bluuebunny/crossref_metadata_2025 huggingface dataset:
Interplay between Reaction and Phase Behaviour in Carbon Dioxide Hydrogenation to Methanol
Authors: Reymond Helena , Amado‐Blanco Victor , Lauper Andreas , Rudolf von Rohr Philipp
Published: December 2016

Condensation promotes CO2 hydrogenation to CH3OH beyond equilibrium through in situ product separation. Although primordial for catalyst and reactor design, triggering conditions as well as the impact on sub‐equilibrium reaction behaviour remain unclear. Herein we used an in‐house designed micro‐view‐cell to gain chemical and physical insights into reaction and phase behaviour under high‐pressure conditions over a commercial Cu/ZnO/Al2O3 catalyst. Raman microscopy and video monitoring, combined with online gas chromatography analysis, allowed the complete characterisation of the reaction bulk up to 450 bar (1 bar=0.1 MPa) and 350 °C. Dew points of typical effluent streams related to a parametric study suggest that the improving reaction performance and reverting selectivities observed from 230 °C strongly correlate with (i) a regime transition from kinetic to thermodynamic, and (ii) a phase transition from a single supercritical to a biphasic reaction mixture. Our results advance a rationale behind transitioning CH3OH selectivities for an improved understanding of CO2 hydrogenation under high pressure.
Microwave‐Assisted Selective Hydrogenation of Furfural to Furfuryl Alcohol Employing a Green and Noble Metal‐Free Copper Catalyst
Authors: Romano Pedro N. , de Almeida João M. A. R. , Carvalho Yuri , Priecel Peter , Falabella Sousa‐Aguiar Eduardo , Lopez‐Sanchez Jose A.
Published: December 2016

Green, inexpensive, and robust copper‐based heterogeneous catalysts achieve 100 % conversion and 99 % selectivity in the conversion of furfural to furfuryl alcohol when using cyclopentyl‐methyl ether as green solvent and microwave reactors at low H2 pressures and mild temperatures. The utilization of pressurized microwave reactors produces a 3–4 fold increase in conversion and an unexpected enhancement in selectivity as compared to the reaction carried out at the same conditions using conventional autoclave reactors. The enhancement in catalytic rate produced by microwave irradiation is temperature dependent. This work highlights that using microwave irradiation in the catalytic hydrogenation of biomass‐derived compounds is a very strong tool for biomass upgrade that offers immense potential in a large number of transformations where it could be a determining factor for commercial exploitation.
Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering
Authors: Shinagawa Tatsuya , Takanabe Kazuhiro
Published: December 2016

Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine‐tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions.
Racing chemistry: A century of challenges and progress
Authors: Kremmer Christopher
Published: December 2016

Horseracing has been called ‘one of the first quintessentially modern sports’. Its urge towards standardization, its mathematically set odds, its concern with weights, and its pioneering embrace of drug‐testing reflect an empirical temperament crucial to its transformation from a gentleman's pastime to a global industry funded by wagering. Ironically, in the late nineteenth century, it was modern science itself, and in particular the purification and synthesis of the drugs of nature, that turned the doping of racing animals – a practice recorded in antiquity – into an organized criminal enterprise. This paper presents original research into the history of racing chemistry in Australia in the context of developments in the field worldwide. Using a case‐study approach based on extensive archival materials, it reveals unpublished diaries kept by an analyst working at Sydney Racing Laboratory in the 1950s that document conflicts between scientists over identification of performance drugs in racing animals. The author presents evidence that augments and revises earlier narratives concerning the history of the establishment of laboratory control at Australian racetracks and the removal of the country's first official analyst for racing, Miss Jean Kimble. The Kimble case illustrates the inevitable political, professional, and personal pressures that bear upon drug‐testing in sports, and also conflicts between scientists over standards and priorities. Copyright © 2016 John Wiley & Sons, Ltd.
Rapid classification and quantification of cocaine in seized powders with ATR‐FTIR and chemometrics
Authors: Eliaerts Joy , Dardenne Pierre , Meert Natalie , Van Durme Filip , Samyn Nele , Janssens Koen , De Wael Karolien
Published: December 2016

Traditionally, fast screening for the presence of cocaine in unknown powders is performed by means of colour tests. The major drawbacks of these tests are subjective colour evaluation depending on the operator (‘50 shades of blue’) and a lack of selectivity. An alternative fast screening technique is Fourier Transform InfraRed (FTIR) spectrometry. This technique provides spectra that are difficult to interpret without specialized expertise and shows a lack of sensitivity for the detection of cocaine in mixtures. To overcome these limitations, a portable FTIR spectrometer using Attenuated Total Reflectance (ATR) sampling was combined with a multivariate technique, called Support Vector Machines (SVM).

Representative street drug powders (n = 482), seized during the period January 2013 to July 2015, and reference powders (n = 33) were used to build and validate a classification model (n = 515) and a quantification model (n = 378). Both models were compared with the conventional chromatographic techniques. The SVM classification model showed a high sensitivity, specificity, and efficiency (99%). The SVM quantification model determined cocaine content with a root mean squared error of prediction (RMSEP) of 6% calculated over a wide working range from 4 to 99 w%.

In conclusion, the developed models resulted in a clear output (cocaine detected or cocaine not detected) and a reliable estimation of the cocaine content in a wide variety of mixtures. The ATR‐FTIR technique combined with SVM is a straightforward, user‐friendly, and fast approach for routine classification and quantification of cocaine in seized powders. Copyright © 2016 John Wiley & Sons, Ltd.
Exploiting interspecific olfactory communication to monitor predators
Authors: Garvey Patrick M. , Glen Alistair S. , Clout Mick N. , Wyse Sarah V. , Nichols Margaret , Pech Roger P.
Published: December 2016

Olfaction is the primary sense of many mammals and subordinate predators use this sense to detect dominant species, thereby reducing the risk of an encounter and facilitating coexistence. Chemical signals can act as repellents or attractants and may therefore have applications for wildlife management. We devised a field experiment to investigate whether dominant predator (ferret Mustela furo) body odor would alter the behavior of three common mesopredators: stoats (Mustela erminea), hedgehogs (Erinaceus europaeus), and ship rats (Rattus rattus). We predicted that apex predator odor would lead to increased detections, and our results support this hypothesis as predator kairomones (interspecific olfactory messages that benefit the receiver) provoked “eavesdropping” behavior by mesopredators. Stoats exhibited the most pronounced responses, with kairomones significantly increasing the number of observations and the time spent at a site, so that their occupancy estimates changed from rare to widespread. Behavioral responses to predator odors can therefore be exploited for conservation and this avenue of research has not yet been extensively explored. A long‐life lure derived from apex predator kairomones could have practical value, especially when there are plentiful resources that reduce the efficiency of food‐based lures. Our results have application for pest management in New Zealand and the technique of using kairomones to monitor predators could have applications for conservation efforts worldwide.
Movements of a deep‐water fish: establishing marine fisheries management boundaries in coastal Arctic waters
Authors: Hussey Nigel E. , Hedges Kevin J. , Barkley Amanda N. , Treble Margaret A. , Peklova Iva , Webber Dale M. , Ferguson Steven H. , Yurkowski David J. , Kessel Steven T. , Bedard Jeannette M. , Fisk Aaron T.
Published: December 2016

Management boundaries that define populations or stocks of fish form the basis of fisheries planning. In the Arctic, decreasing sea ice extent is driving increasing fisheries development, highlighting the need for ecological data to inform management. In Cumberland Sound, southwest Baffin Island, an indigenous community fishery was established in 1987 targeting Greenland halibut (Reinhardtius hippoglossoides) through the ice. Following its development, the Cumberland Sound Management Boundary (CSMB) was designated and a total allowable catch (TAC) assigned to the fishery. The CSMB was based on a sink population of Greenland halibut resident in the northern section of the Sound. Recent fishing activities south of the CSMB, however, raised concerns over fish residency, the effectiveness of the CSMB and the sustainability of the community‐based winter fishery. Through acoustic telemetry monitoring at depths between 400 and 1200 m, and environmental and fisheries data, this study examined the movement patterns of Greenland halibut relative to the CSMB, the biotic and abiotic factors driving fish movement and the dynamics of the winter fishery. Greenland halibut undertook clear seasonal movements between the southern and northern regions of the Sound driven by temperature, dissolved oxygen, and sea ice cover with most fish crossing the CSMB on an annual basis. Over the lifespan of the fishery, landfast ice cover initially declined and then became variable, limiting accessibility to favored fisher locations. Concomitantly, catch per unit effort declined, reflecting the effect of changing ice conditions on the location and effort of the fishery. Ultimately, these telemetry data revealed that fishers now target less productive sites outside of their favored areas and, with continued decreases in ice, the winter fishery might cease to exist. In addition, these novel telemetry data revealed that the CSMB is ineffective and led to its relocation to the entrance of the Sound in 2014. The community fishery can now develop an open‐water fishery in addition to the winter fishery to exploit the TAC, which will ensure the longevity of the fishery under projected climate‐change scenarios. Telemetry shows great promise as a tool for understanding deep‐water species and for directly informing fisheries management of these ecosystems that are inherently complex to study.
Evapotranspiration from a primary subtropical evergreen forest in Southwest China
Authors: Song Qing‐Hai , Braeckevelt Elisa , Zhang Yi‐Ping , Sha Li‐Qing , Zhou Wen‐Jun , Liu Yun‐Tong , Wu Chuan‐Sheng , Lu Zhi‐Yun , Klemm Otto
Published: December 2016

Evapotranspiration (ET) was observed over a 5‐year period at a primary subtropical evergreen forest in southwest China. The study used the eddy covariance method and quantified the precipitation, throughfall, stemflow, soil evaporation, and routine meteorological parameters to analyze the contributions of stand‐level transpiration and canopy interception loss to the total ET. The annual ET ranged between 785 and 901 mm. The average ratios ET–potential evapotranspiration were 0.45 and 0.87 during the dry and wet seasons, respectively. The relative contributions of soil evaporation, stand‐level transpiration, and canopy interception loss to ET were quantified in order to understand their roles in today's climate and in a potential future climate. Solar radiation was a driver for ET, although the occurrence of drought limited the tree transpiration and thus ET. Specifically, deep soil moisture was an important driver of ET during the dry season. During the wet season, the vapor pressure deficit became one of the main drivers. Although the current study did not collect specific data for the effect of fog on ET, fog likely plays an important role in the ecohydrologic system and deserves further investigation. Although the hydrological system is currently stable, it is anticipated that the groundwater recharge from the ecosystem may be largely reduced in the future, likely through climate change and an associated positive temperature–ET feedback loop.
The impact of drought on sap flow of cooccurring Liquidambar formosana Hance and Quercus variabilis Blume in a temperate forest, Central China
Authors: Zhu Liwei , Hu Yanting , Zhao Xiuhua , Zeng Xiaomin , Zhao Ping , Zhang Zhenzhen , Ju Yuxi
Published: December 2016

Diffuse‐ and ring‐porous species with different vessel structures exhibited contrasting water use strategies for adapting to water stress. The sap flow rates of two tree species (diffuse‐porous: Liquidambar formosana Hance; and ring‐porous: Quercus variabilis Blume) under different environmental conditions were monitored in a temperate forest in the south of Henan Province, Central China. The mechanisms underlying the contrasting water use strategies in response to drought stress were explored by analysing the correlation of sap flow per unit sapwood area (Fd) with vapour pressure deficit and the contribution of nocturnal Fd to total water use under different soil water contents. The results showed that the Fd of Q. variabilis decreased under drought conditions, whereas that of L. formosana increased. Under drought stress, stronger stomatal control was shown for both tree species. Stomatal regulation and changes of leaf area jointly led to constant sap flow per unit leaf area (JL) across the seasons for Q. variabilis. The seasonal variations in the ratio of nocturnal mean Fd to total Fd were consistent with those in the daytime mean JL for both tree species. Nocturnal sap flow played a critical role in the increased water use of diffuse‐porous species, L. formosana, under drought conditions. Our study highlights the importance of nocturnal sap flow for water use by forest species. This finding provides insights for future studies of the water cycle in forest ecosystems and demonstrates that such studies should take into account the nocturnal physiological processes of plants.
A life cycle database for parasitic acanthocephalans, cestodes, and nematodes
Authors: Benesh Daniel P. , Lafferty Kevin D. , Kuris Armand
Published: December 2016

Parasitologists have worked out many complex life cycles over the last ~150 yr, yet there have been few efforts to synthesize this information to facilitate comparisons among taxa. Most existing host–parasite databases focus on particular host taxa, do not distinguish final from intermediate hosts, and lack parasite life‐history information. We summarized the known life cycles of trophically transmitted parasitic acanthocephalans, cestodes, and nematodes. For 973 parasite species, we gathered information from the literature on the hosts infected at each stage of the parasite life cycle (8,510 host–parasite species associations), what parasite stage is in each host, and whether parasites need to infect certain hosts to complete the life cycle. We also collected life‐history data for these parasites at each life cycle stage, including 2,313 development time measurements and 7,660 body size measurements. The result is the most comprehensive data summary available for these parasite taxa. In addition to identifying gaps in our knowledge of parasite life cycles, these data can be used to test hypotheses about life cycle evolution, host specificity, parasite life‐history strategies, and the roles of parasites in food webs.
Individual isotopic specializations predict subsequent inter‐individual variation in movement in a freshwater fish
Authors: Harrison P. M. , Gutowsky L. F. G. , Martins E. G. , Ward T. D. , Patterson D. A. , Cooke S. J. , Power M.
Published: December 2016

Despite many similarities and intuitive links between individual dietary specialization and behavioral inter‐individual variation, these phenomena have been studied in isolation, and empirical data confirming relationships between these intraspecific variance sources are lacking. Here we use stable isotope analysis and acoustic telemetry to test the hypothesis that individual specialization in trophic (δ15N) and littoral/pelagic prey reliance (δ13C) covary with inter‐individual variation in movement in a group of 34 free‐swimming burbot (Lota lota). By performing stable isotope analysis on tissues with differing isotopic turnover rates (anal fin and dorsal muscle), in 24 lethally sampled burbot, we demonstrate that individual specialization in trophic niche (δ15N) and littoral/pelagic prey reliance (δ13C) occurred within the population. By performing stable isotope analysis on anal fins of a group of telemetry tagged burbot, we were able to show that interactions between trophic niche and littoral/pelagic prey reliance, explained a significant proportion of the subsequent between‐individual variance in mean movement rates. These findings demonstrate an empirical connection between behavioral inter‐individual variation and dietary specialization, thus providing a substantial expansion of our understanding of the wider ecological consequences of these interesting phenomena.
A global database of ant species abundances
Authors: Gibb Heloise , Dunn Rob R. , Sanders Nathan J. , Grossman Blair F. , Photakis Manoli , Abril Silvia , Agosti Donat , Andersen Alan N. , Angulo Elena , Armbrecht Inge , Arnan Xavier , Baccaro Fabricio B. , Bishop Tom R. , Boulay Raphaël , Brühl Carsten , Castracani Cristina , Cerda Xim , Del Toro Israel , Delsinne Thibaut , Diaz Mireia , Donoso David A. , Ellison Aaron M. , Enriquez Martha L. , Fayle Tom M. , Feener Donald H. , Fisher Brian L. , Fisher Robert N. , Fitzpatrick Matthew C. , Gómez Crisanto , Gotelli Nicholas J. , Gove Aaron , Grasso Donato A. , Groc Sarah , Guenard Benoit , Gunawardene Nihara , Heterick Brian , Hoffmann Benjamin , Janda Milan , Jenkins Clinton , Kaspari Michael , Klimes Petr , Lach Lori , Laeger Thomas , Lattke John , Leponce Maurice , Lessard Jean‐Philippe , Longino John , Lucky Andrea , Luke Sarah H. , Majer Jonathan , McGlynn Terrence P. , Menke Sean , Mezger Dirk , Mori Alessandra , Moses Jimmy , Munyai Thinandavha Caswell , Pacheco Renata , Paknia Omid , Pearce‐Duvet Jessica , Pfeiffer Martin , Philpott Stacy M. , Resasco Julian , Retana Javier , Silva Rogerio R. , Sorger Magdalena D. , Souza Jorge , Suarez Andrew , Tista Melanie , Vasconcelos Heraldo L. , Vonshak Merav , Weiser Michael D. , Yates Michelle , Parr Catherine L.
Published: December 2016

What forces structure ecological assemblages? A key limitation to general insights about assemblage structure is the availability of data that are collected at a small spatial grain (local assemblages) and a large spatial extent (global coverage). Here, we present published and unpublished data from 51 ,388 ant abundance and occurrence records of more than 2,693 species and 7,953 morphospecies from local assemblages collected at 4,212 locations around the world. Ants were selected because they are diverse and abundant globally, comprise a large fraction of animal biomass in most terrestrial communities, and are key contributors to a range of ecosystem functions. Data were collected between 1949 and 2014, and include, for each geo‐referenced sampling site, both the identity of the ants collected and details of sampling design, habitat type, and degree of disturbance. The aim of compiling this data set was to provide comprehensive species abundance data in order to test relationships between assemblage structure and environmental and biogeographic factors. Data were collected using a variety of standardized methods, such as pitfall and Winkler traps, and will be valuable for studies investigating large‐scale forces structuring local assemblages. Understanding such relationships is particularly critical under current rates of global change. We encourage authors holding additional data on systematically collected ant assemblages, especially those in dry and cold, and remote areas, to contact us and contribute their data to this growing data set.
Arbuscular mycorrhizal fungal diversity and natural enemies promote coexistence of tropical tree species
Authors: Bachelot Benedicte , Uriarte María , McGuire Krista L. , Thompson Jill , Zimmerman Jess
Published: December 2016

Negative population feedbacks mediated by natural enemies can promote species coexistence at the community scale through disproportionate mortality of numerically dominant (common) tree species. Simultaneously, associations with arbuscular mycorrhizal fungi (AMF) can result in positive effects on tree populations. Coupling data on seedling foliar damage from herbivores and pathogens and DNA sequencing of soil AMF diversity, we assessed the effects of these factors on tree seedling mortality at local (1 m2) and community (16 ha plot) scales in a tropical rainforest in Puerto Rico. At the local scale, AMF diversity in soil counteracted negative effects from foliar damage on seedling mortality. At the community scale, mortality of seedlings of common tree species increased with foliar damage while rare tree species benefited from soil AMF diversity. Together, the effects of foliar damage and soil AMF diversity on seedling mortality might foster tree species coexistence in this forest.
Changes in flowering functional group affect responses of community phenological sequences to temperature change
Authors: Meng F. D. , Jiang L. L. , Zhang Z. H. , Cui S. J. , Duan J. C. , Wang S. P. , Luo C. Y. , Wang Q. , Zhou Y. , Li X. E. , Zhang L. R. , Li B. W. , Dorji T. , Li Y. N. , Du M. Y.
Published: December 2016

Our ability to predict how temperature modifies phenology at the community scale is limited by our lack of understanding of responses by functional groups of flowering plants. These responses differ among species with different life histories. We performed a reciprocal transplant experiment along four elevation gradients (e.g., 3,200, 3,400, 3,600 and 3,800 m) to investigate the effects of warming (transferred downward) and cooling (transferred upward) on plant flowering functional groups (FFGs) and community phenological sequences (i.e., seven phenological events). Warming significantly decreased early‐spring‐flowering (ESF) plant coverage and increased mid‐summer‐flowering plant (MSF) coverage, while cooling had the opposite effect. All community phenological events were advanced by warming and delayed by cooling except for the date of complete leaf‐coloring, which showed the opposite response. Warming and cooling could cause greater advance or delay in early‐season phenological events of the community through increased coverage of MSF species, and warming could delay late‐season phenological events of the community by increased coverage of ESF species. These results suggested that coverage change of FFGs in the community induced by temperature change could mediate the responses of the community phenological events to temperature change in the future. The response of phenological events to temperature change at the species level may not be sufficient to predict phenological responses at the community‐level due to phenological compensation between species in the community.
Local epiphyte establishment and future metapopulation dynamics in landscapes with different spatiotemporal properties
Authors: Belinchón Rocío , Harrison Philip J. , Mair Louise , Várkonyi Gergely , Snäll Tord
Published: December 2016

Understanding the relative importance of different ecological processes on the metapopulation dynamics of species is the basis for accurately forecasting metapopulation size in fragmented landscapes. Successful local colonization depends on both species dispersal range and how local habitat conditions affect establishment success. Moreover, there is limited understanding of the effects of different spatiotemporal landscape properties on future metapopulation size. We investigate which factors drive the future metapopulation size of the epiphytic model lichen species Lobaria pulmonaria in a managed forest landscape. First, we test the importance of dispersal and local conditions on the colonization–extinction dynamics of the species using Bayesian state‐space modelling of a large‐scale data set collected over a 10‐yr period. Second, we test the importance of dispersal and establishment limitation in explaining establishment probability and subsequent local population growth, based on a 10‐yr propagule sowing experiment. Third, we test how future metapopulation size is affected by different metapopulation and spatiotemporal landscape dynamics, using simulations with the metapopulation models fitted to the empirical data. The colonization probability increased with tree inclination and connectivity, with a mean dispersal distance of 97 m (95% credible intervals, 5–530 m). Local extinctions were mainly deterministic set by tree mortality, but also by tree cutting by forestry. No experimental establishments took place on clearcuts, and in closed forest the establishment probability was higher on trees growing on moist than on dry‐mesic soils. The subsequent local population growth rate increased with increasing bark roughness. The simulations showed that the restricted dispersal range estimated (compared to non‐restricted dispersal range), and short tree rotation length (65 yr instead of 120) had approximately the same negative effects on future metapopulation size, while regeneration of trees creating a random tree pattern instead of an aggregated one had only some negative effect. However, using the colonization rate obtained with the experimentally added diaspores led to a considerable increase in metapopulation size, making the dispersal limitation of the species clear. The future metapopulation size is thus set by the number of host trees located in shady conditions, not isolated from occupied trees, and by the rotation length of these host trees.
Four‐trophic level food webs reveal the cascading impacts of an invasive plant targeted for biocontrol
Authors: López‐Núñez Francisco A. , Heleno Ruben H. , Ribeiro Sérgio , Marchante Hélia , Marchante Elizabete
Published: December 2016

Biological invasions are a major threat to biodiversity and as such understanding their impacts is a research priority. Ecological networks provide a valuable tool to explore such impacts at the community level, and can be particularly insightful for planning and monitoring biocontrol programmes, including the potential for their seldom evaluated indirect non‐target effects. Acacia longifolia is among the worst invasive species in Portugal, and has been recently targeted for biocontrol by a highly specific gall‐wasp. Here we use an ambitious replicated network approach to: (1) identify the mechanisms by which direct and indirect impacts of A. longifolia can cascade from plants to higher trophic levels, including gallers, their parasitoids and inquilines; (2) reveal the structure of the interaction networks between plants, gallers, parasitoids and inquilines before the biocontrol; and (3) explore the potential for indirect interactions among gallers, including those established with the biocontrol agent, via apparent competition. Over a 15‐month period, we collected 31,737 galls from native plants and identified all emerging insects, quantifying the interactions between 219 plant‐, 49 galler‐, 65 parasitoid‐ and 87 inquiline‐species—one of the largest ecological networks to date. No galls were found on any of the 16 alien plant species. Invasion by A. longifolia caused an alarming simplification of plant communities, with cascading effects to higher trophic levels, namely: a decline of overall gall biomass, and on the richness, abundance and biomass of galler insects, their parasitoids, and inquilines. Correspondingly, we detected a significant decline in the richness of interactions between plants and galls. The invasion tended to increase overall interaction evenness by promoting the local extinction of the native plants that sustained more gall species. However, highly idiosyncratic responses hindered the detection of further consistent changes in network topology. Predictions of indirect effects of the biocontrol on native gallers via apparent competition ranged from negligible to highly significant. Such scenarios are incredibly hard to predict, but even if there are risks of indirect effects it is critical to weigh them carefully against the consequences of inaction and invasive species spread.
Manufacturing and Control of a Variable Magnetic Flux Motor Prototype with a Mechanical Adjustment Method
Authors: ISHII TAKAAKI , NONAKA TSUYOSHI , OGA SOHEI , OHTO MOTOMICHI
Published: December 2016

A new structure and control method for a variable magnetic flux motor (VMFM) is proposed to achieve a high‐efficiency electric vehicle (EV) motor drive under a wide range of conditions. A VFMF prototype that was designed by considering the loss was manufactured and evaluated in an experiment. The prototype demonstrated low iron loss and sufficient max torque. Thus, the prototype can provide a high‐efficiency drive with low output, which is frequently the case for EVs. Map control enables a wide phase angle for the vector‐control drive of the VMFM under a changing magnetic flux. Thus, the VMFM provides a high‐efficiency drive under a wide range of conditions.
Synthesis, Structural Elucidation, Cyclic Voltammetry, and Theoretical Modelling of 2‐Ferrocenyl‐4H‐benzo[e][1,3]thiazines and 2‐Aryl‐4H‐ferroceno[e][1,3]thiazines
Authors: Fodor Kinga Judit , Hegedüs Kristóf , Csomós Péter , Fodor Lajos , Gubán Dorottya , Sohár Pál , Csámpai Antal
Published: December 2016

2‐Ferrocenyl‐4H‐benzo[e][1,3]thiazine and its 6,7‐dimethoxy derivative were prepared by a Bischler–Napieralski‐type annulation of the Mannich adducts of ferrocenecarboxamide, formaldehyde, and the corresponding thiophenol. A more efficient synthetic pathway, comprising a directed lithiation/iodination sequence followed by standard functional‐group transformations and a final copper‐catalyzed cyclization, was elaborated to convert [(dimethylamino)methyl]ferrocene into racemic mixtures of the first representatives of planar‐chiral 4H‐ferroceno[e][1,3]thiazines. A similar strategy with 2‐iodobenzyl bromide as the precursor enabled a highly improved synthesis of 2‐ferrocenyl‐4H‐benzo[e][1,3]thiazine. The relative tendency of the new ferrocene‐based thiazines, composed of potential redox sites assembled in different molecular architectures, to behave as donors in single‐electron transfer (SET) reactions was studied by cyclic voltammetry (CV) and DFT calculations. The results disclosed that 2‐ferrocenyl‐4H‐ferroceno[e][1,3]thiazine can undergo two consecutive redox steps and is the most efficient reductant among the prepared models; it has the lowest first half‐cell potential, the highest‐energy highest occupied molecular orbital (HOMO) concentrated on the fused metallocene unit and the lowest first ionization energy.
A Highly Selective and Efficient Copper(II) – “Turn‐On” Fluorescence Imaging Probe for l‐Cysteine
Authors: Maheshwaran Duraiyarasu , Nagendraraj Thavasilingam , Manimaran Paramasivam , Ashokkumar Balasubramaniem , Kumar Mukesh , Mayilmurugan Ramasamy
Published: December 2016

A simple copper(II) complex of the anthracenyl‐appended terpyridine ligand 4′‐(anthracen‐9‐yl)‐2,2′:6′,2′′‐terpyridine (L), [Cu(L)Cl2] (1, ESI‐MS, m/z = 507.08), is reported as a highly selective “turn‐on” optical imaging probe for l‐cysteine. Probe 1 shows a CuII/CuI redox potential [E1/2 = –0.194 V versus normal hydrogen electrode (NHE)] within a biologically viable range. The copper center in 1 adopts a square‐pyramidal geometry (τ = 0.0851), and the Cu–Npy bond (1.970 Å) of the middle pyridine (py) ring is shorter than the other two Cu–Npy bonds (2.069 and 2.040 Å). The Cu–Cl bonds (2.444 and 2.027 Å) are labile enough to be replaced by solvent molecules. The square‐based geometry is further supported by the A∥ value of 156.8 × 10–4 cm–1 determined by electron paramagnetic resonance (EPR) spectroscopy at 70 K. The d–d transition of 1 in acetonitrile/4‐(2‐hydroxyethyl)‐1‐piperazineethanesulfonic acid (acetonitrile/HEPES) buffer at pH 7.34 appears at λ =760 nm (ε = 198 m–1 cm–1), and the ligand‐based transitions are observed at λ = 327–384 nm. The ligand shows strong fluorescence at λ = 430 nm with a quantum yield of 11 %, but its emission intensity is completely quenched on coordination with Cu2+ ions, as in 1. Probe 1 detects l‐cysteine selectively through turn‐on fluorescence intensity at λem = 431 nm with a limit of detection of 1.9 × 10–8 m at pH 7.34. Interestingly, probe 1 is able to visualize exogenously added l‐cysteine in Henrietta Lack cervical cancer (HeLa) cells, human liver hepatocellular carcinoma (HepG2) cells, and human embryonic kidney 293 (HEK293) cells under identical conditions at pH 7.4 in confocal microscopy imaging.
Macro and micro functional components of a spreadable olive by‐product (pâté) generated by new concept of two‐phase decanter
Authors: Lozano‐Sánchez Jesús , Bendini Alessandra , Di Lecce Giuseppe , Valli Enrico , Gallina Toschi Tullia , Segura‐Carretero Antonio
Published: December 2016

In this research, the potential use of a spreadable olive by‐product, so called “pâté,” generated during a modern two‐phase centrifugal processing technique as a natural source of bioactive compounds has been evaluated using advanced separation techniques. For this purpose, the qualitative and quantitative characterization of the lipophilic and hydrophilic fractions were performed to establish the fatty acid composition and phenolic profile of the new spreadable olive by‐product. A typical olive oil fatty acid profile and very high oxidative stability was found for lipid fraction, whereas hydrophilic fraction was characterized by the presence of hydroxytyrosol, ß‐hydroxyverbascoside, oleoside derivative, luteolin, among other. This kind of compounds are well‐known for their beneficial effects in the human health. These results suggest that the spreadable olive by‐product could be used as functional ingredients, in the production of nutraceuticals or for feed industry.

Practical applications: Application of analytical chemistry aimed at utilizing a new olive‐oil by‐product, either through conversion into an affordable source of bioactive compounds and in promoting their overall sustainable management. The obtained results indicate that this by‐product is a potential source of bioactive compounds with applications in the pre‐formulation of functional ingredient for human and animal feeding.

The modern two‐phase centrifuge generates a new spreadable olive by‐product which consists of lipophilic and hydrophilic fractions. The analysis of lipophilic compounds showed a typical olive oil fatty acid profile and very high oxidative stability. Hydrophilic fraction was characterized by the presence of hydroxytyrosol, ß‐hydroxyverbascoside, oleoside derivative, luteolin, among other. This kind of compounds are well‐known for their beneficial effects in the human health. These results suggest that the spreadable olive by‐product could be used as functional ingredients, in the production of nutraceuticals or for feed industry.
Switching of Regioselectivity in a Perfluorohexyl Iodide Mediated Synthesis of Phenylimidazo[1,2‐a]pyridines
Authors: Roslan Irwan Iskandar , Chuah Gaik‐Khuan , Jaenicke Stephan
Published: December 2016

3‐Phenylimidazo[1,2‐a]pyridines were synthesized through the perfluorohexyl iodide mediated coupling of 2‐aminopyridines and phenylacetylenes. In situ iodination of the terminal alkyne by perfluorohexyl iodide reverses the polarity by generating a transient electrophilic iodoalkyne, and this alters the regioselectivity of the phenyl group. The reaction then proceeds by tandem electrophilic alkynylation and cyclization to form the fused‐ring product. The protocol affords the 3‐phenyl isomer with full regioselectivity and is complementary to reported methodologies for the synthesis of the 2‐phenyl isomer starting from the same substrates.
Role of transient receptor potential ankyrin 1 receptors in rodent models of meningeal nociception – Experiments in vitro
Authors: Denner A.C. , Vogler B. , Messlinger K. , De Col R.
Published: December 2016

Background

The TRP channel ankyrin type 1 (TRPA1) is a nonselective cation channel known to be activated by environmental irritants, cold and endogenous mediators of inflammation. Activation of TRPA1 in trigeminal afferents innervating meningeal structures has recently been suggested to be involved in the generation of headaches.

Methods

Two in vitro models of meningeal nociception were employed using the hemisected rodent head preparation, (1) recording of single meningeal afferents and (2) release of calcitonin gene‐related peptide (CGRP) from the cranial dura mater. The role of TRPA1 was examined using the TRPA1 agonists acrolein and mustard oil (MO). BCTC, an inhibitor of TRP vanilloid type 1 receptor channels (TRPV1), and the TRPA1 inhibitor HC030031 as well as mice with genetically deleted TRPA1 and TRPV1 proteins, were used to differentiate between effects.

Results

Acrolein did not cause discharge activity in meningeal Aδ‐ or C‐fibres but increased the electrical activation threshold. Acrolein was also effective in releasing CGRP from the dura of TRPV1−/− but not of TRPA1−/− mice. MO increased the discharge activity of afferent fibres from rat as well as C57 wild‐type and TRPA1−/− but not TRPV1−/− mice. The effect was higher in C57 compared to TRPA1−/− mice.

Conclusion

Sole TRPA1 receptor channel activation releases CGRP and increases the activation threshold of meningeal afferents but does not generate propagated activity, and so would be capable of causing local effects like vasodilatation but not pain generation. In contrast, combined TRPA1 and TRPV1 activation may be rather pronociceptive supporting headache generation.

Significance

Sole activation of TRPA1 receptor channels increases the activation threshold but does not cause propagated action potentials in meningeal afferents. TRPA1 agonists cause CGRP release from rodent dura mater. Peripheral TRPA1 receptors may have a pronociceptive function in trigeminal nociception only in combination with TRPV1.
17 to 23: A novel complementary mini Y‐STR panel to extend the Y‐STR databases from 17 to 23 markers for forensic purposes
Authors: Núñez Carolina , Baeta Miriam , Ibarbia Nerea , Ortueta Urko , Jiménez‐Moreno Susana , Blazquez‐Caeiro José Luis , Builes Juan José , Herrera Rene J. , Martínez‐Jarreta Begoña , de Pancorbo Marian M.
Published: December 2016

A Y‐STR multiplex system has been developed with the purpose of complementing the widely used 17 Y‐STR haplotyping (AmpFlSTR Y Filer® PCR Amplification kit) routinely employed in forensic and population genetic studies. This new multiplex system includes six additional STR loci (DYS576, DYS481, DYS549, DYS533, DYS570, and DYS643) to reach the 23 Y‐STR of the PowerPlex® Y23 System. In addition, this kit includes the DYS456 and DYS385 loci for traceability purposes. Male samples from 625 individuals from ten worldwide populations were genotyped, including three sample sets from populations previously published with the 17 Y‐STR system to expand their current data. Validation studies demonstrated good performance of the panel set in terms of concordance, sensitivity, and stability in the presence of inhibitors and artificially degraded DNA. The results obtained for haplotype diversity and discrimination capacity with this multiplex system were considerably high, providing further evidences of the suitability of this novel Y‐STR system for forensic purposes. Thus, the use of this multiplex for samples previously genotyped with 17 Y‐STRs will be an efficient and low‐cost alternative to complete the set of 23 Y‐STRs and improve allele databases for population and forensic purposes.
Exploring STR signal in the single‐ and multicopy number regimes: Deductions from an in silico model of the entire DNA laboratory process
Authors: Duffy Ken R. , Gurram Neil , Peters Kelsey C. , Wellner Genevieve , Grgicak Catherine M.
Published: December 2016

Short tandem repeat (STR) profiling from DNA samples has long been the bedrock of human identification. The laboratory process is composed of multiple procedures that include quantification, sample dilution, PCR, electrophoresis, and fragment analysis. The end product is a short tandem repeat electropherogram comprised of signal from allele, artifacts, and instrument noise. In order to optimize or alter laboratory protocols, a large number of validation samples must be created at significant expense. As a tool to support that process and to enable the exploration of complex scenarios without costly sample creation, a mechanistic stochastic model that incorporates each of the aforementioned processing features is described herein. The model allows rapid in silico simulation of electropherograms from multicontributor samples and enables detailed investigations of involved scenarios. An implementation of the model that is parameterized by extensive laboratory data is publically available. To illustrate its utility, the model was employed in order to evaluate the effects of sample dilutions, injection time, and cycle number on peak height, and the nature of stutter ratios at low template. We verify the model's findings by comparison with experimentally generated data.
Assessment of disulfide and hinge modifications in monoclonal antibodies
Authors: Moritz Bernd , Stracke Jan Olaf
Published: December 2016

During the last years there was a substantial increase in the use of antibodies and related proteins as therapeutics. The emphasis of the pharmaceutical industry is on IgG1, IgG2, and IgG4 antibodies, which are therefore in the focus of this article. In order to ensure appropriate quality control of such biopharmaceuticals, deep understanding of their chemical degradation pathways and the resulting impact on potency, pharmacokinetics, and safety is required. Criticality of modifications may be specific for individual antibodies and has to be assessed for each molecule. However, some modifications of conserved structure elements occur in all or at least most IgGs. In these cases, criticality assessment may be applicable to related molecules or molecule formats. The relatively low dissociation energy of disulfide bonds and the high flexibility of the hinge region frequently lead to modifications and cleavages. Therefore, the hinge region and disulfide bonds require specific consideration during quality assessment of mAbs. In this review, available literature knowledge on underlying chemical reaction pathways of modifications, analytical methods for quantification and criticality are discussed. The hinge region is prone to cleavage and is involved in pathways that lead to thioether bond formation, cysteine racemization, and iso‐Asp (Asp, aspartic acid) formation. Disulfide or sulfhydryl groups were found to be prone to reductive cleavage, trisulfide formation, cysteinylation, glutathionylation, disulfide bridging to further light chains, and disulfide scrambling. With regard to potency, disulfide cleavage, hinge cleavage, disulfide bridging to further light chains, and cysteinylation were found to influence antigen binding and fragment crystallizable (Fc) effector functionalities. Renal clearance of small fragments may be faster, whereas clearance of larger fragments appears to depend on their neonatal Fc receptor (FcRn) functionality, which in turn may be impeded by disulfide bond cleavage. Certain modifications such as disulfide induced aggregation and heterodimers from different antibodies are generally regarded critical with respect to safety. However, the detection of some modifications in endogenous antibodies isolated from human blood and the possibility of in vivo repair mechanisms may reduce some safety concerns.
A methodology for defining seismic scenario‐structure‐based limit state criteria for rc high‐rise wall buildings using net drift
Authors: Alwaeli Wael , Mwafy Aman , Pilakoutas Kypros , Guadagnini Maurizio
Published: December 2016

As a result of population growth and consequent urbanization, the number of high‐rise buildings is rapidly growing worldwide resulting in increased exposure to multiple‐scenario earthquakes and associated risk. The wide range in frequency contents of possible strong ground motions can have an impact on the seismic response, vulnerability and limit states definitions of RC high‐rise wall structures. Motivated by the pressing need to derive more accurate fragility relations to be used in seismic risk assessment and mitigation of such structures, a methodology is proposed to obtain reliable, Seismic Scenario‐Structure‐Based (SSSB) definitions of limit state criteria. A 30‐story wall building, located in a multi‐seismic scenario study region, is utilized to illustrate the methodology. The building is designed following modern codes and then modeled using nonlinear fiber‐based approach. Uncertainty in ground motions is accounted for by the selection of forty real earthquake records representing two seismic scenarios. Seismic scenario‐based building local response at increasing earthquake intensities is mapped using Multi‐Record Incremental Dynamic Analyses (MRIDAs) with a new scalar intensity measure. Net Inter‐Story Drift (NISD) is selected as a global damage measure based on a parametric study involving seven buildings ranging from 20 to 50 stories. This damage measure is used to link local damage events, including shear, to global response under different seismic scenarios. While the study concludes by proposing SSSB limit state criteria for the sample building, the proposed methodology arrives at a reliable definition of limit state criteria for an inventory of RC high‐rise wall buildings under multiple earthquake scenarios. Copyright © 2016 John Wiley & Sons, Ltd.
The bubble bursts for cavitation in natural rivers: laboratory experiments reveal minor role in bedrock erosion
Authors: Carling Paul A. , Perillo Mauricio , Best Jim , Garcia Marcelo H.
Published: December 2016

The erosion of rock‐bedded channels generally is considered a slow process caused mainly by abrasion due to bedload or suspended sediments, but the mechanisms of rapid erosion remain unclear. Cavitation is a clear‐fluid erosive process, well known for its effect on engineering structures, when water vapour bubbles collapse and the resultant pressure shocks erode the boundary. However, although the occurrence of cavitation erosion in natural watercourses has long been a matter of debate, as yet there are no incontrovertible examples of cavitation damage to natural river beds. Using flume experiments, we show for the first time that only weakly‐cavitating clear‐water flows can occur for the range of flow velocities observed in rivers, and these do not erode medium‐hardness rocks after 68 hours. During this time period, only a very soft rock featured erosional marks due to dissolution. Thus, our results cast significant doubt on the likelihood of identifying cavitation damage in most rivers, and provide pointers to those river systems that might be investigated further to identify cavitation erosion. Copyright © 2016 John Wiley & Sons, Ltd.