bluuebunny/crossref_metadata_2025 huggingface dataset:
A Sugar‐Based Gelator for Marine Oil‐Spill Recovery
Authors: Vibhute Amol M. , Muvvala Venkatanarayana , Sureshan Kana M.
Published: January 2016

Marine oil spills constitute an environmental disaster with severe adverse effects on the economy and ecosystem. Phase‐selective organogelators (PSOGs), molecules that can congeal oil selectively from oil–water mixtures, have been proposed to be useful for oil‐spill recovery. However, a major drawback lies in the mode of application of the PSOG to an oil spill spread over a large area. The proposed method of using carrier solvents is impractical for various reasons. Direct application of the PSOG as a solid, although it would be ideal, is unknown, presumably owing to poor dispersion of the solid through the oil. We have designed five cheap and easy‐to‐make glucose‐derived PSOGs that disperse in the oil phase uniformly when applied as a fine powder. These gelators were shown to selectively congeal many oils, including crude oil, from oil–water mixtures to form stable gels, which is an essential property for efficient oil‐spill recovery. We have demonstrated that these PSOGs can be applied aerially as a solid powder onto a mixture of crude oil and sea water and the congealed oil can then be scooped out. Our innovative mode of application and low cost of the PSOG offers a practical solution to oil‐spill recovery.
Copper‐Catalyzed Borylcupration of Allenylsilanes
Authors: Yuan Weiming , Song Liu , Ma Shengming
Published: January 2016

A highly regio‐ and stereoselective copper‐catalyzed borylcupration of 1,2‐allenylsilanes affords an unexpected regioreversed allylic boronate bearing an extra C−Si bond at the 3‐position, with a thermodynamically disfavored Z geometry. Such stereodefined allylic boronates containing an extra alkenyl silane moiety are very useful organodimetallic reagents for organic synthesis.
A Highly Ion‐Selective Zeolite Flake Layer on Porous Membranes for Flow Battery Applications
Authors: Yuan Zhizhang , Zhu Xiangxue , Li Mingrun , Lu Wenjing , Li Xianfeng , Zhang Huamin
Published: January 2016

Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well‐defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra‐thin ZSM‐35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite‐coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm−2, which is by far the highest value ever reported. These convincing results indicate that zeolite‐coated membranes are promising in battery applications.
Oxychlorination–Dehydrochlorination Chemistry on Bifunctional Ceria Catalysts for Intensified Vinyl Chloride Production
Authors: Scharfe Matthias , Lira‐Parada Pedro A. , Paunović Vladimir , Moser Maximilian , Amrute Amol P. , Pérez‐Ramírez Javier
Published: January 2016

Ceria catalyzes the one‐step production of the vinyl chloride monomer (VCM) from ethylene with a high yield because of its bifunctional character: redox centers oxychlorinate ethylene to ethylene dichloride (EDC), which is subsequently dehydrochlorinated to VCM over strong acid sites generated in situ. Nanocrystalline CeO2 and CeO2‐ZrO2 lead to a VCM yield of 25 % in a single pass, outperforming the best reported systems and reaching industrially attractive levels. The use of CeO2 intensifies the current two‐step process within PVC production encompassing CuCl2‐catalyzed oxychlorination and thermal cracking. In addition, ceria‐based materials offer stability advantages with respect to the archetypical CuCl2‐based catalysts.
Bright Solid‐State Emission of Disilane‐Bridged Donor–Acceptor–Donor and Acceptor–Donor–Acceptor Chromophores
Authors: Shimada Masaki , Tsuchiya Mizuho , Sakamoto Ryota , Yamanoi Yoshinori , Nishibori Eiji , Sugimoto Kunihisa , Nishihara Hiroshi
Published: January 2016

The development of disilane‐bridged donor–acceptor–donor (D‐Si‐Si‐A‐Si‐Si‐D) and acceptor–donor–acceptor (A‐Si‐Si‐D‐Si‐Si‐A) compounds is described. Both types of compound showed strong emission (λem=ca. 500 and ca. 400 nm, respectively) in the solid state with high quantum yields (Φ: up to 0.85). Compound 4 exhibited aggregation‐induced emission enhancement in solution. X‐ray diffraction revealed that the crystal structures of 2, 4, and 12 had no intermolecular π–π interactions to suppress the nonradiative transition in the solid state.
Friedel–Crafts‐Type Intermolecular C−H Silylation of Electron‐Rich Arenes Initiated by Base‐Metal Salts
Authors: Yin Qin , Klare Hendrik F. T. , Oestreich Martin
Published: January 2016

An electrophilic aromatic substitution (SEAr) with a catalytically generated silicon electrophile is reported. Essentially any commercially available base‐metal salt acts as an initiator/catalyst when activated with NaBArF4 . The thus‐generated Lewis acid then promotes the SEAr of electron‐rich arenes with hydrosilanes but not halosilanes. This new C−H silylation was optimized for FeCl2 /NaBArF4 , affording good yields at catalyst loadings as low as 0.5 mol %. The procedure is exceedingly straightforward and comes close to typical Friedel–Crafts methods, where no added base is needed to absorb the released protons.
Synthetic Receptors for the High‐Affinity Recognition of O‐GlcNAc Derivatives
Authors: Rios Pablo , Carter Tom S. , Mooibroek Tiddo J. , Crump Matthew P. , Lisbjerg Micke , Pittelkow Michael , Supekar Nitin T. , Boons Geert‐Jan , Davis Anthony P.
Published: January 2016

The combination of a pyrenyl tetraamine with an isophthaloyl spacer has led to two new water‐soluble carbohydrate receptors (“synthetic lectins”). Both systems show outstanding affinities for derivatives of N‐acetylglucosamine (GlcNAc) in aqueous solution. One receptor binds the methyl glycoside GlcNAc‐β‐OMe with Ka≈20 000 m−1, whereas the other one binds an O‐GlcNAcylated peptide with Ka≈70 000 m−1. These values substantially exceed those usually measured for GlcNAc‐binding lectins. Slow exchange on the NMR timescale enabled structural determinations for several complexes. As expected, the carbohydrate units are sandwiched between the pyrenes, with the alkoxy and NHAc groups emerging at the sides. The high affinity of the GlcNAcyl–peptide complex can be explained by extra‐cavity interactions, raising the possibility of a family of complementary receptors for O‐GlcNAc in different contexts.
Reductive Chlorination and Bromination of Ketones via Trityl Hydrazones
Authors: Reyes Julius R. , Rawal Viresh H.
Published: January 2016

A method is presented for the direct transformation of a ketone to the corresponding reduced alkyl chloride or bromide. The process involves the reaction of a ketone trityl hydrazone with tBuOCl to give a diazene which readily collapses to the α‐chlorocarbinyl radical, reduction of which by a hydrogen atom source gives the alkyl chloride product. The use of N‐bromosuccinimide provides the corresponding alkyl bromide. This unique transformation provides a reductive halogenation that complements Barton's redox‐neutral vinyl halide synthesis.
Superparamagnetic Reduced Graphene Oxide with Large Magnetoresistance: A Surface Modulation Strategy
Authors: Peng Jing , Guo Yuqiao , Lv Haifeng , Dou Xinyu , Chen Qi , Zhao Jiyin , Wu Changzheng , Zhu Xiaojiao , Lin Yue , Lu Wei , Wu Xiaojun , Xie Yi
Published: January 2016

The graphene system is actively pursued in spintronics for its nontrivial sp electron magnetism and its potential for the flexible surface chemical tuning of magnetoelectronic functionality. The magnetoresistance (MR) of graphene can be effectively tuned under high magnetic fields at cryogenic temperatures, but it remains a challenge to achieve sensitive magnetoelectric response under ambient conditions. We report the use of surface modulation to realize superparamagnetism in reduced graphene oxide (rGO) with sensitive magnetic field response. The superparamagnetic rGO was obtained by a mild oxidation process to partially remove the thiol groups covalently bound to the carbon framework, which brings about large low‐field negative MR at room temperature (−8.6 %, 500 Oe, 300 K). This strategy provides a new approach for optimizing the intrinsic magnetoelectric properties of two‐dimensional materials.
Inkjet printing of polyimide insulators for the 3D printing of dielectric materials for microelectronic applications
Authors: Zhang Fan , Tuck Christopher , Hague Richard , He Yinfeng , Saleh Ehab , Li You , Sturgess Craig , Wildman Ricky
Published: January 2016

In this article, we report the first continuous fabrication of inkjet‐printed polyimide films, which were used as insulating layers for the production of capacitors. The polyimide ink was prepared from its precursor poly(amic) acid, and directly printed on to a hot substrate (at around 160 °C) to initialize a rapid thermal imidization. By carefully adjusting the substrate temperature, droplet spacing, droplet velocity, and other printing parameters, polyimide films with good surface morphologies were printed between two conducting layers to fabricate capacitors. In this work, the highest capacitance value, 2.82 ± 0.64 nF, was achieved by capacitors (10 mm × 10 mm) with polyimide insulating layers thinner than 1 μm, suggesting that the polyimide inkjet printing approach is an efficient way for producing dielectric components of microelectronic devices. © 2016 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43361.
Communication growth in minimally verbal children with ASD: The importance of interaction
Authors: DiStefano Charlotte , Shih Wendy , Kaiser Ann , Landa Rebecca , Kasari Connie
Published: January 2016

Little is known about language development in children with Autism Spectrum Disorders (ASD) who remain minimally verbal past age 5. While there is evidence that children can develop language after age 5, we lack detailed information. Studies of this population generally focus on discrete language skills without addressing broader social‐communication abilities. As communication and social deficits are both inherent to ASD, an examination of not only what language skills are acquired, but how those skills are used in interactions is relevant. Research in typical development has examined how communication interchanges (unbroken back‐and‐forth exchanges around a unified purpose) develop, which can be used as a framework for studying minimally verbal children. This study examined the interchange use by 55 children with ASD over the course of a 6‐month play and engagement‐based communication intervention. Half of the children received intervention sessions that also incorporated a speech‐generating device (SGD). Interchanges were coded by: frequency, length, function, and initiator (child or adult). Results indicated that children initiated a large proportion of interchanges and this proportion increased over time. The average length and number of interchanges increased over time, with children in the SGD group showing even greater growth. Finally, children's total number of interchanges at baseline was positively associated with their spoken language gains over the course of intervention. This study supports the crucial relationship between social engagement and expressive language development, and highlights the need to include sustained communication interchanges as a target for intervention with this population. Autism Res 2016, 9: 1093–1102. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Process development of a New Haemophilus influenzae type b conjugate vaccine and the use of mathematical modeling to identify process optimization possibilities
Authors: Hamidi Ahd , Kreeftenberg Hans , v.d. Pol Leo , Ghimire Saroj , v.d. Wielen Luuk A.M. , Ottens Marcel
Published: January 2016

Vaccination is one of the most successful public health interventions being a cost‐effective tool in preventing deaths among young children. The earliest vaccines were developed following empirical methods, creating vaccines by trial and error. New process development tools, for example mathematical modeling, as well as new regulatory initiatives requiring better understanding of both the product and the process are being applied to well‐characterized biopharmaceuticals (for example recombinant proteins). The vaccine industry is still running behind in comparison to these industries. A production process for a new Haemophilus influenzae type b (Hib) conjugate vaccine, including related quality control (QC) tests, was developed and transferred to a number of emerging vaccine manufacturers. This contributed to a sustainable global supply of affordable Hib conjugate vaccines, as illustrated by the market launch of the first Hib vaccine based on this technology in 2007 and concomitant price reduction of Hib vaccines. This paper describes the development approach followed for this Hib conjugate vaccine as well as the mathematical modeling tool applied recently in order to indicate options for further improvements of the initial Hib process. The strategy followed during the process development of this Hib conjugate vaccine was a targeted and integrated approach based on prior knowledge and experience with similar products using multi‐disciplinary expertise. Mathematical modeling was used to develop a predictive model for the initial Hib process (the ‘baseline’ model) as well as an ‘optimized’ model, by proposing a number of process changes which could lead to further reduction in price. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:568–580, 2016
Influence of Microwave Irradiation on the Structural Properties of Carbon‐Supported Hollow Copper Nanoparticles and Their Effect on the Synthesis of Dimethyl Carbonate
Authors: Ren Meijiao , Ren Jun , Hao Panpan , Yang Jinzhou , Wang Donglei , Pei Yongli , Lin Jian‐Ying , Li Zhong
Published: January 2016

Novel activated carbon (AC)‐supported highly dispersed hollow Cu nanoparticles (NPs) (Cu/AC) with exposed {1 1 1} facets have been prepared by microwave irradiation for the synthesis of dimethyl carbonate (DMC). In particular, Cu NPs with a large cavity diameter of 35 nm are formed after irradiation from room temperature to 360 °C within a mere 8 min without additional irradiation, thus benefiting from the rapid heating of the microwave procedure. In this study, an Ostwald ripening mechanism is proposed. DFT calculations are consistent with the analysis of CO temperature‐programmed desorption, which found that Cu(1 1 1) facets are more favorable for the weak adsorption of CO, which supports the formation of DMC. The as‐prepared catalysts exhibit the highest DMC formation rate in terms of turnover frequency and 100 % selectivity for DMC can be achieved. The large surface area of the hollow Cu NPs and the exposed {1 1 1} crystal planes are highlighted as being responsible for the excellent catalytic rate and superior selectivity, respectively.
Influence of Processing on the Physical Stability of Multiple Emulsions Containing a Green Solvent
Authors: García María Carmen , Muñoz José , Alfaro María Carmen , Franco José María
Published: January 2016

The influence of the emulsification process on the microstructure and physical stability of model water‐in‐oil‐in‐water (W/O/W) emulsions formulated with a green solvent and a mixture of amphiphilic copolymers as emulsifiers was investigated. Emulsions were prepared by applying a homogenization step with a rotor‐stator device followed by high‐pressure homogenization. Viscous flow tests, transmitted light optical microscopy, globule size distribution (GSD), and multiple light scattering (MLS) measurements were carried out. The GSDs obtained were the result of a recoalescence due to overprocessing and the coalescence of inner droplets with the outer water phase. MLS detected a main destabilization mechanism by creaming. The passing of the emulsion through a high‐pressure homogenizer (HPH) significantly delayed the creaming process.
Simulation of Cake Filtration for Polydisperse Particles
Authors: Becker Jürgen , Cheng Liping , Kronsbein Cornelia , Wiegmann Andreas
Published: January 2016

When simulating the buildup of a filter cake consisting of polydisperse particles, the choice of the numerical resolution is difficult as particles may cover a large range of diameters. A method was developed that allows to model cake filtration at any resolution. Resolution‐dependent fitting parameters can be found such that the solidity and resistivity of the resulting filter cake will be independent of the chosen resolution. The cake buildup is simulated on the filter media scale. Flow through the porous parts is modeled with the Stokes‐Brinkman equation, which requires the local solidity and flow resistivity of each porous grid cell as input. It is described how to set the local solidity and resistivity such that a given global solidity and flow resistivity of the filter cake is achieved and the simulated pressure drop is independent of the chosen resolution.
Electric Field‐Responsive Nanopores with Ion Selectivity: Controlling Based on Transport Resistance
Authors: Zhu Yudan , Ruan Yang , Wu Ximing , Lu Xiaohua , Zhang Yumeng , Lu Linghong
Published: January 2016

Using external stimuli to control ionic transport behavior in nanopores is an important focus of nanodevice research allowing numerous potential applications. A novel strategy was investigated to control ionic‐transport resistance responses to the electric field intensity in a nanopore and regulate ionic selectivity. Molecular simulations were performed to examine the transport behaviors of K+ and Na+ in a carbon nanotube‐based biomimetic nanopore under different electric fields. The responses of the modified group to the electric field intensity induced variations in ionic transport resistance, which then led to improved ionic selectivity. This result indicates that driving force and resistance are simultaneously affected by external stimuli under nanoconfinement.
Crystalline Layer Formation of Highly Viscous Supersaturated Liquids
Authors: Herfurth Julia , Mahnken Kai , Fabian Jürgen , Ulrich Joachim
Published: January 2016

The handling of highly viscous supersaturated liquids during nucleation and crystal growth is an important challenge. Here, solutions mixed with hydrocolloids were tested for the formation of gelled products enclosed by a crystallized layer of sucrose from the starting liquid mixture. To create reproducible layers on the gel body, the nucleation needs to be initiated by external seed materials. The influence of the hydrocolloids on the crystallization process and therefore the crystal growth in combination with the different seeds for nucleation (starch, icing sugar) was tested and evaluated. Different external seed materials can have an influence on the thickness of the sugar layers. A significant influence on the thickness of the crystalline layers can be found by the use of different highly viscous solutions.
Solvothermal Synthesis of Yolk–Shell CeVO4/C Microspheres as a High‐Performance Anode for Lithium‐Ion Batteries
Authors: Jin Rencheng , Liu Chunping , Sun Lin , Zhang Zhenjiang , Chen Gang
Published: January 2016

Yolk–shell CeVO4/C microspheres are fabricated by a facile solvothermal method, followed by a carbonization process, by using glucose as a precursor. The hierarchical structures supply a high specific surface area and alleviate volume changes during the lithiation–delithiation process. Owing to the unique porous structural features, the yolk–shell CeVO4/C microspheres present a high lithium storage capacity, reaching 580 mAh g−1 at a current density of 100 mA g−1. Furthermore, the microspheres exhibit good cycle stability and high rate performance, for example, in the 100th cycle they display a capacity of 448 mAh g−1 at a current density 100 mA g−1 and a capacity of 292 mAh g−1 at 1000 mA g−1 in the 40th cycle; these values are better than those of pure‐phase yolk–shell CeVO4 microspheres.
Reactive Extraction of Lactic Acid by Using Tri‐n‐octylamine: Structure of the Ionic Phase
Authors: Aimer Matthias , Klemm Elias , Langanke Bernd , Gehrke Helmut , Stubenrauch Cosima
Published: January 2016

Lactic acid is a promising biogenic platform chemical which can be produced by fermentation of cellulose and hemicellulose. However, separating lactic acid from the fermentation broth is extremely costly and technically complex. We therefore investigated whether liquid/liquid extraction of lactic acid with tri‐n‐octylamine is a cost‐effective alternative to the existing downstream processing method. In order to find an answer to this question, the structure of the middle phase of the occurring three‐phase region, which is enriched with up to 20 wt. % lactic acid, was explored. The results of our IR, small‐angle X‐ray scattering and NMR measurements show that this phase is ionic and has a bicontinuous structure. Due to the analogy with bicontinuous microemulsions, it should be possible to further enrich the lactic acid, which could lead to a rethink regarding the design of extraction processes.
A Palladium‐Catalyzed Carbonylation Approach to Eight‐Membered Lactam Derivatives with Antitumor Activity
Authors: Mancuso Raffaella , Raut Dnyaneshwar S. , Marino Nadia , De Luca Giorgio , Giordano Cinzia , Catalano Stefania , Barone Ines , Andò Sebastiano , Gabriele Bartolo
Published: January 2016

The reactivity of 2‐(2‐alkynylphenoxy)anilines under PdI2/KI‐catalyzed oxidative carbonylation conditions has been studied. Although a different reaction pathway could have been operating, N‐palladation followed by CO insertion was the favored pathway with all substrates tested, including those containing an internal or terminal triple bond. This led to the formation of a carbamoylpalladium species, the fate of which, as predicted by theoretical calculations, strongly depended on the nature of the substituent on the triple bond. In particular, 8‐endo‐dig cyclization preferentially occurred when the triple bond was terminal, leading to the formation of carbonylated ζ‐lactam derivatives, the structures of which have been confirmed by XRD analysis. These novel medium‐sized heterocyclic compounds showed antitumor activity against both estrogen receptor‐positive (MCF‐7) and triple negative (MDA‐MB‐231) breast cancer cell lines. In particular, ζ‐lactam 3 j′ may represent a novel and promising antitumor agent because biological tests clearly demonstrate that this compound significantly reduces cell viability and motility in both MCF‐7 and MDA‐MB‐231 breast cancer cell lines, without affecting normal breast epithelial cell viability.
Strategies for the Total Synthesis of Clavicipitic Acid
Authors: Ito Mamoru , Tahara Yu‐ki , Shibata Takanori
Published: January 2016

Clavicipitic acid is an ergot alkaloid, which was isolated from Claviceps strain and Claviceps fusiformis. Its unique tricyclic azepinoindole skeleton has attracted synthetic chemists, and various strategies have been developed for its total synthesis. These strategies can be generally categorized into two types based on the synthetic intermediates, namely, 4‐substituted gramine derivatives and 4‐substituted tryptophan derivatives. This Minireview summarizes the reported total syntheses from the point of these two key intermediates
Co‐Composting of Macrophyte Biomass and Sludge as an Alternative for Sustainable Management of Constructed Wetland By‐Products
Authors: Kouki Soulwène , Saidi Neila , M'hiri Fadhel , Hafiane Amor , Hassen Abdennaceur
Published: January 2016

In Tunisia, the Joogar constructed wetland treating rural wastewater generates annually a considerable biomass of Arundo donax and Typha latifolia with sewage sludge. These by‐products can present a waste management challenge for such systems. The present work focused on recycling of macrophyte residues by co‐composting with sludge. Different quality physico‐chemical parameters (temperature, pH, organic matter (OM), carbon to nitrogen (C/N) ratio, nutrients, and heavy metals) and biological factors (total and faecal bacterial count and germination test) were monitored during the composting cycle. Compost phytotoxicity was assessed through amendment assays. At the end of the composting cycle, temperature, and pH were stabilized at 33°C and 7.34, respectively. OM showed a significant mineralization and the C/N ratio was reduced from 31.7 to 9.0. In addition, pathogens destruction occurred at the later stages of the process. The final germination index of 96% indicated, with the other parameters, the stability and maturity of the macrophyte residues compost. The amendment assay applying compost to soil in a ratio of 1:2 v/v significantly improved the Lens culinaris growth by providing nutrients. The composting process appeared to be as a suitable way of valorisation of constructed wetland wastes, producing stabilized compost that could be sufficient for soil fertilization and plant growth improvement through a beneficial nutrients input.
Fragment‐Based Protein–Protein Interaction Antagonists of a Viral Dimeric Protease
Authors: Gable Jonathan E. , Lee Gregory M. , Acker Timothy M. , Hulce Kaitlin R. , Gonzalez Eric R. , Schweigler Patrick , Melkko Samu , Farady Christopher J. , Craik Charles S.
Published: January 2016

Fragment‐based drug discovery has shown promise as an approach for challenging targets such as protein–protein interfaces. We developed and applied an activity‐based fragment screen against dimeric Kaposi's sarcoma‐associated herpesvirus protease (KSHV Pr) using an optimized fluorogenic substrate. Dose–response determination was performed as a confirmation screen, and NMR spectroscopy was used to map fragment inhibitor binding to KSHV Pr. Kinetic assays demonstrated that several initial hits also inhibit human cytomegalovirus protease (HCMV Pr). Binding of these hits to HCMV Pr was also confirmed by NMR spectroscopy. Despite the use of a target‐agnostic fragment library, more than 80 % of confirmed hits disrupted dimerization and bound to a previously reported pocket at the dimer interface of KSHV Pr, not to the active site. One class of fragments, an aminothiazole scaffold, was further explored using commercially available analogues. These compounds demonstrated greater than 100‐fold improvement of inhibition. This study illustrates the power of fragment‐based screening for these challenging enzymatic targets and provides an example of the potential druggability of pockets at protein–protein interfaces.
Excessive volume of hydrogel injectates may compromise the efficacy for the treatment of acute myocardial infarction
Authors: Wise Peter , Davies Neil H. , Sirry Mazin S. , Kortsmit Jeroen , Dubuis Laura , Chai Chen‐Ket , Baaijens Frank P.T. , Franz Thomas
Published: January 2016

Biomaterial injectates are promising as a therapy for myocardial infarction to inhibit the adverse ventricular remodeling. The current study explored interrelated effects of injectate volume and infarct size on treatment efficacy. A finite element model of a rat heart was utilized to represent ischemic infarcts of 10%, 20%, and 38% of left ventricular wall volume and polyethylene glycol hydrogel injectates of 25%, 50%, and 75% of the infarct volume. Ejection fraction was 49.7% in the healthy left ventricle and 44.9%, 46.4%, 47.4%, and 47.3% in the untreated 10% infarct and treated with 25%, 50%, and 75% injectate, respectively. Maximum end‐systolic infarct fiber stress was 41.6, 53.4, 44.7, 44.0, and 45.3 kPa in the healthy heart, the untreated 10% infarct, and when treated with the three injectate volumes, respectively. Treating the 10% and 38% infarcts with the 25% injectate volume reduced the maximum end‐systolic fiber stress by 16.3% and 34.7% and the associated strain by 30.2% and 9.8%, respectively. The results indicate the existence of a threshold for injectate volume above which efficacy does not further increase but may decrease. The efficacy of an injectate in reducing infarct stress and strain changes with infarct size. Copyright © 2016 John Wiley & Sons, Ltd.
Global‐view coefficients: a data management solution for parallel quantum Monte Carlo applications
Authors: Niu Qingpeng , Dinan James , Tirukkovalur Sravya , Benali Anouar , Kim Jeongnim , Mitas Lubos , Wagner Lucas , Sadayappan P.
Published: January 2016

Quantum Monte Carlo (QMC) applications perform simulation with respect to an initial state of the quantum mechanical system, which is often captured by using a cubic B‐spline basis. This representation is stored as a read‐only table of coefficients and accesses to the table are generated at random as part of the Monte Carlo simulation. Current QMC applications, such as QWalk and QMCPACK, replicate this table at every process or node, which limits scalability because increasing the number of processors does not enable larger systems to be run. We present a partitioned global address space approach to transparently managing this data using Global Arrays in a manner that allows the memory of multiple nodes to be aggregated. We develop an automated data management system that significantly reduces communication overheads, enabling new capabilities for QMC codes. Experimental results with QWalk and QMCPACK demonstrate the effectiveness of the data management system. Copyright © 2016 John Wiley & Sons, Ltd.
Distributed architecture for agents‐based energy negotiation in solar powered micro‐grids
Authors: Amato Alba , Martino Beniamino Di , Scialdone Marco , Venticinque Salvatore
Published: January 2016

The quota of renewable energy production from decentralized sources is increasing even more, affecting the management of current power grids. The lack of alignment between energy produced by photovoltaic panels and the consumption by user's appliances are the main issues that need to be addressed. The usage of energy storages is not yet feasible because of dimensioning problems and costs. The CoSSMic project is developing an innovative autonomic distributed platform that adopts a collaborative approach and distributed knowledge to schedule the usage of consuming devices according to user's preferences and constraints, monitoring data and predicted photovoltaic production. The main objective is the maximization of self‐consumption in a neighborhood. Multi‐agent systems are a good candidate for modeling and managing such kind of systems. In fact, smart grids are geographically distributed systems composed of autonomous and reactive entities among which some are pro‐active and have social abilities. In this paper, we focus on the design and prototype implementation of the multi‐agent systems, that is one of the pillars of the CoSSMic platform, aiming at implementing a distributed scheduler. Copyright © 2016 John Wiley & Sons, Ltd.
An optimal inherently stabilizing routing algorithm for star P2P overlay networks
Authors: Karaata Mehmet Hakan , Alsulaiman Thamer
Published: January 2016

Star graphs possess many desirable properties such as scalable node degrees and diameters, which are essential to facilitate reduced routing table sizes and low maximum path length for routing in large P2P networks. In addition, because a large number of disjoint paths are available and each data/replica in an n‐star can be placed in an (n − 1)‐star, load balancing and alleviation of network bottlenecks can be implemented in star P2P overlay networks. Therefore, star networks have been proposed as viable alternatives to existing overlay topologies for large P2P networks. In this paper, we propose an optimal stabilizing and inherently stabilizing algorithm for routing messages over all disjoint paths between two peers in a star P2P overlay network. The algorithm is optimal in terms of its time complexity in rounds and the length of the longest path traversed by the messages, and fault tolerant due to being stabilizing and inherently stabilizing, allowing the system to withstand transient faults. The algorithm can be used to increase network reliability and survivability in P2P networks. In addition, the usage of all disjoint paths to route messages between two peers leads to increased network bandwidth while distributing the communication overhead across the network and eliminating network bottlenecks in P2P networks. Copyright © 2016 John Wiley & Sons, Ltd.
Topic mining for call centers based on A‐LDA and distributed computing
Authors: Guo Wenming , Liang Lihong , Deng Tianlang
Published: January 2016

Early work on call centers focused on opinion collection, and service acceptance used manual entry to record text information for incoming calls and to count various types of calls. With the development of text mining technologies, it is possible for call centers to become information providers. Although traditional text mining methods have been well studied, no algorithm has been designed specifically for call center data, which contains structured information about the call center in addition to plain text. A telephone call usually has several properties such as caller number, call time, and so on. Aiming at the data characteristics of call centers, in this paper, we propose an improved latent Dirichlet allocation (LDA) model called A‐LDA, which includes information from external‐related attributes and is suitable for building topic mining models for call centers. We present a Gibbs sampling‐distributed computing implementation for our model's inferences and use datasets from China Central Television telephone call center to perform an experiment on topic detection. The results show that A‐LDA, which uses external correlation properties, has a lower perplexity value and a better generalization performance than the traditional LDA method and can find topics associated with values contained by the external attributes. Copyright © 2016 John Wiley & Sons, Ltd.
RTS: road topology‐based scheme for traffic condition estimation via vehicular crowdsensing
Authors: Shao Lu , Wang Cheng , Liu Lu , Jiang Changjun
Published: January 2016

Urban traffic condition usually serves as basic information for some intelligent urban applications, for example, intelligent transportation system. The traditional acquisition of such information is often costly because of the dependencies on infrastructures, such as cameras and loop detectors. Crowdsensing, as a new economic paradigm, can be utilized together with vehicular networks to efficiently gather vehicle‐sensed data for estimating the traffic condition. However, it has the problem of being lack of data uploading efficiency and data usage effectiveness. In this paper, we take into account the topology of the road net to deal with these problems. Specifically, we divide the road net into road sections and junction areas. Based on this division, we introduce a two‐phased data collection and processing scheme named road topology‐based scheme. It leverages the correlations among adjacent roads. In a junction area, data collected by vehicles are first processed and integrated by a sponsor vehicle to locally calculate traffic condition. Both the selection of the sponsor and the calculation of road condition utilize the road correlation. The sponsor then uploads the local data to a server. By employing the inherent relations among roads, the server processes data and estimates traffic condition for the road sections without vehicular data in a global vision. We conduct experiments based on real vehicle trace data. The results indicate that our design can commendably handle the problems of efficiency and effectiveness in traffic condition evaluation using the vehicular crowdsensing data. Copyright © 2016 John Wiley & Sons, Ltd.
Watershed‐ng: an extensible distributed stream processing framework
Authors: Rocha Rodrigo , Hott Bruno , Dias Vinícius , Ferreira Renato , Meira Wagner , Guedes Dorgival
Published: January 2016

Most high‐performance data processing (a.k.a. big data) systems allow users to express their computation using abstractions (like MapReduce), which simplify the extraction of parallelism from applications. Most frameworks, however, do not allow users to specify how communication must take place: That element is deeply embedded into the run‐time system abstractions, making changes hard to implement. In this work, we describe Wathershed‐ng, our re‐engineering of the Watershed system, a framework based on the filter–stream paradigm and originally focused on continuous stream processing. Like other big‐data environments, Watershed provided object‐oriented abstractions to express computation (filters), but the implementation of streams was a run‐time system element. By isolating stream functionality into appropriate classes, combination of communication patterns and reuse of common message handling functions (like compression and blocking) become possible. The new architecture even allows the design of new communication patterns, for example, allowing users to choose MPI, TCP, or shared memory implementations of communication channels as their problem demands. Applications designed for the new interface showed reductions in code size on the order of 50% and above in some cases. The performance results also showed significant improvements, because some implementation bottlenecks were removed in the re‐engineering process. Copyright © 2016 John Wiley & Sons, Ltd.
Hydrothermal Synthesis of TiO2@SnO2 Hybrid Nanoparticles in a Continuous‐Flow Dual‐Stage Reactor
Authors: Hellstern Henrik L. , Bremholm Martin , Mamakhel Aref , Becker Jacob , Iversen Bo B.
Published: January 2016

TiO2@SnO2 hybrid nanocomposites were successfully prepared in gram scale using a dual‐stage hydrothermal continuous‐flow reactor. Temperature and pH in the secondary reactor were found to selectively direct nucleation and growth of the secondary material into either heterogeneous nanocomposites or separate intermixed nanoparticles. At low pH, 2 nm rutile SnO2 nanoparticles were deposited on 9 nm anatase TiO2 particles; the presence of TiO2 was found to suppress formation of larger SnO2 particles. At high pH SnO2 formed separate particles and no deposition on TiO2 was observed. Ball‐milling of TiO2 and SnO2 produced no TiO2@SnO2 composites. This verifies that the composite particles must be formed by nucleation and growth of the secondary precursor on the TiO2. High concentration of secondary precursor led to formation of TiO2 particles embedded in aggregates of SnO2 nanoparticles. The results demonstrate how nanocomposites may be produced in high yield by green chemistry.
Effects of intravenous iron therapy in iron‐deficient patients with systolic heart failure: a meta‐analysis of randomized controlled trials
Authors: Jankowska Ewa A. , Tkaczyszyn Michał , Suchocki Tomasz , Drozd Marcin , von Haehling Stephan , Doehner Wolfram , Banasiak Waldemar , Filippatos Gerasimos , Anker Stefan D. , Ponikowski Piotr
Published: January 2016

Aims

The aim of this study was to assess the net clinical and prognostic effects of intravenous (i.v.) iron therapy in patients with systolic heart failure (HF) and iron deficiency (ID).

Methods and results

We performed an aggregate data meta‐analysis (random effects model) of randomized controlled trials that evaluated the effects of i.v. iron therapy in iron‐deficient patients with systolic HF. We searched electronic databases up to September 2014. We identified five trials which fulfilled the inclusion criteria (509 patients received i.v. iron therapy in comparison with 342 controls). Intravenous iron therapy has been shown to reduce the risk of the combined endpoint of all‐cause death or cardiovascular hospitalization [odds ratio (OR) 0.44, 95% confidence interval (CI) 0.30–0.64, P < 0.0001], and the combined endpoint of cardiovascular death or hospitalization for worsening HF (OR 0.39, 95% CI 0.24–0.63, P = 0.0001). Intravenous iron therapy resulted in a reduction in NYHA class (data are reported as a mean net effect with 95% CIs for all continuous variables) (−0.54 class, 95% CI −0.87 to −0.21, P = 0.001); an increase in 6‐min walking test distance (+31 m, 95% CI 18–43, P < 0.0001); and an improvement in quality of life [Kansas City Cardiomyopathy Questionnaire (KCCQ) score +5.5 points, 95% CI 2.8–8.3, P < 0.0001; European Quality of Life–5 Dimensions (EQ‐5D) score +4.1 points, 95% CI 0.8–7.3, P = 0.01; Minnesota Living With Heart Failure Questionnaire (MLHFQ) score −19 points, 95% CI:–23 to −16, P < 0.0001; and Patient Global Assessment (PGA) +0.70 points, 95% CI 0.31–1.09, P = 0004].

Conclusion

The evidence indicates that i.v. iron therapy in iron‐deficient patients with systolic HF improves outcomes, exercise capacity, and quality of life, and alleviates HF symptoms.
Phase Relations and Physical Properties of Layered Pb‐Containing Nd2MoO6 Compounds
Authors: Voronkova Valentina , Orlova Ekaterina , Kazakov Sergey , Kharitonova Elena , Belov Dmitry
Published: January 2016

The phase relations along the Nd2MoO6–PbO join of the ternary Nd2O3–MoO3–PbO system have been studied by means of solid‐state synthesis in air. The samples with high Pb content underwent a reversible first‐order phase transition near 820 °C. XRD analysis revealed two tetragonal phases, the high‐temperature centric phase (I41/acd) and the low‐temperature acentric phase (I$\bar {4}$2m). In the region of the phase transition, the permittivity of the Pb‐containing samples show a strong lambda‐type anomaly and electrical conductivity increases sharply by one and half orders of magnitude. The conductivities of the Pb‐containing samples reach 10–2 S/cm at 850 °C, which is two orders of magnitude greater than the conductivity of pure Nd2MoO6. The conductivity in such compounds may be due to oxygen ions. A permittivity anomaly, existence of a piezoelectric effect, and the symmetry change from acentric I$\bar {4}$2m to centric I41/acd may indicate an antiferroelectric nature of the phase transition.
Synthesis, Structural Characterization, and Catalytic Activity of Indenyl Tris(N‐pyrrolyl)phosphine Complexes of Ruthenium
Authors: Stark Matthew J. , Shaw Michael J. , Rath Nigam P. , Bauer Eike B.
Published: January 2016

The synthesis, characterization, and catalytic activity of new ruthenium complexes of the tris(N‐pyrrolyl)phosphine ligand [P(pyr)3] are described. The new ruthenium complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] (ind = indenyl, η5‐C9H7–) were synthesized in 73 and 63 % isolated yields, respectively, by thermal ligand exchange of [RuCl(ind)(PPh3)2] with P(pyr)3. The electronic and steric properties of the new complexes were studied through analysis of the X‐ray structures and cyclic voltammetry. The new complexes [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] and the known complex [RuCl(ind){(PPh3)2}] differed only slightly in their steric properties, as seen from the comparable bond lengths and angles around the ruthenium centers. The oxidation potentials of [RuCl(ind)(PPh3){P(pyr)3}] and [RuCl(ind){P(pyr)3}2] of +0.34 and +0.71 V versus Cp2Fe0/+ (Cp = cyclopentadienyl) are substantially higher than that of [RuCl(ind)(PPh3)2] (–0.023 V), in accordance with the enhanced π‐acidity of the P(pyr)3 ligand. The new complexes are catalytically active in the etherification of propargylic alcohols and in the first ruthenium‐catalyzed formation of known and new xanthenones from propargylic alcohols and diketones (18 to 72 h at 90 °C in ClCH2CH2Cl or toluene, 1–2 mol‐% catalyst, 69–22 % isolated yields).
A Chemoenzymatic Route To Prepare Acyclic Nucleoside Analogues
Authors: Palazzolo Martín A. , Nigro Mariano J. , Iribarren Adolfo M. , Lewkowicz Elizabeth Sandra
Published: January 2016

Acyclic nucleosides are potential antiviral and antitumor agents. In this work, their preparation through a novel chemoenzymatic procedure involving the N‐alkylation of a nucleobase and subsequent aldol condensation catalyzed by a dihydroxyacetone phosphate‐dependant aldolase (Rabbit Muscle Aldolase, RAMA) is described.
Nickel‐Catalysed Bis‐Allylation of Activated Nucleophiles with Allyl ­Alcohol
Authors: Blieck Rémi , Azizi Mohamed Salah , Mifleur Alexis , Roger Maxime , Persyn Clément , Sauthier Mathieu , Bonin Hélène
Published: January 2016

Nickel‐based catalysis allows the efficient bis‐allylation of soft nucleophiles with allylic alcohols. The reaction is best promoted by a combination of Ni(cod)2 (cod = cyclooctadienyl) and diphenylphosphinobutane under additive‐free conditions. Alternatively, nickel(II) precursors can be used provided that a reductant is used to generate the nickel(0) species. The NiCl2/Zn combination is particularly simple, and can advantageously replace the use of the more air‐sensitive Ni(cod)2 precursor. The scope of the reaction was studied with nucleophiles and allylic derivatives suitable for bis‐allylation reactions.
Mechanochemical Synthesis, Photophysical Properties, and X‐ray Structures of N‐Heteroacenes
Authors: Sahoo Prasit Kumar , Giri Chandan , Haldar Tuhin Subhra , Puttreddy Rakesh , Rissanen Kari , Mal Prasenjit
Published: January 2016

The described mechanochemical methodology is an example of a proof‐of‐concept in which solution‐based tedious, poor yielding, and difficult syntheses of pyrazaacenes are achieved under solvent‐free ball‐milling conditions; the method is easy, high yielding, time‐efficient, and environmentally benign. The synthesized compounds also include pyrazaacenes (N‐heteroacenes) that are octacene analogues containing pyrene building blocks. The compounds were sparingly soluble in common solvents, and column chromatographic purifications could be avoided after the solvent‐free syntheses. The UV/Vis absorption spectra of the pyrazaacenes show intense absorption bands in the near‐IR region. The single‐crystal X‐ray analyses of selected pyrazaacene derivatives showed pairwise π–π interactions and some C–H···π interactions, which could account for some of the photophysical features of the compounds in the solid state.
Evaluating high‐throughput scale‐down chromatography platforms for increased process understanding
Authors: Feliciano Jessika , Berrill Alex , Ahnfelt Mattias , Brekkan Eggert , Evans Brad , Fung Ziawei , Godavarti Ranga , Nilsson‐Välimaa Kristina , Salm Jeff , Saplakoglu Umay , Switzer Mary , Łącki Karol
Published: January 2016

In the biopharmaceutical industry, well‐executed process development and characterization studies ensure robust manufacturing processes. In conventional chromatography, these studies are carried out in series with ≥10 mL bed volumes, thus requiring large quantities of feed material and operator oversight. For that reason, the screening of large process spaces becomes very expensive and has the potential to negatively impact other projects in a company's portfolio competing for similar resources. In this study, we evaluated the ability of the three high‐throughput process development formats 96‐well filter plates, pipette tips, and mini columns to reduce resources in a late‐phase process characterization Protein A capture step. The study used a Protein A capture step with a single experimental design, mAb feed material, and analytical package. The evaluation was based on how identical batch and dynamic process parameters impacted the quality and process performance attributes of monomer purity, host cell protein levels, and yield. All formats were able to provide similar models for product yield and monomer purity. Except for practical limitations of PreDictor plates, all formats could identify significant factors for host cell protein levels. RoboColumn units enabled dynamic factor evaluation and the results were the most comparable to conventional chromatography.