bluuebunny/crossref_metadata_2025 huggingface dataset:
Stimuli‐Responsive Self‐Assembly of a Naphthalene Diimide by Orthogonal Hydrogen Bonding and Its Coassembly with a Pyrene Derivative by a Pseudo‐Intramolecular Charge‐Transfer Interaction
Authors: Das Anindita , Ghosh Suhrit
Published: December 2013

A naphthalene diimide (NDI) building block containing hydrazide (H1) and hydroxy (H2) groups self‐assembled into a reverse‐vesicular structure in methylcyclohexane by orthogonal H‐bonding and π‐stacking. At an elevated temperature (LCST=43 °C), destruction of the assembled structure owing to selective dissociation of H2–H2 H bonding led to macroscopic precipitation. Further heating resulted in homogeneous redispersion of the sample at 70 °C (UCST) and the formation of a reverse‐micellar structure. In the presence of a pyridine (H3)‐functionalized pyrene (PY) donor, a supramolecular dyad (NDI–PY) was formed by H2–H3 H‐bonding. Slow transformation into an alternate NDI–PY stack occurred by a folding process due to the charge‐transfer interaction between NDI and PY. The mixed NDI–PY assembly exhibited a morphology transition from a reverse micelle (with a NDI–PY mixed‐stack core) below the LCST to another reverse micelle (with a NDI core) above the UCST via a “denatured” intermediate.
On the Molecular Structure and Bonding in a Lithium Bismuth Porphyrin Complex: LiBi(TPP)2
Authors: Balasanthiran Vagulejan , Chisholm Malcolm H. , Durr Christopher B.
Published: December 2013

A new BiLi porphyrin sandwich compound, LiBi(TPP)2 has been synthesized and characterized (TPP=tetraphenylporphyrin). The unique molecular structure of LiBi(TPP)2 is such that the Bi sits between the porphyrins and is directed towards the Li. This complex was shown to remain intact in solution by temperature‐dependent 2D NMR spectroscopy. In order to investigate the potential interaction between these two metals, DFT calculations were used and showed a Bi 6s orbital polarized towards Li which could be indicative of a BiLi dative bond. This bond is remarkably short, 2.87 Å, and is among the shortest BiLi distances seen in a small molecule.
Class III Delocalization in a Cyanide‐Bridged Trimetallic Mixed‐Valence Complex
Authors: Pieslinger German E. , Alborés Pablo , Slep Leonardo D. , Baraldo Luis M.
Published: December 2013

The NIR and IR spectroscopic properties of the cyanide‐bridged complex, trans‐[Ru(dmap)4{(μ‐CN)Ru(py)4Cl}2]3+ (py=pyridine, dmap=4‐dimethylaminopyridine) provide strong evidence that this trimetallic ion behaves as a Class III mixed‐valence species, the first example reported of a cyanide‐bridged system. This has been accomplished by tuning the energy of the fragments in the trimetallic complex to compensate for the intrinsic asymmetry of the cyanide bridge. Moreover, (TD)DFT calculations accurately predict the spectra of the trans‐[Ru(dmap)4{(μ‐CN)Ru(py)4Cl}2]3+ ion and confirms its delocalized nature.
Use of a Phosphonate Methyltransferase in the Identification of the Fosfazinomycin Biosynthetic Gene Cluster
Authors: Gao Jiangtao , Ju Kou‐San , Yu Xiaomin , Velásquez Juan E. , Mukherjee Subha , Lee Jaeheon , Zhao Changming , Evans Bradley S. , Doroghazi James R. , Metcalf William W. , van der Donk Wilfred A.
Published: December 2013

Natural product discovery has been boosted by genome mining approaches, but compound purification is often still challenging. We report an enzymatic strategy for “stable isotope labeling of phosphonates in extract” (SILPE) that facilitates their purification. We used the phosphonate methyltransferase DhpI involved in dehydrophos biosynthesis to methylate a variety of phosphonate natural products in crude spent medium with a mixture of labeled and unlabeled S‐adenosyl methionine. Mass‐guided fractionation then allowed straightforward purification. We illustrate its utility by purifying a phosphonate that led to the identification of the fosfazinomycin biosynthetic gene cluster. This unusual natural product contains a hydrazide linker between a carboxylic acid and a phosphonic acid. Bioinformatic analysis of the gene cluster provides insights into how such a structure might be assembled.
Copper‐Doped CdSe/ZnS Quantum Dots: Controllable Photoactivated Copper(I) Cation Storage and Release Vectors for Catalysis
Authors: Bear Joseph C. , Hollingsworth Nathan , McNaughter Paul D. , Mayes Andrew G. , Ward Michael B. , Nann Thomas , Hogarth Graeme , Parkin Ivan P.
Published: December 2013

The first photoactivated doped quantum dot vector for metal‐ion release has been developed. A facile method for doping copper(I) cations within ZnS quantum dot shells was achieved through the use of metal‐dithiocarbamates, with Cu+ ions elucidated by X‐ray photoelectron spectroscopy. Photoexcitation of the quantum dots has been shown to release Cu+ ions, which was employed as an effective catalyst for the Huisgen [3+2] cycloaddition reaction. The relationship between the extent of doping, catalytic activity, and the fluorescence quenching was also explored.
Evaluation of (S)‐ and (R)‐Misonidazole as GPX Inhibitors: Synthesis, Characterization Including Circular Dichroism and In Vitro Testing on Bovine GPx‐1
Authors: Wilde Felix , Chamseddin Chamseddin , Lemmerhirt Heidi , Bednarski Patrick J. , Jira Thomas , Link Andreas
Published: December 2013

Racemic misonidazole, a radiosensitizer formally used in radiation therapy of cancer and to date still applied, was once reported to exhibit strong inhibitory effects on mouse glutathione peroxidases (GPX). This appeared to qualify misonidazole as a lead structure for the development of novel GPX inhibitors to cause oxidative stress in chemotherapy‐resistant tumors. A unique feature of misonidazole as an inhibitor of GPX is the absence of a thiol functionality. Therefore, it was expected to selectively target inhibition devoid of promiscuous interactions with cations and sulfhydryl groups. We synthesized the isomers of misonidazole and analyzed the ability of chiroptical high‐performance liquid chromatography (HPLC) to identify the particular enantiomers. Due to the chiral pool synthesis, the assignment of the correct configuration could be verified. Finally, we evaluated both isomers for their inhibitory activities on bovine erythrocyte GPx‐1, which is 87% homologous to the human enzyme. Despite the previously reported inhibition of racemic misonidazole on the less homologous mouse GPx‐1, we did not find any significant inhibitory activity on the bovine enzyme for either isomer. Though misonidazole appears unlikely to be an inhibitor of human GPx‐1 activity, we still spotlight misonidazole as a promising fragment‐like lead structure in general.
Synthesis of Quinazolines and Tetrahydroquinazolines: Copper‐Catalyzed Tandem Reactions of 2‐Bromobenzyl Bromides with Aldehydes and Aqueous Ammonia or Amines
Authors: Fan Xuesen , Li Bin , Guo Shenghai , Wang Yuanyuan , Zhang Xinying
Published: December 2013

An efficient synthesis of diversely substituted quinazolines and 1,2,3,4‐tetrahydroquinazolines through copper‐catalyzed tandem reactions of the readily available 2‐bromobenzyl bromides, aldehydes, and aqueous ammonia or amines has been developed. By using ammonia and simple aliphatic amines as the nitrogen source, the present method provides a versatile and practical protocol for the synthesis of quinazolines and 1,2,3,4‐tetrahydroquinazolines.
Alkali‐Metal Trichloroacetates for Dichloromethylenation of Fullerenes: Nucleophilic Addition‐Substitution Route
Authors: Apenova Marina G. , Akhmetov Vladimir A. , Belov Nikita M. , Goryunkov Alexey A. , Ioffe Ilya N. , Lukonina Natalia S. , Markov Vitaliy Yu. , Sidorov Lev N.
Published: December 2013

The first experimental evidence that fullerenes react with alkali‐metal trichloroacetates through a nucleophilic addition‐substitution route, yielding dichloromethylenefullerenes as the final products, is reported. The intermediates, C60(CCl3)− and C70(CCl3)− anions, have been isolated in their protonated forms as ortho‐C60(CCl3)H, as well as three ortho and one para isomer of C70(CCl3)H. The structures were unambiguously determined by means of 1H, 13C, and 1H–13C HMBC NMR spectroscopy along with UV/Vis spectroscopy. The observed regiochemistry was analyzed with the aid of quantum chemical calculations. Conversion of the protonated compounds into the [6,6]‐closed C60/70(CCl2) cycloadducts under basic conditions can be effected only for the ortho isomers, whereas para‐C70(CCl3)H decomposes back into pristine C70.
Extensive frequency selective measurements of radiofrequency fields in outdoor environments performed with a novel mobile monitoring system
Authors: Estenberg Jimmy , Augustsson Torsten
Published: December 2013

A novel, car based, measuring system for estimation of general public outdoor exposure to radiofrequency fields (RF) has been developed. The system enables fast, large area, isotropic spectral measurements with a bandwidth covering the frequency range of 30 MHz to 3 GHz. Measurements have shown that complete mapping of a town with 15000 inhabitants and a path length of 115 km is possible to perform within 1 day. The measured areas were chosen to represent typical rural, urban and city areas of Sweden. The data sets consist of more than 70000 measurements. All measurements were performed during the daytime. The median power density was 16 µW/m2 in rural areas, 270 µW/m2 in urban areas, and 2400 µW/m2 in city areas. In urban and city areas, base stations for mobile phones were clearly the dominating sources of exposure. Bioelectromagnetics. 35:227–230, 2014. © 2013 Wiley Periodicals, Inc.
Networks of lexical borrowing and lateral gene transfer in language and genome evolution
Authors: List Johann‐Mattis , Nelson‐Sathi Shijulal , Geisler Hans , Martin William
Published: December 2013

Like biological species, languages change over time. As noted by Darwin, there are many parallels between language evolution and biological evolution. Insights into these parallels have also undergone change in the past 150 years. Just like genes, words change over time, and language evolution can be likened to genome evolution accordingly, but what kind of evolution? There are fundamental differences between eukaryotic and prokaryotic evolution. In the former, natural variation entails the gradual accumulation of minor mutations in alleles. In the latter, lateral gene transfer is an integral mechanism of natural variation. The study of language evolution using biological methods has attracted much interest of late, most approaches focusing on language tree construction. These approaches may underestimate the important role that borrowing plays in language evolution. Network approaches that were originally designed to study lateral gene transfer may provide more realistic insights into the complexities of language evolution.

Editor's suggested further reading in BioEssaysLinguistic evidence supports date for Homeric epics Abstract
Anaplastic lymphoma kinase gene rearrangements in patients with advanced‐stage non‐small‐cell lung cancer: CT characteristics and response to chemotherapy
Authors: Park Jangchul , Yamaura Hidekazu , Yatabe Yasushi , Hosoda Waki , Kondo Chiaki , Shimizu Junichi , Horio Yoshitsugu , Yoshida Kimihide , Tanaka Kosuke , Oguri Tomoyo , Kobayashi Yoshihisa , Hida Toyoaki
Published: December 2013

Few articles have been published on the imaging findings of anaplastic lymphoma kinase (ALK)‐positive non‐small‐cell lung cancer (NSCLC). To investigate the radiological findings of ALK‐positive NSCLC in the advanced stage, CT scans were examined. In addition, the response to chemotherapy was evaluated. Of the 36 patients with ALK‐rearranged NSCLC, a mass and a nodule were identified in 17 (47.2%) and 16 (44.4%), respectively, indicating that more than 40% had a small‐sized tumor. Overall, 31 (86.1%) patients had lymphadenopathy, seven (19.4%) had extranodal lymph node invasion, and three (8.3%) had lymphangitis. A pleural effusion was seen in 15 patients (41.7%). All but one patient had no ground‐glass opacity (GGO) lesions, indicating that most ALK‐positive tumors showed a solid growth pattern without GGO on CT. Twenty were evaluable for response to chemotherapy; 10 (50.0%) had a partial response (PR), nine (45.0%) had stable disease (SD), and one (5.0%) had progressive disease (PD) with first‐line chemotherapy. With second‐line chemotherapy, five (26.3%) had PR, 11 (57.9%) had SD, and three (15.8%) had PD. The five patients with PR were all treated by using crizotinib. Time to progression was 8.2 months with first‐line chemotherapy, and 6.0 months with second‐line chemotherapy. Advanced‐stage ALK‐positive tumors have a relatively aggressive phenotype, which cannot be inferred from the size of the tumor alone. ALK‐positive patients have a good response to first‐line cytotoxic drugs and to crizotinib as second‐line therapy, but a relatively poor response to cytotoxic drugs as second‐line therapy.
Lack of appreciation of the role of osmotically unresponsive water in cell volume regulation
Authors: Cameron Ivan L. , Fullerton Gary D.
Published: December 2013

The osmotic responsiveness of cell water has been re‐evaluated of reports on the osmotic behaviour of cells. In seven animal cell types, the osmotically unresponsive water (OUR) fraction values ranged from 0.75 to 2.41 g water/g dry mass (g/g), and from 25 to 92% of the total cell water. Protein confirmation, aggregation and crowding play a major, but under‐recognised, role in determining the extent of OUR and the regulation of cell volume. Volume regulation studies that do not take into account the role of OUR must be judged incomplete.
On‐Stream Regeneration of a Sulfur‐Poisoned Ruthenium–Carbon Catalyst Under Hydrothermal Gasification Conditions
Authors: Dreher Marian , Steib Matthias , Nachtegaal Maarten , Wambach Jörg , Vogel Frédéric
Published: December 2013

Catalytic processes that employ Ru catalysts in supercritical water are capable of converting organics, such as wood waste or biosolids, into synthetic natural gas (CH4) with high efficiencies at relatively moderate temperatures of around 400 °C. However, Ru catalysts are prone to S poisoning and are quickly deactivated. As S is ubiquitous in raw biomass and technologies to remove S from hydrothermal biomass feeds are lacking, regeneration protocols that efficiently reactivate S‐poisoned catalysts are required to realize efficient conversion processes and long catalyst lifetimes. In this work, we developed a method to remove S from a S‐poisoned Ru catalyst under hydrothermal conditions through an oxidative treatment in the aqueous phase. By using in situ X‐ray absorption spectroscopy under the reaction conditions, we show that Ru is oxidized by dilute H2O2 at low temperatures, which leads to the removal of adsorbed S species from the catalyst surface. By optimizing the regeneration conditions, it was possible to prevent oxidation of the catalyst carbon support, as revealed by ex situ TEM. This treatment led to a reactivation of the Ru catalyst with a significant increase in carbon‐to‐gas conversion and methane selectivity.
A NiPdB‐PEG(800) Amorphous Alloy Catalyst for the Chemoselective Hydrogenation of Electron‐Deficient Aromatic Substrates
Authors: Bai Guoyi , Zhao Zhen , Dong Huixian , Niu Libo , Wang Yalong , Chen Qingzhi
Published: December 2013

A new Pd and polyethylene glycol 800 [PEG(800)]‐modified NiB [NiPdB‐PEG(800)] amorphous alloy catalyst was prepared, which demonstrated excellent activities, similar to those of noble metal catalysts, in the chemoselective hydrogenation of a series of electron‐deficient aromatic substrates in water. The addition of small amounts of Pd to NiB markedly improved its activity. The Pd not only benefits the dispersion of active species but also contributes to the activity of the catalyst. The accompanying agglomeration can be inhibited with the further addition of PEG(800), which results in the largest surface area, the smallest particle size, and the greatest number of active species, resulting in optimum H2‐chemisorption and accounting for its highest activity. The key factors determining the main reaction products depend not only on the structures of the substrates but also on the character of the solvents. Water is found to be the most effective solvent for most of the substrates.
How Can a Carbene be Active in an Ionic Liquid?
Authors: Thomas Martin , Brehm Martin , Hollóczki Oldamur , Kirchner Barbara
Published: December 2013

The solvation of the carbene 1‐ethyl‐3‐methylimidazole‐2‐ylidene in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate was investigated by ab initio molecular dynamics simulations in order to reveal the interaction between these two highly important classes of materials: N‐heterocyclic carbenes with superb catalytic activity and ionic liquids with advantageous properties as solvents and reaction media. In contrast to previously published data on analogous systems, no hydrogen bond is observed between the hypovalent carbon atom and the most acidic ring hydrogen atoms, as these interaction sites of the imidazolium ring are predominantly occupied by the acetate ions. Keeping the carbene away from the ring hydrogen atoms prevents stabilization of this reactive species, and hence any retarding effect on subsequent reactions, which explains the observed high reactivity of the carbene in acetate‐based ionic liquids. Instead, the carbene exhibits a weaker interaction with the methyl group of the imidazolium cation by forming a hitherto unprecedented kind of C⋅⋅⋅HC hydrogen bond. This unexpected finding not only indicates a novel kind of hydrogen bond for carbenes, but also shows that such interaction sites of the imidazolium cation are not limited to the ring hydrogen atoms. Thus, the results give the solute–solvent interactions within ionic liquids a new perspective, and provide a further, albeit weak, site of interaction to tune in order to achieve the desired environment for any dissolved active ingredient.
Maximum Compaction of Ionic Organic Explosives: Bis(hydroxylammonium) 5,5′‐Dinitromethyl‐3,3′‐bis(1,2,4‐oxadiazolate) and its Derivatives
Authors: Klapötke Thomas M. , Mayr Norbert , Stierstorfer Jörg , Weyrauther Michael
Published: December 2013

Within this contribution on bis(oxadiazoles) we report on bis‐hydroxylammonium 5,5′‐dinitro‐methyl‐3,3′‐bis(1,2,4‐oxadiazolate), which (to the best of our knowledge) shows the highest density (2.00 g cm−3 at 92 K, 1.95 g cm−3 at RT) ever reported for an ionic CHNO explosive. Also the corresponding bis(ammonium) salt shows an outstanding density of 1.95 g cm−3 (173 K). The reaction of the 3,3′‐bis(1,2,4‐oxadiazolyl)‐5,5′‐bis(2,2′‐dinitro)‐diacetic acid diethyl ester with different nitrogen‐rich bases, such as ammonia, hydrazine, hydroxylamine, and triaminoguanidine causes decarboxylation followed by the formation of the corresponding salts (cation/anion stoichiometry 2:1). The reactions are performed at ambient temperature in H2O/MeOH mixtures and furnish qualitatively pure products showing characteristics of typical secondary explosives. The obtained compounds were characterized by multinuclear NMR spectroscopy, IR and Raman spectroscopy, as well as mass spectrometry. Single‐crystal X‐ray diffraction studies were performed and the structures of all compounds were determined at low temperatures. The thermal stability was measured by differential scanning calorimetry (DSC). The sensitivities were explored by using the BAM drophammer and friction test. The heats of formation were calculated by the atomization method based on CBS‐4M enthalpies. With these values and the X‐ray densities, several detonation parameters such as the detonation pressure, velocity, energy, and temperature were computed using the EXPLO5 code.
Compartmental modelling of turbulent fluid flow for the scale‐up of stirred tanks
Authors: Bashiri Hamed , Heniche Mourad , Bertrand François , Chaouki Jamal
Published: December 2013

In this work, the results of single phase CFD simulations of mixing vessels with four baffles agitated by a Rushton turbine are used to determine the parameters of a two‐compartment model that describes the turbulent non‐homogeneities therein. An improved method is proposed to find the boundary between the two characteristic regions. Using this method, the effects of different conventional scale‐up criteria including constant impeller speed, constant impeller tip speed and constant power consumption per liquid volume, on the value of the compartmental model parameters are investigated. It can be observed that the distribution of the turbulent energy dissipation rate and, as a result, the compartmental model parameters change considerably when following conventional scale‐up rules. The concept of a general map of compartment energy dissipation rate and volume ratios, which can be used for the scale‐up of stirred tanks, is introduced.
CFD‐DEM simulation of the spout–annulus interaction in a 3D spouted bed with a conical base
Authors: Yang Shiliang , Luo Kun , Fang Mingming , Fan Jianren
Published: December 2013

Numerical simulation of the gas–solid flow in a three‐dimensionally spouted bed with a conical base is conducted on the base of the CFD–DEM coupling approach. The gas phase is tracked at the computational grid level, while the solid motion is resolved at the particle scale level. The comparison is taken between the calculated results and the experimental data in literature. Hydrodynamics and spout–annulus interaction in the bed are investigated. The results demonstrate that the gas flow in the cylindrical region of the bed shows self‐similarity property. Solid vertical velocity in the central region increases initially and then decreases with bed elevation. The vertical solid transporting intensity is dramatically larger than the lateral one. Furthermore, the spout diameter exhibits a diverging tendency along the axial direction. Spout–annulus interaction intensity can be quantitatively described with solid flux exchanging from the spout boundary. Moreover, the interaction intensity through the spout–annulus interface increases initially, and then diminishes along the axial direction. Besides, the spout diameter and the spout–annulus interaction intensity are enlarged by increasing the spouting velocity.
Pore network simulation for diffusion through a porous membrane: A comparison between Knudsen and Oscillator models
Authors: Adloo Hadi , Esfahany Mohsen Nasr , Ehsani Mohammad Reza
Published: December 2013

Low density permeations of some gases (He, H2, N2, CH4, CO2 and CF4) through micro‐ and mesocarboneous pores were investigated using Knudsen and Oscillator models. Lennard‐Jones model in single layer pores was used to simulate the gas–solid interactions in the Oscillator model. The effects of the pore radius as well as the molecular size and the temperature on the pore diffusivity and the activation energy were studied. The Monte Carlo simulation was then performed to calculate the permeability of these gases in three‐dimensional cubic networks of different connectivities (2.5–6) and different pore size distributions (ra = 2.74 and 6.95 nm). It was shown that for networks with larger pores there is a minor difference between the two models, while a large discrepancy exists in networks with fine pores. Both models tend to have the same permeability as the coordination number decreases. To investigate the accuracy of the models, the simulation results were compared with the experimental selectivities of some pure gases in two different membranes extracted from the literature. It was shown that the Oscillator model can better predict the experimental data in the membranes of smaller pores (i.e. ra = 2.74 nm). However, both models were comparable in membranes of larger pores (ra = 6.95 nm). The capability of the models to predict the activation energy of the diffusion was also studied.
Modulation of Biodistribution, Pharmacokinetics, and Photosensitivity with the Delivery Vehicle of a Bacteriochlorin Photosensitizer for Photodynamic Therapy
Authors: Saavedra Raquel , Rocha Luis B. , Dąbrowski Janusz M. , Arnaut Luis G.
Published: December 2013

Intravenous (i.v.) formulations with various amounts of organic solvents [PEG400, propylene glycol (PG), cremophor EL (CrEL)] were used to deliver a fluorinated sulfonamide bacteriochlorin to mice, rats, and minipigs. Biodistribution studies in mice showed that a low‐content CrEL formulation combines high bioavailability with high tumor‐to‐muscle and tumor‐to‐skin ratios. This formulation was also the most successful in the photodynamic therapy of mice with subcutaneously implanted CT26 murine colon adenocarcinoma tumors. Pharmacokinetic studies in mice and minipigs revealed that with the same low CrEL formulation, the half‐life of the photosensitizer in the central compartment was longer in minipigs. Differences in biodistribution with the various formulations, and in pharmacokinetics between the two animal species with the same formulation, are attributed to the interaction of the formulations with low‐density lipoproteins (LDLs). Skin photosensitivity studies in rats showed that 30 min exposure of the skin to a solar simulator 7 days after i.v. administration of the fluorinated sulfonamide bacteriochlorin at 1 mg kg−1 did not elicit significant skin reactions.
A New SiF–Dipropargyl Glycerol Scaffold as a Versatile Prosthetic Group to Design Dimeric Radioligands: Synthesis of the [18F]BMPPSiF Tracer to Image Serotonin Receptors
Authors: Hazari Puja Panwar , Schulz Jurgen , Vimont Delphine , Chadha Nidhi , Allard Michele , Szlosek‐Pinaud Magali , Fouquet Eric , Mishra Anil Kumar
Published: December 2013

A novel SiX–dipropargyl glycerol scaffold (X: H, F, or 18F) was developed as a versatile prosthetic group that provides technical advantages for the preparation of dimeric radioligands based on silicon fluoride acceptor pre‐ or post‐labeling with fluorine‐18. Rapid conjugation with the prosthetic group takes place in microwave‐assisted click conjugation under mild conditions. Thus, a bivalent homodimeric SiX–dipropargyl glycerol derivatized radioligand, [18F]BMPPSiF, with enhanced affinity was developed by using click conjugation. High uptake of the radioligand was demonstrated in 5‐HT1A receptor‐rich regions in the brain with positron emission tomography. Molecular docking studies (rigid protein–flexible ligand) of BMPPSiF and known antagonists (WAY‐100635, MPPF, and MefWAY) with monomeric, dimeric, and multimeric 5‐HT1A receptor models were performed, with the highest G score obtained for docked BMPPSiF: −6.766 as compared with all three antagonists on the monomeric model. Multimeric induced‐fit docking was also performed to visualize the comparable mode of binding under in vivo conditions, and a notably improved G score of −8.455 was observed for BMPPSiF. These data directly correlate the high binding potential of BMPPSiF with the bivalent binding mode obtained in the biological studies. The present study warrants wide application of the SiX–dipropargyl glycerol prosthetic group in the development of ligands for imaging with enhanced affinity markers for specific targeting based on peptides, nucleosides, and lipids.
PMaC's green queue: a framework for selecting energy optimal DVFS configurations in large scale MPI applications
Authors: Peraza Joshua , Tiwari Ananta , Laurenzano Michael , Carrington Laura , Snavely Allan
Published: December 2013

This article presents Green Queue, a production quality tracing and analysis framework for implementing application aware dynamic voltage and frequency scaling (DVFS) for message passing interface applications in high performance computing. Green Queue makes use of both intertask and intratask DVFS techniques. The intertask technique targets applications where the workload is imbalanced by reducing CPU clock frequency and therefore power draw for ranks with lighter workloads. The intratask technique targets balanced workloads where all tasks are synchronously running the same code. The strategy identifies program phases and selects the energy‐optimal frequency for each by predicting power and measuring the performance responses of each phase to frequency changes. The success of these techniques is evaluated on 1024 cores on Gordon, a supercomputer at the San Diego Supercomputer Center built using Intel Xeon E5‐2670 (Sandybridge) processors. Green Queue achieves up to 21% and 32% energy savings for the intratask and intertask DVFS strategies, respectively. Copyright © 2013 John Wiley & Sons, Ltd.
An efficient protocol for two‐party explicit authenticated key agreement
Authors: Zheng Minghui , Zhou Huihua , Chen Jing
Published: December 2013

Successful and efficient key management plays a critical role toward secured computing and communication systems. Many authenticated key agreement protocols have been proposed to meet the great challenges of information security. The two‐party key agreement protocol can be classified into two categories: implicit and explicit key authentications. This paper investigates the issue on authenticated two‐party key agreement protocol over an insecure public network and extends the existing implicit authenticated key agreement protocol into the explicit one by introducing the authenticators. The advantage of this explicit protocol is that it does not need any fixed public key infrastructure. Furthermore, this explicit protocol is provably secure in the random oracle under the Computation Gap Diffie‐Hellman assumption. Concurrency and Computation: Practice and Experience, 2013.© 2013 Wiley Periodicals, Inc.
A Strategy to Synthesize Hollow Micro/Nanospheres with Tunable Shell Thickness
Authors: Yang Gongzheng , Cui Hao , Wang Chengxin
Published: December 2013

A simple one‐step direct templating method is developed to synthesize hollow carbon and sandwich‐like ZnO/C/ZnO micro/nanospheres. The type and shell thickness of the final products can be controlled by simply adjusting the reaction temperature. The removal of the templates can also be easily controlled during the synthesis. At a low temperature, the templates remain in the products to form hollow sandwich‐like micro/nanospheres. As the reaction temperature rises, the templates are consumed, which results in the preparation of hollow carbon micro/nanospheres. On the basis of a series of experiments, we propose a simple plausible mechanism to address the original strategy for synthesizing these hollow micro/nanospheres. Furthermore, the sandwich‐like ZnO/C/ZnO nanospheres can be used as the anode in lithium‐ion batteries, exhibiting an extraordinary cyclability and a high coulombic efficiency. This approach can be extended to the synthesis of other hollow spheres. Further investigation is underway in our group.
Argon plasma treatment on metal substrates and effects on diamond‐like carbon (DLC) coating properties
Authors: Wasy Abdul , Balakrishnan G. , Lee S. H. , Kim J. K. , Kim D. G. , Kim T. G. , Song J. I.
Published: December 2013

The diamond like carbon coatings (DLC) of 400 nm thickness was deposited by filtered cathodic vacuum arc system. The argon plasma etched and non‐etched tungsten carbide‐cobalt (WC‐Co) and stainless steel (SUS) were used as substrates. The chromium was deposited as an interlayer for diamond like carbon coatings on the etched and non‐etched WC‐Co and SUS substrates. The present research is to evaluate the effect of argon plasma etching of the substrates on microstructure, tribology and adhesion strength of DLC coatings. The films were characterized by field emission scanning electron microscopy, Raman spectroscopy, tribology and scratch tests. The Raman studies showed the broad peak ∼1550 cm−1 indicates the formation of amorphous carbon or diamond‐like carbon. It was found that the DLC coatings on the plasma etched substrates of WC‐Co and SUS have shown the low friction coefficient of ∼0.12–0.14. The DLC coatings on plasma etched substrates of WC‐Co have better adhesion strength. The results showed that the argon plasma etching of substrate reduces the surface roughness to ∼2.5 nm, resulting in smooth morphology, good adhesion and wear resistance as compared to DLC coating on non‐etched substrates. The scanning electron microscopic studies showed that the DLC coated specimens with plasma etched substrates have minimum damage as compared to the DLC coated non etched substrates.
Metastable zone width of SrCl2·6H2O during cooling crystallization
Authors: Qian Yuanyuan , Lu Guimin , Sun Yuzhu , Song Xingfu , Yu Jianguo
Published: December 2013

The metastable zone width (MSZW) of SrCl2·6H2O during cooling crystallization was determined by the focused beam reflectance measurement (FBRM). The effects of the saturation temperature, cooling rate, stirring rate, and Ca2+ ion impurity on the MSZW were investigated. The MSZW increased with the increase in the cooling rate and decreased with the increase in the saturation temperature, stirring rate, and Ca2+ ion concentration. Moreover, the effect of seed crystals on the MSZW was investigated, where two types of seeds were used, namely, seed 1# and 2# with volume mean crystal sizes of 64 and 218 µm, respectively. The seeded MSZW decreased than the unseeded one. The MSZW of seed 1# was greater than that of seed 2# when the same amount of seed was used. The MSZW of seed 1# increased with the increase in the seed loading, whereas that of seed 2# decreased.
Regenerability of Hydrotalcite‐Derived Nickel–Iron Alloy Nanoparticles for Syngas Production from Biomass Tar
Authors: Li Dalin , Koike Mitsuru , Wang Lei , Nakagawa Yoshinao , Xu Ya , Tomishige Keiichi
Published: December 2013

Nickel–iron/magnesium/aluminum bimetallic catalysts were prepared by the calcination and reduction of nickel–magnesium–iron–aluminum hydrotalcite‐like compounds. Characterization suggests that, at iron/nickel≤0.5, both nickel and iron species are homogeneously distributed in the hydrotalcite precursor and incorporated into the Mg(Ni, Fe, Al)O periclase after calcination, giving rise to uniform nickel–iron alloy nanoparticles after reduction. Ni–Fe/Mg/Al (Fe/Ni=0.25) exhibits the best catalytic performance for the steam reforming of tar derived from the pyrolysis of biomass. It is suggested that the uniform nickel–iron alloy nanoparticles and the synergy between nickel and iron are responsible for the high catalytic performance. Moreover, the Ni–Fe/Mg/Al catalyst exhibits much better regenerability toward oxidation–reduction treatment for the removal of deposited coke than that of conventional Ni–Fe/α‐Al2O3. This property can be attributed to the better regeneration of Ni–Fe alloy nanoparticles through the formation and reduction of Mg(Ni, Fe, Al)O.
Deep Eutectic Solvents in Polymerizations: A Greener Alternative to Conventional Syntheses
Authors: del Monte Francisco , Carriazo Daniel , Serrano María C. , Gutiérrez María C. , Ferrer M. Luisa
Published: December 2013

The use of deep eutectic solvents (DESs) that act as all‐in‐one solvent–template–reactant systems offers an interesting green alternative to conventional syntheses in materials science. This Review aims to provide a comprehensive overview to emphasize the similarities and discrepancies between DES‐assisted and conventional syntheses and rationalize certain green features that are common for the three DES‐assisted syntheses described herein: one case of radical polymerization and two cases of polycondensations. For instance, DESs contain the precursor itself and some additional components that either provide certain functionality (e.g., drug delivery and controlled release, or electrical conductivity) to the resulting materials or direct their formation with a particular structure (e.g., hierarchical‐type). Moreover, DESs provide a reaction medium, so polymerizations are ultimately carried out in a solventless fashion. This means that DES‐assisted syntheses match green chemistry principles 2 and 5 because of the economy of reagents and solvents, whereas the functionality incorporated by the second component allows the need for any post‐synthesis derivatization to be minimized or even fully avoided (principle 8). DESs also provide new precursors that favor more efficient polymerization (principle 6) by decreasing the energy input required for reaction progress. Finally, the use of mild reaction conditions in combination with the compositional versatility of DESs, which allows low‐toxic components to be selected, is also of interest from the viewpoint of green chemistry because it opens up the way to design biocompatible and/or eco‐friendly synthetic methods (principle 3).
Development of non‐native vowel discrimination: Improvement without exposure
Authors: Mazuka Reiko , Hasegawa Mihoko , Tsuji Sho
Published: December 2013

The present study tested Japanese 4.5‐ and 10‐month old infants' ability to discriminate three German vowel pairs, none of which are contrastive in Japanese, using a visual habituation–dishabituation paradigm. Japanese adults' discrimination of the same pairs was also tested. The results revealed that Japanese 4.5‐month old infants discriminated the German /bu:k/‐/by:k/ contrast, but they showed no evidence of discriminating the /bi:k/‐/be:k/ or /bu:k/‐/bo:k/ contrasts. Japanese 10‐month old infants, on the other hand, discriminated the German /bi:k/‐/be:k/ contrast, while they showed no evidence of discriminating the /bu:k/‐/by:k/ or /bu:k/‐/bo:k/ contrasts. Japanese adults, in contrast, were highly accurate in their discrimination of all of the pairs. The results indicate that discrimination of non‐native contrasts is not always easy even for young infants, and that their ability to discriminate non‐native contrasts can improve with age even when they receive no exposure to a language in which the given contrast is phonemic. © 2013 Wiley Periodicals, Inc. Dev Psychobiol 56: 192–209, 2014.
Using Arabic Word Identification Fluency to Monitor First‐grade Reading Progress
Authors: Abu‐Hamour Bashir
Published: December 2013

This study examined the applicability, reliability and validity of the Arabic version of the curriculum‐based measurement word identification fluency (CBM WIF) measure in Jordanian students. A sample of 75 first‐grade students, 50 average readers and 25 with reading difficulties, were recruited from two public primary schools. Results indicated that the CBM WIF is a reliable, valid and cost‐effective measure. A 15‐week trial demonstrated the effectiveness of using CBM WIF with the first‐grade students. In addition, CBM WIF was a good predictor of grade point average in the native language. Moreover, students who were struggling with reading scored significantly lower on CBM WIF probes than did average readers. Results suggest that the CBM WIF measures may be useful for evaluating and predicting reading performance in Arabic. Copyright © 2013 John Wiley & Sons, Ltd.
Bruton's tyrosine kinase regulates TLR9 but not TLR7 signaling in human plasmacytoid dendritic cells
Authors: Wang Jingming , Lau Kai‐Yeung , Jung Jimmy , Ravindran Palanikumar , Barrat Franck J.
Published: December 2013

Plasmacytoid dendritic cells (PDCs) represent a key cell type for both innate and adaptive immunity. PDCs express both TLR7 and TLR9 and the recognition of nucleic acids by these two receptors triggers the production of a large amount of type‐I IFN and the induction of PDC maturation into APCs. This unique feature of PDCs is at the basis of clinical development of both TLR7 and TLR9 agonists for infectious diseases, allergy, cancer, and asthma. However, TLR7 and TLR9 recognition of self‐nucleic acids is linked to many autoimmune diseases including lupus, and a better understanding of the signaling pathways of these two receptors in PDCs is thus important. We have identified Bruton's tyrosine kinase (Btk) as an important player for TLR9 but not TLR7 signaling in human PDCs. Blocking Btk using a specific inhibitor leads to the reduction of all TLR9‐induced responses in PDCs, including cytokine production and expression of costimulatory molecules, while this has no impact on the TLR7 response. This identifies Btk as a key molecule in TLR9 signaling in PDCs and is the first demonstration that the TLR7 and TLR9 pathways can be dissociated in human PDCs.
ADAM8 expression in invasive breast cancer promotes tumor dissemination and metastasis
Authors: Romagnoli Mathilde , Mineva Nora D , Polmear Michael , Conrad Catharina , Srinivasan Srimathi , Loussouarn Delphine , Barillé‐Nion Sophie , Georgakoudi Irene , Dagg Áine , McDermott Enda W , Duffy Michael J , McGowan Patricia M. , Schlomann Uwe , Parsons Maddy , Bartsch Jörg W , Sonenshein Gail E
Published: December 2013

The transmembrane metalloprotease‐disintegrin ADAM8 mediates cell adhesion and shedding of ligands, receptors and extracellular matrix components. Here, we report that ADAM8 is abundantly expressed in breast tumors and derived metastases compared to normal tissue, especially in triple‐negative breast cancers (TNBCs). Furthermore, high ADAM8 levels predicted poor patient outcome. Consistently, ADAM8 promoted an aggressive phenotype of TNBC cells in culture. In a mouse orthotopic model, tumors derived from TNBC cells with ADAM8 knockdown failed to grow beyond a palpable size and displayed poor vascularization. Circulating tumor cells and brain metastases were also significantly reduced. Mechanistically, ADAM8 stimulated both angiogenesis through release of VEGF‐A and transendothelial cell migration via β1‐integrin activation. In vivo, treatment with an anti‐ADAM8 antibody from the time of cell inoculation reduced primary tumor burden and metastases. Furthermore, antibody treatment of established tumors profoundly decreased metastases in a resection model. As a non‐essential protein under physiological conditions, ADAM8 represents a promising novel target for treatment of TNBCs, which currently lack targeted therapies and frequently progress with fatal dissemination.
Simulation of an Air‐to‐Water Heat Pump System to Evaluate the Impact of Demand‐Side‐Management Measures on Efficiency and Load‐Shifting Potential
Authors: Miara Marek , Günther Danny , Leitner Zaphod L. , Wapler Jeannette
Published: December 2013

Increasing variable renewable electricity generation in Germany challenges the German electricity supply in terms of mismatch between supply and demand as well as grid stability. Demand side management (DSM), a portfolio of measures to improve the energy system on the consumption side, can contribute to the ability to cope with the upcoming challenges in the future smart power grid.1 Currently, over 500 000 electrical compression heat pumps (HP) provide a potential for DSM in Germany.2, 3, 4 Whereas static load shedding for heat pumps is state‐of‐the‐art, concepts for dynamic load shifting still need to be developed. A variety of heat pump systems (HPS) and control strategies provide different potentials to shift loads. This simulation study has been performed to examine variations of a typical single‐family‐house HPS in terms of efficiency and DSM potential. Six scenarios for 2012 and six scenarios for 2030 are analyzed with varying buffer storage sizes, control strategies, and heat pump capacities. The prior condition for the realization of load shifting through thermal energy storage has been to prevent nominal room temperature changes. The presented results indicate that electrical heat pumps combined with buffer storage are suitable devices for DSM without violating the nominal room temperature. However, the load shifting caused an increased electricity consumption of up to 19 %.
Resolving the Antarctic contribution to sea‐level rise: a hierarchical modelling framework
Authors: Zammit‐Mangion Andrew , Rougier Jonathan , Bamber Jonathan , Schön Nana
Published: December 2013

Determining the Antarctic contribution to sea‐level rise from observational data is a complex problem. The number of physical processes involved (such as ice dynamics and surface climate) exceeds the number of observables, some of which have very poor spatial definition. This has led, in general, to solutions that utilise strong prior assumptions or physically based deterministic models to simplify the problem. Here, we present a new approach for estimating the Antarctic contribution, which only incorporates descriptive aspects of the physically based models in the analysis and in a statistical manner. By combining physical insights with modern spatial statistical modelling techniques, we are able to provide probability distributions on all processes deemed to play a role in both the observed data and the contribution to sea‐level rise. Specifically, we use stochastic partial differential equations and their relation to geostatistical fields to capture our physical understanding and employ a Gaussian Markov random field approach for efficient computation. The method, an instantiation of Bayesian hierarchical modelling, naturally incorporates uncertainty in order to reveal credible intervals on all estimated quantities. The estimated sea‐level rise contribution using this approach corroborates those found using a statistically independent method. © 2013 The Authors.EnvironmetricsPublished by John Wiley & Sons, Ltd.
Stationary and nonstationary generalized extreme value modelling of extreme precipitation over a mountainous area under climate change
Authors: Panagoulia D. , Economou P. , Caroni C.
Published: December 2013

The generalized extreme value (GEV) distribution is often fitted to environmental time series of extreme values such as annual maxima of daily precipitation. We study two methodological issues here. First, we compare criteria for selecting the best model among 16 GEV models that allow nonstationary scale and location parameters. Simulation results showed that both the corrected Akaike information criterion and Bayesian information criterion (BIC) always detected nonstationarity, but the BIC selected the correct model more often except in very small samples. Second, we examined confidence intervals (CIs) for model parameters and other quantities such as the return levels that are usually required for hydrological and climatological time series. Four bootstrap CIs—normal, percentile, basic and bias‐corrected and accelerated—constructed by random‐tresampling, fixed‐tresampling and the parametric bootstrap methods were compared. CIs for parameters of the stationary model do not present major differences. CIs for the more extreme quantiles tend to become very wide for all bootstrap methods. For nonstationary GEV models with linear time dependence of location or log‐linear time dependence of scale, CI coverage probabilities are reasonably accurate for the parameters. For the extreme percentiles, the bias‐corrected and accelerated method is best overall, and the fixed‐tmethod also has good average coverage probabilities. A case study is presented of annual maximum daily precipitation over the mountainous Mesochora catchment in Greece. Analysis of historical data and data generated under two climate scenarios (control run and climate change) supported a stationary GEV model reducing to the Gumbel distribution. Copyright © 2013 John Wiley & Sons, Ltd.