bluuebunny/crossref_metadata_2025 huggingface dataset:
Elastic and Wearable Wire‐Shaped Lithium‐Ion Battery with High Electrochemical Performance
Authors: Ren Jing , Zhang Ye , Bai Wenyu , Chen Xuli , Zhang Zhitao , Fang Xin , Weng Wei , Wang Yonggang , Peng Huisheng
Published: June 2014

A stretchable wire‐shaped lithium‐ion battery is produced from two aligned multi‐walled carbon nanotube/lithium oxide composite yarns as the anode and cathode without extra current collectors and binders. The two composite yarns can be well paired to obtain a safe battery with superior electrochemical properties, such as energy densities of 27 Wh kg−1 or 17.7 mWh cm−3 and power densities of 880 W kg−1 or 0.56 W cm−3, which are an order of magnitude higher than the densities reported for lithium thin‐film batteries. These wire‐shaped batteries are flexible and light, and 97 % of their capacity was maintained after 1000 bending cycles. They are also very elastic as they are based on a modified spring structure, and 84 % of the capacity was maintained after stretching for 200 cycles at a strain of 100 %. Furthermore, these novel wire‐shaped batteries have been woven into lightweight, flexible, and stretchable battery textiles, which reveals possible large‐scale applications.
Thermophorese in Nanoliter‐Tropfen zur Quantifizierung von Aptamer‐Bindungen
Authors: Seidel Susanne A. I. , Markwardt Niklas A. , Lanzmich Simon A. , Braun Dieter
Published: June 2014

Biomolekulare Interaktionen, die von zentraler Bedeutung für Pharmakologie und Diagnostik sind, können durch Thermophorese quantifiziert werden. Diese reagiert empfindlich auf bindungsinduzierte Größen‐, Ladungs‐ oder Konformationsänderungen. Etablierte Kapillarmessungen verbrauchen mindestens 0.5 μL pro Probe. Wir reduzierten den Probenverbrauch um den Faktor 50, indem wir 10‐nL‐Tropfen verwendeten, die mit akustischer Flüssigkeitsübertragung (Labcyte) hergestellt wurden. Die Tropfen wurden in einem Öl‐Tensid‐Gemisch stabilisiert und mit einem Infrarotlaser lokal erwärmt. Temperaturerhöhung, Marangoni‐Fluss und Konzentrationsverteilung wurden mit Fluoreszenzmikroskopie und numerischer Simulation analysiert. In 10‐nL‐Tropfen quantifizierten wir Affinität, Kooperativität und Pufferabhängigkeit des AMP‐Aptamers. Die Miniaturisierung und das 1536‐Well‐Platten‐Format machen die Methode hochdurchsatzfähig und automatisierbar. Dies forciert innovative Anwendungen in der serologischen Diagnostik und markierungsfreien Wirkstoffsuche.
Versatile Preparation of Nonspherical Multiple Hydrogel Core PAM/PEG Emulsions and Hierarchical Hydrogel Microarchitectures
Authors: Guo Song , Yao Tong , Ji Xiaobo , Zeng Changfeng , Wang Chongqing , Zhang Lixiong
Published: June 2014

The preparation of nonspherical materials composed of separated multicomponents by droplet‐based microfluidics remains a challenge. Based on polymerization‐induced phase separation and droplet coalescence in microfluidics, we prepared emulsions of variously shaped PAM/PEG core/shell droplets and hydrogels composed of two separated components, which show flexible and transformable hierarchical structures and microarchitectures. We find that AM/PEG aqueous droplets form a core/shell structure after polymerization resulting from phase separation. Thus multicore/shell droplets are easily produced by coalescence of core/shell structures. By changing the polymerization temperature and the flow rate, the morphology of the multicore droplets and the hydrogel can be easily adjusted. The hydrogels exhibit apparent anisotropy and different protein release rates depending on their structures. The preparation technique is simple and versatile and the resulting hydrogels have potential applications in many fields.
Funktionalisierung eines cyclo‐P5‐Liganden durch Hauptgruppenelement‐Nukleophile
Authors: Mädl Eric , Butovskii Mikhail V. , Balázs Gábor , Peresypkina Eugenia V. , Virovets Alexander V. , Seidl Michael , Scheer Manfred
Published: June 2014

Durch die Reaktion von [Cp*Fe(η5‐P5)] (1; Cp* = η5‐C5Me5) mit verschiedenen Nucleophilen werden beispiellose funktionalisierte Produkte mit einem η4‐P5‐Ring erhalten. Mit LiCH2SiMe3 und LiNMe2 werden die Monoanionen [Cp*Fe(η4‐P5CH2SiMe3)]− bzw. [Cp*Fe(η4‐P5NMe2)]− gebildet. Die Reaktion von 1 mit NaNH2 führt zur Bildung des Trianions [{Cp*Fe(η4‐P5)}2N]3−, während die Reaktion mit LiPH2 [Cp*Fe(η4‐P5PH2)]− als das Hauptprodukt ergibt, mit {[Cp*Fe(η4‐P5)]2PH}2− als Nebenprodukt. Die berechneten Energieprofile der Reaktionen liefern eine Erklärung für die Bildung der unterschiedlichen Produkte.
Size‐Dependent Water Structures in Carbon Nanotubes
Authors: Ohba Tomonori
Published: June 2014

Water surrounded by hydrophobic interfaces affects a variety of chemical reactions and biological activities. Carbon nanotubes (CNTs) can be used to investigate the behavior of water at hydrophobic interfaces. Here, we determined the fundamental unit of water by evaluating the ice‐like cluster formation of water in the limited hydrophobic nanospaces of CNTs, using X‐ray diffraction and molecular simulation analysis. The water in CNTs with a diameter of 1 nm had fewer hydrogen bonds than bulk water under ambient conditions. In CNTs with diameters of 2 and 3 nm, water formed nanoclusters even under ambient conditions, because of prolific hydrogen bonding; predominant ice‐like cluster formation was induced in the 2–3 nm nanospaces. The results confirming the cluster formation in the CNTs also demonstrated that the critical cluster size was 0.8–3.4 nm. The fundamental cluster size was 0.8 nm; these results indicated that 0.8 nm clusters are the fundamental units of water assemblies.
18π‐Electron Tautomeric Benziphthalocyanine: A Functional Near‐Infrared Dye with Tunable Aromaticity
Authors: Toriumi Naoyuki , Muranaka Atsuya , Hirano Keiichi , Yoshida Kengo , Hashizume Daisuke , Uchiyama Masanobu
Published: June 2014

Dihydroxybenziphthalocyanine 1, with bulky aryloxy groups, has been synthesized and characterized by X‐ray crystallography, NMR and UV/Vis‐NIR spectroscopy, and theoretical calculations. Macrocycle 1 is the first example of an aromatic benziphthalocyanine with an 18π‐electron structure, and was found to exist as an equilibrium mixture of weakly aromatic and strongly aromatic tautomers. The aromaticity and near‐IR absorption can be controlled by chemical modification at the reactive resorcinol moiety and by variation of the solvent.
Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes
Authors: Kang Peng , Zhang Sheng , Meyer Thomas J. , Brookhart Maurice
Published: June 2014

An iridium pincer dihydride catalyst was immobilized on carbon nanotube‐coated gas diffusion electrodes (GDEs) by using a non‐covalent binding strategy. The as‐prepared GDEs are efficient, selective, durable, gas permeable electrodes for electrocatalytic reduction of CO2 to formate. High turnover numbers (ca. 54 000) and turnover frequencies (ca. 15 s−1) were enabled by the novel electrode architecture in aqueous solutions saturated in CO2 with added HCO3−.
Unprecedented Strong Lewis Bases—Synthesis and Methyl Cation Affinities of Dimethylamino‐Substituted Terpyridines
Authors: Hommes Paul , Fischer Christina , Lindner Christoph , Zipse Hendrik , Reissig Hans‐Ulrich
Published: June 2014

A versatile method for the synthesis of functionalized 2,2′:6′,2′′‐terpyridines by assembly of the terminal pyridine rings is presented. The cyclization precursors—bis‐β‐ketoenamides—are prepared from 4‐substituted 2,6‐pyridinedicarboxylic acids and acetylacetone or its corresponding enamino ketone. Treatment with trimethylsilyl trifluoromethanesulfonate induces a twofold intramolecular condensation providing an efficient access to 4,4′′‐di‐ and 4,4′,4′′‐trifunctionalized 6,6′′‐dimethyl‐2,2′:6′,2′′‐terpyridines. Using this method, hitherto unknown 4,4′′‐bis(dimethylamino)‐ and 4,4′,4′′‐tris(dimethylamino)terpyridines have been prepared that show remarkably high calculated Lewis basicities.
Optical Control of Acetylcholinesterase with a Tacrine Switch
Authors: Broichhagen Johannes , Jurastow Innokentij , Iwan Katharina , Kummer Wolfgang , Trauner Dirk
Published: June 2014

Photochromic ligands have been used to control a variety of biological functions, especially in neural systems. Recently, much effort has been invested in the photocontrol of ion channels and G‐protein coupled receptors found in the synapse. Herein, we describe the expansion of our photopharmacological approach toward the remote control of an enzyme. Building on hallmark studies dating from the late 1960s, we evaluated photochromic inhibitors of one of the most important enzymes in synaptic transmission, acetylcholinesterase (AChE). Using structure‐based design, we synthesized several azobenzene analogues of the well‐known AChE inhibitor tacrine (THA) and determined their effects on enzymatic activity. One of our compounds, AzoTHA, is a reversible photochromic blocker of AChE in vitro and ex vivo with high affinity and fast kinetics. As such, AzoTHA can be used to control synaptic transmission on the neuromuscular endplate based on the light‐dependent clearance of a neurotransmitter.
Conformationally Constrained Cyclic Peptides: Powerful Scaffolds for Asymmetric Catalysis
Authors: Zheng Lifei , Marcozzi Alessio , Gerasimov Jennifer Y. , Herrmann Andreas
Published: June 2014

Cyclic peptides containing a disulfide bridge were identified as a simple and versatile coordination sphere for asymmetric catalysis. Upon complexation with Cu2+ ions they catalyze Diels–Alder and Friedel–Crafts reactions with high enantioselectivities of up to 99 % ee and 86 % ee, respectively. Moreover, the peptides ligands were systematically optimized with the assistance of “Alanine Scanning”. This biomolecular design could greatly expand the choice of peptide scaffolds for artificial metallopeptide catalysts.
Formal (4+1) Cycloaddition of Methylenecyclopropanes with 7‐Aryl‐1,3,5‐cycloheptatrienes by Triple Gold(I) Catalysis
Authors: Wang Yahui , Muratore Michael E. , Rong Zhouting , Echavarren Antonio M.
Published: June 2014

7‐Aryl‐1,3,5‐cycloheptatrienes react intermolecularly with methylenecyclopropanes in a triple gold(I)‐catalyzed reaction to form cyclopentenes. The same formal (4+1) cycloaddition occurs with cyclobutenes. Other precursors of gold(I) carbenes can also be used as the C1 component of the cycloaddition.
A Reliable Aerosol‐Spray‐Assisted Approach to Produce and Optimize Amorphous Metal Oxide Catalysts for Electrochemical Water Splitting
Authors: Kuai Long , Geng Jing , Chen Changyu , Kan Erjie , Liu Yadong , Wang Qing , Geng Baoyou
Published: June 2014

An aerosol‐spray‐assisted approach (ASAA) is proposed and confirmed as a precisely controllable and continuous method to fabricate amorphous mixed metal oxides for electrochemical water splitting. The proportion of metal elements can be accurately controlled to within (5±5) %. The products can be sustainably obtained, which is highly suitable for industrial applications. ASAA was used to show that Fe6Ni10Ox is the best catalyst among the investigated Fe‐Ni‐Ox series with an overpotential of as low as 0.286 V (10 mA cm−2) and a Tafel slope of 48 mV/decade for the electrochemical oxygen evolution reaction. Therefore, this work contributes a versatile, continuous, and reliable way to produce and optimize amorphous metal oxide catalysts.
Preparation and characterization of membranes obtained from blends of acrylonitrile copolymers with poly(vinyl alcohol)
Authors: Sandu Teodor , Sârbu Andrei , Damian Celina Maria , Marin Adela , Vulpe Silviu , Budinova Temenuzhka , Tsyntsarski Boyko , Yardim M. Ferhat , Sirkecioglu Ahmet
Published: June 2014

New microfiltration and ultrafiltration membranes were obtained using acrylonitrile‐vinyl acetate copolymers in mixture with poly(vinyl alcohol) (PVA). Thus, a blend polymer solution was prepared in dimethylsulfoxide (DMSO) and used to obtain bicomponent polymer membranes by phase inversion. The rheological behavior of the DMSO polymer solutions was, mostly, dilatant at low shear gradients and pseudo plastic with quasi Newtonian tendency at higher gradients. Membranes were characterized by Fourier transform infrared spectrometry (FTIR), optical microscopy, atomic force microscopy, thermal gravimetric analysis‐differential thermal gravimetry, and pure water flux (PWF). FTIR spectra displayed the characteristic bands for acrylonitrile, vinyl acetate, and PVA. The morphology and the porosity can be tailored by the preparation conditions. PVA allows controlling the size of the pores and enables, in principle, to use the resulted membranes as supports for enzyme immobilization. PVA content influences the thermal stability. PWF values depend on the copolymer, on the content in PVA, but also on the coagulation bath composition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41013.
Quantitative electroencephalography: A new approach to the diagnosis of cerebral dysfunction in systemic lupus erythematosus
Authors: Ritchlin Christopher T. , Chabot Robert J. , Alper Kenneth , Buyon Jill , Belmont H. Michael , Roubey Robert , Abramson Steven B.
Published: June 2014

Objective. Neuropsychiatric manifestations are common in patients with systemic lupus erythematosus (SLE), but accurate diagnosis is often difficult. We conducted a prospective study to determine the utility of neurometric quantitative electroencephalography (QEEG) as an indicator of cerebral dysfunction in SLE patients.

Methods. Fifty‐two SLE patients were divided into 4 groups based on the results of neuropsychiatric evaluations. These included patients with objective evidence of neuropsychiatric SLE (NPSLE), patients with neuropsychiatric symptoms, patients with no evidence of NPSLE, and patients with a prior history of NPSLE. All QEEG findings were compared with data in an age‐regressed normative database and with findings in an independent sample of normal subjects.

Results. QEEG sensitivity was 87%, and specificity was 75%. QEEG results were abnormal in 74% of the SLE patients with neuropsychiatric symptoms and in 28% of the patients with no evidence of active NPSLE. QEEG profiles varied as a function of the severity and type of neuropsychiatric manifestation present. Within this patient population, QEEG was more sensitive than magnetic resonance imaging, computed tomography scanning, or conventional EEG.

Conclusion. Neurometric QEEG may be a sensitive indicator of cerebral dysfunction in patients with NPSLE and can differentiate patients with diverse neuropsychiatric manifestations. When combined with a careful clinical history and evaluation, QEEG provides information that may be useful for the early detection of NPSLE and for serial evaluation of disease activity and treatment efficacy.
Calixarene‐Based Chemosensors by Means of Click Chemistry
Authors: Song Miaomiao , Sun Zhongyue , Han Cuiping , Tian Demei , Li Haibing , Kim Jong Seung
Published: June 2014

Click chemistry, a new strategy for organic chemistry, has been widely used in the chemical modification of calixarenes because of its reliability, specificity, biocompatibility, and efficiency. Click‐derived triazoles also play a critical role in sensing ions and molecules. This in‐depth review provides an overview of calixarene‐based chemosensors that incorporate click‐derived triazoles, and their three characteristics (chromogenic, fluorescence, and wettability) are reviewed.
Characterization and analysis of the molecular weight of lignin for biorefining studies
Authors: Tolbert Allison , Akinosho Hannah , Khunsupat Ratayakorn , Naskar Amit K. , Ragauskas Arthur J.
Published: June 2014

The molecular weight of lignin is a fundamental property that influences the recalcitrance of biomass and the valorization of lignin. The determination of the molecular weight of lignin in native biomass is dependent on the bioresources used and the isolation and purification procedures employed. The three most commonly employed isolation methods are milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL). Common characterization techniques for determining the molecular weight of lignin will be addressed, with an emphasis on gel permeation chromatography (GPC). This review also examines the mechanisms behind several biological, physical, and chemical pre‐treatments and their impact on the molecular weight of lignin. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (D) all vary in magnitude depending on the biomass source, pre‐treatment conditions, and isolation method. Additionally, there is a growing body of literature that supports changes in the molecular weight of lignin in response to genetic modifications in the lignin biosynthetic pathways. This review summarizes different procedures for obtaining the molecular weight of lignin that have been used in recent years and highlight future opportunities for applications of lignin. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd
Hydroxamic Acids: A Unique Family of Chemicals with Multiple Biological Activities. Edited by Satya P. Gupta.
Authors: Bugg Timothy
Published: June 2014

Springer, Berlin 2013, X+312 pp., hardcover, € 139.09.—ISBN 978‐3‐642‐38110‐2
Systematic Analysis of Single Droplet Coalescence
Authors: Villwock Jörn , Gebauer Felix , Kamp Johannes , Bart Hans‐Jörg , Kraume Matthias
Published: June 2014

Coalescence behavior in liquid‐liquid dispersions is controlled by various parameters. Thus, data from different research groups can differ significantly. Dynamic coalescence processes were analyzed systematically with the EFCE standard test system toluene/water in two different research laboratories. After comparability was proven with standardized batch settling tests and drop rise velocity measurements, the influence of drop size ratio and varying NaCl and NaOH concentrations on coalescence probability was investigated. Since the ions led to a coalescence inhibition, no clear impact of drop size ratio could be observed. The analysis of drop contact showed longer contact times for increasing equivalent drop diameter. This promotes coalescence and corresponds to film drainage model.
Immobilisation of Flavin‐Adenine‐Dinucleotide‐Dependent Glucose Dehydrogenase α Subunit in Free‐Standing Graphitised Carbon Nanofiber Paper Using a Bifunctional Cross‐Linker for an Enzymatic Biofuel Cell
Authors: Fapyane Deby , Lee Yooseok , Lim Chyi Yan , Ahn Jou‐Hyeon , Kim Seon‐Won , Chang In Seop
Published: June 2014

Free‐standing graphitised carbon nanofiber paper (GCNFp) is fabricated using a dispersion–filtration method and modified by non‐covalent functionalisation with 1‐pyrenebutyric acid N‐hydroxysuccinimide ester—a bifunctional linker reagent—through π–π stacking. This modified GCNFp is then used to immobilise enzymes, and together they form an electrode for enzymatic biofuel cell (EBFC) applications. This fabrication method is shown to be capable of providing a practical platform for enzyme–electrode electrical communication that is faster than comparable systems based on other carbon materials, as calculated from the heterogeneous electron‐transfer rate constant. The GCNFp‐based EBFC reaches a maximum power density at a glucose concentration of 100 mM, yielding 834.9±200, 262.9±15.6 and 147.2±4.70 μW cm−2 for flavin‐adenine‐dinucleotide‐dependent glucose dehydrogenase (FADGDH)–menadione, glucose oxidase (GOX)–menadione, and GOX‐only systems (as the anode), respectively, with laccase as the cathode.
Profile monitoring of reflow process using approximations of mixture second‐order polynomials
Authors: Jen Chih‐Hung , Fan Shu‐Kai S.
Published: June 2014

Lately, profile monitoring has received considerable attention in the statistical process control research field. This paper proposes a novel monitoring framework for the reflow process data, which uses two goodness‐of‐fit criteria to select the change points in the mixture polynomial model. Among change points, the mixture second‐order polynomials are utilized to piecewisely approximate the nonlinear profile data of the reflow process. The well‐known Hotelling T2 and proposed EWMA4 control charts are then employed to monitor the parameter estimates. The experimental results demonstrate that the proposed monitoring framework presents better performances in detecting outlying profiles than the conventional methods in phase I. In phase II, the performance of the proposed framework is assessed in terms of the out‐of‐control average run length. Copyright © 2014 John Wiley & Sons, Ltd.
Molecular Mechanism of a Hotdog‐Fold Acyl‐CoA Thioesterase
Authors: Cantu David C. , Ardèvol Albert , Rovira Carme , Reilly Peter J.
Published: June 2014

Thioesterases are enzymes that hydrolyze thioester bonds between a carbonyl group and a sulfur atom. They catalyze key steps in fatty acid biosynthesis and metabolism, as well as polyketide biosynthesis. The reaction molecular mechanism of most hotdog‐fold acyl‐CoA thioesterases remains unknown, but several hypotheses have been put forward in structural and biochemical investigations. The reaction of a human thioesterase (hTHEM2), representing a thioesterase family with a hotdog fold where a coenzyme A moiety is cleaved, was simulated by quantum mechanics/molecular mechanics metadynamics techniques to elucidate atomic and electronic details of its mechanism, its transition‐state conformation, and the free energy landscape of the process. A single‐displacement acid‐base‐like mechanism, in which a nucleophilic water molecule is activated by an aspartate residue acting as a base, was found, confirming previous experimental proposals. The results provide unambiguous evidence of the formation of a tetrahedral‐like transition state. They also explain the roles of other conserved active‐site residues during the reaction, especially that of a nearby histidine/serine pair that protonates the thioester sulfur atom, the participation of which could not be elucidated from mutation analyses alone.
Thermotropic Luminescent Clustomesogen Showing a Nematic Phase: A Combination of Experimental and Molecular Simulation Studies
Authors: Cortes Maria Amela , Dorson Frederick , Prévôt Marianne , Ghoufi Aziz , Fontaine Bruno , Goujon Florent , Gautier Régis , Cîrcu Viorel , Mériadec Cristelle , Artzner Franck , Folliot Hervé , Cordier Stéphane , Molard Yann
Published: June 2014

Octahedral Mo6 nanoclusters are functionalized with two organic ligands containing cyanobiphenyl (CB) units, giving luminescent hybrid liquid crystals (LC). Although the mesogenic density around the bulky inorganic core is constant, the two hybrids show different LC properties. Interestingly, one of them shows a nematic phase, which is particularly rare for this kind of supermolecular system. This surprising result is explained by using large‐scale molecular dynamic simulations.
Facile Synthesis of Chiral Spirooxindole‐Based Isotetronic Acids and 5‐1H‐Pyrrol‐2‐ones through Cascade Reactions with Bifunctional Organocatalysts
Authors: Guo Wengang , Wang Xu , Zhang Boyu , Shen Shuai , Zhou Xin , Wang Peng , Liu Yan , Li Can
Published: June 2014

Unprecedented organocatalyzed asymmetric cascade reactions have been developed for the facile synthesis of chiral spirooxindole‐based isotetronic acids and 5‐1H‐pyrrol‐2‐ones.The asymmetric 1,2‐addition reactions of α‐ketoesters to isatins and imines by using an acid–base bifunctional 6′‐OH cinchona alkaloid catalyst, followed by cyclization and enolization of the resulting adducts, gave chiral spiroisotetronic acids and 5‐1H‐pyrrol‐2‐ones, respectively, in excellent optical purities (up to 98 % ee). FT‐IR analysis supported the existence of hydrogen‐bonding interaction between the 6′‐OH group of the cinchona catalyst and an isatin carbonyl group, an interaction that might be crucial for catalyst activity and stereocontrol.
Synthesis of Cyclic Alkenylsiloxanes by Semihydrogenation: A Stereospecific Route to (Z)‐Alkenyl Polyenes
Authors: Elbert Bryony L. , Lim Diane S. W. , Gudmundsson Haraldur G. , O'Hanlon Jack A. , Anderson Edward A.
Published: June 2014

Cyclic alkenylsiloxanes were synthesized by semihydrogenation of alkynylsilanes—a reaction previously plagued by poor stereoselectivity. The silanes, which can be synthesized on multigram scale, undergo Hiyama–Denmark coupling to give (Z)‐alkenyl polyene motifs found in bioactive natural products. The ring size of the silane is crucial: five‐membered cyclic siloxanes also couple under fluoride‐free conditions, whilst their six‐membered homologues do not, enabling orthogonality within this structural motif.
On the Hydrostannylation of Aryl Propargylic Alcohols and Their Derivatives: Remarkable Differences in Both Regio‐ and Stereoselectivity in Radical‐ and Nonradical‐Mediated Transformations
Authors: Oderinde Martins S. , Froese Robert D. J. , Organ Michael G.
Published: June 2014

Herein, we describe a highly regio‐ and stereoselective radical‐mediated and molecular‐oxygen (O2)‐dependent hydrostannylation of phenyl propargylic alcohols and their derivatives. There is a significant steric effect on the stereoselectivity of the tin‐radical addition. Further, the uncatalyzed regio‐ and stereoselective hydrostannylation of aryl propargylic alcohols with nBu3SnH and Ph3SnH is also described and occurs with near titration kinetics. Although the uncatalyzed addition with nBu3SnH gave a remarkable γ‐regioselectivity irrespective of the electronic nature of the aryl moiety, addition with Ph3SnH appears to be driven by the electronic nature of the aryl alkynes.
Improving Model and Data Integration Using MOSAIC as Central Data Management Platform
Authors: Kraus Robert , Fillinger Sandra , Tolksdorf Gregor , Minh Duc H. , Merchan‐Restrepo Victor A. , Wozny Günter
Published: June 2014

In this paper, the problem of the data and model management in the lifecycle of a process plant is addressed by presenting the database structure of the modeling and optimization platform MOSAIC. The first step of data integration is done by combining models and plant data into one central database. This has advantages for both plant design and plant optimization. Basic engineering workflows can then be improved. Several database configurations are presented to meet the different requirements with respect to security and open access.
Phase angle for prognostication of survival in patients with advanced cancer: Preliminary findings
Authors: Hui David , Bansal Swati , Morgado Margarita , Dev Rony , Chisholm Gary , Bruera Eduardo
Published: June 2014

BACKGROUND

Accurate survival prediction is essential for decision‐making in cancer therapies and care planning. Objective physiologic measures may improve the accuracy of prognostication. In this prospective study, the authors determined the association of phase angle, handgrip strength, and maximal inspiratory pressure with overall survival in patients with advanced cancer.

METHODS

Hospitalized patients with advanced cancer who were seen by palliative care specialists for consultation were enrolled. Information regarding phase angle, handgrip strength, maximal inspiratory pressure, and known prognostic factors including the Palliative Prognostic Score, Palliative Prognostic Index, serum albumin, and body composition was collected. Univariate and multivariate survival analysis were performed, and the correlation between phase angle and other prognostic variables was examined.

RESULTS

A total of 222 patients were enrolled. The average age of the patients was 55 years (range, 22 years‐79 years); 59% of the patients were female, with a mean Karnofsky performance status of 55 and a median overall survival of 106 days (95% confidence interval [95% CI], 71 days‐128 days). The median survival for patients with phase angle 2 to 2.9°, 3 to 3.9°, 4 to 4.9°, 5 to 5.9° and ≥ 6° was 35 days, 54 days, 112 days, 134 days, and 220 days, respectively (P = .001). On multivariate analysis, phase angle (hazards ratio [HR], 0.86‐per degree increase; 95% CI, 0.74‐0.99 increase [P = .04]), Palliative Prognostic Score (HR, 1.07; 95% CI, 1.02‐1.13 [P = .008]), serum albumin (HR, 0.67; 95% CI, 0.50‐0.91 [P = .009]), and fat‐free mass (HR, 0.98; 95% CI, 0.96‐0.99 [P = .02]) were found to be significantly associated with survival. Phase angle was found to be only weakly (γ < 0.4) associated with other prognostic variables.

CONCLUSIONS

Phase angle was found to be a novel predictor of poor survival, independent of established prognostic factors, in the advanced cancer setting. This objective and noninvasive tool may be useful for bedside prognostication. Cancer 2014;120:2207–2214. © 2014 American Cancer Society.
Factors associated with high burden in caregivers of older adults with cancer
Authors: Hsu Tina , Loscalzo Matthew , Ramani Rupal , Forman Stephen , Popplewell Leslie , Clark Karen , Katheria Vani , Feng Tao , Strowbridge Rex , Rinehart Redmond , Smith Dan , Matthews Keith , Dillehunt Jeff , Hurria Arti
Published: June 2014

BACKGROUND

Older adults with cancer are vulnerable to functional decline, which places greater onus on caregivers. Few studies have prospectively examined burden in caregivers of older cancer patients. The objective of this study was to determine the factors associated with high caregiver burden.

METHODS

In total, 100 caregivers of patients aged ≥65 years with cancer, who were recruited at a single institution, completed questionnaires gauging their perception of the patient's physical, emotional, and social health. The association between these items, cancer‐related factors, sociodemographic factors, and caregiver burden (measured using the Caregiver Strain Index [CSI]) was determined through multivariate analysis.

RESULTS

The median patient age was 70 years (range, 65‐91 years), 70% of patients had advanced disease, and 98% were receiving treatment. Caregivers were mostly women (73%), spouses (68%), and lived with the patient (79%). The median amount of care provided was 10 hours per week. The mean CSI score (± standard deviation) was 3.1 ± 3.2. Most caregivers (75%) reported some burden, with 15% reporting high caregiver burden (CSI score, ≥7). In multivariate analysis, employed caregivers (odds ratio, 4.5; 95% confidence interval, 1.1‐18.4; P = .04) and those caring for patients who required more help with instrumental activities of daily living (Older Americans Resources and Services‐Instrumental Activities of Daily Living score, <12 of a possible 14; odds ratio, 12.4; 95% confidence interval, 2.4‐62.5; P < .001) were more likely to experience high caregiver burden (CSI score, ≥7).

CONCLUSIONS

Caregiver burden is common in those who care for older cancer patients. High burden is more likely in employed caregivers and in those who care for patients who require increased functional assistance. Further studies are needed to determine the unique challenges experienced by caregivers of older adults with cancer and potential interventions to alleviate burden in these caregivers. Cancer 2014;120:2927–2935. © 2014 American Cancer Society.
Treating advanced hepatocellular carcinoma: How to get out of first gear
Authors: Harding James J. , Abou‐Alfa Ghassan K.
Published: June 2014

Hepatocellular carcinoma is a common malignancy with a poor prognosis. Sorafenib is the only systemic therapy known to improve the overall survival of patients with advanced disease. The clinical benefit of sorafenib is modest and the mechanistic basis for its activity is unknown. Four phase 3 clinical trials have failed to improve on sorafenib in the frontline setting and no agent has been shown to impact outcomes after sorafenib failure. Several factors have contributed to this recent stall in drug development but new approaches hold promise and currently are being investigated. This review will focus on the current pipeline of experimental therapeutics for patients with advanced hepatocellular carcinoma and shed a light on scientific limitations that hamper the advancement of new therapies for this disease, and ways around it. Cancer 2014;120:3122–3130. © 2014 American Cancer Society.
On the fate of seasonally plastic traits in a rainforest butterfly under relaxed selection
Authors: Oostra Vicencio , Brakefield Paul M. , Hiltemann Yvonne , Zwaan Bas J. , Brattström Oskar
Published: June 2014

Many organisms display phenotypic plasticity as adaptation to seasonal environmental fluctuations. Often, such seasonal responses entails plasticity of a whole suite of morphological and life‐history traits that together contribute to the adaptive phenotypes in the alternative environments. While phenotypic plasticity in general is a well‐studied phenomenon, little is known about the evolutionary fate of plastic responses if natural selection on plasticity is relaxed. Here, we study whether the presumed ancestral seasonal plasticity of the rainforest butterfly Bicyclus sanaos (Fabricius, 1793) is still retained despite the fact that this species inhabits an environmentally stable habitat. Being exposed to an atypical range of temperatures in the laboratory revealed hidden reaction norms for several traits, including wing pattern. In contrast, reproductive body allocation has lost the plastic response. In the savannah butterfly, B. anynana (Butler, 1879), these traits show strong developmental plasticity as an adaptation to the contrasting environments of its seasonal habitat and they are coordinated via a common developmental hormonal system. Our results for B. sanaos indicate that such integration of plastic traits – as a result of past selection on expressing a coordinated environmental response – can be broken when the optimal reaction norms for those traits diverge in a new environment.
Mitochondria selective S‐nitrosation by mitochondria‐targeted S‐nitrosothiol protects against post‐infarct heart failure in mouse hearts
Authors: Methner Carmen , Chouchani Edward T. , Buonincontri Guido , Pell Victoria R. , Sawiak Stephen J. , Murphy Michael P. , Krieg Thomas
Published: June 2014

Aims

Recently it has been shown that the mitochondria‐targeted S‐nitrosothiol MitoSNO protects against acute ischaemia/reperfusion (IR) injury by inhibiting the reactivation of mitochondrial complex I in the first minutes of reperfusion of ischaemic tissue, thereby preventing free radical formation that underlies IR injury. However, it remains unclear how this transient inhibition of mitochondrial complex I‐mediated free radicals at reperfusion affects the long‐term recovery of the heart following IR injury. Here we determined whether the acute protection by MitoSNO at reperfusion prevented the subsequent development of post‐myocardial infarction heart failure.

Methods and results

Mice were subjected to 30 min left coronary artery occlusion followed by reperfusion and recovery over 28 days. MitoSNO (100 ng/kg) was applied 5 min before the onset of reperfusion followed by 20 min infusion (1 ng/kg/min). Infarct size and cardiac function were measured by magnetic resonance imaging (MRI) 24 h after infarction. MitoSNO‐treated mice exhibited reduced infarct size and preserved function. In addition, MitoSNO at reperfusion improved outcome measures 28 days post‐IR, including preserved systolic function (63.7 ±1.8% LVEF vs. 53.7 ± 2.1% in controls, P = 0.01) and tissue fibrosis.

Conclusions

MitoSNO action acutely at reperfusion reduces infarct size and protects from post‐myocardial infarction heart failure. Therefore, targeted inhibition of mitochondrial complex I in the first minutes of reperfusion by MitoSNO is a rational therapeutic strategy for preventing subsequent heart failure in patients undergoing IR injury.
Tracking in vivo dynamics of NK cells transferred in patients undergoing stem cell transplantation
Authors: Killig Monica , Friedrichs Birte , Meisig Johannes , Gentilini Chiara , Blüthgen Nils , Loddenkemper Christoph , Labopin Myriam , Basara Nadezda , Pfrepper Christian , Niederwieser Dietger W. , Uharek Lutz , Romagnani Chiara
Published: June 2014

Haploidentical stem cell transplantation (haploSCT) offers an alternative treatment option for advanced leukemia patients lacking a HLA‐compatible donor. Transfer of NK cells represents a promising therapeutic option in combination with SCT, as NK cells can promote graft versus leukemia with low risk of GVH disease. In this study, we show results from a phase I/II trial in which 24 acute myeloid leukemia patients underwent haploSCT in combination with early transfer of unmodified NK cells and observed a promising 2‐year overall survival rate of 37%. By performing immunomonitoring and subsequent principal component analysis, we tracked donor NK‐cell dynamics in the patients and distinguished between NK cells reconstituting from CD34+ precursors, giving rise over time to a continuum of multiple differentiation stages, and adoptively transferred NK cells. Transferred NK cells displayed a mature phenotype and proliferated in vivo during the early days after haploSCT even in the absence of exogenous IL‐2 administration. Moreover, we identified the NK‐cell phenotype associated with in vivo expansion. Thus, our study indicates a promising path for adoptive transfer of unmodified NK cells in the treatment of high‐risk acute myeloid leukemia.
Electronic Origin of Out‐of‐Plane Distortions in Porphyrins
Authors: Austeria Muthu P. , Pancharatna Pattath D. , Balakrishnarajan Musiri M.
Published: June 2014

Porphyrins are noninnocent ligands that facilitate redox processes in many biological reactions. Though the porphyrin dianion is planar and aromatic, in many instances, its skeleton exhibits a variety of out‐of‐plane (OOP) distortions, which are primarily attributed to steric factors. Nevertheless, these distortions are suspected to play a hidden role in their biochemical reactions, as the nature of the distortion is conserved for a specific functionality across species. The propensity of porphyrins to assist redox reactions remains mysterious, as oxidation and OOP distortions affect their aromaticity. Our quantum chemical modelling of the two‐electron oxidation of porphyrin reveals that there are definite electronic reasons behind OOP distortions. An extension of the frontier orbital model of Gouterman to include the occupied b1g, b2g and a1g (σ) molecular orbitals (MOs) is necessary to explain the nature and origin of OOP distortions. The distortions are the effect of the mixing of these σ‐type MOs with the π‐type a1u and a2u highest occupied molecular orbitals (HOMOs). These are further facilitated by the flexibility of the internal [16]annulene skeleton of the porphyrin framework. In the absence of transition metal ions, oxidation usually entails pronounced bond alternation along this internal cross owing to a1u/a2u mixing, which leads to the loss of aromaticity. However, this is accompanied by OOP distortions that help to retain the local aromaticity of the pyrrolic rings. Transition metal porphyrins with their energetically accessible d orbitals prefer OOP distortions over bond alternation and effectively conserve aromaticity. For late transition metal ions, the d8 electronic configuration, which is ideal for a square‐planar complex, itself shows a variety of OOP distortions that stabilize the corresponding oxidation state through the mixing of the b1g MO with the a2u MO. For octahedral complexes with d6 configuration of the central metal ion, a two‐electron oxidation is effectively supported by OOP distortions that result from the mixing of the b2g MO with the a2u MO. The a1u MO is usually less prone to mixing as it is concentrated far away from the central metal ion. Despite involving σ–π mixing, these OOP distortions conserve the aromaticity as shown by the computed chemical shifts of the optimized porphyrin systems. In addition to explaining the origin of the noninnocent nature of porphyrins, our results also provides a basis for the rational prediction and control of the OOP distortions to suite the desired biomimetic applications.
Numerical experiments in fire science: a study of ceiling jets
Authors: Johansson Nils , Wahlqvist Jonathan , van Hees Patrick
Published: June 2014

In this paper, a numerical experiment, consisting of 90 simulations in Fire Dynamics Simulator (FDS), is conducted for two different purposes. Firstly, numerical experiments are explored as a research method in fire science, and it is demonstrated that numerical experiments could be used as a complement to traditional fire experiments in fire science research. Secondly, an evaluation of previously derived correlations for ceiling jet excess temperatures and velocities is performed with the help of the results from the numerical experiment. The procedure used in this evaluation constitutes an outline for how a numerical experiment can be conducted in fire science. The evaluation indicates that the existing correlations will give a good estimate of the average temperature in a ceiling jet calculated by FDS. However, the correlations do not give a good estimate of the maximum excess temperature. A new correlation to estimate the maximum temperature has therefor been developed and is presented in the paper. Copyright © 2014 John Wiley & Sons, Ltd.
Evaluation of Hydrogen Crossover through Fuel Cell Membranes
Authors: Schoemaker M. , Misz U. , Beckhaus P. , Heinzel A.
Published: June 2014

Gas crossover is an unavoidable phenomenon in proton exchange fuel cell membranes. Nitrogen and oxygen from the cathode pass through the membrane to the anode, while hydrogen crosses from the anode to the cathode. The hydrogen crossover leads to a reduction in efficiency due to parasitic hydrogen consumption and mixed potentials on the cathode electrode. Furthermore it causes degradation effects and pinhole formation. Hence the hydrogen crossover represents a fundamental factor for the lifetime of a fuel cell and quantification of the crossover is a key factor for membrane qualification.

In this article two in situ electrochemical techniques to evaluate the hydrogen crossover are described, cyclic voltammetry and potential step method. Both methods and the achieved results are compared to each other. Finally the potential step method is applied to evaluate the hydrogen crossover as a function of the anode pressure and the hydrogen permeability coefficients are determined.
Ras‐GRF2 mediates long‐term potentiation, survival, and response to an enriched environment of newborn neurons in the hippocampus
Authors: Darcy Michael J. , Trouche Stéphanie , Jin Shan‐Xue , Feig Larry A.
Published: June 2014

Hippocampal adult neurogenesis contributes to key functions of the dentate gyrus (DG), including contextual discrimination. This is due, at least in part, to the unique form of plasticity that new neurons display at a specific stage of their development when compared with the surrounding principal neurons. In addition, the contribution that newborn neurons make to dentate function can be enhanced by an increase in their numbers induced by a stimulating environment. However, signaling mechanisms that regulate these properties of newborn neurons are poorly understood. Here, we show that Ras‐GRF2 (GRF2), a calcium‐regulated exchange factor that can activate Ras and Rac GTPases, contributes to both of these properties of newborn neurons. Using Ras‐GRF2 knockout mice and wild‐type mice stereotactically injected with retrovirus containing shRNA against the exchange factor, we demonstrate that GRF2 promotes the survival of newborn neurons of the DG at approximately 1–2 weeks after their birth. GRF2 also controls the distinct form of long‐term potentiation that is characteristic of new neurons of the hippocampus through its effector Erk MAP kinase. Moreover, the enhancement of neuron survival that occurs after mice are exposed to an enriched environment also involves GRF2 function. Consistent with these observations, GRF2 knockout mice display defective contextual discrimination. Overall, these findings indicate that GRF2 regulates both the basal level and environmentally induced increase of newborn neuron survival, as well as in the induction of a distinct form of synaptic plasticity of newborn neurons that contributes to distinct features of hippocampus‐derived learning and memory. © 2014 Wiley Periodicals, Inc.
Nuclear receptors and the Warburg effect in cancer
Authors: Thorne James L. , Campbell Moray J.
Published: June 2014

In 1927 Otto Warburg established that tumours derive energy primarily from the conversion of glucose to lactic acid and only partially through cellular respiration involving oxygen. In the 1950s he proposed that all causes of cancer reflected different mechanisms of disabling cellular respiration in favour of fermentation (now termed aerobic glycolysis). The role of aberrant glucose metabolism in cancer is now firmly established. The shift away from oxidative phosphorylation towards the metabolically expensive aerobic glycolysis is somewhat counter‐intuitive given its wasteful nature. Multiple control processes are in place to maintain cellular efficiency and it is likely that these mechanisms are disrupted to facilitate the shift to the reliance on aerobic glycolysis. One such process of cell control is mediated by the nuclear receptor superfamily. This large family of transcription factors plays a significant role in sensing environmental cues and controlling decisions on proliferation, differentiation and cell death for example, to regulate glucose uptake and metabolism and to modulate the actions of oncogenes and tumour suppressors. In this review we highlight mechanisms by which nuclear receptors actions are altered during tumorigenic transformation and can serve to enhance the shift to aerobic glycolysis. At the simplest level, a basic alteration in NR behaviour can serve to enhance glycolytic flux thus providing a basis for enhanced survival within the tumour micro‐environment. Ameliorating the enhanced NR activity in this context may help to sensitize cancer cells to Warburg targeted therapies and may provide future drug targets.
Differential suppression of arousal by sex offenders with intellectual disabilities
Authors: Walker Stephen F. , Joslyn P. Raymond , Vollmer Timothy R. , Hall Astrid
Published: June 2014

Previous research that has evaluated the ability of sex offenders with intellectual disabilities (ID) to suppress sexual arousal has produced mixed results. The current study had 2 purposes: (a) to replicate prior research on arousal suppression by sex offenders with ID and (b) to evaluate whether it is possible for offenders with ID to maintain arousal to nondeviant stimuli while suppressing arousal to deviant stimuli. Both participants were successful in suppressing arousal to deviant stimuli, and 1 participant was successful in maintaining arousal to nondeviant stimuli while suppressing arousal to deviant stimuli.