalyst set the stage for the racemization‐free C−H cyanation of amino acids with excellent levels of positional and chemo selectivity by the new cyanating agent NCFS. Experimental and computational mechanistic studies provided strong support for a synergistic heterobimetallic activation mode, facilitating the key C−C formation.
Cytologic persistence of malignant cells after transurethral resection of bladder tumors: Implications for concomitant manipulation of the urinary tract at the time of endoscopic resection
Authors: Macleod Liam C. , Pham Khanh N. , Agoff S. Nicholas , Dahl Kathryn L. , Pritchett Thomas R. , Corman John M. 
Published: October 2016

BACKGROUNDThe current study was conducted to determine the feasibility of cytologically clearing the bladder of tumor cells after transurethral resection of bladder tumor (TURBT) and aggressive serial bladder washing.METHODSA prospective pilot sample of 20 patients with known bladder masses was enrolled before undergoing TURBT. Preoperative cytology and 4 postoperative cytology specimens were assessed for malignant cells between serial bladder washes. Surgeons assessed tumor grade visually at the time of TURBT.RESULTSSurgeons were able to differentiate high‐grade disease with limited accuracy (75% sensitivity, 92% specificity, 85% negative predictive value, and 86% positive predictive value). For patients with low‐grade disease (12 patients), cytology was atypical in 25% of patients immediately before TURBT and was negative after serial washings in all patients. In patients with high‐grade disease (8 patients), approximately 75% had cytology consistent with high‐grade urothelial carcinoma immediately before TURBT and only 1 patient was cleared cytologically after serial bladder washings.CONCLUSIONSIn patients with high‐grade disease, serial bladder washing after TURBT does not appear to clear malignant cells as detected by cytology. This theoretical oncologic risk should be weighed when considering concomitant upper tract procedures such as retrograde pyelography. Future work is needed to quantify risk. Cancer Cytopathol 2017;125:114–119. © 2016 American Cancer Society.
Platinum Inhibits Low‐Temperature Dry Lean Methane Combustion through Palladium Reduction in Pd−Pt/Al2O3: An In Situ X‐ray Absorption Study
Authors: Nassiri Hanieh , Lee Kee‐Eun , Hu Yongfeng , Hayes Robert E. , Scott Robert W. J. , Semagina Natalia 
Published: October 2016

AbstractPalladium–platinum bimetallic catalysts supported on alumina with palladium/platinum molar ratios ranging from 0.25 to 4 are studied in dry lean methane combustion in the temperature range of 200 to 500 °C. Platinum addition decreases the catalyst activity, which cannot be explained by the decrease in dispersion or the structure sensitivity of the reaction. In situ X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure spectroscopy measurements have been conducted for monometallic Pd, Pt, and 2:1 Pd−Pt catalysts. Monometallic palladium is fully oxidized in the full temperature range, whereas platinum addition promotes palladium reduction, even in a reactive oxidizing environment. The Pd/PdO weight ratio in bimetallic Pd−Pt 2:1 catalysts decreases from 98/2 to 10/90 in the 200–500 °C temperature range under the reaction conditions. Thus, platinum promotes the formation of the reduced palladium phase with a significantly lower activity than that of oxidized palladium. The study sheds light on the effect of platinum on the state of the active palladium surface under low‐temperature dry lean methane combustion conditions, which is important for methane‐emission control devices.
Received and needed social support in relation to sociodemographic and socio‐economic factors in a population of people on sick leave due to heart failure
Authors: Nordgren Lena , Söderlund Anne 
Published: October 2016

AbstractAimsThe aim of this study was to determine differences between sociodemographic and socio‐economic factors for perceptions of received and needed social support in a population of people on sick leave due to heart failure.Methods and resultsA cross‐sectional design was used. A postal questionnaire was distributed to all people in Sweden who had been sick listed due to heart failure during March to May 2012 (N = 1297). The questionnaire measured perceptions of received and needed social support from managers, colleagues at work, family and friends. Differences between groups were estimated with the Mann–Whitney U‐test. The sample included 414 men and 176 women aged 23 to 67 years (mean 58, median 60, SD = 6.75). Respondents with low income received significantly less support than respondents with high income and also needed significantly more support. Respondents with lower educational level needed significantly more support than people with higher education. Unmarried respondents needed significantly more support than married.ConclusionsPeople with lower level of education, those who were unmarried and respondents with low income needed more support than they received. By identification of vulnerable patients, healthcare professionals can tailor and target supportive measures for patients who need extra social support.