bluuebunny/crossref_metadata_2025 huggingface dataset:
Heteromultimetallic Complexes with Redox‐Active Mesoionic Carbenes: Control of Donor Properties and Redox‐Induced Catalysis
Authors: Hettmanczyk Lara , Suntrup Lisa , Klenk Sinja , Hoyer Carolin , Sarkar Biprajit
Published: November 2016

Mesoionic carbenes (MICs) are currently hugely popular as ligands, and triazolylidenes are arguably the most prominent classes of such MICs. Mesoionic carbenes with ferrocenyl substituents are presented that can act as metalloligands for the generation of heteromultimetallic iridium(I) and gold(I) complexes. The ferrocenyl substituents allow for reversible oxidation of these heteromultimetallic complexes, and these oxidation steps have a strong influence on the donor properties of the MICs. Tolman electronic parameters (TEP) determined from analysis of the iridium–carbonyl complexes show that the neutral ferrocenyl–MIC ligands are stronger donors than the imidazolylidene based carbenes, the one‐electron oxidized ferrocenyl MICs are in the range of the tricyclohexyl phosphines and the two‐electron oxidized forms, which are electron‐poor, lie in the range of triphenyl phosphines. Taking advantage of the generation of these electron‐poor MICs, we show their gold(I) complexes are potent catalysts for the synthesis of oxazolines, with complexes of the oxidized MIC ligands, without any additional additive, outperforming their neutral counterparts by almost a factor of ten. These results thus present the first examples of MIC ligands that are reversibly electronically tunable, and show the potential of the oxidized MIC ligands in types of catalysis where electron‐poor ligands are necessary. The potential of MICs for molecular electroactive materials is also shown.
An Unsaturated Four‐Coordinate Dimethyl Dimolybdenum Complex with a Molybdenum–Molybdenum Quadruple Bond
Authors: Curado Natalia , Carrasco Mario , Campos Jesús , Maya Celia , Rodríguez Amor , Ruiz Eliseo , Álvarez Santiago , Carmona Ernesto
Published: November 2016

We describe the synthesis and the molecular and electronic structures of the complex [Mo2Me2{μ‐HC(NDipp)2}2] (2; Dipp=2,6‐iPr2C6H3), which contains a dimetallic core with an Mo–Mo quadruple bond and features uncommon four‐coordinate geometry and has a fourteen‐electron count for each molybdenum atom. The coordination polyhedron approaches a square pyramid, with one of the molybdenum atoms nearly co‐planar with the basal square plane, in which the trans coordination position with respect to the Mo−Me bond is vacant. The other three sites are occupied by two trans nitrogen atoms of different amidinate ligands and the methyl group. The second Mo atom occupies the apex of the pyramid and forms an Mo–Mo bond of length 2.080(1) Å, consistent with a quadruple bond. Compound 2 reacts with tetrahydrofuran (THF) and trimethylphosphine to yield the mono‐adducts [Mo2Me(μ‐Me){μ‐HC(NDipp)2}2(L)] (3⋅THF and 3⋅PMe3, respectively) with one terminal and one bridging methyl group. In contrast, 4‐dimethylaminopyridine (dmap) forms the bis‐adduct [Mo2Me2{μ‐HC(NDipp)2}2(dmap)2] (4), with terminally coordinated methyl groups. Hydrogenolysis of complex 2 leads to the bis(hydride) [Mo2H2{μ‐HC(NDipp)2}2(thf)2] (5⋅THF) with elimination of CH4. Computational, kinetic, and mechanistic studies, which included the use of D2 and of complex 2 labelled with 13C (99 %) at the Mo–CH3 sites, supported the intermediacy of a methyl‐hydride reactive species. A computational DFT analysis of the terminal and bridging coordination of the methyl groups to the Mo≣Mo core is also reported.
ChemInform Abstract: Largest Perfluorometallate [Ti10F45]5‐ Oligomer and Polymeric ([Ti3F13]‐)∞ and ([TiF5]‐) ∞ Anions Prepared as [XeF5]+ Salts.
Authors: Mazej Zoran , Goreshnik Evgeny A.
Published: November 2016

Single crystals of XeF5TiF5 (XeF6·TiF4, (I)), [XeF5]5[Ti10F45] (XeF6·2TiF4, (II)), and [XeF5][Ti3F13] (XeF6·3TiF4, (III)) are grown from anhydrous HF solutions of the products of reactions between XeF2, TiF4 and UV‐irradiated F2 (FEP reaction vessel, 25 °C, 10—20 d; caution: beside the toxicity of anhydrous HF, XeF6 and all of its products are susceptible to moisture and react with H2O forming shock‐sensitve XeO3, a compound that detonates easily).
ChemInform Abstract: Structural and Optical Studies of KErP2O7 Diphosphate.
Authors: Chaker M. , Horchani‐Naifer K. , Ferid M.
Published: November 2016

KErP2O7 is prepared by solid state reaction of a stoichiometric mixture of K2CO3, (NH4)2HPO4, and Er2O3 (Pt crucible, 650 °C, 48 h).
ChemInform Abstract: Multimetal‐Substituted Epsilon‐Iron Oxide ε‐Ga0.31Ti0.05Co0.05 Fe1.59O3 for Next‐Generation Magnetic Recording Tape in the Big‐Data Era.
Authors: Ohkoshi Shin‐ichi , et al.
Published: November 2016

Nanoparticles of the title compound with an average size of 18 nm are synthesized by a sol—gel method from an aqueous solution of Fe(NO3)3, Ga(NO3)3, Co(NO3)2, Ti(SO4)2, and NH3 (1075 °C, 4 h).
ChemInform Abstract: Hydrogen Bond‐Assisted Crystallization: Structure, Growth and Characterization of a New Mixed‐Anion Transition Metal Fluoride Na3NH4(TiF6) (SO4)·H2O.
Authors: Xu Dongdong , Zhang Fangfang , Sun Yanzhou , Yang Zhihua , Dong Xiaoyu , Pan Shilie
Published: November 2016

Single crystals of Na3NH4(TiF6) (SO4)·H2O are grown by hydrothermal reaction of a 3:1:1 molar mixture of Na2SO4, NaF, and (NH4)2TiF6 (autoclave, 210 °C, 4 d; cooling to 25 °C at a rate of 4 °C/h).
ChemInform Abstract: Lead Oxychloride Borates Obtained under Extreme Conditions.
Authors: Siidra Oleg I. , Kabbour Houria , Mentre Olivier , Nazarchuk Evgeny V. , Kegler Philip , Zinyakhina Diana O. , Colmont Marie , Depmeier Wulf
Published: November 2016

Compounds (IV) and (V) are characterized by single crystal XRD and DFT calculations.
ChemInform Abstract: Synthesis and Crystal Structure of Anhydrous Na[MnO4].
Authors: Bauchert Joerg M. , Henning Harald , Schleid Thomas
Published: November 2016

Needle‐shaped, dark purple crystals of anhydrous sodium permanganate are prepared by evaporation of aqueous solutions of Na2SO4 and Ba(MnO4)2 after removal of the precipitate.
ChemInform Abstract: Synthesis, Crystal Structure and Magnetic Properties of the Two Polymorphs of Novel S = 1 Osmate; Li4MgOsO6.
Authors: Nguyen Phoung‐Hieu T. , Kemei Moureen C. , Tan Malinda S. , Derakhshan Shahab
Published: November 2016

Single phase monoclinic Li4MgOsO6 is prepared by solid state reaction of a stoichiometric mixture of Li5OsO6, Os, OsO2, and MgO (pressed pellet, Al2O3 crucible in evacuated silica tubes, 800 °C, 24 h; heating and cooling rates of 100 °C/h).
ChemInform Abstract: Synthesis and Characterization of Sulfamic Acid‐Functionalized Nanoparticles and Study of Its Catalytic Activity for the Oxidation of Sulfides to Sulfoxides.
Authors: Ghorbani‐Choghamarani Arash , Azadi Gouhar
Published: November 2016

Sulfamic acid‐functionalized nanoparticles are shown to be an excellent catalyst for the oxidation of sulfides to sulfoxides by H2O2.
ChemInform Abstract: Reactions of a Novel Modified Red‐Al Reducing Agent with Selected Organic Compounds Containing Representative Functional Groups and Chemoselective Reduction.
Authors: Park Ji Yeon , Shin Won Kyu , Jaladi Ashok Kumar , An Duk Keun
Published: November 2016

The novel reducing agent allows the conversion of ketones, aldehydes, acid chlorides, and anhydrides into alcohols under mild conditions.
ChemInform Abstract: Manganese‐Mediated C—H Alkylation of Unbiased Arenes Using Alkylboronic Acids.
Authors: Castro Susana , Fernandez Juan J. , Fananas Francisco J. , Vicente Ruben , Rodriguez Felix
Published: November 2016

The simple protocol uses primary or secondary unactivated alkylboronic acids for a direct functionalization of various polyaromatic hydrocarbons or benzene (XII).
ChemInform Abstract: Pd‐Catalyzed One‐Pot Sequential Unsymmetrical Cross‐Coupling Reactions of Aryl/Heteroaryl 1,2‐Dihalides.
Authors: Danodia Abhinandan K. , Saunthwal Rakesh K. , Patel Monika , Tiwari Rakesh K. , Verma Akhilesh K.
Published: November 2016

All possible nine combinations of Sonogashira, Heck and Suzuki coupling reactions are efficiently performed according to the title transformation.
ChemInform Abstract: Direct Access to β‐Fluorinated Aldehydes by Nitrite‐Modified Wacker Oxidation.
Authors: Chu Crystal K. , Ziegler Daniel T. , Carr Brian , Wickens Zachary K. , Grubbs Robert H.
Published: November 2016

An aldehyde‐selective Wacker‐type oxidation of allylic fluorides proceeds with a nitrite catalyst.
ChemInform Abstract: An Improved Catalyst for Iodine(I/III)‐Catalyzed Intermolecular C—H Amination.
Authors: Lucchetti Nicola , Scalone Michelangelo , Fantasia Serena , Muniz Kilian
Published: November 2016

1,2‐Diiodobenzene is found to be a potent catalyst precursor for the title reaction, where N‐Troc and N‐phthalimido‐substituted methoxyamines represent the most efficient amination reagents.
ChemInform Abstract: Modular, Catalytic Enantioselective Construction of Quaternary Carbon Stereocenters by Sequential Cross‐Coupling Reactions.
Authors: Potter Bowman , Edelstein Emma K. , Morken James P.
Published: November 2016

A stereospecific Suzuki—Miyaura coupling of highly substituted allylboronates with C‐electrophiles provides a highly regiospecific and enantiospecific access to quarternary carbon centres.
ChemInform Abstract: Catalytic Asymmetric Chlorinative Dearomatization Reaction of Benzofurans.
Authors: Liang Xiao‐Wei , Zheng Chao , You Shu‐Li
Published: November 2016

The title reaction under conditions A) leads to formation of a series of chlorinated spiro[benzofuran‐2,5′‐oxazole]s with 2 contiguous stereocenters.
ChemInform Abstract: Gold‐Catalyzed Intermolecular Ynamide Amination‐Initiated Aza‐Nazarov Cyclization: Access to Functionalized 2‐Aminopyrroles.
Authors: Shu Chao , Wang Yong‐Heng , Shen Cang‐Hai , Ruan Peng‐Peng , Lu Xin , Ye Long‐Wu
Published: November 2016

In comparison to previously developed protocols the presented simple and regioselective method offers a higher flexibility and a broad substrate scope.
ChemInform Abstract: Concise Approach to Pyrrolizino[1,2‐b]indoles from Indole‐Derived Donor—Acceptor Cyclopropanes.
Authors: Villemson Elena V. , Budynina Ekaterina M. , Ivanova Olga A. , Skvortsov Dmitriy A. , Trushkov Igor V. , Melnikov Mikhail Ya.
Published: November 2016

The ring opening of cyclopropanes (I) with sodium azide followed by Krapcho dealkoxycarbonylation and a subsequent Vilsmeier—Haack formylation of resulting azides (II) gives rise to azido aldehydes (IV).
ChemInform Abstract: Silver‐Catalyzed Intramolecular C‐2 Selective Acylation of Indoles with Aldehydes: An Atom‐Economical Entry to Indole‐Indolone Scaffolds.
Authors: Wang Xiaoxia , Li Zhongfeng , Cao Shengli , Rao Honghua
Published: November 2016

The approach is possible under conditions A), B) or C) and affords various functionalized tetracyclic nitrogen skeletons, suitable as new drug‐like components.
ChemInform Abstract: Enantioselective N‐Heterocyclic Carbene‐Catalyzed Synthesis of Saccharine‐Derived Dihydropyridinones with cis‐Selectivity.
Authors: Liang Zhi‐Qin , Wang Dong‐Ling , Zhang Chun‐Lin , Ye Song
Published: November 2016

The products are delivered in high yields and with excellent enantioselectivities.
ChemInform Abstract: RuCl3 Promoted Efficient Synthesis of Z‐Selective Macrocyclic Thiotetralactones via Ring‐Closing Metathesis.
Authors: Muthusamy Sengodagounder , Kumar Muniyappankovilthottam Devaraj
Published: November 2016

Thirteen title compounds, represented by examples (II), (V), (VII), and (IX), which differ in ring size, spacer, and number of either oxygen or sulfur atoms, are prepared following conditions A).
ChemInform Abstract: Nanomagnetic Zirconia‐Based Sulfonic Acid (Fe3O4@ZrO2—Pr—SO3H): A New, Efficient and Recyclable Solid Acid Catalyst for the Protection of Alcohols via HMDS under Solvent Free Conditions.
Authors: Tadjarodi Azadeh , Khodikar Rahim , Ghafuri Hosssein
Published: November 2016

The applied catalytic system is readily prepared in two steps starting from (3‐mercaptopropyl)trimethoxysilane and nano magnetic zirconia.
ChemInform Abstract: Asymmetric Syntheses of (‐)‐Hastanecine, (‐)‐Turneforcidine and (‐)‐Platynecine.
Authors: Brambilla Marta , Davies Stephen G. , Fletcher Ai M. , Roberts Paul M. , Thomson James E.
Published: November 2016

All three diastereomers are prepared in 11 steps starting from commercially available 2,2‐dimethoxyacetaldehyde.
ChemInform Abstract: Aqueous Hydroxylation Mediated Synthesis of Crystalline Calcium Uranate Particles.
Authors: Ding Weixuan , Botha Johannes A. , Hanson Bruce C. , Burke Ian T.
Published: November 2016

In view of suitable long‐term waste forms for depleted U, metal uranates(VI) are solubility limiting U(VI) phases under high pH conditions.
ChemInform Abstract: Sonochemical Procedures; the Main Synthetic Method for Synthesis of Coinage Metal Ion Supramolecular Polymer Nano Structures
Authors: Shahangi Shirazi Fatemeh , Akhbari Kamran
Published: November 2016

Review: 72 refs.
ChemInform Abstract: Tailoring the Catalytic Properties of Metal Nanoparticles via Support Interactions
Authors: Ahmadi M. , Mistry H. , Roldan Cuenya B.
Published: November 2016

Review: 170 refs.
ChemInform Abstract: Cycloaddition and Electrocyclic Reactions of Vinylketenes, Allenylketenes, and Alkynylketenes
Authors: Fu Nanyan , Tidwell Thomas T.
Published: November 2016

Review: mechanism and stereochemistry; 361 refs.
ChemInform Abstract: Modulatory Effects of Silibinin in Various Cell Signaling Pathways Against Liver Disorders and Cancer — A Comprehensive Review
Authors: Li Wei , et al.
Published: November 2016

Review: 189 refs.
ChemInform Abstract: BN‐Embedded Aromatics for Optoelectronic Applications
Authors: Wang Jie‐Yu , Pei Jian
Published: November 2016

Review: [30 refs.
ChemInform Abstract: π‐Conjugated Cyanostilbene‐Based Optoelectric Functional Materials
Authors: Hang Cheng , Wu Hong‐Wei , Zhu Liang‐Liang
Published: November 2016

Review: [55 refs.
ChemInform Abstract: In situ Analyses for Ion Storage Materials
Authors: Yang Junghoon , Muhammad Shoaib , Jo Mi Ru , Kim Hyunchul , Song Kyeongse , Agyeman Daniel Adjei , Kim Yong‐Il , Yoon Won‐Sub , Kang Yong‐Mook
Published: November 2016

Review: such as x‐ray and neutron diffraction, x‐ray absorption spectroscopy, and microscopy; 222 refs.
Rektifikationswürzekochung
Authors: Dillenburger Michael , Hertel Katja , Scheuren Hans
Published: November 2016

Die Würzekochung bei der Bierbereitung soll u. A. unerwünschte Aromastoffe austreiben. Leitkomponente zur Bewertung dieser Abreicherung ist Dimethylsulfid (DMS). Die klassische Kochung mittels direkter Befeuerung wurde weitestgehend von Entspannungsverdampfern abgelöst. Diese bieten Vorteile, das Verdampfungsprinzip wirkt sich allerdings nachteilig auf die Austreibung aus. Durch Kombination aus Forschung und Innovation ist ein System entstanden, welches die Vorteile nutzen läßt, ohne die Nachteile in Kauf nehmen zu müssen: Das Rektifikationswürzekochsystem, welches in diesem Artikel vorgestellt wird.
Enhanced heavy oil recovery using 1‐Ethyl‐3‐Methyl‐Imidazolium Acetate
Authors: Tunnish Ahmed , Shirif Ezeddin , Henni Amr
Published: November 2016

abstract

Injecting chemicals in reservoirs is an efficient technique to improve oil recovery. In this study, a promising room temperature ionic liquid (RTIL), 1‐Ethyl‐3‐Methyl‐Imidazolium Acetate ([EMIM][Ac]), was injected to enhance the extraction of a heavy oil (14° API) from an unconsolidated sand pack at room conditions. [EMIM][Ac] was mixed with two different synthetic brines (0.1 and 1 mass% NaCl), and injected as a continuous displacing phase to improve heavy oil recovery. The results obtained showed that [EMIM][Ac] is an efficient solvent in the enhancement of the oil recovery factor (RF). The effects of [EMIM][Ac] concentration (C) on the interfacial tension (IFT), surface tension (SFT), zeta potential (ZP), pH, and conductivity (COND) were also investigated. The experimental study clearly demonstrates that [EMIM][Ac] is more efficient in enhancing the recovery of heavy oil than sodium dodecyl sulphate (SDS), a well‐known commercial surfactant.
THz Radiation Generation via the Interaction of Ultra‐short Laser Pulses with the Molecular Hydrogen Plasma
Authors: Soltani Gishini M. S. , Ganjovi A. , Saeed M.
Published: November 2016

In this paper, a two dimensional Particle In Cell‐Monte Carlo Collision simulation scheme is used to examine the THz generation via the interaction of high intensity ultra‐short laser pulses with an underdense molecular hydrogen plasma slab. The influences of plasma density, laser pulse duration and its intensity on the induced plasma current density and the subsequent effects on the generated THz signal characteristics are studied. It is observed that the induced current density in the plasma medium and THz spectral intensity are increased at the higher laser pulse intensities, laser pulse durations and plasma densities. Moreover, the generated THz electric field amplitude is reduced at the higher laser pulse durations. A wider frequency range for the generated THz signal is shown at the lower laser pulse durations and higher plasma densities. Additionally, it is found that the induced current density in hydrogen plasma medium is the dominant factor influencing the generation of THz pulse radiation. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Nonlinear Waves in Nonuniform Complex Astrocloud
Authors: Haloi A. , Karmakar P. K.
Published: November 2016

The global nonlinear gravito‐electrostatic eigen‐fluctuation behaviors in large‐scale non‐uniform complex astroclouds in quasi‐neutral hydrodynamic equilibrium are methodologically analyzed. Its composition includes warm lighter electrons, ions; and massive bi‐polar multi‐dust grains (inertial) with partial ionization sourced, via plasma‐contact electrification, in the cloud plasma background. The multi‐fluidic viscous drag effects are conjointly encompassed. The naturalistic equilibrium inhomogeneities, gradient forces and nonlinear convective dynamics are considered without any recourse to the Jeans swindle against the traditional perspective. An inho‐mogeneous multiscale analytical method is meticulously applied to derive a new conjugated non‐integrable coupled (via zeroth‐order factors) pair of variable‐coefficient inhomogeneous Korteweg de‐Vries Burger (i ‐KdVB) equations containing unique form of non‐uniform linear self‐consistent gradient‐driven sinks. A numerical illustrative scheme is procedurally constructed to examine the canonical fluctuations. It is seen that the eigenspectrum coevolves as electrostatic rarefactive damped oscillatory shock‐like structures and self‐gravitational compressive damped oscillatory shock‐like patterns. The irregular damping nature is attributable to the i ‐KdVB sinks. The aperiodicity in the hybrid rapid small downstream wavetrains is speculated to be deep‐rooted in the quasi‐linear gravito‐electrostatic interplay. The phase‐evolutionary dynamics grow as atypical non‐chaotic fixed‐point attractors. We, finally, indicate tentative astronomical applications relevant in large‐scale cosmic structure formation aboard facts and faults. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Simple Approach to Generalization of Child‐Langmuir Law for Non‐Zero Injection Velocities in a Planar Diode
Authors: Ahmady H. , Mehrshahi E. , Ghergherehchi M.
Published: November 2016

An absolutely straightforward study is presented to characterize the space‐charge limited region in a planar diode with non‐zero uniform initial velocity which brings about Liu's result. Unlike Liu's work, our approach is free of mathematical intricacies. In addition to its great simplicity, the presented method gives a good physical insight about the problem. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Lagged cumulative spruce budworm defoliation affects the risk of fire ignition in Ontario, Canada
Authors: James Patrick M. A. , Robert Louis‐Etienne , Wotton B. Mike , Martell David L. , Fleming Richard A.
Published: November 2016

Detailed understanding of forest disturbance interactions is needed for effective forecasting, modelling, and management. Insect outbreaks are a significant forest disturbance that alters forest structure as well as the distribution and connectivity of combustible fuels at broad spatial scales. The effect of insect outbreaks on fire activity is an important but contentious issue with significant policy consequences. The eastern spruce budworm (Choristoneura fumiferana) is a native defoliating insect in eastern North America whose periodic outbreaks create large patches of dead fir and spruce trees. Of particular concern to fire and forest managers is whether these patches represent an increased fire risk, if so, for how long, and how the relationship between defoliation and fire risk varies through space and time. Previous work suggests a temporary increase in flammability in budworm‐killed forests, but regional and seasonal variability in these relationships has not been examined. Using an extensive database on historical lightning‐caused fire ignitions and spruce budworm defoliation between 1963 and 2000, we assess the relative importance of cumulative defoliation and fire weather on the probability of ignition in Ontario, Canada. We modeled fire ignition using a generalized additive logistic regression model that accounts for temporal autocorrelation in fire weather. We compared two ecoregions in eastern Ontario (Abitibi Plains) and western Ontario (Lake of the Woods) that differ in terms of climate, geomorphology, and forest composition. We found that defoliation has the potential to both increase and decrease the probability of ignition depending on the time scale, ecoregion, and season examined. Most importantly, we found that lagged spruce budworm defoliation (8–10 yr) increases the risk of fire ignition whereas recent defoliation (1 yr) can decrease this risk. We also found that historical defoliation has a greater influence on ignition risk during the spring than during the summer fire season. Given predicted increases in forest insect activity due to global change, these results represent important information for fire management agencies that can be used to refine existing models of fire risk.
Atopic dermatitis: A tale of two distinct pathomechanisms that make you itch
Authors: Knol Edward F. , Hijnen DirkJan
Published: November 2016

Atopic dermatitis (AD) or eczema is the most common chronic inflammatory skin disease. It is a multifactorial disease with local and systemic immune changes. Current therapies focus on restoring the local skin barrier or inhibiting immune responses. In this issue of the European Journal of Immunology, Sehra et al. [Eur. J. Immunol. 2016. 46:2609–2613] describe a mouse model with T‐cell‐specific expression of constitutively active Stat6 in Flaky tail mice, which have mutations in the Flg and Tmem79 genes. The authors describe that it is the combination of changes in the skin barrier proteins filaggrin and Tmem79, together with Th2 cytokine signaling in the constitutively active Stat6 transgene, that drives the immune‐pathomechanism in AD. These results are consistent with human studies where it is demonstrated that diminished filaggrin expression in skin is a predisposing factor for AD, but is neither required nor sufficient for disease indicating that additional factors are required for disease development. The current mouse model by Sehra et al. could be instrumental in evaluation new therapeutic strategies for AD.
1st EMBL/DFG Women in Science Network Conference Heidelberg 2016
Authors: Stripecke Renata , Gouttefangeas Cécile , Förster Irmgard
Published: November 2016

The 1st EMBL/DFG Women in Science (WiS) Conference “From Genes, Cells and the Immune System towards Therapies” was held on 19th – 20th September 2016 in Heidelberg, Germany. The WiS conference was funded by nine Collaborative Research Centers (CRCs) of the German Research Council (Deutsche Forschungsgemeinschaft, DFG; Table 1) and benefited from an outstanding hosting environment at the Advanced Training Center of the European Molecular Biology Laboratory (EMBL). Scientific talks focused at genetic, cellular and immunologic mechanisms, and immune therapy, and progress from all stages of development covering basic research to clinical developments was described. The presentations were embedded between structured networking sessions and a round table discussion with representatives of the DFG, EMBL, European Molecular Biology Organisation (EMBO), and the German Society of Immunology (DGfI).
Exploring Partners for the Domino α‐Arylation/Michael Addition Reaction Leading to Tetrahydroisoquinolines
Authors: Solé Daniel , Pérez‐Janer Ferran , García‐Rodeja Yago , Fernández Israel
Published: November 2016

Sulfonates, sulfonamides, and phosphonates have proven useful nucleophiles for palladium‐catalyzed intramolecular α‐arylation reactions leading to tetrahydroisoquinolines. Although the sulfonate α‐arylation reaction can be successfully combined in a domino process with a broad range of Michael acceptors, only vinyl sulfones can be used in Michael additions when starting from sulfonamides. No domino process was developed with the phosphonate derivative. DFT calculations were carried out to gain more insights into the experimental differences observed in the reactions involving these substrates.
A Newly Competitive Electrochemical Sensor for Sensitive Determination of Chrysin Based on Electrochemically Activated Ta2O5 Particles Modified Carbon Paste Electrode
Authors: Xie Zhengkun , Wu Yongmei , Kai Sheng , Li Gaiping , Ye Baoxian
Published: November 2016

A novel electrochemically activated doped Ta2O5 particles modified carbon paste electrode (EA‐Ta2O5‐CPE) was prepared and applied for selective and sensitive determination of chrysin. X‐ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) techniques and cyclic voltammetry (CV) were used to characterize the Ta2O5 particles and investigate the electrochemical response of the sensor. Compared with bare CPE, the doped Ta2O5 modified electrode got much more porous by electrochemical treatment and exhibited larger effective surface area, more reactive site and excellent electrochemical catalytic activity toward the oxidation of chrysin. Under optimum conditions by LSV, the oxidation peak currents responded to chrysin linearly over a concentration range from 5.0×10−8 to 7.0×10−6 mol L−1 with a detection limit of 2.0×10−8 mol L−1 (5.08 ng mL−1). The fabricated sensor showed anti‐interference ability against the biological common interferents (i.e. baicalein, baicalin) and provided to be reliable for the determination of chrysin in Chinese medicinal herb Oroxylum indicum and chrysin capsules samples with satisfactory results.
A Simple Electrochemical Aptamer Cytosensor for Direct Detection of Chronic Myelogenous Leukemia K562 Cells
Authors: Yu Tianxiao , Zhang Hui , Huang Zhenglan , Luo Zhenhong , Huang Ningshu , Ding Shijia , Feng Wenli
Published: November 2016

A simple and rapid electrochemical aptamer cytosensor has been developed for direct detection of chronic myelogenous leukemia (CML) K562 cells based on a specific aptamer and a biotin conjugated concanavalin A (bio‐ConA) detection probe. The K562 cell could be specifically recognized by T2‐KK1B10 capture aptamer pre‐immobilized on gold modified electrode surface. Then, bio‐ConA was added in the reaction to identify K562 cell surface mannose, resulting in an aptamer‐K562 cell‐bio‐ConA sandwich complex. Finally, streptavidin conjugated alkaline phosphatase (ST‐ALP) combined with the bio‐ConA to catalyze α‐naphthyl (α‐NP) phosphate to form α‐naphthol which is highly electroactive at an operating voltage of 180 mV (vs. Ag/AgCl). Under optimum conditions, the DPV signals were proportional to the logarithm of K562 cell from 1×102 to 1×107 cells mL−1 with a detection limit of 79 cells mL−1. The cytosensor also exhibited high selectivity, stability and reproducibility. When applied to detect K562 cells in human blood samples, recoveries between 79.6 %–93.3 % were obtained, indicating the developed biosensor would be a potential alternative tool for CML K562 cell detection in real biological samples.
Combination of Flow Injection Analysis and Fast Scan Differential Pulse Voltammetry for the Determination of Antioxidants
Authors: Bavol Dmytro , Dejmkova Hana , Scampicchio Matteo , Zima Jiri , Barek Jiri
Published: November 2016

Fast‐scan differential pulse voltammetry (FSDPV) is an electroanalytical technique that uses high scan rate to record voltammograms within several milliseconds and ensures high temporal resolution. Here, a FSDPV on a glassy carbon working electrode in combination with a flow injection analysis (FIA) system was developed and characterized using the hydroquinone/quinone redox system. Later, enhanced resolution of the technique was confirmed with the parallel determination of caffeic acid and p‐coumaric acid. Finally, the optimized procedure has been applied for the first time to determine capsacinoids in chili pepper and total phenols in extra virgin olive oils. The proposed procedure is fast, simple, and enables the monitoring of complex samples in real‐time.
First Electroanalytical Studies of Profluralin with Square Wave Voltammetry Using Glassy Carbon Electrode
Authors: Smarzewska Sylwia , Jasińska Agnieszka , Ciesielski Witold , Guziejewski Dariusz
Published: November 2016

The electrochemical behaviour of profluralin (PFL) was investigated with square wave voltammetry (SWV) and cyclic voltammetry at bare and modified with graphene, graphene oxide, reduced graphene oxide, carbon nanotubes glassy carbon electrode. The influence of various factors such as pH, buffer composition, ionic surfactants and voltammetric parameters was studied. The best results in terms of signal shape and intensity were recorded in 0.04 M Britton‐Robinson buffer at pH 2.0 at −0.43 V versus Ag/AgCl. In acidic medium profluralin produces single cathodic signal of an irreversible nature. Observed peak (two superimposed signals from two nitro groups) is a result of PFL reduction controlled by diffusion processes. Linearity of peak currents (Ip) vs. concentrations of profluralin was found in the range of 1.0×10−7 to 1.0×10−6 M with a detection limit of 2.6×10−8 M using fast and sensitive SWV. The developed method has been applied for the quantitative analysis of profluralin in spiked environmental samples with very good average recoveries in the range from 98.6 to 99.9 % with a mean relative standard deviation of 4.0 %.
Passage of fiproles and imidacloprid from urban pest control uses through wastewater treatment plants in northern California, USA
Authors: Sadaria Akash M. , Sutton Rebecca , Moran Kelly D. , Teerlink Jennifer , Brown Jackson Vanfleet , Halden Rolf U.
Published: November 2016

Urban pest control insecticides—specifically fipronil and its 4 major degradates (fipronil sulfone, sulfide, desulfinyl, and amide), as well as imidacloprid—were monitored during drought conditions in 8 San Francisco Bay (San Francisco, CA, USA) wastewater treatment plants (WWTPs). In influent and effluent, ubiquitous detections were obtained in units of ng/L for fipronil (13–88 ng/L), fipronil sulfone (1–28 ng/L), fipronil sulfide (1–5 ng/L), and imidacloprid (58–306 ng/L). Partitioning was also investigated; in influent, 100% of imidacloprid and 62 ± 9% of total fiproles (fipronil and degradates) were present in the dissolved state, with the balance being bound to filter-removable particulates. Targeted insecticides persisted during wastewater treatment, regardless of treatment technology utilized (imidacloprid: 93 ± 17%; total fiproles: 65 ± 11% remaining), with partitioning into sludge (3.7–151.1 μg/kg dry wt as fipronil) accounting for minor losses of total fiproles entering WWTPs. The load of total fiproles was fairly consistent across the facilities but fiprole speciation varied. This first regional study on fiprole and imidacloprid occurrences in raw and treated California sewage revealed ubiquity and marked persistence to conventional treatment of both phenylpyrazole and neonicotinoid compounds. Flea and tick control agents for pets are identified as potential sources of pesticides in sewage meriting further investigation and inclusion in chemical-specific risk assessments. Environ Toxicol Chem 2017;36:1473–1482. © 2016 SETAC
Evaluating the potential of effluent extracts from pulp and paper mills in Canada, Brazil, and New Zealand to affect fish reproduction: Estrogenic effects in fish
Authors: Orrego Rodrigo , Milestone Craig B. , Hewitt L. Mark , Guchardi John , Heid-Furley Tatiana , Slade Alison , MacLatchy Deborah L. , Holdway Douglas
Published: November 2016

The authors examined the potential of pulp mill effluent from pulp-producing countries (Canada, Brazil, New Zealand) to affect fish reproduction. Specifically, the estrogenic effects in juvenile rainbow trout (Oncorhynchus mykiss) pulse-exposed to 11 different mill effluent extracts (intraperitoneal injections of solid-phase extraction–dichloromethane nonpolar fraction). The results indicated that effluent extracts were estrogenic in juvenile trout irrespective of the gender, as reflected by increasing level of plasma vitellogenin (VTG; Brazil > New Zealand > Canada). Despite the high variability observed among mills, differences in VTG levels were related to the type of mill process (kraft > elementary chlorine-free kraft > thermomechanical pulping). Moreover, effluent treatments did not appear to significantly decrease VTG induction. A consistent estrogenic effect was observed in those mills that process a combination of feedstocks (softwood and hardwood), with the highest increase in VTG related to eucalyptus feedstock. The results demonstrate significant estrogenic effects of pulp mill effluents on chronically exposed juvenile trout, suggesting that in vivo metabolic activation of precursors is necessary to cause the observed increases in VTG levels. This molecular estrogenic response provides a useful starting point for predicting population-level impacts through the adverse outcome pathway methodology. Environ Toxicol Chem 2017;36:1547–1555. © 2016 SETAC
A toxicokinetic model for fish including multiphase sorption features
Authors: Larisch Wolfgang , Brown Trevor N. , Goss Kai-Uwe
Published: November 2016

In the scientific field of physiologically based toxicokinetic modeling the complexity of the model used depends on the complexity of the problem to be handled, leading to a broad range of existing models from simple 1-box models to complex multicompartment models. Most of these models work with lumped parameters, for example, an uptake efficiency parameter that can only be obtained with a fit of experimental data. The authors’ goal was a model that is completely based on well-defined physiological and physicochemical parameters. Lumped parameters fitted on training data sets would limit the model's applicability. This would enable a new view on process understanding for uptake, distribution, and elimination procedures. Eventual goals are a better localization of chemicals within the organism itself, and to set the stage for future extensions toward ionic compounds and active transport across membranes. The model evaluation reported in the present study has shown that uptake, clearance, and bioaccumulation data for nonpolar chemicals are well predicted. Environ Toxicol Chem 2017;36:1538–1546. © 2016 SETAC
Durability of Response to Zoledronate Treatment and Competing Mortality in Paget's Disease of Bone
Authors: Cundy Tim , Maslowski Katherine , Grey Andrew , Reid Ian R
Published: November 2016

There has been a marked secular trend in recent decades toward patients with Paget's disease presenting at a greater age and having less extensive skeletal involvement. Over a similar time frame more potent bisphosphonates with a long duration of effect have been developed, raising the prospect of many patients needing only once in a lifetime treatment. We studied a cohort of 107 patients who had been treated with intravenous zoledronate for the first time at a mean age of 76 years. Sequential measurements of the bone turnover marker procollagen-1 NT-peptide (P1NP) were made for up to 10 years. By 9 years, 64% showed some loss of zoledronate effect (defined as a doubling of P1NP from the nadir value after treatment), but only 14% had a biochemical relapse (defined as a P1NP value >80 μg/L). The mortality rate was substantially greater than the relapse rate—by 10 years more than half the cohort had died (p < 0.0001). We conclude that for the majority of older people with Paget's disease a single intravenous infusion of zoledronate will provide disease suppression for the remainder of their lives. © 2016 American Society for Bone and Mineral Research.

Abstract

The potent, long-acting, bisphosphonate zoledronate is now commonly used in the treatment of Paget's disease, but contemporary patients tend to present later in life and to have fewer bones involved than formerly. This work reports that up to 10 years after zoledronate treatment, patients with Paget's disease are nearly four times more likely to die (competing mortality) than suffer biochemical relapse. Most patients with Paget's disease will probably need such treatment only once.
E‐Cigarette Vapor Induces an Apoptotic Response in Human Gingival Epithelial Cells Through the Caspase‐3 Pathway
Authors: Rouabhia Mahmoud , Park Hyun Jin , Semlali Abdelhabib , Zakrzewski Andrew , Chmielewski Witold , Chakir Jamila
Published: November 2016

Electronic cigarettes represent an increasingly significant proportion of today's consumable tobacco products. E‐cigarettes contain several chemicals which may promote oral diseases. The aim of this study was to investigate the effect of e‐cigarette vapor on human gingival epithelial cells. Results show that e‐cigarette vapor altered the morphology of cells from small cuboidal form to large undefined shapes. Both single and multiple exposures to e‐cigarette vapor led to a bulky morphology with large faint nuclei and an enlarged cytoplasm. E‐cigarette vapor also increased L‐lactate dehydrogenase (LDH) activity in the targeted cells. This activity was greater with repeated exposures. Furthermore, e‐cigarette vapor increased apoptotic/necrotic epithelial cell percentages compared to that observed in the control. Epithelial cell apoptosis was confirmed by TUNEL assay showing that exposure to e‐cigarette vapor increased apoptotic cell numbers, particularly after two and three exposures. This negative effect involved the caspase‐3 pathway, the activity of which was greater with repeated exposure and which decreased following the use of caspase‐3 inhibitor. The adverse effects of e‐cigarette vapor on gingival epithelial cells may lead to dysregulated gingival cell function and result in oral disease. J. Cell. Physiol. 232: 1539–1547, 2017. © 2016 Wiley Periodicals, Inc.
A 60‐year reconstructed high‐resolution local meteorological data set in Central Sahel (1950–2009): evaluation, analysis and application to land surface modelling
Authors: Leauthaud C. , Cappelaere B. , Demarty J. , Guichard F. , Velluet C. , Kergoat L. , Vischel T. , Grippa M. , Mouhaimouni M. , Bouzou Moussa I. , Mainassara I. , Sultan B.
Published: November 2016

ABSTRACT

The Sahel has experienced strong climate variability in the past decades. Understanding its implications for natural and cultivated ecosystems is pivotal in a context of high population growth and mainly agriculture‐based livelihoods. However, efforts to model processes at the land–atmosphere interface are hindered, particularly when the multi‐decadal timescale is targeted, as climatic data are scarce, largely incomplete and often unreliable.

This study presents the generation of a long‐term, high‐temporal resolution, multivariate local climatic data set for Niamey, Central Sahel. The continuous series spans the period 1950–2009 at a 30‐min timescale and includes ground station‐based meteorological variables (precipitation, air temperature, relative and specific humidity, air pressure, wind speed, downwelling long‐ and short‐wave radiation) as well as process‐modelled surface fluxes (upwelling long‐ and short‐wave radiation, latent, sensible and soil heat fluxes and surface temperature). A combination of complementary techniques (linear/spline regressions, a multivariate analogue method, artificial neural networks and recursive gap filling) was used to reconstruct missing meteorological data. The complete surface energy budget was then obtained for two dominant land cover types, fallow bush and millet, by applying the meteorological forcing data set to a finely field‐calibrated land surface model. Uncertainty in reconstructed data was expressed by means of a stochastic ensemble of plausible historical time series.

Climatological statistics were computed at sub‐daily to decadal timescales and compared with local, regional and global data sets such as CRU and ERA‐Interim. The reconstructed precipitation statistics, ∼1 °C increase in mean annual temperature from 1950 to 2009, and mean diurnal and annual cycles for all variables were in good agreement with previous studies. The new data set, denoted NAD (Niamey Airport‐derived set) and publicly available, can be used to investigate the water and energy cycles in Central Sahel, while the methodology can be applied to reconstruct series at other stations.
Skill of ECMWF system‐4 ensemble seasonal climate forecasts for East Africa
Authors: Ogutu Geoffrey E. O. , Franssen Wietse H. P. , Supit Iwan , Omondi P. , Hutjes Ronald W.A.
Published: November 2016

This study evaluates the potential use of the ECMWF System‐4 seasonal forecasts (S4) for impact analysis over East Africa. For use, these forecasts should have skill and small biases. We used the 15‐member ensemble of 7‐month forecasts initiated every month, and tested forecast skill of precipitation (tp), near‐surface air temperature (tas) and surface downwelling shortwave radiation (rsds). We validated the 30‐year (1981–2010) hindcast version of S4 against the WFDEI reanalysis (WATCH Forcing Data ERA‐Interim) and to independent relevant observational data sets. Probabilistic skill is assessed using anomaly correlation, ranked probability skill score (RPSS) and the relative operating curve skill score (ROCSS) at both grid cell and over six distinct homogeneous rainfall regions for the three growing seasons of East Africa (i.e. MAM, JJA and OND).

S4 exhibits a wet bias in OND, a dry bias in MAM and a mix of both in JJA. Temperature biases are similar in all seasons, constant with lead‐time and correlate with elevation. Biases in rsds correlate with cloud/rain patterns. Bias correction clears biases but does not affect probabilistic skills.

Predictability of the three variables varies with season, location and lead‐time. The choice of validating dataset plays little role in the regional patterns and magnitudes of probabilistic skill scores. The OND tp forecasts show skill over a larger area up to 3 months lead‐time compared to MAM and JJA. Upper‐ and lower‐tercile tp forecasts are 20–80% better than climatology. Temperature forecasts are skillful for at least 3 months lead‐time and they are 40–100% better than climatology. The rsds is less skillful than tp and tas in all seasons when verified against WFDEI but higher in all lead months against the alternative datasets. The forecast system captures El‐Niño Southern Oscillation (ENSO)‐related anomalous years with region‐dependent skill.
Increased expression of interleukin‐23 associated with progression of colorectal cancer
Authors: Hu Wan‐Hsiang , Chen Hong‐Hwa , Yen Shao‐Lun , Huang Hsuan‐Ying , Hsiao Chang‐Chun , Chuang Jiin‐Haur
Published: November 2016

Background and Objectives

The prognostic significance of interleukin‐23 in colorectal cancer remains unclear. We designed this study to investigate the association between colorectal cancer and interleukin‐23 (IL‐23) or interleukin‐23 receptor (IL‐23R) expression and the resulting clinical features and survival.

Methods

Immunohistochemical staining was performed for IL‐23 and IL‐23R in colorectal cancer samples. H‐score was calculated to compare the expression of IL‐23 and IL‐23R. The median of H‐score was used as the cut‐off value to separate patients into high or low expression groups. The differences in clinicopathological features were evaluated. Cox regression hazard ratios were used for survival analysis.

Results

A total of 129 colorectal cancer patients were enrolled. H‐score for the late TNM stage patients was higher than that for the early TNM stage patients (P = 0.002). Patients with high IL‐23 expression were associated with advanced pathological T category (P < 0.001) and late TNM stage (P = 0.003). High IL‐23 expression was associated with poor 5‐year disease‐free survival and overall survival in patients (P = 0.048 and P = 0.028, respectively). Multivariate adjustment demonstrated a significant association between high IL‐23 expression and overall survival (hazard ratio = 1.865, P = 0.041).

Conclusions

Elevated IL‐23 expression was associated with poor outcome and can be used as a prognostic biomarker for colorectal cancer. J. Surg. Oncol. 2017;115:208–212. © 2016 Wiley Periodicals, Inc.
Analysis of streptokinase by validated liquid chromatography methods and correlation with an in vitro bioassay
Authors: Cardoso Clóvis Dervil Appratto , Perobelli Rafaela Ferreira , Xavier Bruna , Maldaner Fernanda Pavani Stamm , da Silva Francielle Santos , Dalmora Sérgio Luiz
Published: November 2016

Reversed‐phase and size‐exclusion liquid chromatography methods were validated for the assessment of streptokinase. The reversed‐phase method was carried out on a Jupiter C4 column (250 mm × 4.6 mm id) maintained at 25°C. The mobile phase consisted of 50 mM sodium sulfate solution pH 7.0 and methanol (90:10, v/v), run isocratically at a flow rate of 0.8 mL/min. The size‐exclusion method was carried out on a Protein KW 802.5 column (300 mm × 8.0 mm id), at 25°C. The mobile phase consisted of 40 mM sodium acetate solution pH 7.0, run isocratically at a flow rate of 1.0 mL/min. Retention times were 19.3 min, and 14.1 min, and calibration curves were linear over the concentration range of 0.25–250 μg/mL (25.75–25 750 IU/mL) (r2 = 0.9997) and 5–80 μg/mL (515–8240 IU/mL) (r2 = 0.9996), respectively, for reversed‐phase and size exclusion, with detection at 220 and 204 nm. Chromatographic methods were employed in conjunction with the in vitro bioassay for the content/potency assessment of Streptokinase, contributing to improve the quality control and ensure the efficacy of the biotherapeutic.
Thermo‐Responsive Complexes of c‐Myc Antisense Oligonucleotide with Block Copolymer of Poly(OEGMA) and Quaternized Poly(4‐Vinylpyridine)
Authors: Topuzogullari Murat , Elalmis Yeliz Basaran , Isoglu Sevil Dincer
Published: November 2016

Solution behavior of thermo‐responsive polymers and their complexes with biological macromolecules may be affected by environmental conditions, such as the concentration of macromolecular components, pH, ion concentration, etc. Therefore, a thermo‐responsive polymer and its complexes should be characterized in detail to observe their responses against possible environments under physiological conditions before biological applications. To briefly indicate this important issue, thermo‐responsive block copolymer of quaternized poly(4‐vinylpyridine) and poly(oligoethyleneglycol methyl ether methacrylate) as a potential nonviral vector has been synthesized. Polyelectrolyte complexes of this copolymer with the antisense oligonucleotide of c‐Myc oncogene are also thermo‐responsive but, have lower LCST (lower critical solution temperature) values compared to individual copolymer. LCST values of complexes decrease with molar ratio of macromolecular components and presence of salt. Dilution of solutions also affects solution behavior of complexes and causes a significant decrease in size and an increase in LCST, which indicates possible effects of severe dilutions in the blood stream.

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