bluuebunny/crossref_metadata_2025 huggingface dataset:
Silica‐Supported Molybdenum Alkylidyne N‐Heterocyclic Carbene Catalysts: Relevance of Site Isolation to Catalytic Performance
Authors: Hauser Philipp M. , Hunger Michael , Buchmeiser Michael R.
Published: January 2018

The immobilization of the molybdenum alkylidyne complex [(p‐OMe‐C6H4C≡)Mo(OCMe(CF3)2)3⋅DME] (DME=1,2‐dimethoxyethane) on silica using a silica‐supported N‐heterocyclic carbene (NHC), that is, 1,3‐di(isopropyl)imidazol‐2‐ylidene, is reported. Two different types of silica, that is, silica 60 and partially dehydroxylated silica 60 obtained via heating to 650 °C (SiO2‐650) were used. In both cases, excess silanol groups were end‐capped with trimethylsilyl chloride. Immobilization of both the NHC precursor and the metal alkylidyne was followed by 19F magic angle spinning (MAS) and 13C cross‐polarization magic angle spinning (CPMAS) NMR and inductively‐coupled optical emission spectroscopy (ICP–OES). The metal alkylidyne supported on both types of silica was active in alkyne metathesis and showed activity for a series of functional 2‐alkynes. Most importantly, the metal alkylidyne supported on SiO2‐650 displayed a substantially higher alkyne metathesis activity than the homogeneous analog or the one supported on regular silica, which is attributed to a site isolation effect and, as a result, reduced bimolecular decomposition.
Coupling of Methane to Ethane, Ethylene, and Aromatics over Nickel on Ceria–Zirconia at Low Temperatures
Authors: Okolie Chukwuemeka , Lyu Yimeng , Kovarik Libor , Stavitski Eli , Sievers Carsten
Published: January 2018

Methane is converted over nickel on ceria zirconia (Ni/CZ) into ethane, aromatics, and hydrogen at steady state up to the thermodynamic limit at temperatures of 350 to 500 °C. At 450 and 500 °C, traces of ethylene are also produced. Ni/NiO particles activate methane and couple the resulting surface species to hydrocarbon products. Large Ni particles are responsible for the formation of carbonaceous deposits. Furthermore, aromatics are formed on these sites. Smaller Ni/NiO particles are responsible for the formation of ethane and ethylene and appear to provide sustained activity. It is suggested that these Ni sites are too small to assemble aromatic deposits, and hence they remain active throughout the reaction.
POM & MOF‐based Electrocatalysts for Energy‐related Reactions
Authors: Freire Cristina , Fernandes Diana M. , Nunes Marta , Abdelkader Victor K.
Published: January 2018

Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies and the development of highly efficient and cost‐effective materials is one of the current major challenges. This results from the current global energy crisis, reflected in the depletion of fossil fuels and growth of the environmental pollution, which has stimulated the development of novel renewable energy storage and conversion technologies. Currently, several electrocatalysts have been proposed and among them are the polyoxometalates (POMs), the metal‐organic frameworks (MOFs) and their based composites.
Mesoporous Carbon Nitride Supported Pd and Pd‐Ni Nanoparticles as Highly Efficient Catalyst for Catalytic Hydrolysis of NH3BH3
Authors: Wang Wei , Lu Zhang‐Hui , Luo Yan , Zou Aihua , Yao Qilu , Chen Xiangshu
Published: January 2018

Highly dispersed Pd and PdNi nanoparticles (NPs) have been successfully immobilized on mesoporous carbon nitride (MCN) through a facile co‐reduction approach. The resulting Pd/MCN catalyst shows excellent catalytic performance for hydrogen release from an ammonia borane (AB) aqueous solution with a turnover frequency (TOF) value of 125 mol H2 mol metal−1 min−1 at room temperature, which is among the highest values for monometallic Pd‐based catalysts reported to date. The catalytic performance of the Pd NPs can be further enhanced by alloying with Ni or Co atoms. Among all the synthesized PdxNi100−x/MCN nanocomposites (NCs) with different Ni/Pd ratios, the Pd74Ni26/MCN catalyst exhibits the best catalytic performance with a TOF of 246.8 mol H2 mol metal−1 min−1. The high activity of Pd/MCN and Pd74Ni26/MCN are largely dependent on the features of the ultrafine metallic NPs immobilized by MCN, the interfacial interaction between the MCN matrix and metallic NPs, and the accessible open porous structure for mass transfer.
Heterogenized C‐Scorpionate Iron(II) Complex on Nanostructured Carbon Materials as Recyclable Catalysts for Microwave‐Assisted Oxidation Reactions
Authors: Ribeiro Ana P. C. , Martins Luísa M. D. R. S. , Carabineiro Sónia A. C. , Buijnsters Josephus G. , Figueiredo José L. , Pombeiro Armando J. L.
Published: January 2018

The C‐scorpionate iron(II) complex [FeCl2(Tpm)] [Tpm=κ3‐HC(C3H3N2)3] (1) was immobilized on five different nanostructured carbon materials (nanodiamonds, graphene nanoplatelets, graphene oxide, reduced graphene oxide, and nanohorns) to produce active, selective, and recyclable catalysts for alkane and alcohol oxidations. The heterogenized systems (including the first ever reported complexes supported on carbon nanohorns) exhibited good activity concomitant with rather high selectivity to the formation of ketone alcohol (KA) oil (cyclohexanol and cyclohexanone mixture, yields up to 29 %) from microwave‐assisted oxidation of cyclohexane, and allowed their easy recovery and reuse, at least for five consecutive cycles maintaining 90.3 % of the initial activity. Moreover, the functionalized nanodiamond supports (used for the first time as supports for iron complexes) were also able to effectively (yields up to 97 %) catalyze the microwave‐induced oxidation of 1‐ and 2‐phenylethanol to acetophenone and 2‐phenylacetaldehyde, respectively, and could be reused for seven consecutive cycles without losing catalytic activity.
Gold Nanoparticle/Multi‐walled Carbon Nanotube Hybrid as a Stable Catalyst for the Oxygen Reduction Reaction
Authors: Xiang Li , Luo Zhihong , Hu Chengliang , Bian Zhicheng , Lu Jianwei , Cao Yuan‐Cheng , Luo Kun
Published: January 2018

A gold nanoparticle/multi‐walled carbon nanotube (Au/MWNTs) hybrid was prepared following the scalable one‐pot reduction of chloroauric acid with tetrakis(hydroxymethyl)chloride in the presence of MWNTs. TEM, XRD, FTIR, XPS, and thermogravimetric analyses indicate that gold nanoparticles (Au NPs, d≈2.9 nm) protected with the tris(hydroxymethyl)oxide (THPO) ligand were deposited on the MWNTs, where no Oswald ripening was observed for the Au NPs after 3000 voltammetric cycling. The Au/MWNTs hybrid with THPO ligand exhibits an impressive catalytic activity toward the oxygen reduction reaction (ORR), following a direct four‐electron mechanism in alkaline solution, and it also manifests excellent long‐term cycling durability and tolerance to the possible crossover methanol. This demonstrates prospective for the hybrid to serve as a stable ORR catalyst for direct methanol fuel cells.
Rates of Chemical Reactions Embedded in a Metabolic Network by Dissolution Dynamic Nuclear Polarisation NMR
Authors: Sadet Aude , Weber Emmanuelle M. M. , Jhajharia Aditya , Kurzbach Dennis , Bodenhausen Geoffrey , Miclet Emeric , Abergel Daniel
Published: January 2018

The isomerisation of 6‐phosphogluconolactones and their hydrolyses into 6‐phosphogluconic acid form a non enzymatic side cycle of the pentose‐phosphate pathway (PPP) in cells. Dissolution dynamic nuclear polarisation can be used for determining the kinetic rates of the involved transformations in real time. It is found that the hydrolysis of both lactones is significantly slower than the isomerisation process, thereby shedding new light onto this subtle chemical process.
Sigma‐ versus Pi‐Dimerization Modes of Triangulene
Authors: Mou Zhongyu , Kertesz Miklos
Published: January 2018

We show that the diradicaloid triangulene, a graphene nano‐flake molecule, can aggregate in a variety of dimerization modes. We found by density functional theory modeling a number of triangulene dimers including six doubly bonded σ‐dimers in addition to the previously reported six pancake bonded π‐dimer isomers. The σ‐dimers display a wide range of stabilities: the interaction energy of the most stable σ‐dimer is −25.17 kcal mol−1. Besides the doubly bonded σ‐dimers with closed shell ground states, we also found an open‐shell singly σ‐bonded diradicaloid dimer. We found an interesting isomerization route between a doubly bonded σ‐dimer, a singly bonded σ‐dimer with a low‐lying triplet state and two π‐bonded dimers with low‐lying quintet states. Derivatives of triangulene, trioxo‐triangulenes (TOTs) have been previously characterized experimentally. Here, we show the reasons why so far only the π‐dimer but not the σ‐dimer was experimentally observed for all TOTs.
Secondary Metabolites from Escovopsis weberi and Their Role in Attacking the Garden Fungus of Leaf‐Cutting Ants
Authors: Dhodary Basanta , Schilg Michele , Wirth Rainer , Spiteller Dieter
Published: January 2018

The specialized, fungal pathogen Escovopsis weberi threatens the mutualistic symbiosis between leaf‐cutting ants and their garden fungus (Leucoagaricus gongylophorus). Because E. weberi can overwhelm L. gongylophorus without direct contact, it was suspected to secrete toxins. Using NMR and mass spectrometry, we identified several secondary metabolites produced by E. weberi. E. weberi produces five shearinine‐type indole triterpenoids including two novel derivatives, shearinine L and shearinine M, as well as the polyketides, emodin and cycloarthropsone. Cycloarthropsone and emodin strongly inhibited the growth of the garden fungus L. gongylophorous at 0.8 and 0.7 μmol, respectively. Emodin was also active against Streptomyces microbial symbionts (0.3 μmol) of leaf‐cutting ants. Shearinine L instead did not affect the growth of L. gongylophorus in agar diffusion assays. However, in dual choice behavioral assays Acromyrmex octospinosus ants clearly avoided substrate treated with shearinine L for the garden fungus after a 2 d learning period, indicating that the ants quickly learn to avoid shearinine L.
Comparison of Commercial and Reacetylated Chitosan with Regard to Their Flocculation Quality
Authors: Haufe Sandra , Bohrisch Jörg , Bratskaya Svetlana Y. , Schwarz Simona
Published: January 2018

Chitosan steht seit einigen Jahren im Fokus biologisch orientierter Forschung sowohl in der Modifizierung als auch in der Anwendung. Es hat eine Vielzahl von Vorteilen gegenüber synthetischen Produkten, es ist z. B. nicht toxisch. In dieser Arbeit wurden die Chitosane reacetyliert und charakterisiert. Reacetylierte Chitosane lösen sich ohne Zusätze in Wasser und zeigen gute Flockungseigenschaften. Die Flockung von reacetylierten und kommerziellen Chitosanen wurde verglichen. Molmasse, pH‐Wert und der Salzgehalt im System nehmen großen Einfluss auf die Lage und Breite der Flockungsfenster.
Comprendre les pratiques des experts pour être en mesure de contrôler leur activité – l’exemple du trading
Authors: Jardat Rémi , Méric Jérôme , Sfez Flora
Published: January 2018

Experts are important actors of organizational control. Nevertheless, experience suggests that they must be controlled as well. This is particularly the case for traders in financial institutions. We first identify the limits of traditional control patterns when the managing the activities of experts is at stake. Hyperspecialization, which is the ability to act within different logics and multiple time horizons, suggests that multidimensional representations of these activities be adopted and made explicit, which has the potential to prevent such activities from turning problematic. By examining bank risks and conducting additional interviews with actors from bank trading services, we recommend that multiple components of complexity be preserved when dealing with expert‐related operational risks, instead of reducing this complexity to a single concept. Such an approach implies to turn back expertise against itself. Copyright © 2017 ASAC. Published by John Wiley & Sons, Ltd.
Antithrombotic therapy in peripheral artery disease: A review of the EUCLID trial results and current ongoing trials
Authors: Ward Rachael , Long Chandler , Patel Manesh R. , Jones William S.
Published: January 2018

In addition to risk‐factor modification, antithrombotic therapy is the hallmark of management to reduce cardiovascular ischemic events in patients with peripheral artery disease (PAD). Currently, the guidelines recommend long‐term antiplatelet therapy with aspirin or clopidogrel in this patient population to reduce myocardial infarction, stroke, and vascular death. Past outcomes studies have shown some benefit of ticagrelor, another antiplatelet agent, as compared with clopidogrel in patients with coronary disease and concomitant PAD. However, most recently, the Examining Use of Ticagrelor in Peripheral Artery Disease (EUCLID) trial has shown no additional benefit of ticagrelor over clopidogrel. In this trial, a minority of patients had concomitant coronary artery disease, making it unique to previous studies. The EUCLID trial's evidence of neutrality between clopidogrel and ticagrelor sheds light into the complexity of studying the PAD population and the continued need to meticulously design trials to investigate the optimal therapies. The topics that will be discussed in this review include the role of antiplatelet therapy in the management of patients with PAD, a review of the EUCLID trial results and the important factors to be considered in interpreting the surprising results, and promising recent ongoing clinical trials assessing therapies in the treatment of patients with PAD.
Association between clinical factors and self‐underestimation of cardiovascular risk in subjects submitted to a routine health evaluation
Authors: Helou Thais N. , Santos Raul D. , Laurinavicius Antonio G. , Bittencourt Marcio Sommer , Pesaro Antonio E.P. , Franco Fabio G.M. , Conceição Raquel D.O. , Carvalho José A.M. , Silva Fernando M.F. , Wajngarten Mauricio , Katz Marcelo
Published: January 2018

Background

The perception of cardiovascular (CV) risk is essential for adoption of healthy behaviors. However, subjects underestimate their own risk.

Hypothesis

Clinical characteristics might be associated with self‐underestimation of CV risk.

Methods

This is a retrospective, cross‐sectional study of individuals submitted to routine health evaluation between 2006 and 2012, with calculated lifetime risk score (LRS) indicating intermediate or high risk for CV disease (CVD). Self‐perception of risk was compared with LRS. Logistic regression analysis was performed to test the association between clinical characteristics and subjective underestimation of CV risk.

Results

Data from 5863 subjects (age 49.4 ± 7.1 years; 19.9% female) were collected for analysis. The LRS indicated an intermediate risk for CVD in 45.7% and a high risk in 54.3% of individuals. The self‐perception of CV risk was underestimated compared with the LRS in 4918 (83.9%) subjects. In the adjusted logistic regression model, age (odds ratio [OR]: 1.28, 95% confidence interval [CI]: 1.10‐1.47 per 10 years, P = 0.001), smoking (OR: 1.99, 95% CI: 1.40‐2.83, P < 0.001), dyslipidemia (OR: 1.21, 95% CI: 1.01‐1.46, P = 0.045), physical activity (OR: 1.66, 95% CI: 1.36‐2.02, P < 0.001), and use of antihypertensive (OR: 1.49, 95% CI: 1.15‐1.92, P = 0.002) and lipid‐lowering medications (OR: 2.13, 95% CI: 1.56‐2.91, P < 0.001) were associated with higher chance of risk underestimation, whereas higher body mass index (OR: 0.92, 95% CI: 0.90‐0.94, P < 0.001), depressive symptoms (OR: 0.46, 95% CI: 0.37‐0.57, P < 0.001), and stress (OR: 0.41, 95% CI: 0.33‐0.50, P < 0.001) decreased the chance.

Conclusions

Among individuals submitted to routine medical evaluation, aging, smoking, dyslipidemia, physical activity, and use of antihypertensive and lipid‐lowering medications were associated with higher chance of CV risk underestimation. Subjects with these characteristics may benefit from a more careful risk orientation.
Variation in practice patterns and outcomes across United Network for Organ Sharing allocation regions
Authors: Srinivasan Dushyanth , Vaccaro Benjamin , Rao Pooja , Ghosh Rohit , Warier Prashant , Ahmad Tariq , Desai Nihar
Published: January 2018

Background

The number of heart transplants performed is limited by organ availability and is managed by the United Network for Organ Sharing (UNOS). Efforts are underway to make organ disbursement more equitable as demand increases.

Hypothesis

Significant variation exists in contemporary patterns of care, wait times, and outcomes among patients undergoing heart transplantation across UNOS regions.

Methods

We identified adult patients undergoing first, single‐organ heart transplantation between January 2006 and December 2014 in the UNOS dataset and compared sociodemographic and clinical profiles, wait times, use of mechanical circulatory support (MCS), status at time of transplantation, and 1‐year survival across UNOS regions.

Results

We analyzed 17 096 patients undergoing heart transplantation. There were no differences in age, sex, renal function, and peripheral vascular resistance across regions; however, there was 3‐fold variation in median wait time (range, 48–166 days) across UNOS regions. Proportion of patients undergoing transplantation with status 1A ranged from 36% to 79% across regions (P < 0.01), and percentage of patients hospitalized at time of transplantation varied from 41% to 98%. There was also marked variation in MCS and inotrope utilization (28%–57% and 25%–58%, respectively; P < 0.001). Durable ventricular assist device implantation varied from 20% to 44% (P < 0.001), and intra‐aortic balloon pump utilization ranged from 4% to 18%.

Conclusions

Marked differences exist in patterns of care across UNOS regions that generally trend with differences in waitlist time. Novel policy initiatives are required to address disparities in access to allografts and ensure equitable and efficient allocation of organs.
Comprehensive analysis of area‐specific and time‐dependent changes in gene expression in the motor cortex of macaque monkeys during recovery from spinal cord injury
Authors: Higo Noriyuki , Sato Akira , Yamamoto Tatsuya , Oishi Takao , Nishimura Yukio , Murata Yumi , Onoe Hirotaka , Isa Tadashi , Kojima Toshio
Published: January 2018

The present study aimed to assess the molecular bases of cortical compensatory mechanisms following spinal cord injury in primates. To accomplish this, comprehensive changes in gene expression were investigated in the bilateral primary motor cortex (M1), dorsal premotor cortex (PMd), and ventral premotor cortex (PMv) after a unilateral lesion of the lateral corticospinal tract (l‐CST). At 2 weeks after the lesion, a large number of genes exhibited altered expression levels in the contralesional M1, which is directly linked to the lesioned l‐CST. Gene ontology and network analyses indicated that these changes in gene expression are involved in the atrophy and plasticity changes observed in neurons. Orchestrated gene expression changes were present when behavioral recovery was attained 3 months after the lesion, particularly among the bilateral premotor areas, and a large number of these genes are involved in plasticity. Moreover, several genes abundantly expressed in M1 of intact monkeys were upregulated in both the PMd and PMv after the l‐CST lesion. These area‐specific and time‐dependent changes in gene expression may underlie the molecular mechanisms of functional recovery following a lesion of the l‐CST.
An efficient iterative graph data processing framework based on bulk synchronous parallel model
Authors: Liu Chao , Zeng Deze , Yao Hong , Yan Xuesong , Yu Linchen , Fu Zhangjie
Published: January 2018

Graph data processing has been widely applied in a variety of domains such as industry, science, social network, and so on. It therefore has stimulated many efforts devoted to this area. To embrace the fast development trend of big graph data, graph data processing based on Pregel‐like systems has been regarded as one of the most promising ways and has widely attracted the attention of researchers. However, it still remains in its early stage and there still exist many challenges. In Pregel, the superstep synchronization is time consuming as the graph data iteration operation requires multiple synchronizations. Furthermore, the graph data partition strategy adopted by Pregel fails to support load balancing, therefore causing the increase of network I/O overhead as the scale of graph data grows. To address these issues, this paper presents an efficient computational framework for graph data processing based on the bulk synchronous parallel model. The global synchronization control mechanism is improved by determining the start time of the next round of superstep through counting the number of global message files. Furthermore, an improved graph data partition mechanism based on a balanced hash method is proposed to reduce the communication overhead between different partitions of sub‐graph computational tasks. We also re‐design the PageRank algorithm to verify the effectiveness of the proposed framework. Experimental results on different real‐world datasets verify the efficiency of our proposed framework as it outperforms Giraph (an open source Pregel‐like system) by 58%−69%, and achieves 10×−17× performance improvement over Hadoop.
On the Action of General Anesthetics on Cellular Function: Barbiturate Alters the Exocytosis of Catecholamines in a Model Cell System
Authors: Ye Daixin , Ewing Andrew
Published: January 2018

General anesthetics are essential in many areas, however, the cellular mechanisms of anesthetic‐induced amnesia and unconsciousness are incompletely understood. Exocytosis is the main mechanism of signal transduction and neuronal communication through the release of chemical transmitters from vesicles to the extracellular environment. Here, we use disk electrodes placed on top of PC12 cells to show that treatment with barbiturate induces fewer molecules released during exocytosis and changes the event dynamics perhaps by inducing a less stable fusion pore that is prone to close faster during partial exocytosis. Larger events are essentially abolished. However, use of intracellular vesicle impact electrochemical cytometry using a nano‐tip electrode inserted into a cell shows that the distribution of vesicle transmitter content does not change after barbiturate treatment. This indicates that barbiturate selectively alters the pore size of larger events or perhaps differentially between types of vesicles. Alteration of exocytosis in this manner could be linked to the effects of general anesthetics on memory loss.
Atmospheric Dry Hydrogen Plasma Reduction of Inkjet‐Printed Flexible Graphene Oxide Electrodes
Authors: Homola Tomáš , Pospíšil Jan , Krumpolec Richard , Souček Pavel , Dzik Petr , Weiter Martin , Černák Mirko
Published: January 2018

This study concerns a low‐temperature method for dry hydrogen plasma reduction of inkjet‐printed flexible graphene oxide (GO) electrodes, an approach compatible with processes envisaged for the manufacture of flexible electronics. The processing of GO to reduced graphene oxide (rGO) was performed in 1–64 s, and sp2/sp2+sp3 carbon concentration increased from approximately 20 % to 90 %. Since the plasma reduction was associated with an etching effect, the optimal reduction time occurred between 8 and 16 s. The surface showed good mechanical stability when deposited on polyethylene terephthalate flexible foils and significantly lower sheet resistance after plasma reduction. This method for dry plasma reduction could be important for large‐area hydrogenation and reduction of GO flexible surfaces, with present and potential applications in a wide variety of emerging technologies.
Improvement of diagnostic performance of pathologists by reducing the number of pathologists responsible for thyroid fine needle aspiration cytology: An institutional experience
Authors: Seok Jae Yeon , An Jungsuk , Cho Hyun Yee
Published: January 2018

Background

Various efforts have been made to improve the diagnostic accuracy of thyroid fine needle aspiration (FNA) cytology. We changed the diagnostic system by reducing the number of pathologists responsible for the thyroid FNA cytology in the routine work, and analyzed the effect on the pathologist's diagnostic performance.

Methods

Since March 1, 2015, 3 pathologists have been responsible for diagnostic thyroid FNA, previously undertaken by 9 equally. We compared the prechange period (three months, 319 nodules) and the postchange period (12 months, 1194 nodules).

Results

The turnaround time was shortened from 1.4 ± 0.7 days to 0.9 ± 0.5 days (P < .001). The utilization rate of the Bethesda system for Reporting Thyroid Cytopathology (TBSRTC) increased from 92.5% to 99.8%. Diagnostic rates of categories that are confirmative [II (benign) and VI (malignant)] increased, while the inadequate (I) or indeterminate (III) categories decreased. With category IV (follicular neoplasm), a challenging category in our country, an elevated malignancy rate was found at follow‐up. Overall, the diagnostic performance was improved in terms of sensitivity (from 98.5% to 99.2%) and specificity (from 94.4% to 98.4%), with reduced false‐negative rates (from 1.5% to 0.8%) and false‐positive rates (from 2.9% to 1.1%). The area under the receiver operating characteristic curve increased from 0.861 to 0.958.

Conclusion

Reducing the number of pathologists responsible for diagnostic thyroid FNA cytology resulted in a higher utilization rate of TBSRTC, and more rapid and accurate diagnosis.
Explicit incipient motion of cohesive and non‐cohesive sediments using simple hydraulics
Authors: Woldegiorgis Befekadu Taddesse , Van Griensven Ann , Bauwens Willy
Published: January 2018

Existing dimensionless expressions that represent the incipient motion of sediments are based on studies of non‐cohesive sediments. Because of the complex behaviour of cohesive sediments, many simulators also assume non‐cohesiveness when simulating the erosion of cohesive sediments. However, studies show that the critical shear force needed for entrainment is much higher for consolidated cohesive sediments than for similarly sized non‐cohesive sediments. Treating cohesive sediments as non‐cohesive sediments thus will introduce a significant error with regard to quantifying the eroded sediment mass. On the other hand, the existing expressions of non‐cohesive sediments require relatively detailed hydraulic calculations to estimate the shear velocity or the bed shear stress and thus cannot be used with simplified simulators. Therefore, it is essential to have a versatile simple explicit method that estimates the incipient motion condition of both the consolidated cohesive and non‐cohesive sediments whenever needed. In this paper, explicit analytical expressions are proposed that simulate the incipient motion of consolidated cohesive and non‐cohesive sediments, based on the critical erosion curves of the Hjulström–Sundborg–Miedema diagram. The new method reproduces the latter diagram with high precision. It also mimics the critical incipient condition of non‐cohesive sediments determined by a well‐known analytical method for other experimental data sets and for the East Fork River without the need of an iterative solution. The new approach provides essential information for estimating the entrainment condition of pebbles or finer sediments. Besides, the use of the mean flow velocity and the flow depth as predictors of incipient condition allows for its easy and efficient implementation in conceptual simulators that do not perform detailed hydraulic calculations and for use by modelers that are not familiar with the hydrotechnical literature. It also reduces the computation time required for simulation.
Auditory structural connectivity in preterm and healthy term infants during the first postnatal year
Authors: Zubiaurre‐Elorza Leire , Linke Annika C. , Herzmann Charlotte , Wild Conor J. , Duffy Hester , Lee David S.C. , Han Victor K. , Cusack Rhodri
Published: January 2018

Assessing language development in the first postnatal year is difficult, as receptive and expressive skills are rudimentary. Although outward manifestations of change are limited, the auditory language system is thought to undergo critical development at this age, as the foundations are laid for the rapid onset of spoken language in the second and third years. We recruited 11 infants, 7 healthy controls (gestational age = 40.69 ± 0.56; range from 40 to 41.43) and preterm babies (gestational age = 28.04 ± 0.95; range from 27.43 to 29.43) who underwent a Magnetic Resonance Imaging study during the first postnatal year (age at scan = 194.18 ± 97.98). We assessed white matter tracts using diffusion‐weighted magnetic resonance imaging with probabilistic tractography. Fractional anisotropy was found to be largely mature even at one month, although there was a little further increase during the first postnatal year in both the acoustic radiation and the direct brainstem‐Heschl's pathway.
Synthesis, Electrochemistry, and Optical Properties of Half‐Sandwich Ruthenium Complexes Bearing Triarylamine‐Anthracenes
Authors: Kovalski Eduard , Korb Marcus , Hildebrandt Alexander
Published: January 2018

The complex [CpRuII(dppe)(taae)] {Cp = η5‐C5H5, dppe = 1,2‐(PPh2)2‐C2H4, taae = 10‐ethynyl‐N,N‐di‐p‐tolylanthracen‐9‐amine} has been synthesized in a multistep reaction protocol including Sonogashira C,C‐ and Buchwald–Hartwig C,N‐ cross coupling reactions. Electrochemical and spectroscopic studies suggest a high degree of delocalization between the ruthenium and triarylamine termini through the anthracene bridge, forming a donor–π–acceptor (D–π–A) dye whose π–π* transitions exhibit charge‐transfer character in the monocationic oxidation state.
Olive (Olea europaea L. cv. Galega vulgar) Seed Oil: A First Insight into the Major Lipid Composition of a Promising Agro‐Industrial By‐Product at Two Ripeness Stages
Authors: Alves Eliana , Rey Felisa , Costa Elisabete da , Moreira Ana S. P. , Pato Luísa , Pato Luís , Domingues Maria do Rosário M. , Domingues Pedro
Published: January 2018

Olive seeds are promising industrial by‐products whose study acquires relevance both for valuing their biotechnological potential and for discriminating the origin and/or the edaphoclimatic conditions of olives. Herein, the fatty acid (FA) and triacylglycerol (TAG) profiles of total lipid extracts and neutral lipid fractions from olive seeds (Olea europaea L. cv. Galega vulgar), at two ripeness stages, are analyzed by mass spectrometry (MS)‐based approaches. In both olive seeds (green and ripe), the predominant FA are C18:1(n‐9) (56%), C18:2(n‐6) (17%), and C16:0 (18%). The seeds also contained the essential FA C18:3(n‐3) (0.11%). Ripeness led to a decrease of saturated FA and an increase of unsaturated FA. In total lipid extracts, major FA (C18:1(n‐9) and C18:0) could distinguish green from ripe olives (p < 0.05). In neutral lipid fractions, besides major FA (C18:1(n‐9) and C16:0), minor ones (C14:0, C18:3(n‐3), C20:0, and C22:0) could distinguish ripeness stages (p < 0.05). The relative amount of nine TAG is significantly different between green and ripe olives (p < 0.05), of which six are minor TAG. Olive seeds and their oil are a good source of n‐9 monounsaturated FA, and n‐6 and n‐3 polyunsaturated FA, being n‐3 higher in ripe olives. The ripeness stage can be distinguished by minor FA and minor TAG using MS.

Practical Applications: Considering the high proportion of unsaturated and essential FA that make up olive seeds/olive seed oil, and knowing how these proportions shift according to olive ripeness, will allow different industries to explore several potential applications of these promising agro‐industrial by‐products. Besides, profiling the FA and TAG composition of olive seed oil by MS‐based lipidomic approaches reveals that both the highest and the lowest abundant lipid molecules within these classes might be used as potential biochemical markers to discriminate these oils based on fruit ripeness stage.

Olive seed oil is rich in mono‐ (56%) and in polyunsaturated (17%) fatty acids (FA). During ripeness, saturated FA decrease and unsaturated increase. Minor FA of neutral lipid fraction can distinguish green and ripe olive seed oils. Less abundant triacylglycerols allow discriminating seed oils from different ripeness stages. Based on its major lipid composition, olive seed oil has several potential applications within different industries.
Assessment of a high‐order MUSCL method for rotor flows
Authors: Jimenez‐Garcia A. , Barakos G. N.
Published: January 2018

This work presents the implementation of a high‐order, finite‐volume scheme suitable for rotor flows. The formulation is based on the variable extrapolation MUSCL‐scheme, where high‐order spatial accuracy (up to fourth‐order) is achieved using correction terms obtained through successive differentiation. A variety of results are presented, including 2‐ and 3‐dimensional test cases. Results with the proposed scheme, showed better wake and higher resolution of vortical structures compared with the standard MUSCL, even when coarse meshes were employed. The method was also demonstrated for 3‐dimensional unsteady flows using overset and moving grids for the UH‐60A rotor in forward flight and the Enhanced Rotorcraft Innovative Concept Achievement tiltrotor in aeroplane mode. For medium grids, the present method adds reasonable CPU and memory overheads and offers good accuracy on relatively coarse grids.
Nutritional composition and antinutritional properties of maize ogi cofermented with pigeon pea
Authors: Okafor Uchechukwu I. , Omemu Adebunkola M. , Obadina Adewale O. , Bankole Mobolaji O. , Adeyeye Samuel A. O.
Published: January 2018

Maize was cofermented with pigeon pea for ogi production and evaluated for nutritional (proximate composition, minerals, vitamins, and amino acid profile analyses) and antinutritional (phytate, tannin, and trypsin inhibitor activity analyses) qualities. White maize and pigeon pea were mixed at ratios of 90:10, 80:20, 70:30, 60:40, and 50:50, respectively, with 100:0 serving as the control. Mixtures were cofermented for 96 hr at 27°C ± 2°C and nutritional, mineral, and antinutritional qualities were analyzed using analysis of variance. Results of proximate analysis showed that the values were significantly difference at p ≤ .05. Maize cofermented with pigeon pea at a ratio of 60:40 had the highest protein (22.79 mg/100 g), fat (19.27 mg/100 g), ash (2.98 mg/100 g), crude fiber (0.73 mg/100 g), and lowest moisture (1.98 mg/100 g) content, and was significantly (p ≤ .05) different from the other ratios. Of all the mixtures analyzed, 60:40 was significantly (p ≤ .05) different and had the highest Vitamin B1, B2, and B3 contents. Amino acid profile results showed that maize cofermented with pigeon pea at a ratio of 60:40 showed the highest contents of lysine (93.95 mg/g), tryptophan (20.38 mg/g), isoleucine (54.78 mg/g), phenylalanine (86.23 mg/g), leucine (109.55 mg/g), and valine (68.29 mg/g), respectively, and was significantly (p ≤ .05) different from the other ratios. Results of antinutritional analysis showed low phytate, tannin, and trypsin inhibitor values in maize cofermented with pigeon pea at a ratio of 60:40 when compared with other ratios. The cofermented maize‐pigeon pea product 60:40 had high amino acid profile than the others.
The effect of inulin as a fat substitute on the physicochemical and sensory properties of chicken sausages
Authors: Alaei Fereshteh , Hojjatoleslamy Mohammad , Hashemi Dehkordi Seyyed Majid
Published: January 2018

Due to its high thermal resistance and compatibility with the sausage emulsion system, the long‐chain inulin can be used as a fat substitute in the formulation of this product. This study was conducted to investigate the effect of inulin on the physicochemical, textural, and sensory properties of chicken sausages. The study included treatments of 25%, 50%, 75%, and 100% substitution. After preparing the samples, their physicochemical, textural, calorimetric, and sensory properties were evaluated. The treatment of 100% substitution of inulin had the maximum amount of sugar (29.90%), moisture (72.63%), protein (51.34), ash (6.95%), and salt (4.02%) (dry basis). The fat content was decreased with the increased levels of inulin substitution (p < .05). The increased amount of inulin reduced hardness, cohesiveness, gumminess, and stringiness, but increased springiness and chewiness up to the 25% substitution of inulin. The highest color difference and hue angle were related to 100% substitution treatment. The sensory evaluation of the samples showed that with the increase in the amount of inulin, the mean scores of the factors including color, appearance, and texture were increased, but the mean scores of smell and mouthfeel were decreased. Overall, the substitution of the entire fat existing in the formulation of the sausage with inulin led to the best physicochemical, textural, colorimetric, and sensory results. The use of inulin could be recommended as a fat substitute in the formulation of chicken sausages.
Effect of time to simulation and treatment for patients with oropharyngeal cancer receiving definitive radiotherapy in the era of risk stratification using smoking and human papillomavirus status
Authors: Amsbaugh Mark J. , Yusuf Mehran , Cash Elizabeth , Silverman Craig , Potts Kevin , Dunlap Neal
Published: January 2018

Background

The effect of increasing time to definitive radiotherapy (RT) for patients with oropharyngeal squamous cell carcinoma (SCC) is unknown.

Methods

Nodal tumor volumes at staging and simulation were compared for patients with oropharyngeal SCC. Time from staging to initiation of RT was tabulated. The primary endpoint of interest was nodal progression at simulation.

Results

Increasing time to simulation was associated with nodal progression in 144 patients (r = 0.474; P < .001). Patients with human papillomavirus (HPV)‐associated oropharyngeal SCC were more likely to have nodal progression (50% vs 26%; P = .008). A threshold of 32 days was associated (sensitivity 77.9% and specificity 60.2%) with nodal progression (P < .001). Increasing time from staging to treatment initiation was associated with a greater risk of distant failure (hazard ratio [HR] 4.157; 95% confidence interval [CI] 1.170‐14.764) but not progression‐free survival (PFS; P = .179) or overall survival (OS; P = .474).

Conclusion

Increasing time before RT for patients with oropharyngeal SCC is associated with nodal progression and increased hazard of distant failure, although not PFS or OS in our population.
The roles of channels and hillslopes in rainfall/run‐off lag times during intense storms in a steep catchment
Authors: Asano Yuko , Uchida Taro
Published: January 2018

The response time (lag time) between rainfall input and run‐off output in headwater catchments is a key parameter for flood prediction. Lag times are expected to be controlled by run‐off processes, both on hillslopes and in channels. To demonstrate these effects on peak lag times within a 4.5‐km2 catchment, we measured stream water levels at up to 16 channel locations at 1‐min intervals and compared the lag times with topographic indices describing the length and gradient of the hillslope and channel flow path. We captured storm events with a total precipitation of 38–198 mm and maximum hourly precipitation intensity of 9–90 mm/hr. There were positive relationships between lag time and flow path length as well as the ratio of the flow path length and the square root of the gradient of channels for the most intense storms, demonstrating that channel flow paths generally defined the variation in lag times. Topographic analysis showed that hillslope flow path lengths were similar among locations, whereas channel flow path length increased almost one order of magnitude with a 100‐fold increase in catchment area. Thus, the relative importance of hillslope flow path decreased with increasing catchment area. Our results indicate that the variation in lag times is small when hillslopes are sufficiently wet; thus, catchment‐scale variation in lag times can be explained almost entirely by channel processes. Detailed topographic channel information can improve prediction of flood peak timing, whereas hillslopes can be treated as homogeneous during large flood events.
The effects of initial soil moisture conditions on swale flow hydrographs
Authors: Rujner Hendrik , Leonhardt Günther , Marsalek Jiri , Perttu Anna‐Maria , Viklander Maria
Published: January 2018

The effects of soil water content (SWC) on the formation of run‐off in grass swales draining into a storm sewer system were studied in two 30‐m test swales with trapezoidal cross sections. Swale 1 was built in a loamy fine‐sand soil, on a slope of 1.5%, and Swale 2 was built in a sandy loam soil, on a slope of 0.7%. In experimental runs, the swales were irrigated with 2 flow rates reproducing run‐off from block rainfalls with intensities approximately corresponding to 2‐month and 3‐year events. Run‐off experiments were conducted for initial SWC (SWCini) ranging from 0.18 to 0.43 m3/m3. For low SWCini, the run‐off volume was greatly reduced by up to 82%, but at high SWCini, the volume reduction was as low as 15%. The relative swale flow volume reductions decreased with increasing SWCini and, for the conditions studied, indicated a transition of the dominating swale functions from run‐off dissipation to conveyance. Run‐off flow peaks were reduced proportionally to the flow volume reductions, in the range from 4% to 55%. The swale outflow hydrograph lag times varied from 5 to 15 min, with the high values corresponding to low SWCini. Analysis of swale inflow/outflow hydrographs for high SWCini allowed estimations of the saturated hydraulic conductivities as 3.27 and 4.84 cm/hr in Swales 1 and 2, respectively. Such estimates differed from averages (N = 9) of double‐ring infiltrometer measurements (9.41 and 1.78 cm/hr). Irregularities in swale bottom slopes created bottom surface depression storage of 0.35 and 0.61 m3 for Swales 1 and 2, respectively, and functioned similarly as check berms contributing to run‐off attenuation. The experimental findings offer implications for drainage swale planning and design: (a) SWCini strongly affect swale functioning in run‐off dissipation and conveyance during the early phase of run‐off, which is particularly important for design storms and their antecedent moisture conditions, and (b) concerning the longevity of swale operation, Swale 1 remains fully functional even after almost 60 years of operation, as judged from its attractive appearance, good infiltration rates (3.27 cm/hr), and high flow capacity.
Inflammatory potential of diet and risk of pancreatic cancer in the Prostate, Lung, Colorectal and Ovarian (PLCO) Cancer Screening Trial
Authors: Zheng Jiali , Merchant Anwar T. , Wirth Michael D. , Zhang Jiajia , Antwi Samuel O. , Shoaibi Azza , Shivappa Nitin , Stolzenberg‐Solomon Rachael Z. , Hebert James R. , Steck Susan E.
Published: January 2018

Inflammation plays a central role in pancreatic cancer etiology and can be modulated by diet. We aimed to examine the association between the inflammatory potential of diet, assessed with the Dietary Inflammatory Index (DII®), and pancreatic cancer risk in the Prostate, Lung, Colorectal and Ovarian Cancer Screening Trial prospective cohort. Our study included 101,449 participants aged 52–78 years at baseline who completed both baseline questionnaire and a diet history questionnaire. Energy‐adjusted DII (E‐DII) scores were computed based on food and supplement intake. Cox proportional hazards models and time dependent Cox models were used to estimate hazard ratios (HRs) and 95% confidence intervals (CIs) with participants in the lowest E‐DII quintile (most anti‐inflammatory scores) as referent. After a median 8.5 years of follow‐up, 328 pancreatic cancer cases were identified. E‐DII scores were not associated with pancreatic cancer risk in the multivariable model (HRQ5vsQ1 = 0.94; 95% CI = 0.66–1.35; p‐trend = 0.43). Time significantly modified the association (p‐interaction = 0.01). During follow up <4 years, there was suggestive evidence of an inverse association between E‐DII and pancreatic cancer (HRQ5vsQ1 = 0.60; 95% CI = 0.35–1.02; p‐trend = 0.20) while there was a significant positive trend in the follow up ≥4 years (HRQ5vsQ1 = 1.31; 95% CI = 0.83–2.08; p‐trend = 0.03). Similar results were observed for E‐DII from food only. Our study does not support an association between inflammatory potential of diet and pancreatic cancer risk; however, heterogeneous results were obtained with different follow‐up times. These divergent associations may result from the influences of undetected disease in the short‐term.
Heterozygosis in aromatic amino acid decarboxylase deficiency: Evidence for a positive interallelic complementation between R347Q and R358H mutations
Authors: Montioli Riccardo , Janson Giacomo , Paiardini Alessandro , Bertoldi Mariarita , Borri Voltattorni Carla
Published: January 2018

Aromatic amino acid or Dopa decarboxylase (AADC or DDC) is a homodimeric pyridoxal 5’‐phosphate (PLP) enzyme responsible for the generation of the neurotransmitters dopamine and serotonin. AADC deficiency is a rare inborn disease caused by mutations of the AADC gene leading to a defect of AADC enzyme and resulting in impaired dopamine and serotonin synthesis. Until now, only the molecular effects of homozygous mutations were analyzed. However, although heterozygous carriers of AADC deficiency were identified, the molecular aspects of their enzymatic phenotypes are not yet investigated. Here, we focus our attention on the R347Q/R358H and R347Q/R160W heterozygous mutations, and report for the first time the isolation and characterization, in the purified recombinant form, of the R347Q/R358H heterodimer and of the R358H homodimer. The results, integrated with those already known of the R347Q homodimeric variant, provide evidence that (i) the R358H mutation strongly reduces the PLP‐binding affinity and the catalytic activity, and (ii) a positive interallelic complementation exists between the R347Q and the R358H mutations. Bioinformatics analyses provide the structural basis for these data. Unfortunately, the R347Q/R160W heterodimer was not obtained in a sufficient amount to allow its purification and characterization. Nevertheless, the biochemical features of the R160W homodimer give a contribution to the enzymatic phenotype of the heterozygous R347Q/R160W and suggest the possible relevance of Arg160 in the proper folding of human DDC. © 2018 IUBMB Life, 70(3):215–223, 2018
Rapid generation of three‐dimensional microchannels for vascularization using a subtractive printing technique
Authors: Burtch Stephanie R. , Sameti Mahyar , Olmstead Richard T. , Bashur Chris A.
Published: January 2018

The development of tissue‐engineered products has been limited by lack of a perfused microvasculature that delivers nutrients and maintains cell viability. Current strategies to promote vascularization such as additive three‐dimensional printing techniques have limitations. This study validates the use of an ultra‐fast laser subtractive printing technique to generate capillary‐sized channels in hydrogels prepopulated with cells by demonstrating cell viability relative to the photodisrupted channels in the gel. The system can move the focal spot laterally in the gel at a rate of 2500 mm/s by using a galvanometric scanner to raster the in plane focal spot. A Galilean telescope allows z‐axis movement. Blended hydrogels of polyethylene glycol and collagen with a range of optical clarities, mechanical properties and swelling behavior were tested to demonstrate that the subtractive printing process for writing vascular channels is compatible with all of the blended hydrogels tested. Channel width and patterns were controlled by adjusting the laser energy and focal spot positioning, respectively. After treatment, high cell viability was observed at distances greater than or equal to 18 μm from the fabricated channels. Overall, this study demonstrates a flexible technique that has the potential to rapidly generate channels in tissue‐engineered constructs.