bluuebunny/crossref_metadata_2025_split huggingface dataset:
Simultaneous Dual Encoding of Three‐Dimensional Structures by Light‐Induced Modular Ligation
Authors: Claus Tanja K. , Richter Benjamin , Hahn Vincent , Welle Alexander , Kayser Sven , Wegener Martin , Bastmeyer Martin , Delaittre Guillaume , Barner‐Kowollik Christopher 
Published: February 2016

AbstractA highly efficient strategy for the simultaneous dual surface encoding of 2D and 3D microscaffolds is reported. The combination of an oligo(ethylene glycol)‐based network with two novel and readily synthesized monomers with photoreactive side chains yields two new photoresists, which can be used for the fabrication of microstructures (by two‐photon polymerization) that exhibit a dual‐photoreactive surface. By combining both functional photoresists into one scaffold, a dual functionalization pattern can be obtained by a single irradiation step in the presence of adequate reaction partners based on a self‐sorting mechanism. The versatility of the approach is shown by the dual patterning of halogenated and fluorescent markers as well as proteins. Furthermore, we introduce a new ToF–SIMS mode (“delayed extraction”) for the characterization of the obtained microstructures that combines high mass resolution with improved lateral resolution.
Double layer capacitance for different thicknesses of carbon overlay and types of electrolytes: a circuit analogue approach
Authors: Singh S. , Supriya  , Rakib S. K. A. , Chavhan M. P. , Ganguly S. 
Published: February 2016

AbstractElectrochemical double layer capacitor (EDLC) complements batteries in addressing the intermittency problems in non‐renewable energy sources. Here, the charge is stored in double layer in porous materials that offer high internal surface area. At the time of charging or discharging the capacitor, the transport of ions through the pore network involves resistance that influences the effectiveness of storage. This article presents the impedance spectroscopy data to analyse the resistance inside the pore. The equivalent circuits were fitted here to explain the complex impedance curve. The resistive and capacitive elements and their arrangement were studied for different thicknesses of the activated carbon overlay. The effect of binder on the internal surface area of activated carbon powder was evaluated through BET analysis and scanning electron microscopy. The results were compared for two electrolytes. Aqueous solution of potassium chloride as an aqueous electrolyte, and tetra ethyl ammonium tetra fluoroborate in acetonitrile as an organic electrolyte were used in this study. Copyright © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Hydrodynamics of macroscopic particles in slurry suspensions
Authors: Wadnerkar Divyamaan , Agrawal Madhusuden , Tade Moses O. , Pareek Vishnu 
Published: February 2016

AbstractSlurry systems in mineral processing processes often behave as pseudo‐plastic fluids, where the viscosity of the slurry changes as a function of the shear imparted. Thus, characterizing motion of macroscopic objects through such systems is a challenging task because the viscous forces on it vary rapidly. In this paper, we have studied motion of falling spherical particles in non‐Newtonian fluid using a novel macroscopic particle model (MPM). The simulation results were compared with the available experimental data and analytical correlations, where MPM was found to be effective in accurately determining the forces acting on particle during fluid–particle interaction. Thus, it was concluded that MPM is a computationally viable solution for resolving hydrodynamics of macroscopic particles in slurries, especially for its ability to accurately capture the acceleration of particles, which is significantly lower when compared with that in Newtonian fluids. The validated MPM model was used to investigate the effect of particle properties on the motion of particle and yield‐structure of fluid. For low Reynolds number, the well‐known toroidal yielded structure of fluid was observed with particle equator as centre and √2dp diameter. Beyond the Reynolds number to Bingham number ratio of 10, a wake was formed behind the particle that increased with increasing Reynolds number. © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Sergeant Major Edgar Allan Poe
Authors: Tieman John Samuel 
Published: February 2016

AbstractUsing psychoanalytic theory, it is the primary purpose of this article to frame Edgar Allan Poe's history as an enlisted man in the United States Army. For Poe, these were years of accomplishments as both artist and soldier. When researching this article, two forms of comment are readily detected. Military historians immediately understand the significance in Poe's meteoric rise to sergeant major. But these writers tend not to appreciate the literary history. Literary historians often note that Poe was an enlisted soldier, but, beyond that, seem not to appreciate that information. In none of this is there any sense that Poe sought, and for two years found, a degree of emotional stability. The social structure of the army contained and maintained Poe's psychic structure. This intertwining of the military and the literary, coupled with an understanding of psycho‐social development, is the frame needed to understand Sergeant Major Poe. Copyright © 2016 John Wiley & Sons, Ltd.
Programmable DNA Hydrogels Assembled from Multidomain DNA Strands
Authors: Jiang Huiling , Pan Victor , Vivek Skanda , Weeks Eric R. , Ke Yonggang 
Published: February 2016

AbstractHydrogels are important in biological and medical applications, such as drug delivery and tissue engineering. DNA hydrogels have attracted significant attention due to the programmability and biocompatibility of the material. We developed a series of low‐cost one‐strand DNA hydrogels self‐assembled from single‐stranded DNA monomers containing multiple palindromic domains. This new hydrogel design is simple and programmable. Thermal stability, mechanical properties, and loading capacity of these one‐strand DNA hydrogels can be readily regulated by simply adjusting the DNA domains.
Nuclear extrusion precedes discharge of genomic DNA fibers during tunicamycin‐induced neutrophil extracellular trap‐osis (NETosis)‐like cell death in cultured human leukemia cells
Authors: Nakayama Tomofumi , Saitoh Noriko , Morotomi‐Yano Keiko , Yano Ken‐ichi , Nakao Mitsuyoshi , Saitoh Hisato 
Published: February 2016

AbstractWe previously reported that the nucleoside antibiotic tunicamycin (TN), a protein glycosylation inhibitor triggering unfolded protein response (UPR), induced neutrophil extracellular trap‐osis (NETosis)‐like cellular suicide and, thus, discharged genomic DNA fibers to extracellular spaces in a range of human myeloid cell lines under serum‐free conditions. In this study, we further evaluated the effect of TN on human promyelocytic leukemia HL‐60 cells using time‐lapse microscopy. Our assay revealed a previously unappreciated early event induced by TN‐exposure, in which, at 30–60 min after TN addition, the cells extruded their nuclei into the extracellular space, followed by discharge of DNA fibers to form NET‐like structures. Intriguingly, neither nuclear extrusion nor DNA discharge was observed when cells were exposed to inducers of UPR, such as brefeldin A, thapsigargin, or dithiothreitol. Our findings revealed novel nuclear dynamics during TN‐induced NETosis‐like cellular suicide in HL‐60 cells and suggested that the toxicological effect of TN on nuclear extrusion and DNA discharge was not a simple UPR.
Preterm premature rupture of membrane after polypectomy using an Endoloop polydioxanone suture II™
Authors: Aoki Shigeru , Hayashi Mariko , Seki Kazuo , Hirahara Fumiki 
Published: February 2016

Key Clinical MessagePolypectomy using an Endoloop PDS II™ during pregnancy can be responsible for miscarriage and preterm delivery. Cervical polyps should not be removed in pregnant women except in cases where a malignancy is suspected.
A Combined Catalyst of Pt Nanoparticles and TiO2 with Water‐Tolerant Lewis Acid Sites for One‐Pot Conversion of Glycerol to Lactic Acid
Authors: Komanoya Tasuku , Suzuki Ayaka , Nakajima Kiyotaka , Kitano Masaaki , Kamata Keigo , Hara Michikazu 
Published: February 2016

AbstractCatalytic conversion of glycerol to valuable chemicals has been recognized as an attractive and challenging reaction in biorefinery. In this paper, we demonstrated that a combined catalyst of Pt nanoparticles and TiO2 worked as a highly active catalyst for the one‐pot conversion of glycerol to lactic acid in water. The yield of lactic acid reached 63 % under oxygen atmosphere without the use of any additives such as strong bases, and the catalyst could be reused without significant loss of the catalytic performance. The mechanistic studies revealed that Pt nanoparticles on TiO2 selectively oxidized glycerol to C3 aldehyde/ketone, and Lewis acid sites on TiO2 smoothly promoted the dehydration and rehydration/rearrangement reactions of the intermediates to produce lactic acid efficiently.
Aqueous‐Phase Hydrogenation of Saturated and Unsaturated Ketones and Aldehydes over Supported Platinum–Rhenium Catalysts
Authors: Falcone Derek D. , Hack John H. , Davis Robert J. 
Published: February 2016

AbstractThe hydrogenation rates of C=C and C=O bonds in methyl vinyl ketone and crotonaldehyde were measured over a series of silica‐supported Pt‐Re catalysts (1:1 atomic ratio of Pt/Re) in liquid water with H2 (15 psig) at 333 K. The hydrogenation of methyl vinyl ketone did not produce any unsaturated alcohol because of the rapid hydrogenation of C=C relative to that of C=O. The addition of Re to Pt impacted the rate of C=C hydrogenation negatively in methyl vinyl ketone and crotonaldehyde, but promoted the selectivity of C=O hydrogenation in crotonaldehyde in which the unsaturated alcohol increased from 5 % on Pt to 21 % on Pt‐Re. The addition of Re to Pt also promoted the rate of C=O hydrogenation in 2‐butanone, whereas little effect was observed during the hydrogenation of butanal. The results of electron microscopy and H2 chemisorption on the Pt‐Re catalysts showed the increasing interaction between Pt and Re with the increasing metal weight loading, and results from rate measurements suggest that oxophilic Re can be used to promote the Pt‐catalyzed hydrogenation of carbonyl groups in multifunctional molecules.
Controlling the Morphology and Efficiency of Nanostructured Molybdenum Nitride Electrocatalysts for the Hydrogen Evolution Reaction
Authors: Ojha Kasinath , Saha Soumen , Kumar Bharat , Hazra Kiran Shankar , Ganguli Ashok K. 
Published: February 2016

AbstractAmong catalysts based on non‐noble metals, Mo‐based materials are important for hydrogen evolution because of their low cost, good conductivity, and catalytic efficiency. This study demonstrates a facile two‐step synthesis of Mo2N nanostructures assembled from 5–8 nm particles with graphitic carbon nitride as the nitrogen source. These Mo2N nanostructures of various morphologies (hexagons, triangles, and nanowires) show a very high activity and stability in acidic media during water electrolysis. Their nanostructures were characterized by using powder XRD, electron microscopy, N2 gas adsorption analysis, and X‐ray photoelectron spectroscopy. Hydrogen evolution reaction parameters, which include the Tafel slope, charge transfer resistance, and stability, were analyzed by using linear sweep voltammetry and electrochemical impedance spectroscopy. Thin hexagonal sheets of Mo2N show the highest apparent electrocatalytic activity (current density of 197 mA cm−2geometric at −400 mV vs. the reversible hydrogen electrode) and excellent stability in an acidic medium with a small onset potential of 90 mV and a Tafel slope of 145 mV decade−1. The lowest Tafel slope was observed for Mo2N nanowires.
Acylation of β‐Amino Esters and Hydrolysis of β‐Amido Esters: Candida antarctica Lipase A as a Chemoselective Deprotection Catalyst
Authors: Mäenpää Harri , Kanerva Liisa T. , Liljeblad Arto 
Published: February 2016

AbstractN‐Acylation by lipase A from Candida antarctica (CAL‐A) in ethyl butanoate was applied to the kinetic resolution of tert‐butyl esters of 3‐amino‐3‐phenylpropanoic acid (E>100), 3‐amino‐4‐methylpentanoic acid (E>100) and 3‐aminobutanoic acid (E=60) on 1.0–2.0 m scale. With the N‐acylated resolution products, the exceptional ability of CAL‐A to hydrolyse amides and bulky tert‐butyl esters was then studied. In all N‐acylated tert‐butyl esters, chemoselectivity favoured the amide bond cleavage. The tert‐butyl ester bond was left intact with 3‐amino‐3‐phenylpropanoate, whereas with 3‐amino‐4‐methylpentanoate and 3‐aminobutanoate the CAL‐A‐catalysed hydrolysis of tert‐butyl ester followed the amide hydrolysis.
Copper‐Fiber‐Structured Pd–Au–CuOx: Preparation and Catalytic Performance in the Vapor‐Phase Hydrogenation of Dimethyl Oxalate to Ethylene Glycol
Authors: Han Lupeng , Zhang Li , Zhao Guofeng , Chen Yanfei , Zhang Qiaofei , Chai Ruijuan , Liu Ye , Lu Yong 
Published: February 2016

AbstractCu‐fiber‐structured ternary Pd–Au–CuOx catalysts engineered from nano‐ to macro‐scales have been developed for the vapor‐phase dimethyl oxalate (DMO) hydrogenation to ethylene glycol (EG), with the aid of galvanic deposition of Pd and Au onto a thin‐sheet microfibrous structure using 8 μm Cu fiber. Effects of Pd and Au loadings and their ratio have been investigated on the catalyst performance as well as the reaction conditions including reaction temperature and pressure, liquid weight hourly space velocity, and H2/DMO ratio. The promising 0.1 Pd–0.5 Au–CuOx/Cu‐fiber catalyst is capable of converting 97–99 % DMO into EG product at a selectivity of 90–93 %. This catalyst is stable for at least 200 h. The Pd–Au–Cu2O synergistically promotes the hydrogenation activity and stabilizes Cu+ sites to suppress deep reduction deactivation.
Branched Selectivity in the Pd‐Catalysed Methoxycarbonylation of 1‐Alkenes
Authors: Arderne Charmaine , Guzei llia A. , Holzapfel Cedric W. , Bredenkamp Tyler 
Published: February 2016

AbstractThe methoxycarbonylation of alkenes by palladium(II) complexes with P,O‐donor ligands [(2‐methoxyphenyl)diphenylphosphine (L‐2), bis(2‐methoxyphenyl) phenyl phosphine (L‐3) and tris(2‐methoxyphenyl) phosphine (L‐4)] has been investigated. The results show that the Pd complexes derived from these ligands provide high regioselectivity for the branched esters from 1‐pentene and 1‐hexene (>80 %). Various parameters (including temperature, pressure, acid concentration) were optimized to improve the performance of the catalyst system. Higher temperatures afforded higher regioselectivity; but effected rapid catalyst decomposition. Acceptable turnover frequencies, conversions as well as catalyst stability could be obtained at higher L/Pd ratios. The dramatic change in regioselectivity is rationalised on the basis of the hemi‐lability of the o‐methoxy moiety, which may lead to ligand dissociation from L2PdX2 (L=ligand, X=Cl) rather than the expected dissociation of X. In support of our hypothesis, direct evidence for the coordination of the o‐methoxy to the Pd centre was demonstrated by the crystal structure. To the best of our knowledge, this work provides the first reported route to valuable branched esters through the methoxycarbonylation of alkenes at suitable rates.
Putrescine Transaminases for the Synthesis of Saturated Nitrogen Heterocycles from Polyamines
Authors: Slabu Iustina , Galman James L. , Weise Nicholas J. , Lloyd Richard C. , Turner Nicholas J. 
Published: February 2016

AbstractPutrescine transaminase (pATA; EC 2.6.1.82) catalyzes the transfer of an amino group from terminal diamine donor molecules to keto acid acceptors by using pyridoxal‐5′‐phosphate as a cofactor. The ygjG genes from Escherichia coli K12, Bacillus megaterium, and Bacillus mycoides were successfully cloned and expressed in E. coli BL21(DE3) cells. The three putrescine transaminases were all shown to prefer diaminoalkanes as substrates and thereby generated cyclic imines from the ω‐amino aldehyde intermediates. The addition of a mild chemical reducing agent rapidly reduced the imine intermediate in situ to furnish a range of N‐heterocycle products. We applied pATA in a biomimetic synthesis of 2,3‐dihydro‐1H‐indolizinium‐containing targets, notably the bioactive alkaloid ficuseptine.
Engineering the Morphology of Carbon Materials: 2D Porous Carbon Nanosheets for High‐Performance Supercapacitors
Authors: Yuan Kai , Hu Ting , Xu Yazhou , Graf Robert , Brunklaus Gunther , Forster Michael , Chen Yiwang , Scherf Ullrich 
Published: February 2016

AbstractCompared with traditional porous carbon materials, two‐dimensional (2D) porous carbon materials with a high aspect ratio and a continuous hierarchical porous structure are promising candidates for the construction of supercapacitor electrode materials. Herein, well‐defined, graphene‐based conjugated microporous polymer sheets (G‐CMPs) were prepared in a graphene‐inspired synthetic strategy. Thereby, 4‐iodophenyl‐substituted graphene (RGO‐I) templates not only effectively hinder the aggregation between the adjacent graphene layers but also provide an efficient template for the growth of porous CMPs onto the graphene surface. Moreover, our G‐CMPs could be converted into 2D porous carbon nanosheets by pyrolysis. The synergism of high aspect ratio and high specific surface area, the presence of graphene‐based conduction paths and hierarchical pore systems ensure a high ion‐accessible surface area of the corresponding supercapacitor electrodes thus allowing accelerated electron and ion diffusion/transport and leading to high specific capacitance as well as good rate capability and cycling stability.
Strongly Coupled Architectures of Cobalt Phosphide Nanoparticles Assembled on Graphene as Bifunctional Electrocatalysts for Water Splitting
Authors: Huang Huawei , Yu Chang , Yang Juan , Zhao Changtai , Han Xiaotong , Liu Zhibin , Qiu Jieshan 
Published: February 2016

AbstractEfficient bifunctional electrocatalysts for both the cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER) are crucial for water splitting in a sustainable energy system. A strategy for fabricating strongly coupled cobalt phosphide (CoP)/graphene (G) architectures composed of CoP nanoparticles and G is described. Benefiting from synergetic effects of a dual support system of CoP for electroactive sites and G to enhance charge transfer, low overpotentials of 120 mV for the HER (0.5 m H2SO4) and 292 mV for the OER (1 m KOH) are required to achieve current densities of 10 mA cm−2. The as‐prepared CoP/G composites, which serve as bifunctional catalysts for both HER and OER in complete water splitting, can generate a current density of 10 mA cm−2 at 1.626 V. The present strategy provides a novel and efficient method for configuring high‐efficiency electrocatalysts for energy‐related storage and conversion devices.
Radical Cyclisation of α‐Halo Aluminium Acetals: A Mechanistic Study
Authors: Bénéteau Romain , Boussonnière Anne , Rouaud Jean‐Christophe , Lebreton Jacques , Graton Jérôme , Jacquemin Denis , Sebban Muriel , Oulyadi Hassan , Hamdoun Ghanem , Hancock Amber N. , Schiesser Carl H. , Dénès Fabrice 
Published: February 2016

Abstractα‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences.
Synthesis of Redshifted Azobenzene Photoswitches by Late‐Stage Functionalization
Authors: Konrad David B. , Frank James A. , Trauner Dirk 
Published: February 2016

AbstractAzobenzenes are versatile photoswitches that can be cycled between their trans‐ and cis‐configuration with light. The wavelengths required for this isomerization are substantially shifted from the UV to the visible range through tetra‐ortho‐chlorination. These halogenated azobenzenes display unique photoswitching characteristics, but their syntheses remain limited and inefficient. A new general method for the synthesis of tetra‐ortho‐chloro azobenzenes has been developed, which relies on direct palladium(II)‐catalyzed C−H activation of pre‐existing standard azobenzenes. This late‐stage functionalization has a broad substrate scope and can be used to create a variety of useful building blocks for the construction of more elaborate redshifted photopharmaceuticals. This method is used to prepare red‐AzCA‐4, a photoswitchable vanilloid that enables optical control of the cation channel TRPV1 with visible light.
Multimetallic Architectures from the Self‐assembly of Amino Acids and Tris(2‐pyridylmethyl)amine Zinc(II) Complexes: Circular Dichroism Enhancement by Chromophores Organization
Authors: Badetti Elena , Wurst Klaus , Licini Giulia , Zonta Cristiano 
Published: February 2016

AbstractStereodynamic optical probes are becoming very popular for their capability to act as molecular sensors for the determination of the enantiomeric excess (ee) of chiral compounds. Herein, we describe a new molecular architecture formed by the self‐assembly of three zinc metal ions, two modified tris(2‐pyridylmethyl)amine ligands, and two amino acids. This system is the structural and functional serendipitous evolution of our previous probe for the determination of amino acids ee. In the new system, one of the metals templates in close proximity two chromophores enhancing their exciton coupling.
Piling Up Pillar[5]arenes To Self‐Assemble Nanotubes
Authors: Nierengarten Iwona , Guerra Sebastiano , Ben Aziza Haifa , Holler Michel , Abidi Rym , Barberá Joaquín , Deschenaux Robert , Nierengarten Jean‐François 
Published: February 2016

AbstractNew liquid‐crystalline pillar[5]arene derivatives have been prepared by grafting first‐generation Percec‐type poly(benzylether) dendrons onto the macrocyclic scaffold. The molecules adopt a disc‐shaped structure perfectly suited for self‐organization into a columnar liquid‐crystalline phase. In this way, the pillar[5]arene cores are piled up, thus forming a nanotubular wire encased within a shell of peripheral dendrons. The capability of pillar[5]arenes to form inclusion complexes has been also exploited. Specifically, detailed binding studies have been carried out in solution with 1,6‐dicyanohexane as the guest. Inclusion complexes have also been prepared in the solid state. Supramolecular organization into the Colh mesophase has been deduced from X‐ray diffraction data and found to be similar to that observed within the crystal lattice of a model inclusion complex prepared from 1,4‐dimethoxypillar[5]arene and 1,6‐dicyanohexane.