bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Methanation of CO2: A Review
Authors: Ghaib Karim , Nitz Korbinian , Ben‐Fares Fatima‐Zahrae
Published: November 2016

The chemical methanation of CO2 may become a ubiquitous process for the production of renewable substitute natural gas from any CO2 source coupled with renewable hydrogen. The produced gas can be fed into the natural gas pipeline or used as fuel. Over the past few years, great efforts have been made in developing the process of CO2 methanation. In this paper, the chemical methanation, which is the most common process, is reviewed. The purpose is to present a comprehensive updated review of the process. The CO2 methanation, covering the process mechanisms, thermodynamics, catalysts, kinetics, and reactors are discussed with the aim to outline the pathways for the future development of the methanation process.
Type III Polyketide Synthases: Functional Classification and Phylogenomics
Authors: Shimizu Yugo , Ogata Hiroyuki , Goto Susumu
Published: November 2016

Polyketide synthases (PKSs) catalyze the sequential condensation of simple acetate units to produce a large class of natural products, including pharmacologically valuable compounds. PKSs are classified into three types on the basis of their domain structures; type III PKSs have the simplest domain structure, although their products have various structures and functions. The sequence–function relationship is fundamental for predicting enzyme functions, but it has not been well investigated in type III PKSs to date. Consequently, the current methods for predicting type III PKS functions are still immature in comparison with those that target type I/II PKSs. In this review we summarize the current functional and phylogenomic knowledge about type III PKSs and propose a new classification of their enzymatic reactions. We also discuss possible directions for the development of better computational tools for functional prediction of type III PKS homologues.
Tetrazine‐Responsive Self‐immolative Linkers
Authors: Neumann Kevin , Jain Sarthak , Gambardella Alessia , Walker Sarah E. , Valero Elsa , Lilienkampf Annamaria , Bradley Mark
Published: November 2016

Molecules that undergo activation or modulation following the addition of benign external small‐molecule chemical stimuli have numerous applications. Here, we report the highly efficient “decaging” of a variety of moieties by activation of a “self‐immolative” linker, by application of water‐soluble and stable tetrazine, including the controlled delivery of doxorubicin in a cellular context.
Median arcuate ligament syndrome: case presentation and video‐illustrated laparoscopic management
Authors: El Asmar Antoine , El Rassi Ziad
Published: November 2016

Key Clinical Message

Laparoscopic release of the median arcuate ligament, to relieve symptomatic compression of the celiac trunk, is the ideal approach when performed in a specialized center, by a surgeon with the adequate experience in advanced laparoscopic surgery.
Approaches for Dispatchable Biomass Plants with Particular Focus on Steam Storage Devices
Authors: Stark Matthias , Sonnleitner Matthias , Zörner Wilfried , Greenough Rick
Published: November 2016

An increasing share of fluctuating energy generation leads to new challenges in power grids. In addition, the demand for flexible power plants is growing. Solid biomass‐fueled combined heat and power (CHP) plants are able to get modified into dispatchable power plants. Boundaries for this operation mode are summarized and several measures to achieve a flexible power generation in biomass CHP plants are concluded. The integration of a high‐temperature storage system for buffering the plants' steam seems to be the most promising, however, the least investigated option. The tasks and necessary features of such storage systems were investigated and an overview of available technologies and systems for the storage of steam is given.
Nafion‐Free Carbon‐Supported Electrocatalysts with Superior Hydrogen Evolution Reaction Performance by Soft Templating
Authors: Bernsmeier Denis , Bernicke Michael , Ortel Erik , Bergmann Arno , Lippitz Andreas , Nissen Jörg , Schmack Roman , Strasser Peter , Polte Jörg , Kraehnert Ralph
Published: November 2016

Efficient water electrolysis requires electrode coatings with high catalytic activity. Platinum efficiently catalyzes the hydrogen evolution reaction in acidic environments, but is a rare and expensive metal. The activity achieved per metal atom can be increased if small Pt particles are dispersed onto electrically conductive, highly accessible and stable support materials. However, the addition of Nafion, a typical binder material used in the manufacture of electrode coatings, can decrease catalytic activity by the blocking of pores and active surface sites. A new approach is reported for the direct synthesis of highly active Nafion‐free Pt/C catalyst films consisting of small Pt nanoparticles supported in size‐controlled mesopores of a conductive carbon film. The synthesis relies on the co‐deposition of suitable Pt and C precursors in the presence of polymer micelles, which act as pore templates. Subsequent carbonization in an inert atmosphere produces porous catalyst films with controlled film thickness, pore size and particle size. The catalysts clearly outperform all Nafion‐based Pt/C catalysts reported in the literature, particularly at high current densities.
CuCo2O4‐Gd0.1Ce0.9O1.95 as a Potential Cathode Material for Intermediate Temperature Solid Oxide Fuel Cells
Authors: Shao Lin , Wang Pengxiang , Sun Chengzhi , Fan Lishuang , Zhang Naiqing , Sun Kening
Published: November 2016

CuCo2O4‐Gd0.1Ce0.9O1.95 (GDC) composite was investigated as a potentially promising cathode material for intermediate temperature solid oxide fuel cells (IT‐SOFCs). The CuCo2O4‐GDC composite cathodes were characterized via X‐ray diffraction, scanning electron microscopy and thermal expansion. CuCo2O4‐GDC composites exhibited a good chemical compatibility and thermal compatibility for each composition. Introduction of the GDC nanoparticles increased the length of TPBs and enhanced the electrochemical activities of the CuCo2O4‐GDC composite cathode. The polarization resistance with addition of 60 wt.% of GDC showed the least value of 0.09 Ω cm2 at 800 °C. The results demonstrated that CuCo2O4‐GDC composite would be a promising cathode material for IT‐SOFCs.
Heteroacene Synthesis through C−S Cross‐Coupling/5‐endo‐digCyclization
Authors: Oechsle Peter , Flörke Ulrich , Egold Hans , Paradies Jan
Published: November 2016

Highly efficient, one‐step synthesis of sulfur‐containing heteroacenes was achieved through palladium‐catalyzed C−S cross‐coupling of bis‐alkynes with thioacetate as hydrogen sulfide surrogate. Heteroacenes consisting of three, five, and seven fused aromatic rings were obtained in a single catalytic step by four‐, six‐, and eightfold C−S bond formation.
Deeper Insight into the Factors Controlling H2 Activation by Geminal Aminoborane‐Based Frustrated Lewis Pairs
Authors: Yepes Diana , Jaque Pablo , Fernández Israel
Published: November 2016

H2 activation mediated by geminal aminoborane‐based frustrated Lewis pairs (FLPs; R2N‐CH2‐BR′2) has been computationally explored within the density functional theory framework. It is found that the activation barrier of this process as well as the geometry of the corresponding transition states strongly depend on the nature of the substituents directly attached either to the acidic or the basic centers of the FLPs. The physical factors controlling the whole activation path are quantitatively described in detail by means of the activation strain model of reactivity combined with the energy decomposition analysis method. This methodology suggests a highly orbital‐controlled mechanism where the degree of charge transfer cooperativity between the most important donor–acceptor orbital interactions, namely LP(N)→σ*(H2) and σ(H2)→pπ(B), along the reaction coordinate constitutes a suitable indicator of the reaction barrier.
Effects of Metal Blending in Random Bimetallic Single‐Chain Magnets: Synergetic, Antagonistic, or Innocent
Authors: Wang Yan‐Qin , Yue Qi , Gao En‐Qing
Published: November 2016

A family of isomorphous three‐dimensional metal–organic frameworks based on bimetallic (FeCo, FeNi, and CoNi) chains with random metal sites have been prepared and magnetically characterized. The solid‐solution‐type bimetallic materials inherit intrachain ferromagnetic interactions and single‐chain‐magnet (SCM) behaviors from the homometallic parent materials. Interestingly, different composition dependence of magnetic behaviors has been found. The FeII1−xNiIIx series (0≤x≤1) show an innocent composition dependence, where the blocking temperature of slow relaxation decreases monotonically as FeII is replaced by less anisotropic NiII. The FeII1−xCoIIx series show an unexpected antagonistic blending effect on slow relaxation: blending FeII and CoII tends to depress the spin dynamics, and the bimetallic materials with intermediate composition show significantly lower blocking temperature than both FeII and CoII materials. This is quite the opposite of what happens in the Co1−xNix series, where CoII and NiII seem to have a synergetic effect so that slow relaxation in bimetallic systems can be promoted to higher temperature than both CoII and NiII materials.
Gold(I) NHC Complexes: Antiproliferative Activity, Cellular Uptake, Inhibition of Mammalian and Bacterial Thioredoxin Reductases, and Gram‐Positive Directed Antibacterial Effects
Authors: Schmidt Claudia , Karge Bianka , Misgeld Rainer , Prokop Aram , Franke Raimo , Brönstrup Mark , Ott Ingo
Published: November 2016

Gold complexes with N‐heterocyclic carbene (NHC) ligands represent a promising class of metallodrugs for the treatment of cancer or infectious diseases. In this report, the synthesis and the biological evaluation of halogen‐containing NHC‐AuI‐Cl complexes are described. The complexes 1 and 5 a–5 f displayed good cytotoxic activity against tumor cells, and cellular uptake studies suggested that an intact Au‐NHC fragment is essential for the accumulation of high amounts of both the metal and the NHC ligand. However, the bioavailability was negatively affected by serum components of the cell culture media and was influenced by likely transformations of the complex. One example (5 d) efficiently induced apoptosis in vincristine‐ and daunorubicin‐resistant P‐glycoprotein overexpressing Nalm‐6 leukemia cells. Cellular uptake studies with this compound showed that both the wild‐type and resistant Nalm‐6 cells accumulated comparable amounts of gold, indicating that the gold drug was not excreted by P‐glycoprotein or other efflux transporters. The effective inhibition of mammalian and bacterial thioredoxin reductases (TrxR) was confirmed for all of the gold complexes. Antibacterial screening of the gold complexes showed a particularly high activity against Gram‐positive strains, reflecting their high dependence on an intact Trx/TrxR system. This result is of particular interest as the inhibition of bacterial TrxR represents a relatively little explored mechanism of new anti‐infectives.
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

The 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

A 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.
Dynamic simulation of coupled transmission processes and reaction mechanisms in porous calcined limestone
Authors: Li Mingchun , Yang Hao , Song Lanting , Wu Yusheng , Liang Jiyan
Published: November 2016

The particle reaction model and dynamic reaction characteristics of limestone over a wide particle size range from 0.15 to 10 mm were studied by thermogravimetric analysis and nitrogen adsorption‐desorption techniques. A clear boundary between the sintered porous product layer and the undecomposed part was found by field emission scanning electron microscopy (FESEM) analysis. A dynamic coupling model considering the effects of varied pore structure and transport resistances was established based on the appropriate particle reaction model, which allowed us to predict the decomposition ratio and reaction regimes in a broad range of particle sizes. The dynamic characteristics of pore size distribution and reaction mechanisms were discussed. Over the defined particle size range and calcination temperature range, the diffusion of gaseous product through porous product layer will become the rate determining factor as the ratio of (r0‐rc)/r0 corresponding to 25 % Damköhler number above 0.35.
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

An 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

One 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.
Renal cancer subtypes: Should we be lumping or splitting for therapeutic decision making?
Authors: Haake Scott M. , Rathmell W. Kimryn
Published: November 2016

The treatment of advanced renal cell carcinoma has posed a challenge for decades, in part because of common themes related to intrinsic resistance to cytotoxic chemotherapy and the obscure biology of these cancer types. Forward movement in the treatment of the renal cell carcinomas thus can be approached in 2 ways: by splitting the tumor types along histologic and molecular features, in the hopes of coupling highly precision‐focused therapy on a subset of patients who have disease with the most potential for benefit; or by lumping the various biologies and histologies together, to include the rarer renal cell carcinoma types with the more common types. The former strategy satisfies the desire for customized precision in treatment delivery, whereas the latter strategy allows clinicians to offer a wider therapeutic menu in a set of diseases we are continuing to learn about on a physiologic and molecular level. Cancer 2017;123:200–209. © 2016 American Cancer Society.
The impact of health insurance on cancer care in disadvantaged communities
Authors: Abdelsattar Zaid M. , Hendren Samantha , Wong Sandra L.
Published: November 2016

BACKGROUND

Individuals 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.

METHODS

This 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.

RESULTS

A 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).

CONCLUSIONS

Cancer 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.
Pax3 overexpression induces cell aggregation and perturbs commissural axon projection during embryonic spinal cord development
Authors: Lin Juntang , Fu Sulei , Yang Ciqing , Redies Christoph
Published: November 2016

Pax3 is a transcription factor that belongs to the paired box family. In the developing spinal cord it is expressed in the dorsal commissural neurons, which project ascending axons contralaterally to form proper spinal cord–brain circuitry. While it has been shown that Pax3 induces cell aggregation in vitro, little is known about the role of Pax3 in cell aggregation and spinal circuit formation in vivo. We have reported that Pax3 is involved in neuron differentiation and that its overexpression induces ectopic cadherin‐7 expression. In this study we report that Pax3 overexpression also induces cell aggregation in vivo. Tissue sections and open book preparations revealed that Pax3 overexpression prevents commissural axons from projecting to the contralateral side of the spinal cord. Cells overexpressing Pax3 aggregated in cell clusters that contained shortened neurites with perturbed axon growth and elongation. Pax3‐specific shRNA partially rescued the morphological change induced by Pax3 overexpression in vivo. Our results indicate that the normal expression of Pax3 is necessary for proper axonal pathway finding and commissural axon projection. In conclusion, Pax3 regulates neural circuit formation during embryonic development. J. Comp. Neurol. 525:1618–1632, 2017. © 2016 Wiley Periodicals, Inc.
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

Imaging 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

The 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

This 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

Molecular 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

Livestock 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

Human 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

There 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

In 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.
Reactivity and Structural Diversity in the Reaction of Guanidine 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene with CO2, CS2, and Other Heterocumulenes
Authors: von Wolff Niklas , Villiers Claude , Thuéry Pierre , Lefèvre Guillaume , Ephritikhine Michel , Cantat Thibault
Published: November 2016

The guanidine 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) reacted with the heterocumulenes CO2, CS2, iPr2NCNiPr2, p‐tolylNCO, and p‐tolylNCS to give three types of products: TBD–CO2 (1) and TBD–p‐tolylNCS (5), resulting from the addition of the cumulene to TBD, TBD(–H)({iPrNH}–C=N{iPr}) (3) and TBD(–H)(p‐tolylNHCO) (4), resulting from addition of the N–H bond of TBD to the C=N bond of the cumulene, and the dithiocarbamate salt [TBDH][TBD(–H)CS2] (2) after transfer of a proton to a second molecule of TBD. Competition reactions indicated that the stability of the compounds decreases in the order 4 > 5 > 1 > 2 > 3. DFT calculations showed that the relative stabilities of the products are governed by both the Lewis acidity of the heterocumulene and the Brønsted basicity of the TBD(–H)–cumulene anion, whereas their distinct structures are determined by the latter, with the most basic site governing the geometry of the final product.
A Direct, Versatile, and Chemoselective Synthesis of Vinylogous Bis‐ and Monourethanes/amides and β‐Keto Esters by Aza‐Knoevenagel‐Type Reactions of Tertiary Amides with Enolates
Authors: Huang Pei‐Qiang , Ou Wei
Published: November 2016

Full details of our investigations into aza‐Knoevenagel‐type reactions with common tertiary amides as the electrophilic partner are reported. The method is based on the addition of stabilized carbanionic nucleophiles to the amides, which are activated in situ with triflic anhydride (Tf2O). The reaction proceeds under mild conditions and tolerates several sensitive functional groups including enamide and tert‐butyldimethylsilyloxy (TBSO) groups. Significantly, with amides bearing more reactive ester, cyano, and aldehyde groups, the reaction occurs chemoselectively at the least reactive amide group. Such “umpolung” of the chemoselectivity in C=C bond formation is challenging, rare, and of synthetic value. Vinylogous bis‐urethanes (aza‐Knoevenagel‐type condensation products), vinylogous urethanes, and vinylogous amides can be synthesized by employing enolates/carbanions generated from methyl ketones, malonic acid monoester, 2‐phenylacetate, or (benzylsulfonyl)benzene. Moreover, when higher homologues of acetate were used, β‐keto esters were obtained directly from amides. The method has been applied to the one‐step syntheses of several known key intermediates in the total syntheses of alkaloids and 4‐quinolone antibiotics. An efficient and mild intramolecular Friedel–Crafts‐type cyclization of an anilinyl ester has also been achieved with Tf2O as an effective promoter. This amide‐based method is a direct and umpoled alternative to the versatile but stepwise one based on thionation and the Eschenmoser sulfide contraction.
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

A 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.
Identification and natural functions of cyclic lipopeptides from Bacillus amyloliquefaciens An6
Authors: Ben Ayed Hanen , Hmidet Noomen , Béchet Max , Jacques Philippe , Nasri Moncef
Published: November 2016

Lipopeptides constitute a structurally diverse group of metabolites produced by various bacterial and fungal genera. In the past decades, research on lipopeptides has been fueled by their surfactant activities. However, natural functions of lipopeptides compounds have received considerably less attention. The aim of this study was to isolate and identify the lipopeptides from Bacillus amyloliquefaciens An6, and further evaluate their biological activities. An6 lipopeptides were detected by PCR using degenerated primers and MALDI‐TOF‐MS. An6 strain was found to produce surfactin, fengycin, and bacillomycin. Following their purification, the in vitro antioxidant activity of An6 lipopeptides was studied through different assays. The scavenging effect on 1,1‐diphenyl‐2‐picrylhydrazyl radicals at a dosage of 0.75 mg/mL was 81%. Its reducing power was concentration‐dependant and reached a maximum of 1.07 at 2.5 mg/mL. Moreover, they showed a strong inhibition of β‐carotene bleaching. An6 lipopeptides mixture was also found to display significant antimicrobial activity against several Gram‐positive, Gram‐negative bacteria, and fungal strains. An6 lipopeptides were insensitive to proteolytic enzymes, stable between pH 4.0 and 12.0, and resistant to high temperature. Our results provided enough evidence proving that An6 lipopeptides could be used as functional‐food components.
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

As 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

Carbon 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

Objective

The 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.

Method

Patients 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.

Results

The 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.

Discussion

A 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.
Exposure to ultraviolet radiation late in development increases the toxicity of oil to mahi-mahi (Coryphaena hippurus) embryos
Authors: Sweet Lauren E. , Magnuson Jason , Garner T. Ross , Alloy Matthew M. , Stieglitz John D. , Benetti Daniel , Grosell Martin , Roberts Aaron P.
Published: November 2016

The Deepwater Horizon oil spill in 2010 overlapped with the spawning of many pelagic fish species in the Gulf of Mexico, including mahi-mahi (Coryphaena hippurus). Polycyclic aromatic hydrocarbons (PAHs) released during the spill have been shown to cause photo-induced toxicity under ultraviolet (UV) radiation. In the present study, mahi-mahi embryos were exposed to high-energy water accommodated fractions of source and naturally weathered oils for up to 48 h. The timing of co-exposure with UV radiation varied between an early development exposure for 8 h or a late development exposure for 8 h. The UV co-exposure had a photo-induced toxic effect on hatching success for all oil types and exposure scenarios. A more sensitive developmental window to photo-induced toxicity was observed when UV exposure occurred late in development. Source Oil B was over 6-fold more toxic, and Massachusetts source oil was 1.6-fold more toxic when the embryos were co-exposed to UV light late in development. Furthermore, weathered oil from the surface co-exposure with UV late in development resulted in bradycardia in the mahi-mahi. The present study provides evidence that the developmental window when UV co-exposure occurs has a significant effect on the degree of photo-induced toxicity of oil and that UV co-exposure may exacerbate long-term cardiac effects in developing fish. Environ Toxicol Chem 2017;36:1592–1598. © 2016 SETAC
Mercury exposure may influence fluctuating asymmetry in waterbirds
Authors: Herring Garth , Eagles-Smith Collin A. , Ackerman Joshua T.
Published: November 2016

Variation in avian bilateral symmetry can be an indicator of developmental instability in response to a variety of stressors, including environmental contaminants. The authors used composite measures of fluctuating asymmetry to examine the influence of mercury concentrations in 2 tissues on fluctuating asymmetry within 4 waterbird species. Fluctuating asymmetry increased with mercury concentrations in whole blood and breast feathers of Forster's terns (Sterna forsteri), a species with elevated mercury concentrations. Specifically, fluctuating asymmetry in rectrix feather 1 was the most strongly correlated structural variable of those tested (wing chord, tarsus, primary feather 10, rectrix feather 6) with mercury concentrations in Forster's terns. However, for American avocets (Recurvirostra americana), black-necked stilts (Himantopus mexicanus), and Caspian terns (Hydroprogne caspia), the authors found no relationship between fluctuating asymmetry and either whole-blood or breast feather mercury concentrations, even though these species had moderate to elevated mercury exposure. The results indicate that mercury contamination may act as an environmental stressor during development and feather growth and contribute to fluctuating asymmetry of some species of highly contaminated waterbirds. Environ Toxicol Chem 2017;36:1599–1605. Published 2016 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.