bluuebunny/crossref_metadata_2025 huggingface dataset:
Seismicity and active tectonics in the Alboran Sea, Western Mediterranean: Constraints from an offshore‐onshore seismological network and swath bathymetry data
Authors: Grevemeyer Ingo , Gràcia Eulàlia , Villaseñor Antonio , Leuchters Wiebke , Watts Anthony B.
Published: November 2015

Seismicity and tectonic structure of the Alboran Sea were derived from a large amphibious seismological network deployed in the offshore basins and onshore in Spain and Morocco, an area where the convergence between the African and Eurasian plates causes distributed deformation. Crustal structure derived from local earthquake data suggests that the Alboran Sea is underlain by thinned continental crust with a mean thickness of about 20 km. During the 5 months of offshore network operation, a total of 229 local earthquakes were located within the Alboran Sea and neighboring areas. Earthquakes were generally crustal events, and in the offshore domain, most of them occurred at crustal levels of 2 to 15 km depth. Earthquakes in the Alboran Sea are poorly related to large‐scale tectonic features and form a 20 to 40 km wide NNE‐SSW trending belt of seismicity between Adra (Spain) and Al Hoceima (Morocco), supporting the case for a major left‐lateral shear zone across the Alboran Sea. Such a shear zone is in accord with high‐resolution bathymetric data and seismic reflection imaging, indicating a number of small active fault zones, some of which offset the seafloor, rather than supporting a well‐defined discrete plate boundary fault. Moreover, a number of large faults known to be active as evidenced from bathymetry, seismic reflection, and paleoseismic data such as the Yusuf and Carboneras faults were seismically inactive. Earthquakes below the Western Alboran Basin occurred at 70 to 110 km depth and hence reflected intermediate depth seismicity related to subducted lithosphere.
Identifying an index of subsurface volatiles on Mars through an analysis of impact crater morphometry using principal component analysis
Authors: Jones Eriita
Published: November 2015

Layered ejecta craters comprise a significant fraction of the ejecta on Mars and may form from the excavation of subsurface volatiles, such as ice. A recent global catalogue identified extensive numbers of layered ejecta craters and their properties and is examined here. In this study over 10,000 single‐layered and double‐layered ejecta craters were analyzed by principal component analysis. Principal component analysis revealed the existence of four significant principal components for single‐layered ejecta craters, and five for double‐layered ejecta craters, which accounted for 73% and 80% of the sample variances, respectively. The first three PCs were interpreted as indices of impactor energy, target volatiles, and impactor angle. The fourth component for both morphologies was interpreted as a resurfacing index. The fifth component for double‐layered craters was identified as an index of preservation of the impact feature. Using the putative target volatile index identified through principal component analysis, the spatial distribution of potential subsurface volatiles, both past and geologically recent, is mapped.
Regulation of methane production, oxidation, and emission by vascular plants and bryophytes in ponds of the northeast Siberian polygonal tundra
Authors: Knoblauch Christian , Spott Oliver , Evgrafova Svetlana , Kutzbach Lars , Pfeiffer Eva‐Maria
Published: November 2015

Methane (CH4) production, oxidation, and emission were studied in ponds of the permafrost‐affected polygonal tundra in northeast Siberia. Microbial degradation of organic matter in water‐saturated soils is the most important source for the climate‐relevant trace gas CH4. Although ponds and lakes cover a substantial fraction of the land surface of northern Siberia, data on CH4 fluxes from these water bodies are scarce. Summer CH4 fluxes were measured with closed chambers at the margins of ponds vegetated by vascular plants and in their centers without vascular plants. Furthermore, CH4 and oxygen concentration gradients, stable carbon isotope signatures of dissolved and emitted CH4, and microbial CH4 production and CH4 oxidation were determined. Mean summer fluxes were significantly higher at the margins of the ponds (46.1 ± 15.4 mg CH4 m−2 d−1) than at the centers (5.9 ± 8.2 mg CH4 m−2 d−1). CH4 transport was dominated by diffusion in most open water sites, but substantial ebullitive fluxes (12.0 ± 8.1 mg CH4 m−2 d−1) were detected in one pond. Plant‐mediated transport accounted for 70 to 90% of total CH4 fluxes above emerged vegetation. In the absence of vascular plants, 61 to 99% of the CH4 produced in the anoxic bottom soil was consumed in a layer of the submerged moss Scorpidium scorpioides, which covered the bottoms of the ponds. The fraction of CH4 oxidized was lower at sites with vascular plants since CH4 was predominantly transported through their aerenchyma, thereby bypassing the CH4 oxidation zone in the moss layer. These results emphasize the importance of moss‐associated CH4 oxidation causing low CH4 fluxes from the studied Siberian ponds.
Introduction to a special section on ecohydrology of semiarid environments: Confronting mathematical models with ecosystem complexity
Authors: Svoray Tal , Assouline Shmuel , Katul Gabriel
Published: November 2015

Current literature provides large number of publications about ecohydrological processes and their effect on the biota in drylands. Given the limited laboratory and field experiments in such systems, many of these publications are based on mathematical models of varying complexity. The underlying implicit assumption is that the data set used to evaluate these models covers the parameter space of conditions that characterize drylands and that the models represent the actual processes with acceptable certainty. However, a question raised is to what extent these mathematical models are valid when confronted with observed ecosystem complexity? This Introduction reviews the 16 papers that comprise the Special Section on Eco‐hydrology of Semiarid Environments: Confronting Mathematical Models with Ecosystem Complexity. The subjects studied in these papers include rainfall regime, infiltration and preferential flow, evaporation and evapotranspiration, annual net primary production, dispersal and invasion, and vegetation greening. The findings in the papers published in this Special Section show that innovative mathematical modeling approaches can represent actual field measurements. Hence, there are strong grounds for suggesting that mathematical models can contribute to greater understanding of ecosystem complexity through characterization of space‐time dynamics of biomass and water storage as well as their multiscale interactions. However, the generality of the models and their low‐dimensional representation of many processes may also be a “curse” that results in failures when particulars of an ecosystem are required. It is envisaged that the search for a unifying “general” model, while seductive, may remain elusive in the foreseeable future. It is for this reason that improving the merger between experiments and models of various degrees of complexity continues to shape the future research agenda.
Isolation of Mesenchymal Stem Cells from Amniotic Fluid and Placenta
Authors: Graham Christopher D. , Fauza Dario O.
Published: November 2015

Diverse progenitor cell populations, including mesenchymal, hematopoietic, trophoblastic, and possibly more primitive stem cells can be isolated from the amniotic fluid and the placenta. At least some of the amniotic and placental cells share a common origin, namely the inner cell mass of the morula. Indeed, most types of progenitor cells that can be isolated from these two sources share many characteristics. This unit will focus solely on the mesenchymal stem cells, the most abundant progenitor cell population found therein and, unlike some of the other stem cell types, present all through gestation. Protocols for isolation, expansion, freezing, and thawing of these cells are presented. Preference is given to the simplest methods available for any given procedure. © 2015 by John Wiley & Sons, Inc.
Convergence of the recursive identification algorithms for multivariate pseudo‐linear regressive systems
Authors: Wang Xuehai , Ding Feng
Published: November 2015

The performance analysis of the recursive algorithms for the multivariate systems with an autoregressive moving average noise process is still open. This paper analyzes the convergence of two recursive identification algorithms, the multivariate recursive generalized extended least squares algorithm and the multivariate generalized extended stochastic gradient algorithm, for pseudo‐linear multivariate systems and proves that the parameter estimation errors consistently converge to zero under persistent excitation conditions. The simulation results show that the proposed algorithms work well. Copyright © 2015 John Wiley & Sons, Ltd.
From Mass Customisation to Design ‘Democratisation’
Authors: Kolarevic Branko
Published: November 2015

Centuries of capitalism and democracy in North America have led to a landscape that can be characterised by an unrelenting normalcy and uniformity, whether it is rows of family houses behind picket fences in suburbia or clusters of glazed towers in downtown districts. Here, Branko Kolarevic, Professor and Chair in Integrated Design at the University of Calgary Faculty of Environmental Design, questions why at a time that the production of consumer goods has been revolutionised by mass customisation, buildings and cities have remained largely resistant to its forces.
OCEAN CN Consultancy Network: Second Development Zone, Umekita Area, Osaka, Japan
Authors: Verebes Tom
Published: November 2015

OCEAN CN Consultancy Network is a Hong Kong‐based specialist design consultancy with links to Beijing, Shanghai and London. Its work spans architecture and urbanism. In Asia, an adaptive and interactive approach has been developed for urban masterplanning, as well as for infrastructural and cultural projects. Here Guest‐Editor and Creative Director of OCEAN CN Tom Verebes describes the network's invited competition entry for the Second Development Zone of the Umekita Area in Osaka, which in its adaptive approach embraces local specificity and variable futures scenarios in its adoption of customisation and new technologies.
Beyond osteogenesis imperfecta: Causes of fractures during infancy and childhood
Authors: Bronicki Lucas M. , Stevenson Roger E. , Spranger Jürgen W.
Published: November 2015

Fractures in infancy or early childhood require prompt evaluation with consideration of accidental or non‐accidental trauma as well as a large number of genetic disorders that predispose to fractures. Bone fragility has been reported in more than 100 genetic disorders, including skeletal dysplasias, inborn errors of metabolism and congenital insensitivity to pain. Most of these disorders are rare but often have distinctive clinical or radiographic findings to assist in the diagnosis. Gene sequencing is available, albeit connective tissue and skeletal dysplasia panels and biochemical studies are only helpful in a minority of cases. This article presents the clinical, radiographic, and molecular profiles of the most common heritable disorders other than osteogenesis imperfecta with increased bone fragility. In addition, the clinicians must consider non‐heritable influences such as extreme prematurity, prenatal viral infection and neoplasia in the diagnostic process. © 2015 Wiley Periodicals, Inc.
Patients electing medical vs surgical treatment: emotional domain of the Rhinosinusitis Disability Index associates with treatment selection
Authors: Orb Quinn , Mace Jess C. , DeConde Adam S. , Steele Toby O. , Cox Steve T. , Smith Timothy L. , Alt Jeremiah A.
Published: November 2015

Background

The Rhinosinusitis Disability Index (RSDI) consists of multiple subdomains shown to be useful in studying chronic rhinosinusitis (CRS). The objective of this study was to determine if RSDI subdomain scores are associated with selection of treatment modality (endoscopic sinus surgery [ESS] or continued medical management [CMM]) in subjects with CRS.

Methods

Patients with CRS were prospectively enrolled into a multi‐institutional cohort study. Following an initial period of medical management, patients elected to undergo treatment with either ESS or CMM. Baseline RSDI total and subdomain scores were compared between patients electing different treatment modalities.

Results

A total of 684 subjects were enrolled with 122 (17.8%) electing CMM and 562 (82.2%) electing ESS. When compared to patients undergoing CMM, patients electing ESS exhibited significantly higher mean baseline RSDI total scores (mean ± standard deviation [SD]: 48.1 ± 24.9 vs 40.1 ± 24.1; p = 0.001) and subdomain scores (emotional: 13.2 ± 9.1 vs 10.4 ± 8.3; p = 0.001; functional: 15.3 ± 8.9 vs 12.6 ± 8.4; p = 0.002; and physical: 19.6 ± 9.3 vs 17.1 ± 9.6; p = 0.007). Emotional subdomain scores were found to be the most associated with choice of treatment modality.

Conclusion

Patients with CRS electing ESS had worse baseline RSDI total and subdomain scores compared to those electing CMM. Although both rhinologic and nonrhinologic symptoms contributed to the selection of treatment modality, emotional symptoms appeared to exhibit the greatest influence on patient‐centered treatment decisions.
Chinon‐katalysierte, selektive Oxidation organischer Moleküle
Authors: Wendlandt Alison E. , Stahl Shannon S.
Published: November 2015

Chinone sind gebräuchliche, stöchiometrisch eingesetzte Reagentien in der organischen Chemie. para‐Chinone mit hohem Reduktionspotential wie DDQ und Chloranil werden verbreitet angewendet und fördern normalerweise die Hydridabstraktion. In den letzten Jahren wurden viele katalytische Anwendungen dieser Methoden entwickelt, wobei das oxidierte Chinon in situ mithilfe von Übergangsmetallen, O2 oder Elektrochemie regeneriert wird. Ergänzende Studien haben zur Entdeckung einer anderen Klasse von Chinonen geführt, die den ortho‐Chinon‐Cofaktoren in Kupfer‐Amin‐Oxidasen ähneln und effiziente und selektive aerobe und/oder elektrochemische Dehydrierungen von Aminen vermitteln. Letztgenannte Reaktionen laufen gewöhnlich über elektrophile Transaminierungs‐ und/oder Additions‐Eliminierungs‐Reaktionsmechanismen anstelle von Hydridabstraktionspfaden ab. Die gesammelten Beobachtungen zeigen, dass die Chinonstruktur einen signifikanten Einfluss auf den Reaktionsmechanismus ausübt und somit bedeutende Auswirkungen auf die Entwicklung neuer Chinonreagentien und Chinon‐katalysierter Umwandlungen hat.
Formal Direct Cross‐Coupling of Phenols with Amines
Authors: Chen Zhengwang , Zeng Huiying , Girard Simon A. , Wang Feng , Chen Ning , Li Chao‐Jun
Published: November 2015

The transition‐metal‐catalyzed amination of aryl halides has been the most powerful method for the formation of aryl amines over the past decades. Phenols are regarded as ideal alternatives to aryl halides as coupling partners in cross‐couplings. An efficient palladium‐catalyzed formal cross‐coupling of phenols with various amines and anilines has now been developed. A variety of substituted phenols were compatible with the standard reaction conditions. Secondary and tertiary aryl amines could thus be synthesized in moderate to excellent yields.
Quinone‐Catalyzed Selective Oxidation of Organic Molecules
Authors: Wendlandt Alison E. , Stahl Shannon S.
Published: November 2015

Quinones are common stoichiometric reagents in organic chemistry. Para‐quinones with high reduction potentials, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry, or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho‐quinone cofactors in copper amine oxidases and mediate the efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed by electrophilic transamination and/or addition‐elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and has important implications for the development of new quinone reagents and quinone‐catalyzed transformations.
External‐Photocatalyst‐Free Visible‐Light‐Mediated Synthesis of Indolizines
Authors: Sahoo Basudev , Hopkinson Matthew N. , Glorius Frank
Published: November 2015

A visible‐light‐mediated synthesis of valuable polycyclic indolizine heterocycles from easily accessed brominated pyridine and enol carbamate derivatives has been developed. This process, which operates at room temperature under irradiation from readily available light sources, does not require the addition of an external photocatalyst. Instead, an investigation into the reaction mechanism indicates that the indolizine products themselves may be in some way involved in mediating and accelerating their own formation. Preliminary studies also show that these simple heterocyclic compounds may be capable of facilitating other visible‐light‐mediated transformations.
Standardized catch and survival rates, and effect of a ban on shark retention, Palau pelagic longline fishery
Authors: Gilman Eric , Chaloupka Milani , Merrifield Matt , Malsol Nanette D. , Cook Chuck
Published: November 2015

Pelagic longline fisheries affect both market and vulnerable bycatch species and can have broad effects on community structure and processes.

Observer data from the Palau longline fishery were analysed to identify opportunities to mitigate vulnerable species bycatch, determine temporal trends in local abundance, and assess changes following a ban on shark retention and wire leaders. Catch and haulback condition data for bigeye and yellowfin tunas, blue and silky sharks and pelagic stingrays were fitted to standardized catch and survival rate models.

The fishery caught silky and blue sharks, olive ridley sea turtles and other species of conservation concern.

Changing from shallow sets to deep daytime sets might reduce shark and sea turtle catch rates but increase turtle haulback mortality rates, maintain economically viable tuna catch rates, but increase catch rates of pelagic stingrays, a lower conservation concern than main caught species of sharks and turtles.

Focusing fishing effort during the middle of the calendar year would maximize yellowfin tuna and minimize silky shark standardized catch rates, but maximize blue shark catch rates.

A large decline in shark fishing mortality rate very likely occurred following a ban on shark retention and wire leaders. This was due to large reductions in the nominal shark catch rate and shark retention, partially offset by decreases in the shark haulback survival rate and pre‐catch survival rate. Significantly higher blue shark and lower pelagic stingray nominal catch rates occurred on wire vs. monofilament leaders. Significantly higher blue shark and lower yellowfin tuna nominal catch rates occurred on sets using shallow ‘shark lines’. It is a research priority to compare the probability of shark pre‐catch survival after escaping from monofilament leaders with an ingested hook and trailing line to the survival probability when captured on wire leaders.

Copyright © 2015 John Wiley & Sons, Ltd.
Benzothiazole‐Pyimidine‐Based BF2 Complex for Selective Detection of Cysteine
Authors: Liu Qingsong , Zhang Changli , Wang Xiaoqing , Gong Shuwen , He Weijiang , Liu Zhipeng
Published: November 2015

Due to the similar structure and reactivity of cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), the simultaneous discrimination of Cys over Hcy and GSH by a single fluorescent sensor is still a great challenge. In this work, a benzothiazole‐pyimidine‐based boron difluoride complex (BPB) was developed as a new fluorescent sensor for Cys. The sensor exhibits a highly selective “turn‐on” response to cysteine over Hcy, GSH and other amino acids in aqueous solution at physiological pH. The observed pseudo‐first‐order rate constant for the reaction of BPB with Cys was calculated to be about 0.062 min−1. The detection limit of this sensor for Cys was determined to be 332 nm, and bioimaging of exogenous Cys by this sensor was successfully applied in living cells, thus indicating that this sensor holds great potential for biological applications.
Transcranial magnetic stimulation in autism spectrum disorder: Challenges, promise, and roadmap for future research
Authors: Oberman Lindsay M. , Enticott Peter G. , Casanova Manuel F. , Rotenberg Alexander , Pascual‐Leone Alvaro , McCracken James T. ,   the TMS in ASD Consensus Group
Published: November 2015

Autism Spectrum Disorder (ASD) is a behaviorally defined complex neurodevelopmental syndrome characterized by impairments in social communication, by the presence of restricted and repetitive behaviors, interests and activities, and by abnormalities in sensory reactivity. Transcranial magnetic stimulation (TMS) is a promising, emerging tool for the study and potential treatment of ASD. Recent studies suggest that TMS measures provide rapid and noninvasive pathophysiological ASD biomarkers. Furthermore, repetitive TMS (rTMS) may represent a novel treatment strategy for reducing some of the core and associated ASD symptoms. However, the available literature on the TMS use in ASD is preliminary, composed of studies with methodological limitations. Thus, off‐label clinical rTMS use for therapeutic interventions in ASD without an investigational device exemption and outside of an IRB approved research trial is premature pending further, adequately powered and controlled trials. Leaders in this field have gathered annually for a two‐day conference (prior to the 2014 and 2015 International Meeting for Autism Research, IMFAR) to share recent progress, promote collaboration across laboratories, and establish consensus on protocols. Here we review the literature in the use of TMS in ASD in the context of the unique challenges required for the study and exploration of treatment strategies in this population. We also suggest future directions for this field of investigations. While its true potential in ASD has yet to be delineated, TMS represents an innovative research tool and a novel, possibly transformative approach to the treatment of neurodevelopmental disorders. Autism Res 2016, 9: 184–203. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
A physiologically based pharmacokinetic model to predict the pharmacokinetics of highly protein‐bound drugs and the impact of errors in plasma protein binding
Authors: Ye Min , Nagar Swati , Korzekwa Ken
Published: November 2015

Predicting the pharmacokinetics of highly protein‐bound drugs is difficult. Also, since historical plasma protein binding data were often collected using unbuffered plasma, the resulting inaccurate binding data could contribute to incorrect predictions. This study uses a generic physiologically based pharmacokinetic (PBPK) model to predict human plasma concentration–time profiles for 22 highly protein‐bound drugs. Tissue distribution was estimated from in vitro drug lipophilicity data, plasma protein binding and the blood: plasma ratio. Clearance was predicted with a well‐stirred liver model. Underestimated hepatic clearance for acidic and neutral compounds was corrected by an empirical scaling factor. Predicted values (pharmacokinetic parameters, plasma concentration–time profile) were compared with observed data to evaluate the model accuracy. Of the 22 drugs, less than a 2‐fold error was obtained for the terminal elimination half‐life (t1/2, 100% of drugs), peak plasma concentration (Cmax, 100%), area under the plasma concentration–time curve (AUC0‐t, 95.4%), clearance (CLh, 95.4%), mean residence time (MRT, 95.4%) and steady state volume (Vss, 90.9%). The impact of fup errors on CLh and Vss prediction was evaluated. Errors in fup resulted in proportional errors in clearance prediction for low‐clearance compounds, and in Vss prediction for high‐volume neutral drugs. For high‐volume basic drugs, errors in fup did not propagate to errors in Vss prediction. This is due to the cancellation of errors in the calculations for tissue partitioning of basic drugs. Overall, plasma profiles were well simulated with the present PBPK model. Copyright © 2016 John Wiley & Sons, Ltd.
PUGNAc induces protein ubiquitination in C2C12 myotube cells
Authors: Park Ja‐Hye , Lee Jeong‐Eun , Moon Pyong‐Gon , Baek Moon‐Chang
Published: November 2015

O‐linked β‐N‐acetylglucosaminylation (O‐GlcNAcylation) regulates many cellular processes including the cell cycle, cell signaling, and protein trafficking. Dysregulation of O‐GlcNAcylation may be involved in the development of insulin resistance and type 2 diabetes. Therefore, it is necessary to identify cellular proteins that are induced by elevated O‐GlcNAcylation. Here, using adenosine 5′‐triphosphate affinity chromatography, we employed a proteomic approach in order to identify differentially expressed proteins in response to treatment with the O‐GlcNAcase inhibitor, O‐(2‐acetamido‐2‐deoxy‐d‐glucopyranosylidene)amino‐N‐phenylcarbamate (PUGNAc), in mouse C2C12 myotube cells. Among 205 selected genes, we identified 68 nucleotide‐binding proteins, 14 proteins that have adenosinetriphosphatase activity, and 10 proteins with ligase activity. Upregulation of proteins, including ubiquitin‐activating enzyme E1, proteasome subunit 20S, cullin‐associated NEDD8‐dissociated protein 1, ezrin, and downregulation of the protein nucleoside diphosphate kinase B, were confirmed by western blot analysis. In particular, we found that the protein ubiquitination level in C2C12 cells was increased by PUGNAc treatment. This is the first report of quantitative proteomic profiles of myotube cells after treatment with PUGNAc, and our results demonstrate the potential to enhance understanding of the relationship between insulin resistance, O‐GlcNAc, and PUGNAc in the future. Copyright © 2015 John Wiley & Sons, Ltd.
DFT Investigation on the Competition of the Water–Gas Shift Reaction Versus Methanation on Clean and Potassium‐Modified Nickel(1 1 1) Surfaces
Authors: Zhou Mingxia , Liu Bin
Published: November 2015

We used periodic DFT calculations to investigate the effect of alkali promoter on the selectivity of the water‐gas shift reaction (WGSR) explicitly on the Ni(1 1 1) surface. On clean Ni(1 1 1), the WGSR redox and carboxyl pathways are both kinetically competitive. The selectivity of the WGSR can be affected by methanation on Ni, in which the C−O bond cleavage pathway of CHO is the most competitive. A Ni(1 1 1) surface modified with K adatoms was used to further understand the promoter effects on the WGSR selectivity. A combined energetic and kinetic analysis from DFT calculations indicates that the K adatom stabilizes certain reactive intermediates (e.g., H2O, CO) thermodynamically but is energetically neutral or even repulsive toward other intermediates. As a result, WGSR pathways benefit from the presence of K adatoms compared to the competing methanation pathway. This study thus confirmed the promoting effects of alkali metals on the WGSR with DFT‐based mechanistic insights.
Influence of Alkalinity on the Efficiency and Catalyst Behavior of Photo‐Assisted Processes
Authors: Merayo Noemí , Hermosilla Daphne , Jefferson Bruce , Blanco Ángeles
Published: November 2015

The influence of carbonates on TiO2 photocatalysis and the photo‐Fenton process using Fe0 as catalyst is unraveled. The aggregation behavior of each catalyst was monitored under different reaction conditions in order to assess the effect of carbonates on their performance. Carbonates drastically reduced the efficiency of photocatalysis because of aggregation of the TiO2 catalyst, which led to the reduction of adsorbed pollutants. The addition of carbonates to the photo‐Fenton process did not produce this strong catalyst aggregation. Therefore, oxidation‐reduction reactions on the catalyst surface were not much reduced, and the efficiency of this process was not as strongly affected as that of TiO2 photocatalysis.
Design of Vacuum‐Cleaned Dust Filters with Modular Filter Units
Authors: Laminger Thomas , Wolfslehner Johannes , Höflinger Wilhelm
Published: November 2015

For vacuum‐cleaned dust filters with a small moving suck‐off nozzle as cleaning device no calculation methods exist to determine design parameters like the needed traverse velocity of the nozzle or the filter area. A method to calculate the total filter area or the number of parallel working filter modules with fixed filter area is presented. Well‐known equations for the design of a cleanable multichamber jet‐pulse filter were modified to take into account a continuous regeneration of a vacuum‐cleaned dust filter by a suck‐off nozzle. For vacuum cleaning of the filter it was considered that the regeneration period depends on the suck‐off nozzle traverse velocity and the unique cleaning pattern and length of the suck‐off nozzle traverse pathway. An example for the calculation of the necessary number of parallel working modules for the determination of the filter area of large filter apparatus with vacuum cleaning is described.
Synthesis of Migrastatin Analogues as Inhibitors of Tumour Cell Migration: Exploring Structural Change in and on the Macrocyclic Ring
Authors: Lo Re Daniele , Zhou Ying , Mucha Joanna , Jones Leigh F. , Leahy Lorraine , Santocanale Corrado , Krol Magdalena , Murphy Paul V.
Published: November 2015

Migrastatin and isomigrastatin analogues have been synthesised in order to contribute to structure–activity studies on tumour cell migration inhibitors. These include macrocycles varying in ring size, functionality and alkene stereochemistry, as well as glucuronides. The synthesis work included application of the Saegusa–Ito reaction for regio‐ and stereoselective unsaturated macroketone formation, diastereoselective Brown allylation to generate 9‐methylmigrastatin analogues and chelation‐induced anomerisation to vary glucuronide configuration. Compounds were tested in vitro against both breast and pancreatic cancer cell lines and inhibition of tumour cell migration was observed in both wound‐healing (scratch) and Boyden chamber assays. One unsaturated macroketone showed low affinity for a range of secondary drug targets, indicating it is at low risk of displaying adverse side effects.
Resistive Switching Nanodevices Based on Metal–Organic Frameworks
Authors: Wang Zhengbang , Nminibapiel David , Shrestha Pragya , Liu Jianxi , Guo Wei , Weidler Peter G. , Baumgart Helmut , Wöll Christof , Redel Engelbert
Published: November 2015

SURMOF (surface‐anchored metal–organic frameworks) thin films exhibit exciting chemical and physical properties, which can be modulated in a straightforward fashion to achieve specific benefits for numerous applications in future technologies. Here, we report a detailed characterization of resistive switching in crystalline SURMOF films of around ≈10, ≈20 and ≈50 nm thicknesses. These demonstrated switching characteristics combined with the ability to deposit monolithically oriented crystalline HKUST‐1 films with well‐defined thicknesses in the nm‐range on conductive substrates serving as bottom electrodes and to lithographically fabricate top‐electrodes opens up the possibility to employ these metal–organic hybrid materials as solid state devices for potential nonvolatile resistive random access memory (RRAM) memory applications. MOF bipolar switching RRAM devices based on SURMOFs with thicknesses of 10±5 nm, 20±5 nm and 50±5 nm show exceptionally promising performance. The huge flexibility of MOF materials with regards to device applications is demonstrated by loading guest molecules into the pores of these framework materials. In the case of ferrocene infiltration, we show that the already impressive performance of the SURMOF‐RRAM devices can be further improved. The results demonstrate the great potential of SURMOF thin films for the implementation of novel and scalable active materials for the next generation of digital processing and organic‐based microelectronic devices.
First Occurrence of Tetrazines in Aqueous Solution: Electrochemistry and Fluorescence
Authors: Fritea Luminiţa , Audebert Pierre , Galmiche Laurent , Gorgy Karine , Le Goff Alan , Villalonga Reynaldo , Săndulescu Robert , Cosnier Serge
Published: November 2015

The photophysical and electrochemical properties of tetrazines substituted by linear 2,3‐naphtalimide antennas and/or adamantane groups specifically dedicated to host–guest interactions with cyclodextrins are studied both in organic and aqueous media. In acetonitrile solvent, the reduction potential of tetrazine leading to the anion radical is shifted, depending on the electron‐withdrawing power of the substituent of the tetrazines. Due to the hydrophobic character of these compounds, their solubilization in aqueous solution is achieved successively in presence of either β‐cyclodextrins or gold nanoparticules modified by β‐cyclodextrins. We demonstrate that the formation of the inclusion compound tetrazine–cyclodextrin allows the solubilization of the tetrazines in aqueous solution. The supramolecular assemblies obtained in water retain tetrazine's emission properties, yielding a yellow fluorescence.
A Rational Synthetic Approach to 2,5‐Diphenyl‐β‐silyl Phospholes
Authors: Klintuch Dieter , Krekić Kristijan , Bruhn Clemens , Benkő Zoltán , Pietschnig Rudolf
Published: November 2015

Systematic access to β‐silyl‐substituted phospholes is reported. The synthesis proceeds through the addition of lithium phosphanide to a diyne and silylation of the intermediate β‐lithio phosphole. By following this approach, mono and disilylation has been accomplished and the reactivity of the β‐silyl phospholes towards oxidation with chalcogens and conversion into phospholides has been explored. The silyl units have a significant impact on the fluorescence properties of the phosphole system, leading to increased Stokes shifts and blueshifted absorption with redshifted emission. The key compounds have been characterized by multinuclear NMR spectroscopy, mass spectrometry, and, in part, by single‐crystal X‐ray diffraction analysis.
Substituent Effects on Physical Properties and Catalytic Activities toward Water Oxidation in Mononuclear Ruthenium Complexes
Authors: Sato Yoichi , Takizawa Shin‐ya , Murata Shigeru
Published: November 2015

A series of monomeric RuII complexes [Ru(bda)(pyR)2] (H2bda = 2,2′‐bipyridine‐6,6′‐dicarboxylic acid, pyR = pyridine with a substituent R at the 4‐position) were prepared, and the effects of substituent groups on the pyridine ligands of the complexes on catalytic activities toward water oxidation, as well as on photophysical and electrochemical properties, were examined. An increase in the electron‐withdrawing ability of the substituent results in a redshift of the absorption maximum assigned to the transition from the d orbital of Ru to the π* orbitals of the pyridine ligands, and an increase in the oxidation potential of the complex. These results are reasonably explained in terms of the variation of the energy level of molecular orbitals induced by the substituent group, which is supported by density functional theory calculations. The substituent effect on catalytic activity toward photochemical water oxidation using [Ru(bpy)3]2+ (bpy = 2,2′‐bipyridine) and S2O82– as a sensitizer and a sacrificial electron acceptor, respectively, is essentially analogous to that toward chemical water oxidation using CeIV as an oxidant in which the complexes with electron‐withdrawing groups exhibit better performance than those with electron‐donating groups. However, the Hammett analysis demonstrates that the catalytic activities of the complexes toward chemical and photochemical water oxidation show no straightforward dependence on the electronic nature of the substituent group, which suggests that a step accelerated by electron‐donating groups also contributes to the overall rate of water oxidation.
A first approach towards the development of geographical origin tracing models for North Moroccan olive oils based on triacylglycerols profiles
Authors: Bajoub Aadil , Medina‐Rodríguez Santiago , Hurtado‐Fernández Elena , Ajal El Amine , Ouazzani Noureddine , Fernández‐Gutiérrez Alberto , Carrasco‐Pancorbo Alegría
Published: November 2015

The triacylglycerols composition of monovarietal Picholine Marocaine olive oils, produced in seven of the most productive areas in northern Morocco, has been established for the first time, starting a register of typicality and geographical identity of Moroccan olive oils. Two hundred seventy‐nine olive samples were collected over two consecutive crop seasons (2011/2012 (n = 140) and 2012/2013 (n = 139)), the analysis of the triacylglycerol profiles of the obtained oils was performed using high performance liquid chromatography, the influence of the region of provenance was investigated, and chemometric data analysis (including principal components analysis, linear discriminant analysis, partial least squares–discriminant analysis, and soft independent modeling of class analogies) was used to differentiate the studied samples according to their geographical origin. Twenty‐one triacylglycerols were characterized and the variability observed among the studied samples could be related to the production area. The combination of triacylglycerols composition with chemometrics provided a powerful tool to verify the geographical origin of north Moroccan olive oils.

Practical applications: Moroccan legislations established Geographic Indication labels for adding value to typical products. However, the general procedure to control the geographical authenticity of these protected products remains based on the traceability of their production and there is a lack of appropriate and reliable tools for their geographical unambiguous authentication and control. In this work, geographical authentication models for classifying olive oil samples (based on triacylglycerols composition) have been developed and evaluated, achieving adequate classification and prediction rates for oils coming from the main north Moroccan olive growing areas. The results obtained herein, could represent a significant contribution to the control of the geographical authenticity of Moroccan olive oils.

The triacylglycerols composition of monovarietal Picholine Marocaine olive oils, from seven of the most productive areas in northern Morocco, is established in this study, analyzing 279 olive samples (over two consecutive crop seasons) by high performance liquid chromatography and Chemometrics.
Phytosterol oxidation products (POP) in foods with added phytosterols and estimation of their daily intake: A literature review
Authors: Lin Yuguang , Knol Diny , Trautwein Elke A.
Published: November 2015

To evaluate the content of phytosterol oxidation products (POP) of foods with added phytosterols, in total 14 studies measuring POP contents of foods with added phytosterols were systematically reviewed. In non‐heated or stored foods, POP contents were low, ranging from (medians) 0.03–3.6 mg/100 g with corresponding oxidation rates of phytosterols (ORP) of 0.03–0.06%. In fat‐based foods with 8% of added free plant sterols (FPS), plant sterol esters (PSE) or plant stanol esters (PAE) pan‐fried at 160–200°C for 5–10 min, median POP contents were 72.0, 38.1, and 4.9 mg/100 g, respectively, with a median ORP of 0.90, 0.48, and 0.06%. Hence resistance to thermal oxidation was in the order of PAE > PSE > FPS. POP formation was highest in enriched butter followed by margarine and rapeseed oil. In margarines with 7.5–10.5% added PSE oven‐heated at 140–200°C for 5–30 min, median POP content was 0.3 mg/100 g. Further heating under same temperature conditions but for 60–120 min markedly increased POP formation to 384.3 mg/100 g. Estimated daily upper POP intake was 47.7 mg/d (equivalent to 0.69 mg/kg BW/d) for foods with added PSE and 78.3 mg/d (equivalent to 1.12 mg/kg BW/d) for foods with added FPS as calculated by multiplying the advised upper daily phytosterol intake of 3 g/d with the 90% quantile values of ORP. In conclusion, heating temperature and time, chemical form of phytosterols added and the food matrix are determinants of POP formation in foods with added phytosterols, leading to an increase in POP contents.

Practical applications: Phytosterol oxidation products (POP) are formed in foods containing phytosterols especially when exposed to heat treatment. This review summarising POP contents in foods with added phytosterols in their free and esterified forms reveals that heating temperature and time, the chemical form of phytosterols added and the food matrix itself are determinants of POP formation with heating temperature and time having the biggest impact. The estimated upper daily intakes of POP is 78.3 mg/d for fat‐based products with added free plant sterols and 47.7 mg/d for fat‐based products with added plant sterol esters.

Phytosterols in foods are susceptible to oxidation to form phytosterol oxidation products (POP). This review summarizes literature data regarding POP contents of foods with added phytosterols that were exposed to storage and heat treatments.
Ion‐selective Electrodes with 3D Nanostructured Conducting Polymer Solid Contact
Authors: Szűcs Júlia , Lindfors Tom , Bobacka Johan , Gyurcsányi Róbert E.
Published: November 2015

Until now both ion‐to‐electron transducers as well as large surface area nanostructured conducting materials were successfully used as solid contacts for polymer‐based ion‐selective electrodes. We were interested to explore the combination of these two approaches by fabricating ordered electrically conducting polymer (ECP) nanostructures using 3D nanosphere lithography and electrosynthesis to provide a high surface area and capacitive interface for solid contact ion‐selective electrodes (SC‐ISEs). For these studies we used poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT(PSS)) films with 750 nm diameter interconnected pores as the intermediate layer between a glassy carbon electrode and a Ag+ ‐selective polymeric membrane. We also investigated the feasibility of loading the voids created in the polymer film with a lipophilic redox mediator (1,1’‐dimethylferrocene) to provide the respective ISEs with well‐defined/controllable E0 values. These expectations were fulfilled as the standard deviation of E0 values were reduced with almost an order of magnitude for 3D nanostructured SC‐ISEs filled with the redox mediator as compared to their redox mediator‐free analogs. The detrimental effect of the redox mediator extraction into the plasticized PVC‐based ion‐selective membrane (ISM) was efficiently suppressed by replacing the PVC‐based ISMs with a low diffusivity silicone rubber matrix.
Capillary zone electrophoresis tandem mass spectrometry detects low concentration host cell impurities in monoclonal antibodies
Authors: Zhu Guijie , Sun Liangliang , Heidbrink‐Thompson Jennifer , Kuntumalla Srilatha , Lin Hung‐yu , Larkin Christopher J. , McGivney James B. , Dovichi Norman J.
Published: November 2015

We have evaluated CZE‐ESI‐MS/MS for detection of trace amounts of host cell protein impurities in recombinant therapeutics. Compared to previously published procedures, we have optimized the buffer pH used in the formation of a pH junction to increase injection volume. We also prepared a 5‐point calibration curve by spiking 12 standard proteins into a solution of a human mAb. A custom CZE‐MS/MS system was used to analyze the tryptic digest of this mixture without depletion of the antibody. CZE generated a ∼70‐min separation window (∼90‐min total analysis duration) and ∼300‐peak capacity. We also analyzed the sample using ultra‐performance LC‐MS/MS. CZE‐MS/MS generated approximately five times higher base peak intensity and more peptide identifications for low‐level spiked proteins. Both methods detected all proteins spiked at ∼100 ppm level with respect to the antibody.
Dielectrophoretic behavior of PEGylated RNase A inside a microchannel with diamond‐shaped insulating posts
Authors: Mata‐Gómez Marco A. , Gallo‐Villanueva Roberto C. , González‐Valdez José , Martínez‐Chapa Sergio O. , Rito‐Palomares Marco
Published: November 2015

Ribonuclease A (RNase A) has proven potential as a therapeutic agent, especially in its PEGylated form. Grafting of PEG molecules to this protein yields mono‐PEGylated (mono‐PEG) and di‐PEGylated (di‐PEG) RNase A conjugates, and the unreacted protein. Mono‐PEG RNase A is of great interest. The use of electrokinetic forces in microdevices represents a novel alternative to chromatographic methods to separate this specie. This work describes the dielectrophoretic behavior of the main protein products of the RNase A PEGylation inside a microchannel with insulators under direct current electric fields. This approach represents the first step in route to design micro‐bioprocesses to separate PEGylated RNase A from unreacted native protein. The three proteins exhibited different dielectrophoretic behaviors. All of them experienced a marked streaming pattern at 3000 V consistent with positive dielectrophoresis. Native protein was not captured at any of the conditions tested, while mono‐PEG RNase A and di‐PEG RNase A were captured presumably due to positive dielectrophoresis at 4000 and 2500 V, respectively. Concentration of mono‐PEG RNase A with a maximal enrichment efficiency of ≈9.6 times the feed concentration was achieved in few seconds. These findings open the possibility of designing novel devices for rapid separation, concentration, and recovery of PEGylated RNase A in a one‐step operation.
Application of capacitively coupled contactless conductivity as an external detector for zone electrophoresis in poly(dimethylsiloxane) chips
Authors: Koczka Péter I. , Bodoki Ede , Gáspár Attila
Published: November 2015

In this work, lab‐made PDMS microfluidic chips were matched to a capacitively coupled contactless conductivity detector (C4D) having external in‐plane electrodes (eDAQ, Australia). The advantages of this type of C4D are the choice to reversibly place or remove the microchip onto/from the detector and to freely variate the position of the detection (separation length) on the microchip. The thickness of the bottom layer of the PDMS chip was optimized to achieve sensitive detection during the electrophoretic separation. PDMS chips with 100 μm bottom layer used with the C4D platform were tested by CZE of a mixture of seven anions and different types of real samples. Using split‐flow pressure sample injection and effective length of 6.5 cm, the numbers of theoretical plates were in the range of 4000–6000 (63 000–93 000/m) and the LODs amounted to 3.66–14.7 μmol/L (0.13–2.26 μg/mL) for the studied anions.
Impact of the Solar Eclipse from 20th March 2015 on the German Electrical Supply—Simulation and Analysis
Authors: Killinger Sven , Kreifels Niklas , Burger Bruno , Müller Björn , Stiff George , Wittwer Christof
Published: November 2015

Though solar eclipses are traditionally thought of as astronomic events with no real bearing on society, in fact they do manage to influence processes of practical importance by affecting the energy conversion of photovoltaic systems. The main goal of this study is to explore what could have happened to the German power supply and its reliability during the partial solar eclipse on the 20th March 2015. Comparing results of a simulation with an ex post analysis shows that: 1.) the possible effects could be predicted very accurately, 2.) the electrical supply was not threatened during the solar eclipse and would not have been subject to problems, even in a worst‐case scenario, 3.) the actual solar power gradients during the eclipse exceeded the maximum solar power gradients during normal operation observed in the past by at least a factor of two, and 4.) grid frequency analysis for the day of the solar eclipse shows that the maximum and minimum frequency values are well within manageable limits.