bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis, characterization, spectroscopic and theoretical studies of transition metal complexes of new nano Schiff base derived from l‐histidine and 2‐acetylferrocene and evaluation of biological and anticancer activities
Authors: Mahmoud Walaa H. , Omar M.M. , Sayed Fatma N. , Mohamed Gehad G.
Published: May 2018

A new Schiff base derived from the condensation of 2‐acetylferrocene with l‐histidine was prepared and characterized using elemental analyses and spectroscopic methods. Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of the Schiff base were prepared and characterized using various physicochemical methods such as elemental analysis, Fourier transform infrared and UV–visible spectroscopies, molar conductance, thermal analysis and scanning electron microscopy (SEM). Both ligand and complexes were investigated for their biological and anticancer activities. The elemental analyses showed that complexes were formed in a metal‐to‐ligand ratio of 1:1 stoichiometry. The spectral analyses proved that the ligand was tridentate and all complexes had an octahedral geometry, except the Zn(II) complex that was tetrahedral. SEM showed that the ligand and its Cd(II) complex were of nanometric structure. The molecular and electronic structure of the free ligand was optimized theoretically and the quantum chemical parameters were calculated. The molecular structure can be used to investigate the coordination sites and the total charge density around each atom. According to anticancer studies, Cd(II) complex was recommended to be used as anti‐breast cancer drug as it had very low IC50 (3.5 μg ml−1). Molecular docking was used to predict the binding between the free ligand and its Cd(II) complex and crystal structure of Staphylococcus aureus (PDB ID: 3Q8u), receptors of breast cancer mutant oxidoreductase (PDB ID: 3Hb5) and crystal structure of Escherichia coli (PDB ID: 3 T88) and to identify the binding mode and the crucial functional groups interacting with the three proteins.
A robust UV–visible light‐driven SBA‐15‐PS/phthalhydrazide nanohybrid material with enhanced photocatalytic activity in the photodegradation of methyl orange
Authors: Tayebee R. , Mohammadzadeh Kakhki R. , Audebert P. , Amini M. M. , Salehi M. , Mahdizadeh Ghohe N. , Mandanipour V. , Karimipour G.R.
Published: May 2018

SBA‐15‐PS/phthalhydrazide (PHD) is presented as a new heterogeneous inorganic–organic nanohybrid photocatalyst with high stability, superior recyclability and remarkable performance in the degradation of methyl orange (MO). Distinctive parameters, including photocatalyst and dye concentrations, pH and degradation time, were assessed for MO degradation catalysed by SBA‐15‐PS/PHD. This new heterogeneous nanocatalyst was characterized using Fourier transform infrared and UV–visible spectroscopies, thermogravimetric analysis, scanning and transmission electron microscopies and elemental analysis. Photodegradation of MO of up to 92% under the optimum conditions (photocatalyst = 0.015 g, [MO] = 4 ppm, pH = 2) was accomplished in 25 min using SBA‐15‐PS/PHD. A preliminary kinetic investigation was performed, and pseudo‐first‐order kinetics with a high rate constant (0.068 min−1) was found for MO degradation. Additional results showed that the photodegradation of MO was increased in the presence of hole scavengers. Therefore a photoreduction mechanism for MO degradation is proposed.
Improved stability and dispersity of ZnO@PANI nanocomposites aqueous suspension
Authors: Jin Xin , Liu Guangrong , Bao Chongzhuo , Chen Mingxin , Huang Qiang
Published: May 2018

The high dispersion and stability of a nanocomposites suspension are required as a crucial factor in many of their applications. In this study, ZnO nanosheets covered with polyaniline (PANI) thin layer (ZnO@PANI) were synthesized by a simple in‐situ polymerization. The as‐prepared ZnO@PANI powders were well characterized by XRD, Raman, FTIR, XPS and photoluminescence spectra, as well as SEM and TEM techniques. The effect of PANI incorporation on the chemical dissolution and dispersing stability of ZnO aqueous suspension was investigated. Dissolution experiments showed that the dissolution of ZnO was effectively restrained by the surface‐hybridized PANI layer. ZnO@PANI suspension can be more stable in a wider pH range. Dynamic Light Scattering (DLS) analysis indicated that ZnO@PANI particles were thoroughly dispersed in the neutral and alkaline solution as proven by the emergence of a single distribution with a high diffused intensity. Sedimentation experiments suggested that ZnO@PANI suspension was a more stable dispersion taking into account the effect of pH and ionic strength.
Sulfur/PAN/acetylene black composite prepared by a solution processing technique for lithium–sulfur batteries
Authors: K Krishnaveni , R Subadevi , M Raja , T PremKumar , M Sivakumar
Published: May 2018

A sulfur/poly(acrylonitrile)–PAN/acetylene black–AB composite, comprising sulfur and PAN encapsulated in the pores of AB was prepared by a solution‐based technique with dimethyl sulfoxide as the solvent. The composite was characterized by TGA, X‐ray diffraction, FTIR, Raman, SEM, TEM, and BET studies. The composite exhibited a high discharge capacity of 1330 mAh/g in the first cycle. The AB additive plays multiple roles in the composite, acting as a conducting matrix for electron transport and as a porous framework that adsorbs and retains electrolyte. The presence of PAN along with the porous carbon matrix in the composite provides the necessary resilience to absorb strains due to volume expansion during cycling. The observed improved performance of the composite is primarily attributed to the small size and homogeneous distribution of sulfur in the composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46598.
Reagent‐induced asymmetric induction in addition reaction of reduced glutathione onto bis‐Mannich chalcones
Authors: Bernardes Aline , D'Oliveira Giulio D. C. , Silezin Aneta , Kuzma Mónika , Molnár Szilárd , Noda Pérez Caridad , Perjési Pál
Published: May 2018

The stereochemistry of non‐enzyme catalyzed nucleophilic addition of GSH to 4′‐hydroxychalcone 1 and its bis‐Mannich derivative 2 was investigated at different pH values (pH 3.2, 6.1, 7.4, and 8.0). The stereochemical outcome of the reactions was evaluated by HPLC‐UV‐Vis method. Under strongly acidic conditions (pH 3.2), an unexpected diastereoselective addition of GSH onto the bis‐Mannich derivative 2 was observed. Such a selectivity could not be observed in the similar reaction of 2 with N‐acetylcysteine. The observed stereoselectivity can be rationalized by ion‐pair formation between the protonated Mannich nitrogens and the deprotonated GSH(glutamate)‐carboxylate. To the best of our knowledge, this is the first example of reagent‐induced asymmetric induction in Michael‐type additions of thiols.
N‐Heterocyclic Carbene‐Protected Ag Nanoparticles Immobilized on Polyacrylonitrile Fiber as Efficient Catalysts for a Three‐Component Coupling Reaction
Authors: Cao Jian , Tian Hongqi
Published: May 2018

Metal nanoparticles (NPs) are routinely stabilized by the introduction of capping agents or their distribution on supports. In this context, we report the preparation and characterization of N‐heterocyclic carbene (NHC)‐stabilized silver NPs supported on polyacrylonitrile fiber (PANF). As a result, Ag loadings of up to 8 % and particle sizes of 11.0±3.2 nm were achieved. This novel nanocomposite catalyst demonstrated high activity in addition to excellent stability and reusability in the three‐component reaction between alkynes, haloalkanes, and amines. In this system, the AgNPs were stabilized by both a support effect and a ligand effect. The unique NHC‐protected AgNP structure and the PANF support provide a synergistic effect in the deprotonation of Csp−H bonds, with turnover numbers of up to 3500. This catalyst was successfully recycled over eight runs without any significant loss in activity, and with no significant aggregation of the AgNPs. Moreover, implementation of a flow system with PANF‐NHC@Ag as catalyst leads to an efficient productivity of 57 mmol h−1.
Protein kinase Cδ (PKCδ) involved in the regulation of pAkt1 (Ser473) on the release of mouse oocytes from diplotene arrest
Authors: Liu Lingling , Li Sen , Li Hanwen , Yu Dahai , Li Chunyu , Li Gensong , Cao Yu , Feng Chen , Deng Xin
Published: May 2018

Defects in meiotic maturation may lead to chromosome segregation errors and genomic instability. Previous reports indicated that protein kinase C delta (PKCδ) may interact with microtubule organizing center‐associated protein to play a role on meiotic spindle organization of mammalian oocytes. In this study, we explored the potential role of protein kinase B alpha (PKBα/Akt1), PKCδ, and their relationship on meiotic maturation of mouse oocytes. We examined the expression and localization of pAkt1 (Ser473) and/or pPKCδ (Thr505) under the treatment of SH‐6 or Sotrastaurin. With the increasing of SH‐6 concentrations, we observed that the protein levels of pAkt1 (Ser473) and the percentages of GVBD were decreased gradually. And the distribution of pAkt1 (Ser473), Cdc25B, pCdc2 (Tyr15), and α‐tubulin around nucleus was also highly disordered under the treatment of 10‐μM SH‐6, a special inhibitor of pAkt1 (Ser473). In addition, the levels of pAkt1 (Ser473) were decreased with the treatment of Sotrastaurin, an inhibitor of PKCδ, suggesting that Akt1 may be one of the downstream targets of PKCδ. So, we deduced that PKCδ may be involved in regulating the release from diplotene arrest of mouse oocytes by controlling the levels of pAkt1 Ser473.

Significance of the study

As a drug target, Akt is still the focus of research in somatic and fertilized eggs. Here, our data depicted a series of molecular events of pAkt1 (Ser473) and PKCδ via their special inhibitor and antibody in order to analyse their role and relationship on the release of mouse oocytes from diplotene arrest. Our results may offer important data for clinic research scientist to recognize the target role of pAkt1 (Ser473) via PKCδ in cell cycle regulation.
Comparative Evaluation of OpenFOAM® and ANSYS® Fluent for the Modeling of Annular Reactors
Authors: Ariza Cristian , Casado Cintia , Wang Ruo-Qian , Adams Eric , Marugán Javier
Published: May 2018

A three‐dimensional numerical model was solved for a turbulent incompressible steady flow and the discrepancies and similarities between the software OpenFOAM® and ANSYS® Fluent on the flow modeling were analyzed. The evaluation was performed for the meshing, setup, and simulation step of the modeling process. Outcomes were contrasted with experimental data to validate the fluid flow obtained with both softwares. With this aim, an experimental pulse‐response technique was applied to obtain the residence time distribution (RTD) curve to be compared with the RTD curves achieved from the modeling. Additionally, images of the tracer transport in the experimental reactor were taken, showing good agreement with the computational fluid dynamics (CFD) predictions.
Water Flux Reduction in Microfiltration Membranes: A Pore Network Study
Authors: Abdoli S. Majid , Shafiei Sirous , Raoof Amir , Ebadi Amanollah , Jafarzadeh Yoones , Aslannejad Hamed
Published: May 2018

A 3D pore network model was developed to simulate the removal of dextran from water. Advanced scanning electron microscopy combined with focused ion beam analysis was used to obtain the sizes of the different pore networks that represent the microscopic structure of a porous membrane. The required input transport parameters for modeling were obtained by performing dynamic experiments on dextran adsorption within the pores of a polysulfone membrane. The simulated flux changes demonstrated a good agreement with the experimental data showing that such a model can be used to study the effects of various parameters during the process. Specifically, the results showed an increase in the applied pressure, decreased membrane thickness, increased pore size, while small sizes of contaminant molecules lead to a rise of the flux passing through the membrane.
Sustainable Conversion of Glycerol into Value‐Added Chemicals by Selective Electro‐Oxidation on Pt‐Based Catalysts
Authors: Zhou Yongfang , Shen Yi , Piao Jinhua
Published: May 2018

Electro‐oxidation of glycerol affords a totally green route to produce high value‐added chemicals. Herein, we report a study on glycerol electro‐oxidation over a series of graphene nanosheet supported Pt (Pt/GNS), PtNi (PtNi/GNS), PtRu (PtRu/GNS), PtRh (PtRh/GNS), PtRuNi (PtRuNi/GNS), and PtRhNi (PtRhNi/GNS) catalysts in alkaline solution. The activity of the catalysts was evaluated by cyclic voltammetry, linear sweep voltammetry, and chronoamperometric measurements. The PtRh/GNS and PtRhNi/GNS catalysts exhibited superior activity in terms of higher current densities and lower onset potentials. The products of glycerol oxidation formed at potentials of −0.4, −0.1, and 0.2 V, were systematically analyzed by high performance liquid chromatography (HPLC). Five compounds as products from glycerol electro‐oxidation catalyzed by the prepared materials were found, including glyceraldehyde, glycolic acid, tartronic acid, glyceric acid and oxalate acid. The product distribution at the different potentials was investigated for all catalysts. A maximum glycolic acid selectivity of 65.4 % was obtained for the Pt/GNS catalyst at 0.2 V while a maximum glyceric acid selectivity of 47.7 % was achieved using the PtNi/GNS catalyst at −0.1 V. It was found that the introduction of Ru facilitated the formation of C3 products while the addition of Rh was beneficial for the formation of C2 products. Based on HPLC results, the pathways of glycerol electro‐oxidation by the prepared catalysts were proposed.
Aromaticity and Antiaromaticity in Zintl Clusters
Authors: Liu Chao , Popov Ivan A. , Chen Zhongfang , Boldyrev Alexander I. , Sun Zhong‐Ming
Published: May 2018

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this Minireview, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.
Pd‐Catalyzed Consecutive C−H‐Arylation‐Triggered Cyclotrimerization: Synthesis of Star‐Shaped Benzotristhiazoles and Benzotrisoxazoles
Authors: Xu Zhanqiang , Oniwa Kazuaki , Kikuchi Hiromasa , Bao Ming , Yamamoto Yoshinori , Jin Tienan , Terada Masahiro
Published: May 2018

Star‐shaped π‐extended molecules comprising discotic aromatic cores and peripheral π‐conjugated arms have attracted significant attention as diverse optoelectronic materials in terms of their large π‐surface, tunable self‐assembly, enhanced charge transport and fluorescence, and liquid crystallinity. Although many efforts have been made in the construction of various aromatic discotic cores, a new class of C3‐symmetric star‐shaped discotic π‐molecules consisting of electron‐deficient benzotristhiazole and benzotrisoxazole cores, which are expected to exhibit distinct optoelectronic properties, remains unexplored owing to the unachievable synthetic approaches involved in their synthesis. Herein, we report a novel and highly efficient Pd‐catalyzed cyclotrimerization of the functionalized thiazoles or oxazoles for the construction of a new class of discotic molecules of benzotristhiazole and benzotrisoxazole central cores with star‐shaped π‐conjugated arms. The combination of [Pd2(dba)3]/XPhos (dba=dibenzylideneacetone) catalyst systems with the 4‐bromo‐substituted thiazole enables the formation of a sufficiently stable thiazole–Pd species that participates in the subsequent C−H arylations consecutively to form the corresponding cyclic trimer products. This new class of star‐shaped discotic π‐extended products showed tunable energy levels and high fluorescence quantum yields that make them promising candidates for optoelectronic applications.
Synthesis, Spectroscopic Characterization, and Redox Reactivity of a Cyclic (Alkyl) Amino Carbene‐Derived Arsamethine Cyanine Dye
Authors: Melancon Kortney M. , Gildner M. Brenton , Hudnall Todd W.
Published: May 2018

In our efforts to prepare a diarsenic allotrope supported by two cyclic alkyl amino carbene (CAAC) ligands we stumbled upon the synthesis of the first carbene‐supported chloroarsinidene 3, which has been fully characterized by a combination of NMR spectroscopic and XRD methods. Although further reduction of 3 was not possible, we found that addition of a second equivalent of CAAC in refluxing toluene afforded the first example of a crystallographically characterized arsamethine cyanine dye (4). The arsenic(I) dye is structurally similar to phosphorus analogues, and contains an arsenide anion with two stereochemically active lone pairs supported by two iminium ligands. The UV/Visible spectrum and redox chemistry of 4 were also explored. Upon reduction with one equivalent of KC8, 3 is reduced to the originally targeted CAAC2As2 allotrope 6, whereas oxidation provides access to the first example of an arsenic(II) radical dication (5).
A novel Color Rendition Chart for digital tongue image calibration
Authors: Zhang Bob , Nie Wei , Zhao Shuping
Published: May 2018

Digital tongue images are usually acquired by a camera under specific illumination environments. In order to guarantee better color representation of the tongue body, we propose a novel tongue Color Rendition Chart acting as a color reference to be used in color calibration algorithms to standardize the captured tongue images. First, based on a large tongue image database captured with our digital tongue image acquisition system, we establish a statistical tongue color gamut. Then, from the first step, different quantities of colors in the Color Rendition Chart are determined via experimentation. Afterwards, results using X‐Rite's ColorChecker® Color Rendition Chart (a standard in the color calibration field) are compared with the proposed tongue Color Rendition Chart by applying the color difference calculation formula of CIELAB and CIEDE2000 as a reference for the mean color calibration error. The results show that the proposed tongue Color Rendition Chart, which has 24 colors, produces a much smaller error (CIELAB —8.0755/CIEDE 2000—6.3482) compared with X‐Rite's ColorChecker® Color Rendition Chart (CIELAB 1976—14.7836/CIEDE 2000—11.7686). This demonstrates the effectiveness of the novel tongue Color Rendition Chart.
High‐level event identification in social media
Authors: Dashdorj Zolzaya , Altangerel Erdenebaatar
Published: May 2018

The increasing numbers of large data sets generated by information technologies provide a great opportunity to better understand emerging topics in human society. Retrieving real‐world events from such data, particularly free‐text data, is a complicated task in Natural Language Processing and Location‐based Social Networks. In this work, we propose a new approach, which recognizes geo‐referenced high‐level events/activities mentioned in web sources adopting open gazetteers: OpenStreetMap and Google Maps. Our approach demonstrated on sampled news articles identifies events associated with the relevant topics using a latent Dirichlet allocation. This research is an essential step towards recommendation systems, urban planning, and monitoring.
Intelligent air quality detection based on genetic algorithm and neural network: An urban China case study
Authors: Zhang Bi , Li Wei
Published: May 2018

Scientific and objective evaluations of atmospheric quality have become a primary task for researchers with the continuous development of modern industrial processes. At present, various approaches are used in monitoring air quality. The core factors of these approaches are the selection and establishment of an intelligent evaluation model. In this study, we designed a fuzzy genetic neural network model that fuses data based on the characteristics of autonomic learning and self‐organization and optimizes the fuzzy system by using the neural network model. A simulation was conducted to verify the feasibility of the algorithm. Results indicate that the proposed algorithm is not only a highly objective, scientific, and accurate method for detecting atmospheric environmental quality but also a practical solution.
Salmonella Typhimurium Infection of Human Monocyte‐Derived Macrophages
Authors: Lathrop Stephanie K. , Cooper Kendal G. , Binder Kelsey A. , Starr Tregei , Mampilli Veena , Detweiler Corrella S. , Steele‐Mortimer Olivia
Published: May 2018

The successful infection of macrophages by non‐typhoidal serovars of Salmonella enterica is likely essential to the establishment of the systemic disease they sometimes cause in susceptible human populations. However, the interactions between Salmonella and human macrophages are not widely studied, with mouse macrophages being a much more common model system. Fundamental differences between mouse and human macrophages make this less than ideal. Additionally, the inability of human macrophage‐like cell lines to replicate some properties of primary macrophages makes the use of primary cells desirable. Here we present protocols to study the infection of human monocyte‐derived macrophages with Salmonella Typhimurium. These include a method for differentiating monocyte‐derived macrophages in vitro and protocols for infecting them with Salmonella Typhimurium, as well as assays to measure the extent of infection, replication, and death. These protocols are useful for the investigation of both bacterial and host factors that determine the outcome of infection. © 2018 by John Wiley & Sons, Inc.
Enhanced Furfural Yields from Xylose Dehydration in the γ‐Valerolactone/Water Solvent System at Elevated Temperatures
Authors: Sener Canan , Motagamwala Ali Hussain , Alonso David Martin , Dumesic James A.
Published: May 2018

High yields of furfural (>90 %) were achieved from xylose dehydration in a sustainable solvent system composed of γ‐valerolactone (GVL), a biomass derived solvent, and water. It is identified that high reaction temperatures (e.g., 498 K) are required to achieve high furfural yield. Additionally, it is shown that the furfural yield at these temperatures is independent of the initial xylose concentration, and high furfural yield is obtained for industrially relevant xylose concentrations (10 wt %). A reaction kinetics model is developed to describe the experimental data obtained with solvent system composed of 80 wt % GVL and 20 wt % water across the range of reaction conditions studied (473–523 K, 1–10 mm acid catalyst, 66–660 mm xylose concentration). The kinetic model demonstrates that furfural loss owing to bimolecular condensation of xylose and furfural is minimized at elevated temperature, whereas carbon loss owing to xylose degradation increases with increasing temperature. Accordingly, the optimal temperature range for xylose dehydration to furfural in the GVL/H2O solvent system is identified to be from 480 to 500 K. Under these reaction conditions, furfural yield of 93 % is achieved at 97 % xylan conversion from lignocellulosic biomass (maple wood).
Habitat connectivity is determined by the scale of habitat loss and dispersal strategy
Authors: Edelsparre Allan H. , Shahid Ashif , Fitzpatrick Mark J.
Published: May 2018

Understanding factors that ameliorate the impact of habitat loss is a major focus of conservation research. One key factor influencing species persistence and evolution is the ability to disperse across increasingly patchy landscapes. Here we ask whether interpatch distance (a proxy for habitat loss) and dispersal strategy can interact to form thresholds where connectivity breaks down. We assayed dispersal across a range of interpatch distances in fruit flies carrying allelic variants of a gene known to underlie differences in dispersal strategy. Dispersal‐limited flies experienced a distinct negative threshold in connectivity at greater interpatch distances, and this was not observed in more dispersive flies. Consequently, this differential response of dispersal‐limited and more dispersive flies to decreasing connectivity suggests that habitat loss could have important implications on the evolution and maintenance of genetic variation underlying dispersal strategy.
Heterogeneity of aquatic ecosystems in a developing city for construction of civilized freshwater ecology, China
Authors: Zhao Changsen , Yu Xinyi , Yang Shengtian , Wang Xuefeng , Sun Changlei , Zhang Yuan , Dong Baoen , Shao Nanfang
Published: May 2018

Rapid degradation of global ecosystems seriously impacted the sustainable development of human society and economy. Understanding the heterogeneity of aquatic ecosystems is significantly helpful for ecological remediation. The success of restoration in Jinan City, the first pilot city for the construction of civilized freshwater ecology, will determine the fundamental improvement of the living environment of human beings in China. This paper studied the tempo‐spatial heterogeneity of aquatic ecosystems in Jinan using canonical correspondence analysis and random forest methods, based on data regarding aquatic ecology collected during field investigations from 2014 to 2015. Results showed that water depth and flow velocity in hydrological factors had the greatest impact on the distribution of fish and zoobenthos, and conductivity and total hardness in water quality factors had the greatest effect on both 2 communities; the biodiversity of fish and zoobenthos were better in the eastern than in the western region, and better in the mountain areas than in the plains; the quality of aquatic ecosystems in most regions of Jinan was in general good except for that in the 2 regions close to urban area that were severely affected by human activities. These results could provide a scientific basis for policymaking for ecological restoration and construction of civilized freshwater ecology, which will ensure successful maintenance and remediation of river ecosystems in the important city. This methodological framework could provide a reference for aquatic ecological rehabilitation both in China and worldwide.
Role of Silver Nanoclusters in the Enhanced Photocatalytic Activity of Cerium Oxide Nanoparticles
Authors: Samai Boby , Chall Sayantani , Mati Soumya Sundar , Bhattacharya Subhash Chandra
Published: May 2018

We have designed a silver‐nanocluster‐supported cerium oxide nanoparticle composite (AgNC/CeO2) to overcome the inapplicability of CeO2 as a photocatalyst due to a large band gap. A hydrothermal‐based synthetic strategy was followed to prepare spherical cerium oxide nanoparticles (CeO2 NPs). The AgNCs were synthesized separately. In the final step, silver‐nanocluster‐supported CeO2 nanoparticle composites were fabricated by simply mixing CeO2 and various concentrations of AgNC and stirring for 48 hours. The as‐prepared AgNC/CeO2 nanocomposites were employed as photocatalysts to study the degradation of the dye Acridine Red (AR) under UV light illumination. The results showed that the photocatalytic activities of the AgNC/CeO2 were enhanced several times compared with pure CeO2 NPs, even with a very low loading of AgNC (ca. 3 %). The increased catalytic activity of the AgNC/CeO2 nanocomposites was interpreted mechanistically by including the participation of reactive oxygen species, and corroborated experimentally. Thus, the AgNCs provide a convenient approach to improving the photocatalytic activity of CeO2 NPs.
Cu5In3‐Cu3In2 Revisited
Authors: Lidin Sven , Piao Shuying
Published: May 2018

The η‐phase field of the Cu–In system is unusually rich and shows wealth of phases that are all related to the B8 (NiAs/Ni2In) type. Previous electron diffraction work has revealed extensive super structure ordering; in this study, we report single crystal diffraction experiments on high‐quality samples of two of the phases in the system, ht1‐Cu5In3 and ht2‐Cu5In3. Both these phases constitute super structures, caused by the ordering of interstitials. The structure ht2‐Cu5In3 is a relatively simple structure with a bidimensional modulation but where only first order satellites are visible, indicating incomplete order whereas ht1‐Cu5In3 displays many high order satellites and the refined structure exhibit nearly perfect order with step‐function‐like occupancy domains. The refinement of the structure of ht1‐Cu5In3 is challenging for several reasons. It is difficult to integrate the data because of the unusual combination of very closely spaced satellites caused by q‐vectors close to (1/3 1/3 0) and a paucity of reflections in total, caused by the small substructure. A second challenge is the refinement of what amounts to a two‐dimensional step function. In effect, the shape of a two‐dimensional occupation domain is defined by a Fourier series and the problem of defining that shape is non‐trivial.
Magnetic Properties of LnIII–CuII 15‐Metallacrown‐5 Dimers with Terephthalate (LnIII = Pr, Nd, Sm, Eu)
Authors: Pavlishchuk Anna V. , Kolotilov Sergey V. , Zeller Matthias , Lofland Samuel E. , Addison Anthony W.
Published: May 2018

Metathesis of the isomorphous 15‐metallacrown‐5 complexes {[LnCu5(GlyHA)5(SO4)(H2O)6.5]}2(SO4)·6H2O (LnIII = Pr, Nd, Sm, Eu; GlyHA2– = glycinehydroxamate) with excess p‐bdc2– (p‐bdc2– = terephthalate) gave pairs of isomorphous complexes {[LnCu5(GlyHA)5(CO3)(H2O)4]2(p‐bdc)}·15H2O [Ln = Pr (1) and Nd (2)] and {[LnCu5(GlyHA)5(SO4)(H2O)x]2(p‐bdc)}·yH2O [Sm (3) x = 5, y = 12; Eu (4), x = 4, y = 14] as outcomes of partial sulfate replacement. Complexes 1–4 are discrete dimers with two 15‐metallacrown‐5 blocks {LnCu5}3+, a bridging p‐bdc2– and a bidentate capping anion on each Ln3+. The anion caps in 1 and 2 are carbonates from atmospheric CO2 capture, while in 3 and 4 the anion caps are sulfates. Between 3 K and 300 K, intrametallacycle antiferromagnetic exchange interactions amongst the Cu2+ dominate the magnetic properties of 1–4, while for the Ln3+, spin‐orbit coupling and crystal field effects are significant, the former being greater for Sm3+ and Eu3+. The experimental χMT vs. T data were fitted with an additive model reflecting the dominance of the Cu···Cu superexchange, while Ln3+···Cu2+ exchange interactions were taken into account through a molecular field approach. The best‐fit values (–2JCu–Cu) for the intercopper superexchange interactions range from 88 to 120 cm–1; the g‐factors, spin‐orbit coupling (λ) and axial crystal field splitting (Δ) parameter values are typical for LnIII.
Trifluoromethylthiolation of α‐Chloroaldehydes: Access to Quaternary SCF3‐Containing Centers
Authors: Gelat Fabien , Poisson Thomas , Biju Akkattu T. , Pannecoucke Xavier , Besset Tatiana
Published: May 2018

In this study, a straightforward methodology was developed to access quaternary α‐trifluoromethylthiolated chloroaldehydes. Using the Munavalli reagent as the electrophilic SCF3 source, a base‐catalyzed trifluoromethylthiolation reaction with a panel of α‐chloroaldehydes was successfully achieved under mild reaction conditions. The α‐trifluoromethylthiolated chloroaldehydes were obtained in moderate to high yields (up to 88 %). This approach demonstrated a good functional‐group tolerance and offered access to highly functionalized quaternary trifluoromethylthiolated aldehydes, inaccessible so far. The development of an enantioselective version was investigated by using a chiral phase‐transfer catalyst, giving the enantioenriched product in moderate enantiomeric excess.
Synthesis of Enantiopure PZM21: A Biased Agonist of the Mu‐Opioid Receptor
Authors: Perrey David , Zhang Dehui , Nguyen Thuy , Carroll F. Ivy , Ko Mei‐Chuan , Zhang Yanan
Published: May 2018

PZM21 (1) was recently reported as a biased agonist of the mu‐opioid receptor (MOR) with improved antinociceptive effects and reduced side effects compared with traditional opioid‐based analgesics. The original synthesis of PZM21 with the desired (S,S) configuration required the separation of a diastereomeric mixture in the final step by using chiral HPLC. A concise synthesis of 1 has now been developed in the enantiomeric pure form starting with commercially available l‐alanine and proceeding via a chiral aziridine as a key intermediate. The final product was obtained as the (S,S) diastereomer in seven steps in 22.5 % yield from l‐alanine. This synthetic strategy could be readily applied to the development of PZM21 analogues at the thiophenyl position.
Stereochemical Stability and Absolute Configuration of Atropisomeric Alkylthioporphyrazines by Dynamic NMR and HPLC Studies and Computational Analysis of HPLC‐ECD Recorded Spectra
Authors: Belviso Sandra , Santoro Ernesto , Lelj Francesco , Casarini Daniele , Villani Claudio , Franzini Roberta , Superchi Stefano
Published: May 2018

The conformational and stereodynamic properties of a pyrene‐substituted ethylthioporphyrazine (PzPy), promising as a dye for organic optoelectronic applications and light‐harvesting systems, have been investigated by DFT computations and variable‐temperature NMR and HPLC. In PzPy, rotation around the pyrene–macrocycle bond is hindered and the molecule displays atropisomerism, existing as a pair of enantiomers, thus representing the first chiral alkyl‐porphyrazine to be reported in the literature. The rotational barrier (ΔG‡ ≈ 22.0 kcal mol–1), measured by variable‐temperature HPLC experiments, allows chromatographic separation of the enantiomers on a chiral stationary phase below 0 °C, whereas racemization spontaneously occurs at room temperature. The absolute configurations of the eluted enantiomers were also determined by computational analysis of their electronic circular dichroism spectra. The influence of alkyl chain length and metal complexation on the molecular stereodynamic properties have also been investigated by studying its novel octylthio derivative (PzPy‐octyl) and PdII complex (PdPzPy), respectively. The latter also is the first example of a PdII–alkylthioporphyrazine complex. Given that PzPy has been used in the preparation of hybrid materials with nanocarbons for optoelectronic applications, the presence of an axial chirality element may play a key role in its interaction with semiconducting chiral nanotubes.
The effect of simulated space radiation on the N‐glycosylation of human immunoglobulin G1
Authors: Szarka Mate , Szilasi Szabolcs , Donczo Boglarka , Sarkozy Daniel , Rajta Istvan , Guttman Andras
Published: May 2018

On a roundtrip to Mars, astronauts are expectedly exposed to an approximate amount of radiation that exceeds the lifetime limits on Earth. This elevated radiation dose is mainly due to Galactic Cosmic Rays and Solar Particle Events. Specific patterns of the N‐glycosylation of human Igs have already been associated with various ailments such as autoimmune diseases, malignant transformation, chronic inflammation, and ageing. The focus of our work was to investigate the effect of low‐energy proton irradiation on the IgG N‐glycosylation profile with the goal if disease associated changes could be detected during space travel and not altered by space radiation. Two ionization sources were used during the experiments, a Van de Graaff generator for the irradiation of solidified hIgG samples in vacuum, and a Tandetron accelerator to irradiate hIgG samples in aqueous solution form. Structural carbohydrate analysis was accomplished by CE with laser induced fluorescent detection to determine the effects of simulated space radiation on N‐glycosylation of hIgG1 samples. Our results revealed that even several thousand times higher radiation doses that of astronauts can suffer during long duration missions beyond the shielding environment of Low Earth Orbit, no changes were observed in hIgG1 N‐glycosylation. Consequently, changes in N‐linked carbohydrate profile of IgG1 can be used as molecular diagnostic tools in space.
Real‐time monitoring of ethanol production during Pichia stipitis NRRL Y‐7124 alcoholic fermentation using transflection near infrared spectroscopy
Authors: Corro‐Herrera Víctor Abel , Gómez‐Rodríguez Javier , Hayward‐Jones Patricia Margaret , Barradas‐Dermitz Dulce María , Gschaedler‐Mathis Anne Christine , Aguilar‐Uscanga María Guadalupe
Published: May 2018

The application of in situ near‐infrared spectroscopy monitoring of xylose metabolizing yeast such as Pichia stipitis for ethanol production with semisynthetic media, applying chemometrics, was investigated. During the process in a bioreactor, biomass, glucose, xylose, ethanol, acetic acid, and glycerol determinations were performed by a transflection probe immersed in the culture broth and connected to a near‐infrared process analyzer. Wavelength windows in near‐infrared spectra recorded between 800 and 2200 nm were pretreated using Savitzky–Golay smoothing, second derivative and multiplicative scattering correction in order to perform a partial least squares regression and generate the calibration models. These calibration models were tested by external validation (78 samples). Calibration and validation criteria were defined and evaluated in order to generate robust and reliable models for an alcoholic fermentation process matrix. Moreover, regressions coefficients (β) and variable influence in the projection plots were used to assess the results. A novelty is the use of β versus VIP dispersion plots to determine which vectors have more influence on the response in order to improve process comprehension and operability. Validated models were used in a real‐time monitoring during P. stipitis NRRL Y7124 semisynthetic media fermentations.
Design Methodology for Electrocaloric Cooling Systems
Authors: Blumenthal Philipp , Raatz Annika
Published: May 2018

For over a decade now, the electrocaloric effect (ECE) and electrocaloric (EC) cooling have been the subject of increasing research activities. Research on electrocaloric materials (ECM) is quite advanced; however, significant progress on EC cooling systems is still missing. Therefore, a methodological approach for the structured development of EC cooling systems is presented here. It is based on the well‐known V‐Model and integrates different tools, as a classification of device types, influencing factors, and numerical simulation methods. The methodology can be used to structure development processes and to identify favorable geometrical and operating parameters of an EC cooling device. The methodology is validated with a demonstrator, which is designed, built, and practically tested for over 2000 h. With this small‐scale device and a low electrical field strength of 3 kV mm−1, a temperature span of over 1.1 K could be achieved.
Changes in eating disorder characteristics over the years
Authors: Probst Michel , Kürsa Kärt , Van Damme Tine , Diedens Jolien , Vanderlinden Johan
Published: May 2018

Since 1980, the diagnostic criteria of patients with eating disorders (ED) have changed over the years. Are these changes also expressed in the clinical features of the ED patients? A cross‐sectional sample was drawn consisting of 100 consecutive female patients' files diagnosed with anorexia nervosa (AN) and bulimia nervosa (BN) and bulimia nervosa and admitted at an inpatient unit from the first of January 1990, 2000, and 2010, respectively. Several reliable and well‐validated questionnaires (Eating Disorder Inventory, Body Attitude Test, Symptom Checklist, and the Beck Depression Inventory) were administered and scores were compared. The ratio AN/BN remained the same (65/35). No differences were found between the three cohorts except for depression, which increased over the years. This pattern is the same for the subsamples of anorexia nervosa and bulimia nervosa. Specific characteristics of eating disorder pathology did not change across time.
Drone photogrammetry and KMeans point cloud filtering to create high resolution topographic and inundation models of coastal sediment archives
Authors: Callow J.N. , May S.M. , Leopold M.
Published: May 2018

Coastal areas are vulnerable to the impacts of tropical cyclones (TC), tsunamis and other water super‐elevation events, but the frequency of these events is often poorly represented by conventional records. Coastal overwash deposits (including washover fans) can provide a longer‐term archive of event frequency. Because of their low‐gradient geomorphic form, washover fans require high accuracy (centimetre‐resolution) topographic models to understand patterns of connectivity and dynamics that control archive formation. Using images collected by a remotely piloted aircraft system (RPAS, or ‘drone’) and Structure‐from‐Motion (SfM) photogrammetry techniques, we apply a novel point‐cloud filtering technique based on KMeans classification of the R‐G‐B colour of each X‐Y‐Z point to remove vegetation and create a centimetre‐resolution and accuracy bare‐earth digital terrain model (DTM) of a washover fan in Exmouth Gulf (Western Australia).

Using the RPAS‐SfM orphophoto and DEM data, supported by ground‐penetrating radar (GPR) and field stratigraphic analysis, we show how this approach can be applied to understand dynamics controlling low‐gradient geomorphic landforms, using an example of a washover fan sedimentary archive in northwestern Australia created by extreme overwash events. Our approach reveals the likely role of backflooding and terrestrial runoff in creating backwater environment for sub‐aqueous deposition and good sediment preservation and identifies key areas to target for detailed dating and stratigraphic analysis of a potentially decadal to sub‐millennial resolution sediment archive of TC activity. Copyright © 2018 John Wiley & Sons, Ltd.
Do IMF fiscal forecasts add value?
Authors: An Zidong , Jalles João Tovar , Loungani Prakash , Sousa Ricardo M.
Published: May 2018

We used a panel of 29 advanced and emerging market countries to investigate whether the IMF's World Economic Outlook (WEO) fiscal forecasts add value in terms of forecast accuracy and information content, relative to private sector forecasts (from Consensus Economics). We find that: (i) WEO forecasts are not significantly less accurate than Consensus forecasts; (ii) WEO and Consensus forecasts tend to mutually encompass one another; and (iii) each source of forecasts appears to contain some information that is not embedded in the other source.
Proximate composition, functional, and pasting properties of wheat and groundnut protein concentrate flour blends
Authors: Ocheme Ocheme Boniface , Adedeji Olajide Emmanuel , Chinma Chiemela Enyinnaya , Yakubu Caleb Maina , Ajibo Ugochukwu Happiness
Published: May 2018

This study investigated the effect of groundnut protein concentrate inclusion on the quality of wheat flour. Wheat and groundnut concentrate flours were blended (%, w/w) at ratios 100:0, 95:5, 90:10, 85:15, and 80:20, with 100% wheat flour serving as the control sample. Subsequently, proximate composition, functional, and pasting properties of blends were determined using established methods. Protein content of the concentrate was 72.80%. Significant (p < .05) increase in protein content of the flour blends was recorded with increasing concentration of groundnut protein concentrate and decreasing concentration of wheat flour. Highest protein content of 28.87% was recorded in blend with 20% groundnut protein concentrate. Fat, ash, and crude fiber contents ranged from 1.93% to 8.84%, 0.70% to 1.13%, and 0.84% to 1.23%, respectively. Carbohydrate decreased significantly (p < .05) with increasing concentration of groundnut protein concentrate. Bulk density and swelling capacity of the flour blends reduced significantly (p < .05) with increasing level of groundnut protein concentrate flour while solubility index, water absorption, emulsion, and foaming capacities increased. Peak time, peak, trough, breakdown, final, and setback viscosities of the flour blends reduced with groundnut protein concentrate inclusion while the pasting temperature reduced. Overall, wheat/groundnut protein concentrate flour blends showed good functional and pasting properties.
An exploration of the non‐iterative time trade‐off method to value health states
Authors: Feng Yan , Hole Arne Risa , Karimi Milad , Tsuchiya Aki , van Hout Ben
Published: May 2018

Time Trade‐Off (TTO) usually relies on “iteration,” which is susceptible to bias. Discrete Choice Experiment with duration (or DCETTO) is free of such bias, but respondents find this cognitively more challenging. This paper explores non‐iterative TTO with or without lead time: NI(LT)TTO. In NI(LT)TTO, respondents see a series of independent pairwise choices without iteration (similar to DCETTO), but one of the two scenarios always involves full health for a shorter duration (similar to TTO). We compare three different “types” of NI(LT)TTO relative to DCETTO. Each type is presented in two “modes”: (a) verbally tabulated (as in a DCE) and (b) with visual aids (as in a TTO). The study has 8 survey variants, each with 12 experimental choice tasks and a 13th task with a logically determined answer. Data on the 12 experimental choices from an online survey of 6,618 respondents are modelled, by variant, using conditional logistic regressions. The results indicate that NI(LT)TTO is feasible, but some relatively mild states appear to have implausibly low predicted values, and the range of predicted values is much narrower than in DCETTO. The presentation of NI(LT)TTO tasks needs further improvement.
High preoperative plasma vasohibin‐1 concentration predicts better prognosis in patients with non–small cell lung carcinoma
Authors: Watanabe Tatsuaki , Hosaka Tomoko , Ohmori‐Matsuda Kaori , Suzuki Yasuhiro , Suzuki Hirotoshi , Yabuki Hiroshi , Matsuda Yasushi , Noda Masafumi , Sakurada Akira , Okada Yoshinori , Sato Yasufumi
Published: May 2018

Background and Aim

Vasohibin‐1 (VASH1) is an angiogenesis inhibitor synthesized and secreted by endothelial cells, whose expression is induced by angiogenic stimuli such as vascular endothelial growth factor. We have previously demonstrated that VASH1 is immunohistochemically evident in endothelial cells in the tumor microenvironment of patients with non–small cell lung cancer (NSCLC) and is positively correlated with that of vascular endothelial growth factor in cancer cells. Here, we determined the preoperative plasma concentration of VASH1 in patients with NSCLC and evaluated the association between the preoperative VASH1 levels and certain outcomes.

Methods

We analyzed presurgical plasma VASH1 concentrations in a total of 79 lung cancer patients (51 males and 28 females; 34‐83 y of age; 46 adenocarcinomas, 27 squamous cell carcinomas, and 6 other types) who underwent lung resection. The impact of preoperative VASH1 level was analyzed using clinical characteristics and prognosis.

Results

Plasma VASH1 concentration ranged from 34.1 to 1190.4 fmol/mL. We divided the patients into 3 groups according to plasma VASH1 level for this assessment: low VASH1 group (n = 26), medium VASH1 group (n = 27), and high VASH1 group (n = 26). The death and recurrence rates of the high, medium, and low VASH1 groups were 5.5, 16.2, and 12.7 per 100 person‐years, respectively. Multivariate adjusted hazard ratio of death and recurrence of the high VASH1 group was lower than that of the low VASH1 group (hazard ratio 0.42; 95% CI 0.17‐0.99).

Conclusion

The present analysis suggests that high preoperative plasma VASH1 concentration is associated with better prognosis in patients with NSCLC. We propose preoperative VASH1 level as a biomarker for the prognosis of patients with non–small cell lung carcinoma.