bluuebunny/crossref_metadata_2025_split huggingface dataset:
How Do Phosphinates React with Unactivated Alkenes Under Organic Photocatalyzed Conditions? Substrate Scope and Mechanistic Insights
Authors: Fausti Giovanni , Morlet‐Savary Fabrice , Lalevée Jacques , Gaumont Annie‐Claude , Lakhdar Sami 
Published: November 2016

AbstractThe first visible‐light‐mediated, metal‐free hydrophosphinylation of unactivated alkenes with ethyl and butyl phosphinates is described. The reaction works with a low catalyst loading of 9‐mesityl‐10‐methylacridinium perchlorate (Fukuzumi photocatalyst, 0.5 mol %) in the presence of diphenyliodonium triflate as oxidant. The reaction proceeds smoothly and covers a broad scope of substrates. Detailed mechanistic investigations, including EPR spectroscopy, fluorescence and steady‐state photolysis, allowed the mechanism of this photoreaction to be rationalized.
Pentafluoroethyl Bismuth Compounds
Authors: Solyntjes Sven , Bader Julia , Neumann Beate , Stammler Hans‐Georg , Ignat'ev Nikolai , Hoge Berthold 
Published: November 2016

AbstractA series of tris‐, bis‐, and mono(pentafluoroethyl)bismuthanes of the type (C2F5)nBiX3–n (X=F, Cl, Br, I) and transition metal complexes are accessible by a sophisticated pentafluoroethylation protocol. Chemical properties, induced by the strongly electron‐withdrawing character of C2F5 groups, are described for representative examples. Moreover, the first molecular structures of perfluoroalkyl bismuthanes and bismuthates obtained by X‐ray diffraction are presented.
Stereoselective Synthesis of cis‐2,5‐Disubstituted Pyrrolidines via Copper‐Catalyzed Cyclization of Alkenes
Authors: Cai Sai‐Hu , Da Bing‐Chao , Zhou Jia‐Hui , Xu Yun‐He , Loh Teck‐Peng 
Published: November 2016

AbstractAn efficient methodology for the stereoselective synthesis of cis‐2,5‐disubstituted pyrrolidines using copper catalyst was developed. The corresponding cis‐2,5‐disubstituted pyrrolidines could be obtained in reasonable yields and with good stereoselectivities in the presence of 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine as ligand and 1‐methyl‐2‐pyrrolidinone as solvent.
A Quinacrine Analogue Selective Against Gastric Cancer Cells: Insight from Biochemical and Biophysical Studies
Authors: Gomes Ana , Fernandes Iva , Teixeira Cátia , Mateus Nuno , Sottomayor M. J. , Gomes Paula 
Published: November 2016

AbstractOne of the earliest synthetic antimalarial drugs, quinacrine, was recently reported as interesting for the treatment of acute myeloid leukemia. Inspired by this and similar findings, we evaluated a set of quinacrine analogues against gastric (MKN‐28), colon (Caco‐2), and breast (MFC‐7) cancer cell lines and one normal human fibroblast cell line (HFF‐1). All the compounds, previously developed by us as dual‐stage antimalarial leads, displayed antiproliferative activity, and one of the set stood out as selective toward the gastric cancer cell line, MKN‐28. Interestingly, this compound was transported across an in vitro MKN‐28 model cell line in low amounts, and approximately 80 % was trapped inside those cells. Nuclear targeting of the same compound and its interactions with calf thymus DNA were assessed through combined fluorescence microscopy, spectroscopy, and calorimetry studies, which provided evidence for the compound's ability to reach the nucleus and to interact with DNA.
The impact of health insurance on cancer care in disadvantaged communities
Authors: Abdelsattar Zaid M. , Hendren Samantha , Wong Sandra L. 
Published: November 2016

BACKGROUNDIndividuals from disadvantaged communities are among the millions of uninsured Americans gaining insurance under the Affordable Care Act. The extent to which health insurance can mitigate the effects of the social determinants of health on cancer care is unknown.METHODSThis study linked the Surveillance, Epidemiology, and End Results registries to US Census data to study patients diagnosed with the 4 leading causes of cancer deaths between 2007 and 2011. A county‐level social determinant score was developed with 5 measures of wealth, education, and employment. Patients were stratified into quintiles, with the lowest quintile representing the most disadvantaged communities. Logistic regression and Cox proportional hazards models were used to estimate associations and cancer‐specific survival.RESULTSA total of 364,507 patients aged 18 to 64 years were identified (134,105 with breast cancer, 106,914 with prostate cancer, 62,606 with lung cancer, and 60,882 with colorectal cancer). Overall, patients from the most disadvantaged communities (median household income, $42,885; patients below the poverty level, 22%; patients completing college, 17%) were more likely to present with distant disease (odds ratio, 1.6; P < .001) and were less likely to receive cancer‐directed surgery (odds ratio, 0.8; P < .001) than the least disadvantaged communities (median income, $78,249; patients below the poverty level, 9%; patients completing college, 42%). The differences persisted across quintiles regardless of the insurance status. The effect of having insurance on cancer‐specific survival was more pronounced in disadvantaged communities (relative benefit at 3 years, 40% vs 31%). However, it did not fully mitigate the effect of social determinants on mortality (hazard ratio, 0.75 vs 0.68; P < .001).CONCLUSIONSCancer patients from disadvantaged communities benefit most from health insurance, and there is a reduction in disparities in outcome. However, the gap produced by social determinants of health cannot be bridged by insurance alone. Cancer 2017;123:1219–1227. © 2016 American Cancer Society.
Exploring Morphological and Biochemical Linkages in Fungal Growth with Label‐Free Light Sheet Microscopy and Raman Spectroscopy
Authors: Siddhanta Soumik , Paidi Santosh Kumar , Bushley Kathryn , Prasad Ram , Barman Ishan 
Published: November 2016

AbstractImaging tip growth in fungal hyphae is highly warranted to unravel the molecular mechanism of this extraordinarily precise and localized phenomenon. In situ probing of fungal cultures, however, have been challenging due to their inherent complexity and light penetration issues associated with conventional optical imaging. In this work, we report a label‐free approach using a combination of light sheet microscopy and Raman spectroscopy to obtain concomitant morphological and biochemical information from the growing specimen. We show that the variance in morphology in the symbiotic fungus Piriformospora indica are rooted in the underlying differences in chemical composition in the specific growth zones. Our findings suggest that this potent two‐pronged approach can comprehensively characterize growth areas and elucidate microbe interactions in still developing colonies with high sensitivity and multiplexing capability.
Metal Triflates for the Production of Aromatics from Lignin
Authors: Deuss Peter J. , Lahive Ciaran W. , Lancefield Christopher S. , Westwood Nicholas J. , Kamer Paul C. J. , Barta Katalin , de Vries Johannes G. 
Published: November 2016

AbstractThe depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy‐to‐handle metal triflates (M(OTf)x). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2‐acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol or methyl aromatics obtained by catalytic decarbonylation. Notably, when the method was ultimately tested on lignin, especially Fe(OTf)3 proved very effective and the phenolic C2‐acetal products were obtained in an excellent, 19.3±3.2 wt % yield.
Synthesis of Alkaline‐Soluble Cellulose Methyl Carbamate Using a Reactive Deep Eutectic Solvent
Authors: Sirviö Juho Antti , Heiskanen Juha P. 
Published: November 2016

AbstractThis study presents the use of a reactive deep eutectic solvent (DES) for the chemical modification of wood cellulose fibers. DES based on dimethylurea and ZnCl2 was used to synthetize cellulose methyl carbamate (CMeC). This synthesis was performed at elevated temperature under solvent‐free conditions. Chemical characterization based on FTIR and NMR indicated that methyl carbamate was successfully introduced to cellulose, and a degree of substitution (DS) of 0.17 was obtained after 3 h of reaction at 150 °C. The product with a DS of 0.17 exhibited good alkaline solubility (in 3 % NaOH solution) after freeze‐thawing, whereas the original cellulose fibers were practically insoluble even in 9 % NaOH. As dimethylurea can be produced from CO2, this method can be used as a sustainable way to obtain novel cellulose materials with desirable properties for use in a wide range of applications.
The Use of Molecular Oxygen in Pharmaceutical Manufacturing: Is Flow the Way to Go?
Authors: Hone Christopher A. , Roberge Dominique M. , Kappe C. Oliver 
Published: November 2016

AbstractMolecular oxygen is arguably the greenest reagent available to the organic chemist. Most commonly, a diluted form of oxygen gas, consisting of less than 10 % O2 in N2 (“synthetic air”), is used in pharmaceutical and fine chemical batch manufacturing to effectively address safety concerns when handling molecular oxygen. Concentrations of O2 in N2 below 10 % are generally required to prevent the risk of combustions in the presence of flammable organic solvents (“limiting oxygen concentration”). Nonetheless, the use of pure oxygen is more efficient than using O2 diluted with N2 and can often provide enhanced reaction rates, resulting in significant improvements in product quality and process efficiency. This Concept takes into account recent studies to make the argument that, for liquid‐phase aerobic oxidations, pure oxygen can indeed be handled safely on large scale by employing continuous‐flow reactors, while also providing highly convincing synthetic and manufacturing benefits.
Greenhouse gas emissions from dairy manure management in a Mediterranean environment
Authors: Owen Justine J. , Silver Whendee L. 
Published: November 2016

AbstractLivestock agriculture is a major source of anthropogenic greenhouse gas (GHG) emissions, with a substantial proportion of emissions derived from manure management. Accurate estimates of emissions related to management practices and climate are needed for identifying the best approaches to minimize, and potentially mitigate, GHG emissions. Current emissions models such as those of the IPCC, however, are based on emissions factors that have not been broadly tested against field‐scale measurements, due to a lack of data. We used a diverse set of measurements over 22 months across a range of substrate conditions on a working dairy to determine patterns and controls on soil‐based GHG fluxes. Although dairy soils and substrates differed by management unit, GHG fluxes were poorly predicted by these or climate variables. The manure pile had the greatest GHG emissions, and though temperature increased and O2 concentration decreased following mixing, we detected almost no change in GHG fluxes due to mixing. Corral fluxes were characterized by hotspots and hot moments driven by patterns in deposition. Annual scraping kept the soil and accumulated manure pack thin, producing drier conditions, particularly in the warm dry season. Summed over area, corral fluxes had the greatest non‐CO2 global warming potential. The field had net CH4 consumption, but CH4 uptake was insufficient to offset N2O emissions on an area basis. All sites emitted N2O with a similar or greater climate impact than CH4. Our results highlight the importance of N2O emissions, a less commonly measured GHG, from manure management and present potential opportunities for GHG emissions reductions.
Persistence of trophic hotspots and relation to human impacts within an upwelling marine ecosystem
Authors: Santora Jarrod A. , Sydeman William J. , Schroeder Isaac D. , Field John C. , Miller Rebecca R. , Wells Brian K. 
Published: November 2016

AbstractHuman impacts (e.g., fishing, pollution, and shipping) on pelagic ecosystems are increasing, causing concerns about stresses on marine food webs. Maintaining predator–prey relationships through protection of pelagic hotspots is crucial for conservation and management of living marine resources. Biotic components of pelagic, plankton‐based, ecosystems exhibit high variability in abundance in time and space (i.e., extreme patchiness), requiring investigation of persistence of abundance across trophic levels to resolve trophic hotspots. Using a 26‐yr record of indicators for primary production, secondary (zooplankton and larval fish), and tertiary (seabirds) consumers, we show distributions of trophic hotspots in the southern California Current Ecosystem result from interactions between a strong upwelling center and a productive retention zone with enhanced nutrients, which concentrate prey and predators across multiple trophic levels. Trophic hotspots also overlap with human impacts, including fisheries extraction of coastal pelagic and groundfish species, as well as intense commercial shipping traffic. Spatial overlap of trophic hotspots with fisheries and shipping increases vulnerability of the ecosystem to localized depletion of forage fish, ship strikes on marine mammals, and pollution. This study represents a critical step toward resolving pelagic areas of high conservation interest for planktonic ecosystems and may serve as a model for other ocean regions where ecosystem‐based management and marine spatial planning of pelagic ecosystems is warranted.
Differential matrix use by Neotropical birds based on species traits and landscape condition
Authors: Kennedy Christina M. , Zipkin Elise F. , Marra Peter P. 
Published: November 2016

AbstractThere is considerable uncertainty about the role of human‐modified habitats in supporting species in fragmented landscapes. This is because few studies sample outside of native habitats in the “matrix.” Those that do, often fail to sample landscapes in a way that accounts for the confounding effects of native habitat pattern and species detection biases that can obscure species responses. We employed multi‐species hierarchical occupancy models to determine the use of human‐modified habitats by Neotropical birds in landscapes that were similar in forest amount and configuration but surrounded by a matrix of agriculture (predominately pasture), bauxite mining (surface mining for aluminum), or suburban development in central Jamaica. We found that the vast majority of bird species used the matrix: with the highest mean occurrences for open‐associated, followed by generalist, and last forest‐associated species. Migrant species had higher mean occurrences in all matrix types relative to resident species. Contrary to our expectation, mean occurrence for the entire species community, and for forest‐associated and migrant species, were highest in bauxite, intermediate in suburban, and lowest in agriculture. Open‐associated species had higher occurrences in both bauxite and agricultural matrices, whereas generalist species had higher occurrences in suburban matrices. Additional behavioral observations indicated that Neotropical birds used matrix areas, particularly scattered trees, to acquire food, and secondarily, as movement conduits. Matrix use patterns reflected the differential availability of potential resources and structural connectivity across the three landscape types, but only for those species adapted to open/edge environments and with generalized habitat requirements. Patterns of matrix use by forest specialists reflected the differential levels of degradation of the native forest; thus, we propose that higher matrix use for forest‐dependent species may be induced by diminished within‐forest resources. These results underscore that effective management of human‐modified matrices requires in‐depth understanding of the trade‐offs between the benefits available in the matrix and the impacts on the disturbance of native habitats.
Effect of initial soil properties on six‐year growth of 15 tree species in tropical restoration plantings
Authors: Martínez‐Garza Cristina , Campo Julio , Ricker Martin , Tobón Wolke 
Published: November 2016

AbstractIn restoration plantings in degraded pastures, initial soil nutrient status may lead to differential growth of tropical tree species with diverse life history attributes and capacity for N2fixation. In 2006, we planted 1,440 seedlings of 15 native tree species in 16 fenced plots (30 × 30 m) in a 60‐year‐old pasture in Los Tuxtlas, Veracruz, Mexico, in two planting combinations. In the first year, we evaluated bulk density,pH, the concentration of organic carbon (C), total nitrogen (N), ammonia (), nitrate (), and total phosphorus (P) in the upper soil profile (0–20 cm in depth) of all plots. The first two axes of two principal component analyses explained more than 60% of the variation in soil variables: The axes were related to increasing bulk density,,, total N concentration, andpH. Average relative growth rates in diameter at the stem base of the juvenile trees after 6 years were higher for pioneer (45.7%) and N2‐fixing species (47.6%) than for nonpioneer (34.7%) and nonfixing species (36.2%). Most N2‐fixing species and those with the slowest growth rates did not respond to soil attributes. Tree species benefited from higherpHlevels and existing litter biomass. The pioneersFicus yoponensis,Cecropia obtusifolia, andHeliocarpus appendiculatus, and the N2‐fixing nonpioneersCojoba arborea,Inga sinacae, andPlatymiscium dimorphandrumwere promising for forest restoration on our site, given their high growth rates.
Access to Phylogeny from Voltammetric Fingerprints of Seeds: the Asparagus Case
Authors: Doménech‐Carbó Antonio , Ibars Ana M. , Prieto‐Mossi Josefa , Estrelles Elena , Doménech‐Carbó María Teresa , Ortiz‐Miranda Annette S. , Martini Mariele , Lee Yu 
Published: November 2016

AbstractA methodology for characterizing vegetal taxonomic groups from the voltammetric fingerprints of polyphenolic components of seeds is described. It is based on recording the voltammetric response of microparticulate films deposited on glassy carbon electrodes from seed extracts using different organic solvents. The obtained responses in contact with aqueous electrolytes provided characteristic voltammetric profiles at the level of genera/subgenera and/or families using bivariant and multivariant chemometric methods. The voltammograms of 14 species from 5 different families provided family‐characteristic patterns. Analysis of voltammetric responses for a set of 20 species of the Asparagus genus from four continents permits to discriminate the genetic lines represented by the Asparagus, Protasparagus and Myrsiphyllum subgenera.
Integrated Research as Key to the Development of a Sustainable Geothermal Energy Technology
Authors: Meller Carola , Bremer Judith , Baur Sabine , Bergfeldt Thomas , Blum Philipp , Canic Tina , Eiche Elisabeth , Gaucher Emmanuel , Hagenmeyer Veit , Heberling Frank , Held Sebastian , Herfurth Sarah , Isele Jörg , Kling Tobias , Kuhn Dietmar , Kumar Ankit , Mayer Dominik , Müller Birgit , Neumann Thomas , Nestler Britta , Nitschke Fabian , Nothstein Alexandra , Nusiaputra Yodha , Orywall Pia , Peters Max , Sahara David , Schäfer Thorsten , Schill Eva , Schilling Frank , Schröder Elisabeth , Selzer Michael , Stoll Madeleine , Wiemer Hans‐Joachim , Wolf Stefanie , Zimmermann Michael , Kohl Thomas 
Published: November 2016

AbstractAs estimated by the International Energy Agency, geothermal power can contribute to 3.5 % of worldwide power and 3.9 % to heat production by 2050. This includes the development of enhanced geothermal systems (EGSs) in low‐enthalpy systems. EGS technology is still in an early stage of development. Pushing EGS technologies towards market maturity requires a long‐term strategic approach and massive investments in research and development. Comprehensive multidisciplinary research programs that combine fundamental and applied concepts to tackle technological, economic, ecological, and safety challenges along the EGS process chain are needed. The Karlsruhe Institute of Technology (KIT) has defined a broad research program on EGS technology development following the necessity of a transdisciplinary approach. The research concept is embedded in the national research program of the Helmholtz Association and is structured in four clusters: reservoir characterization and engineering, thermal water circuit, materials and geoprocesses, and power plant operation. The proximity to industry, closely interlinked with fundamental research, forms the basis of a target‐orientated concept. The present paper aims to give an overview of geothermal research at KIT and emphasizes the need for concerted research efforts at the international level to accelerate technological breakthrough of EGS as an essential part of a future sustainable energy system.
Evaluation of the Impact of Surface Reconstruction on Rough Electrodeposited Copper‐Based Catalysts for Carbon Dioxide Electroreduction
Authors: Karaiskakis Alexandros N. , Biddinger Elizabeth J. 
Published: November 2016

AbstractCarbon dioxide electroreduction (CO2ELR) can combine the use of a gaseous waste byproduct (CO2) with electricity from renewable sources to produce low‐carbon fuels and useful chemicals. Recent reports pointed out the superior performance of rough copper polycrystalline catalysts; however, reconstruction that takes place on such surfaces is under investigation. This report highlights the importance of copper surface reconstruction on rough surfaces during CO2ELR. Electrodeposited copper‐based catalysts composed primarily of Cu(111) were examined under CO2ELR conditions, and it was found that they underwent reconstruction towards Cu(200). The main hydrocarbon product of electrodeposited copper‐based catalysts with Cu(200) was CH4. The Cu/Cu catalyst achieved up to 40 % Faradaic efficiency (FE) to CH4 and low H2 efficiency (16 % FE) at −1.07 V versus the reversible hydrogen electrode (RHE), at a current density of −86 mA cm−2. This study provides new insights regarding the correlation of copper crystal orientation and selectivity on rough copper surfaces and the impact of copper reconstruction on the reaction.
Aggression Regulation in Day Treatment of Eating Disorders: Two‐Centre RCT of a Brief Body and Movement‐Oriented Intervention
Authors: Boerhout Cees , Swart Marte , Voskamp Marjon , Troquete Nadine A. C. , van Busschbach Jooske T. , Hoek Hans W. 
Published: November 2016

AbstractObjectiveThe objective is to evaluate a body and movement‐oriented intervention on aggression regulation, specifically aimed towards reducing anger internalization in patients with an eating disorder.MethodPatients were randomized to treatment‐as‐usual (TAU) plus the intervention (n = 38) or to TAU only (n = 32). The intervention was delivered by a psychomotor therapist. TAU consisted of multidisciplinary day treatment (3–5 days per week during 3–9 months). Anger coping (Self‐Expression and Control Scale) and eating pathology (Eating Disorder Examination‐Self‐report Questionnaire) were measured at baseline and follow‐up. Differences between pre‐intervention and post‐intervention scores were tested by using repeated measures ANOVA.ResultsThe intervention group showed a significantly larger decrease of anger internalization than the control group (η2 = 0.16, p = 0.001). Both groups showed a significant reduction in eating pathology, but differences between groups were not significant.DiscussionA body and movement‐oriented therapy seems a viable add‐on for treating anger internalization in patients with an eating disorder. Copyright © 2016 John Wiley & Sons, Ltd and Eating Disorders Association.