bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractThe 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

AbstractClavicipitic 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
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

AbstractFragment‐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

SummaryBiomaterial 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

SummaryQuantum 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

SummaryThe 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

SummaryStar 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

SummaryEarly 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

SummaryUrban 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

SummaryMost 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

AbstractTiO2@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

AimsThe 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 resultsWe 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].ConclusionThe 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

AbstractThe 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

AbstractThe 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

AbstractAcyclic 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

AbstractNickel‐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

AbstractThe 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.