bluuebunny/crossref_metadata_2025 huggingface dataset:
Synergistic Effects of Metals in a Promising RuII−PtII Assembly for a Combined Anticancer Approach: Theoretical Exploration of the Photophysical Properties
Authors: Alberto Marta E. , Russo Nino , Adamo Carlo
Published: June 2016

RuII−PtII complexes are a class of bioactive molecules of interest as anticancer agents that combine a light‐absorbing chromophore with a cisplatin‐like unit. The results of a DFT and TDDFT investigation of a RuII complex and its conjugate with a cis‐PtCl2 moiety reveal that a synergistic effect of the metals makes the assembly a promising multitarget anticancer drug. Inspection of type I and type II photoreactions and spin–orbit coupling computations reveals that the cis‐PtCl2 moiety improves the photophysical properties of the RuII chromophore, ensuring efficient singlet oxygen generation and making the assembly suitable for photodynamic therapy. At the same time, the RuII chromophore promotes a new alternative activation mechanism of the PtII ligand via a triplet metal‐to‐ligand charge transfer (3MLCT) state, before reaching the biological target. The importance of the supramolecular architecture is accurately derived, opening interesting new perspectives on the use of bimetallic RuII−PtII assemblies in a combined anticancer approach.
Gadolinium(III) Porpholactones as Efficient and Robust Singlet Oxygen Photosensitizers
Authors: Ke Xian‐Sheng , Ning Yingying , Tang Juan , Hu Ji‐Yun , Yin Hao‐Yan , Wang Gao‐Xiang , Yang Zi‐Shu , Jie Jialong , Liu Kunhui , Meng Zhao‐Sha , Zhang Zongyao , Su Hongmei , Shu Chunying , Zhang Jun‐Long
Published: June 2016

Construction of GdIII photosensitizers is important for designing theranostic agents owing to the unique properties arising from seven unpaired f electrons of the Gd3+ ion. Combining these with the advantages of porpholactones with tunable NIR absorption, we herein report the synthesis of GdIII complexes Gd‐1–4 (1, porphyrin; 2, porpholactone; 3 and 4, cis‐ and trans‐porphodilactone, respectively) and investigated their function as singlet oxygen (1O2) photosensitizers. These Gd complexes displayed 1O2 quantum yields (ΦΔs) from 0.64–0.99 with the order Gd‐1<Gd‐2<Gd‐3<Gd‐4. The gradually enhanced 1O2 sensitization after β‐oxazolone moiety replacement was ascribed to the narrowing of the energy gap (ΔE) between the lowest triplet states (T1) of the ligand and the energy level of the 1Δg→3Σg transition of 1O2. In particular, Gd‐4 is capable of excitation in the visible to NIR region (400–700 nm) with a quantum yield near unity. These Gd complexes were first demonstrated as efficient photosensitizers in photocatalysis such as oxidative C−H bond functionalization of secondary or tertiary amines, and the oxygenation of the natural product cholesterol. Finally, after glycosylation, these water‐soluble Gd complexes showed potential applications in photodynamic therapy (PDT) in HeLa cells. This work revealed that GdIII complexes of “bioinspired” β‐modified porpholactones are efficient NIR photosensitizers and form a chemical basis to construct appealing photocatalysts and theranostic agents based on lanthanides.
Heterogenized Water Oxidation Catalysts Prepared by Immobilizing Kläui‐Type Organometallic Precursors
Authors: Pastori Gabriele , Wahab Khaja , Bucci Alberto , Bellachioma Gianfranco , Zuccaccia Cristiano , Llorca Jordi , Idriss Hicham , Macchioni Alceo
Published: June 2016

An efficient heterogenized water oxidation catalyst (2_TiO2) has been synthesized by immobilizing the Kläui‐type organometallic precursor [Cp*Ir{P(O)(OH)2}3]Na (2, Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl ligand) onto rutile TiO2. Iridium is homogeneously distributed at the molecular and atomic/small cluster level in 2_TiO2 and 2′_TiO2 (solid catalyst recovered after the first catalytic run), respectively, as indicated by STEM‐HAADF (scanning transmission electron microscopy ‐ high angle annular dark field) studies. 2′_TiO2 exhibits TOF values up to 23.7 min−1 in the oxidation of water to O2 driven by NaIO4 at nearly neutral pH, and a TON only limited by the amount of NaIO4 used, as indicated by multiple run experiments. Furthermore, while roughly 40 % leaching is observed during the first catalytic run, 2′_TiO2 does not undergo any further leaching even when in contact with strongly basic solutions and completely maintains its activity for thousands of cycles. NMR studies, in combination with ICP‐OES (inductively coupled plasma optical emission spectrometry), indicate that the activation of 2_TiO2 occurs through the initial oxidative dissociation of PO43−, ultimately leading to active centers in which a 1:1 P/Ir ratio is present (derived from the removal of two PO43− units) likely missing the Cp* ligand.
A Highly Selective Fluorescence Turn‐On Sensor for Extracellular Calcium Ion Detection
Authors: Sui Binglin , Liu Xinglei , Wang Mengyuan , Belfield Kevin D.
Published: June 2016

A highly water‐soluble, fluorescence turn‐on sensor for Ca2+ is reported. The sensor affords high selectivity in sensing Ca2+ over other biologically important metal cations. The dissociation constant of the sensor in binding Ca2+ is 0.92 mm. Fluorescence microscopy experiments demonstrate that the sensor is cell‐impermeable and capable of detecting extracellular Ca2+.
Formation of C(sp3)–C(sp3) Bonds through Nickel‐Catalyzed Decarboxylative Olefin Hydroalkylation Reactions
Authors: Lu Xi , Xiao Bin , Liu Lei , Fu Yao
Published: June 2016

Olefins and carboxylic acids are among the most important feedstock compounds. They are commonly found in natural products and drug molecules. We report a new reaction of nickel‐catalyzed decarboxylative olefin hydroalkylation, which provides a novel practical strategy for the construction of C(sp3)−C(sp3) bonds. This reaction can tolerate a variety of synthetically relevant functional groups and shows good chemo‐ and regioselectivity. It enables cross‐coupling of complex organic molecules containing olefin groups and carboxylic acid groups in a convergent fashion.
Superlegierungen
Authors: Feil Sylvia
Published: June 2016

Die mechanischen Eigenschaften von Werkstoffen hängen nicht nur von ihrer chemischen Zusammensetzung ab, sondern insbesondere auch von den in ihnen enthaltenen Kristalldefekten. Werden diese Defekte verstanden, lassen sich mit diesem Wissen gezielt neue Legierungen entwerfen, statt sie wie bislang durch Versuch und Irrtum zu entwickeln.
Die Zeitschaltuhr
Authors: Groß Michael
Published: June 2016

Wenn Sie nach Peking oder Mexiko fliegen, kann es gut sein, dass Sie eine Woche brauchen, um ihren Schlafrhythmus der dortigen Ortszeit anzupassen. Und wenn Sie zwei Wochen später zurückreisen, haben Sie denselben Ärger wieder, nur in umgekehrter Richtung. Der Jetlag macht uns auf sehr eindrucksvolle Weise deutlich, dass wir eine innere Uhr besitzen, die zunächst einmal versucht, ihren 24‐Stunden‐Rhythmus weiterzuführen, auch wenn wir in einer anderen Zeitzone landen.
Synthesis and Antimicrobial Activity of Albicidin Derivatives with Variations of the Central Cyanoalanine Building Block
Authors: Grätz Stefan , Kerwat Dennis , Kretz Julian , von Eckardstein Leonard , Semsary Siamak , Seidel Maria , Kunert Maria , Weston John B. , Süssmuth R. D.
Published: June 2016

To investigate the pharmacophore regions of the antibiotic albicidin, derivatives with variations on the central amino acid were synthesized. Charged as well as uncharged residues were chosen to explore the influence of charge, chirality, and steric bulk. The bioactivity of the newly synthesized derivatives was determined by a microdilution technique to obtain minimum inhibitory concentrations (MIC) values. The compounds were also tested in a cell‐free system to obtain information about their ability to inhibit their primary target, DNA gyrase. It was then shown that derivatives with uncharged side chains retain antibacterial activity, whereas incorporation of charged amino acid residues decreases the antibacterial activity dramatically, possibly due to restricted cell penetration of these derivatives. From the newly synthesized derivatives, the threonine derivative shows the most promising results in both tests. The information will help to develop the features of albicidin toward more drug‐like structures.
Building a Better Quaternary Ammonium Compound (QAC): Branched Tetracationic Antiseptic Amphiphiles
Authors: Forman Megan E. , Jennings Megan C. , Wuest William M. , Minbiole Kevin P. C.
Published: June 2016

Bacteria contaminate surfaces in a wide variety of environments, causing severe problems across a number of industries. In a continuation of our campaign to develop novel antibacterial quaternary ammonium compounds (QACs) as useful antiseptics, we have identified a starting material bearing four tertiary amines, enabling the rapid synthesis of several tris‐ and tetracationic QACs. Herein we report the synthesis and biological activity of a series of 24 multiQACs deemed the “superT” family, and an investigation of the role of cationic charge in antimicrobial and anti‐biofilm activity, as well as toxicity. This class represents the most potent series of QACs reported to date against methicillin‐resistantStaphylococcus aureus(MRSA), with minimum inhibitory concentrations (MICs) and minimum biofilm eradication concentrations (MBECs) as low as 0.25 and 25 μm, respectively. Based on the significant cell‐surface‐charge differences between bacterial and eukaryotic cells, in certain cases we observed excellent efficacy‐to‐toxicity profiles, exceeding a 100‐fold differential. This work further elucidates the chemical underpinnings of disinfectant efficacy versus toxicity based on cationic charge.
Immunoprecipitation
Authors: Bonifacino Juan S. , Gershlick David C. , Dell'Angelica Esteban C.
Published: June 2016

Selective immunoprecipitation of proteins is a useful tool for characterizing proteins and protein‐protein interactions. Clear step‐by‐step protocols are provided for preparing lysates of cells and yeast under a variety of conditions, for binding the antibody to a solid matrix, and for performing the actual immunoprecipitation. An additional method is provided for increasing the specificity of the technique by reprecipitating the antigen with the same or a different antibody. © 2016 by John Wiley & Sons, Inc.
On the Additivity of Molecular Fragment Dipole Moments of 5‐Substituted Indole Derivatives
Authors: Wilke Josefin , Wilke Martin , Brand Christian , Meerts W. Leo , Schmitt Michael
Published: June 2016

The estimate of the magnitude and the orientation of molecular electric dipole moments from the vector sum of bond or fragment dipole moments is a widely used approach in chemistry. However, the limitations of this intuitive model have rarely been tested experimentally, particularly for electronically excited states. Herein, we find rules for a number of indole derivatives by using rotationally resolved electronic Stark spectroscopy and ab initio calculations. Based on a natural‐bond‐orbital analysis, we discuss whether the vector additivity rule can be applied in a given electronic state. From a comparison of the experimental data with ab initio calculations, we deduced that the additivity model does not apply when the flow of electron density from the substituent is opposed to that inside the chromophore.
Efficient and Scalable Production of 2D Material Dispersions using Hexahydroxytriphenylene as a Versatile Exfoliant and Dispersant
Authors: Liu Gang , Komatsu Naoki
Published: June 2016

The front cover artwork is provided by the group of Prof. N. Komatsu (Kyoto University, Japan). The image shows the wet process of graphene exfoliation in the presence of hexahydroxytriphenylene. Read the full text of the article at 10.1002/cphc.201600187.
Light on Chirality: Absolute Asymmetric Formation of Chiral Molecules Relevant in Prebiotic Evolution
Authors: Myrgorodska Iuliia , Meinert Cornelia , Hoffmann Søren V. , Jones Nykola C. , Nahon Laurent , Meierhenrich Uwe J.
Published: June 2016

Homochirality is a distinct property of living matter manifested by the unichiral molecular units of genetic material and of proteins, namely, d‐deoxyribose and l‐amino acids. These molecular subunits or their precursors have been shown to form under various prebiotic conditions in racemic form. However, the nature of the chiral influence, which results in the first breakage of molecular symmetry, remains unclear. In this respect, the photochemical model of enantioselection has gained particular importance in recent years. In this model, the interaction of circularly polarized light with racemic molecules generated in the interstellar medium is considered to be the main driving force of enantiomeric discrimination in early prebiotic evolution. Cometary ice simulations, l‐enantio‐enriched amino acids in meteorites, and the detection of circularly polarized electromagnetic radiation in star‐forming regions provide evidence for photochirogenesis. The recent discovery of aldehydes in the cometary nucleus of 67P/Churyumov–Gerasimenko by means of the Cometary Sampling and Composition (COSAC) experiment on board the Rosetta lander Philae, along with the detection of aldehydes and aldopentoses (including chiral ribose) in simulated interstellar ice analogues, provide a direct link between laboratory simulations and cometary composition. In the context of these new findings, this review will provide an overview of the role of chiral molecules in prebiotic evolution with special emphasis on their chiroptical properties and absolute asymmetric photosynthesis.
Intestinal Preparation Techniques for Histological Analysis in the Mouse
Authors: Williams Jonathan M. , Duckworth Carrie A. , Vowell Kate , Burkitt Michael D. , Pritchard D. Mark
Published: June 2016

The murine intestinal tract represents a difficult organ system to study due to its long convoluted tubular structure, narrow diameter, and delicate mucosa which undergoes rapid changes after sampling prior to fixation. These features do not make for easy histological analysis as rapid fixation in situ, or after simple removal without careful dissection, results in poor postfixation tissue handling and limited options for high quality histological sections. Collecting meaningful quantitative data by analysis of this tissue is further complicated by the anatomical changes in structure along its length. This article describes two methods of intestinal sampling at necropsy that allow systematic histological analysis of the entire intestinal tract, either through examination of cross sections (circumferences) by the gut bundling technique or longitudinal sections by the adapted Swiss roll technique, together with basic methods for data collection. © 2016 by John Wiley & Sons, Inc.
Overview of Innovative Mouse Models for Imaging Neuroinflammation
Authors: Caravagna Céline , Jaouën Alexandre , Debarbieux Franck , Rougon Geneviève
Published: June 2016

Neuroinflammation demands a comprehensive appraisal in situ to gain in‐depth knowledge on the roles of particular cells and molecules and their potential roles in therapy. Because of the lack of appropriate tools, direct visualization of cells has been poorly investigated up to the present. In this context, reporter mice expressing cell‐specific fluorescent proteins, combined with multiphoton microscopy, provide a window into cellular processes in living animals. In addition, the ability to collect multiple fluorescent colors from the same sample makes in vivo microscopy uniquely useful for characterizing many parameters from the same area, supporting powerful correlative analyses. Here, we present an overview of the advantages and limitations of this approach, with the purpose of providing insight into the neuroinflammation field. We also provide a review of existing fluorescent mouse models and describe how these models have been used in studies of neuroinflammation. Finally, the potential for developing advanced genetic tools and imaging resources is discussed. © 2016 by John Wiley & Sons, Inc.
Pre‐Steady‐State Kinetic Analysis of Single‐Nucleotide Incorporation by DNA Polymerases
Authors: Su Yan , Peter Guengerich F.
Published: June 2016

Pre‐steady‐state kinetic analysis is a powerful and widely used method to obtain multiple kinetic parameters. This protocol provides a step‐by‐step procedure for pre‐steady‐state kinetic analysis of single‐nucleotide incorporation by a DNA polymerase. It describes the experimental details of DNA substrate annealing, reaction mixture preparation, handling of the RQF‐3 rapid quench‐flow instrument, denaturing polyacrylamide DNA gel preparation, electrophoresis, quantitation, and data analysis. The core and unique part of this protocol is the rationale for preparation of the reaction mixture (the ratio of the polymerase to the DNA substrate) and methods for conducting pre‐steady‐state assays on an RQF‐3 rapid quench‐flow instrument, as well as data interpretation after analysis. In addition, the methods for the DNA substrate annealing and DNA polyacrylamide gel preparation, electrophoresis, quantitation and analysis are suitable for use in other studies. © 2016 by John Wiley & Sons, Inc.
Green Diesel from Kraft Lignin in Three Steps
Authors: Löfstedt Joakim , Dahlstrand Christian , Orebom Alexander , Meuzelaar Gerrit , Sawadjoon Supaporn , Galkin Maxim V. , Agback Peter , Wimby Martin , Corresa Elena , Mathieu Yannick , Sauvanaud Laurent , Eriksson Sören , Corma Avelino , Samec Joseph S. M.
Published: June 2016

Precipitated kraft lignin from black liquor was converted into green diesel in three steps. A mild Ni‐catalyzed transfer hydrogenation/hydrogenolysis using 2‐propanol generated a lignin residue in which the ethers, carbonyls, and olefins were reduced. An organocatalyzed esterification of the lignin residue with an in situ prepared tall oil fatty acid anhydride gave an esterified lignin residue that was soluble in light gas oil. The esterified lignin residue was coprocessed with light gas oil in a continous hydrotreater to produce a green diesel. This approach will enable the development of new techniques to process commercial lignin in existing oil refinery infrastructures to standardized transportation fuels in the future.
Sensor Properties of Pristine and Functionalized Carbon Nanohorns
Authors: Valentini Federica , Ciambella Elena , Boaretto Aldrei , Rizzitelli Giuseppe , Carbone Marilena , Conte Valeria , Cataldo Franco , Russo Valeria , Casari Carlo Spartaco , Chillura‐Martino Delia Francesca , Caponetti Eugenio , Bonchio Marcella , Giacalone Francesco , Syrgiannis Zois , Prato Maurizio
Published: June 2016

Nanodispersions of pristine single‐wall carbon nanohorns (i.e., p‐SWCNHs) and oxidized‐SWCNHs (i.e.; o‐SWCNHs) were used to modify screen printed electrode (SPE). p‐SWCNHs and o‐SWCNHs were fully characterized by using several analytical techniques, as: HR‐TEM (High Resolution‐Transmission Electron Microscopy), FE‐SEM/EDX (Field Emission‐Scanning Electron Microscopy/Energy Dispersive X‐ray Analysis), Raman spectroscopy, thermogravimetric analysis, differential thermal analysis (DTA), and the Brunauer‐Emmett‐Teller (BET) method. The chemically modified SPEs were also characterized with Cyclic Voltammetry (CV), using several different electro‐active targets. In all cases, p‐SWCNHs showed better performances than those obtained for o‐SWCNHs as well as with respect to conventional Glassy Carbon (GC) electrodes, in terms of peak currents, significant shift at lower redox‐potential ranges and enhanced heterogeneous apparent kinetic constants.
Electrocatalytic Activities of Graphene/Nile Blue Nanocomposite Toward Determination of Hydrogen Peroxide and Nitrite Ion
Authors: Shervedani Reza Karimi , Ansarifar Elham , Foroushani Marzieh Samiei
Published: June 2016

Electrocatalytic activities of graphene nanosheets/Nile blue nanocomposite, synthesized and adsorbed simultaneously on the glassy carbon (GC−GNs−NB) electrode, are investigated. The nanocomposite was characterized by ATR−FTIR, FESEM and voltammetry. Activity of the electrode toward reduction of H2O2 and oxidation of NO2− was studied electrochemically. Values of 1.95 and 0.730 mM are found for the Michaelis−Menten constant of the electrode toward H2O2 and NO2−, respectively. Wide dynamic response ranges were observed for the electrode, with DLs of 0.22 μM H2O2 and 1.1 μM NO2−. Effect of interferences was studied. The sensor was successfully tested for H2O2 and NO2− contents in real samples, respectively.
Flow in a Paper‐based Bioactive Channel – Study on Electrochemical Detection of Glucose and Uric Acid
Authors: WitkowskaNery Emilia , Santhiago Murilo , Kubota Lauro T.
Published: June 2016

Although paper‐based analysis is known for centuries, only during the last decade this simple substrate became an object of detailed microfluidic studies. In order to obtain optimum performance and separation of the analytes in a microfluidic channel, devices should be optimized, both in terms of architecture and paper properties. Enzyme immobilization methods can not only increase the storage stability but also have an impact on the flow in paper matrix, providing additional charges, and changing the porous structure of paper. Therefore it should be guaranteed that the method of choice will not obstruct the flux in the final device. Paper‐based device proposed in this study was composed of a bioactive channel, Pt working electrode, pencil drawn pseudo‐reference electrode, a buffer filled sponge providing the wicking solution and a stack of wicking pads to guarantee continuous flow. Based on our previous research we chose 4 methods of enzyme immobilization relying on different phenomena (adsorption, covalent linkage, layer‐by‐layer, capsules). Different channel architectures were also evaluated in order to achieve optimum time of the enzymatic reaction, separation of peaks and the time of measurement. Experimental results were compared with computer simulations. Final device could quantify glucose (2.0–10.0 mmol L−1) and uric acid (0.1–1.2 mmol L−1) in their clinical range with good repeatability.
Ordered Mesoporous Carbon/Titanium Carbide Composites as Support Materials for Platinum Catalysts
Authors: Zhao Gang , Zhao Tianshou , Yan Xiaohui , Zeng Lin , Xu Jianbo
Published: June 2016

Ordered mesoporous carbon/titanium carbide composites (OMC/TiC) are synthesized by using Pluronic F127 and titanium isoproxide as the structure‐directing agent and titanium precursor. Characterizations confirm the formation of an ordered mesoporous textural structure and the formation of nanocrystals of TiC in the framework of carbon. By using the resultant OMC/TiC as the support material, a platinum catalyst (Pt/OMC/TiC) is then prepared. Electrochemical measurements show that a higher activity for the methanol oxidization reaction and oxygen reduction reaction can be observed for the Pt/OMC/TiC, compared to Pt/OMC and a commercial Pt/C catalyst. The results obtained in the present work suggest that the synthesized OMC/TiC is a promising support material for platinum catalysts in proton exchange membrane fuel cells and direct methanol fuel cells.
Experimental Study on the Characteristics of Ignition during Microwave Drying of Lignite
Authors: Song Zhanlong , Yao Liansheng , Jing Chuanming , Zhao Xiqiang , Wang Wenlong , Mao Yanpeng , Ma Chunyuan
Published: June 2016

The spontaneous combustion of lignite during microwave drying was evaluated with the focus on the effects of, for example, microwave power and output mode, the final temperature of the samples, and the oxygen content of the drying atmosphere on the moisture contents corresponding to the ignition (IMCs). This empirical study was performed using a laboratory‐scale microwave oven. The lowest IMCs and the optimal drying effect of lignite were achieved using a power level of 60 W g−1, final surface temperature of 85–90 °C, and a lower oxygen content; pulsed microwave radiation could significantly lower the risk of ignition by reducing the overall surface temperature. In addition, the ignition temperatures at different moisture contents were measured comparatively by using conventional and microwave heating methods. Fourier transform infrared analyses of the samples revealed that microwave drying can upgrade the coal rank without affecting the coal quality.
Seismic retrofit of reinforced concrete frames using buckling‐restrained braces with bearing block load transfer mechanism
Authors: Pan Kuan‐Yu , Wu An‐Chien , Tsai Keh‐Chyuan , Li Chao‐Hsien , Khoo Hsen‐Han
Published: June 2016

A new method of retrofitting reinforced concrete (RC) frames with buckling‐restrained braces (BRBs) to improve frame strength, stiffness and energy dissipation is proposed. Instead of typical post‐installed anchors, load is transferred between the BRB and RC frame through compression bearing between an installed steel frame connected to the BRB, and high‐strength mortar blocks constructed at the four corners of the RC frame. This avoids complex on‐site anchor installation, and does not limit the allowable brace force by the anchor strength. Cyclic displacements of increasing amplitudes were imposed on two RC frame specimens retrofitted with different BRB strength capacities. In one of the frames, the bearing blocks were reinforced with wire mesh to mitigate cracking. A third RC frame was also tested as a benchmark to evaluate the retrofit strength and stiffness enhancements. Test results indicate that the proposed method efficiently transferred loads between the BRBs and RC frames, increasing the frame lateral strength while achieving good ductility and energy‐dissipating capacity. When the bearing block was reinforced with wire mesh, the maximum frame lateral strength and stiffness were more than 2.2 and 3.5 times the RC frame without the BRB respectively. The BRB imposes additional shear demands through the bearing blocks to both ends of the RC beam and column member discontinuity regions (D‐regions). The softened strut‐and‐tie model satisfactorily estimated the shear capacities of the D‐regions. A simplified calculation and a detailed PISA3D analysis were shown to effectively predict member demands to within 13.8% difference of the measured test results. Copyright © 2016 John Wiley & Sons, Ltd.
Influence of connection typology on seismic response of MR‐Frames with and without ‘set‐backs’
Authors: Montuori Rosario , Nastri Elide , Piluso Vincenzo , Troisi Marina
Published: June 2016

The work presented is aimed at the investigation of the influence of beam‐to‐column connections on the seismic response of MR‐Frames, with and without ‘set‐backs’, designed according to the Theory of Plastic Mechanism Control. The investigated connection typologies are four partial strength connections whose structural details have been designed to obtain the same flexural resistance. The first three joints are designed by means of hierarchy criteria based on the component approach and are characterized by different location of the weakest joint component, leading to different values of joint rotational stiffness and plastic rotation supply and affecting the shape of the hysteresis loops governing the dissipative capacity. The last typology is a beam‐to‐column connection equipped with friction pads devoted to the dissipation of the earthquake input energy, thus preventing the connection damage. An appropriate modelling is needed to accurately represent both strength and deformation characteristics, especially with reference to partial‐strength connections where the dissipation of the earthquake input energy occurs. To this aim, beam‐to‐column joints are modelled by means of rotational inelastic springs located at the ends of the beams whose moment‐rotation curve is characterized by a cyclic behaviour which accounts for stiffness and strength degradation and pinching phenomena. The parameters characterizing the cyclic hysteretic behaviour have been calibrated on the base of experimental results aiming to the best fitting. Successively, the prediction of the structural response of MR‐Frames, both regular frames and frames with set‐backs, equipped with such connections has been carried out by means of both push‐over and Incremental Dynamic Analyses. Copyright © 2016 John Wiley & Sons, Ltd.
Influence of earthquake ground‐motion duration on damage estimation: application to steel moment resisting frames
Authors: Barbosa Andre R. , Ribeiro Filipe L. A. , Neves Luis A. C.
Published: June 2016

This paper presents an analytical study evaluating the influence of ground motion duration on structural damage of 3‐story, 9‐story, and 20‐story SAC steel moment resisting frame buildings designed for downtown Seattle, WA, USA, using pre‐Northridge codes. Two‐dimensional nonlinear finite element models of the buildings are used to estimate the damage induced by the ground motions. A set of 44 ground motions is used to study the combined effect of spectral acceleration and ground motion significant duration on drift and damage measures. In addition, 10 spectrally equivalent short‐duration shallow crustal ground motions and long‐duration subduction zone records are selected to isolate duration effect and assess its effect on the response. For each ground motion pair, incremental dynamic analyses are performed at at least 20 intensity levels and response measures such as peak interstory drift ratio and energy dissipated are tracked. These response measures are combined into two damage metrics that account for the ductility and energy dissipation. Results indicate that the duration of the ground motion influences, above all, the combined damage measures, although some effect on drift‐based response measures is also observed for larger levels of drift. These results indicate that because the current assessment methodologies do not capture the effects of ground motion duration, both performance‐based and code‐based assessment methodologies should be revised to consider damage measures that are sensitive to duration. Copyright © 2016 John Wiley & Sons, Ltd
The Influence of Temperature and Composition on the Operation of Al Anodes for Aluminum‐Air Batteries
Authors: Ilyukhina A. V. , Zhuk A. Z. , Kleymenov B. V. , Ilyukhin A. S. , Nagayama M.
Published: June 2016

The influence of composition and temperature on the anode polarization and corrosion rate of pure Al and Al‐In anodic alloys in 8M NaON electrolyte has been investigated. High current density (more than 800 mA cm−2) and faradaic efficiency over 97% were observed for all investigated alloys at 60 °C. Lower temperature provides lower current density (200–300 mA cm−2 at 40 °C, and less than 100 mA cm−2 at 25 °C).

Different formation of the product reaction layers was observed for pure aluminum and Al–0.41In alloy, leading to the different polarization character of the samples.

The comparison of two Al‐In alloys with similar composition has been carried out. Al–0.45In alloy having a coarse‐grained structure had a more positive no‐current potential and lower value of anode limiting current (200 mA cm−2 vs. 300 mA cm−2) compared with the fine‐grained Al–0.41In alloy, as well as greater parasitic corrosion rate and greater no‐current corrosion.

The current‐voltage, power and discharge characteristics of the aluminum‐air cell with Al–0.41In anode and gas diffusion cathode have been investigated. Open circuit voltage of the cell is 1.934 V and the maximum power density of the cell is 240 mW cm−2 at the voltage of 1.3 V.
Carbon Nanotubes and Nanohorn Hybrid Composite Buckypaper as Microporous Layer for Proton Exchange Membrane Fuel Cell
Authors: Ebenezer D. , Neelima K. , Jagannatham M. , Haridoss P.
Published: June 2016

In the present work, carbon nanotubes (CNT) and CNT‐carbon nanohorns (CNH) (0, 30, 50, 70 and 100 wt.% CNH) composite Buckypapers (BPs) were fabricated using vacuum filtration technique. Structure and property relation of composite BPs were studied using scanning electron microscope, four probe technique, BET surface area and contact angle measurements. Properties such as electrical conductivity, hydrophobic nature and microstructure of CNT‐30 wt.% CNH composite BP are superior to other composite BP. Hence, CNT‐30 wt.% CNH composite BP is chosen as a microporous layer (MPL) for PEMFCs and tested in fuel cell testing fixture. Polarization studies reveal that the cells performance with composite BPs is comparable with SGL‐MPL based cell. Hydrogen pumping and polarization studies of the cells confirms that composite BPs act as a good MPL at anode as well as cathode at 0.4 to 0.8 V. Hence, CNT‐CNH composite BPs are potential candidates for PEMFC applications.
Analyzing Association Mapping in Pedigree‐Based GWAS Using a Penalized Multitrait Mixed Model
Authors: Liu Jin , Yang Can , Shi Xingjie , Li Cong , Huang Jian , Zhao Hongyu , Ma Shuangge
Published: June 2016

Genome‐wide association studies (GWAS) have led to the identification of many genetic variants associated with complex diseases in the past 10 years. Penalization methods, with significant numerical and statistical advantages, have been extensively adopted in analyzing GWAS. This study has been partly motivated by the analysis of Genetic Analysis Workshop (GAW) 18 data, which have two notable characteristics. First, the subjects are from a small number of pedigrees and hence related. Second, for each subject, multiple correlated traits have been measured. Most of the existing penalization methods assume independence between subjects and traits and can be suboptimal. There are a few methods in the literature based on mixed modeling that can accommodate correlations. However, they cannot fully accommodate the two types of correlations while conducting effective marker selection. In this study, we develop a penalized multitrait mixed modeling approach. It accommodates the two different types of correlations and includes several existing methods as special cases. Effective penalization is adopted for marker selection. Simulation demonstrates its satisfactory performance. The GAW 18 data are analyzed using the proposed method.
Cognitive performance in unipolar old‐age depression: a longitudinal study
Authors: Pantzar Alexandra , Atti Anna Rita , Fratiglioni Laura , Fastbom Johan , Bäckman Lars , Laukka Erika J.
Published: June 2016

Objective

Previous studies on cognitive deficits in acute and remitted states of old‐age depression have shown mixed findings. The episodic nature of depression makes repeated assessment of cognitive performance important in order to address reversibility and stability of cognitive deficits.

Methods

Dementia‐free older participants (≥60 years) from the population‐based Swedish National Study on Aging and Care in Kungsholmen who completed neuropsychological testing at baseline (T1) and follow‐up (T2) formed the basis of the study sample. Participants were grouped according to depression status at T1 and T2: depressed–remitted (n = 32), remitted–depressed (n = 45), and nondepressed–depressed (n = 29). These groups were compared with a group of randomly selected and matched (age, gender, education, and follow‐up time) healthy controls (n = 106) over a period of maximum 6 years.

Results

Mixed ANCOVAs, controlling for age and gender, revealed depression‐related deficits for processing speed, attention, executive function, and category fluency. In remitted states, only processing speed and attention were affected. However, these deficits were attenuated after exclusion of persons using benzodiazepine medications. A general pattern of cognitive decline was observed across all groups for processing speed, executive function, category fluency, and episodic and semantic memory; persons transitioning from a nondepressed to depressed state tended to show exacerbated cognitive decline.

Conclusions

The results support the notion that cognitive deficits in depression may be more transient than stable. Consequently, cognitive deficits in depression might be regarded as potential treatment targets rather than stable vulnerabilities. As such, repeated assessment of cognitive functioning may provide an additional marker of treatment response.
Brain activity and connectivity in response to negative affective stimuli: Impact of dysphoric mood and sex across diagnoses
Authors: Mareckova Klara , Holsen Laura M. , Admon Roee , Makris Nikos , Seidman Larry , Buka Stephen , Whitfield‐Gabrieli Susan , Goldstein Jill M.
Published: June 2016

Negative affective stimuli elicit behavioral and neural responses which vary on a continuum from adaptive to maladaptive, yet are typically investigated in a dichotomous manner (healthy controls vs. psychiatric diagnoses). This practice may limit our ability to fully capture variance from acute responses to negative affective stimuli to psychopathology at the extreme end. To address this, we conducted a functional magnetic resonance imaging study to examine the neural responses to negative valence/high arousal and neutral valence/low arousal images as a function of dysphoric mood and sex across individuals (n = 99) who represented traditional categories of healthy controls, major depressive disorder, bipolar psychosis, and schizophrenia. Observation of negative (vs. neutral) stimuli elicited blood oxygen‐level dependent responses in the following circuitry: periaqueductal gray, hypothalamus (HYPO), amygdala (AMYG), hippocampus (HIPP), orbitofrontal cortex (OFC), medial prefrontal cortex (mPFC), and greater connectivity between AMYG and mPFC. Across all subjects, severity of dysphoric mood was associated with hyperactivity of HYPO, and, among females, right (R) AMYG. Females also demonstrated inverse relationships between severity of dysphoric mood and connectivity between HYPO ‐ R OFC, R AMYG ‐ R OFC, and R AMYG ‐ R HIPP. Overall, our findings demonstrated sex‐dependent deficits in response to negative affective stimuli increasing as a function of dysphoric mood state. Females demonstrated greater inability to regulate arousal as mood became more dysphoric. These findings contribute to elucidating biosignatures associated with response to negative stimuli across disorders and suggest the importance of a sex‐dependent lens in determining these biosignatures. Hum Brain Mapp 37:3733–3744, 2016. © 2016 Wiley Periodicals, Inc.
Epigenetic regulation of reelin expression in multiple myeloma
Authors: Lin Liang , Wang Pingzhang , Liu Xue , Zhao Dandan , Zhang Yan , Hao Jie , Liang Xiaodong , Huang Xiaojun , Lu Jin , Ge Qing
Published: June 2016

Reelin (RELN) is a secreted extracellular matrix glycoprotein associated with the positioning and migration of neuronal cells and a few types of non‐neuronal cells. We have previously reported RELN expression in multiple myeloma cells. High RELN expression was associated with poor prognosis and enhanced myeloma cell adhesion and survival. To examine the epigenetic regulation of RELN expression, its promoter methylation status in myeloma‐derived cell lines and primary tumour cells from myeloma patients were analysed. RELN expression was moderate in CD19+ B cells and was upregulated in CD138+ plasma cells. A further upregulated RELN transcription was found in multiple myeloma cells. High expressions of RELN in myeloma cell lines as well as in patients were associated with hypomethylation in RELN promoter region. Demethylation increased RELN transcription in vitro. Together, we established that the methylation status of the promoter proximal cytosine‐phospho‐guanine dinucleotides determines the expression of RELN in myeloma cells. Copyright © 2016 John Wiley & Sons, Ltd.
Does Domestic Intimate Partner Aggression Affect Career Outcomes? The Role of Perceived Organizational Support
Authors: Tolentino Laramie R. , Garcia Patrick Raymund James M. , Restubog Simon Lloyd D. , Scott Kristin L. , Aquino Karl
Published: June 2016

Drawing upon the conservation of resources theory, we developed and tested a moderated mediation model linking domestic intimate partner aggression (IPA) to job performance and career advancement. Our model posits that the indirect relationship between IPA and career advancement via in‐role performance and organizational citizenship behaviors (OCBs) is moderated by perceived organizational support (POS). Overall, multisource and multiwave data obtained from two independent samples of employed women from the Philippines supported our predictions. Specifically, results suggest that: (1) IPA was negatively associated with supervisor‐rated in‐role performance and OCBs; (2) there was a stronger negative relationship between IPA and in‐role performance and OCBs for employees with low as opposed to those with high levels of POS; and (3) the conditional indirect effects of IPA in predicting supervisor‐rated promotability and actual promotion via in‐role performance and OCBs were stronger under conditions of low as opposed to high POS. Implications for theory and practice are discussed. © 2016 Wiley Periodicals, Inc.
Integrated ecosystem services assessment: Valuation of changes due to sea level rise in Galveston Bay, Texas, USA
Authors: Yoskowitz David , Carollo Cristina , Pollack Jennifer Beseres , Santos Carlota , Welder Kathleen
Published: June 2016

The goal of the present study was to identify the potential changes in ecosystem service values provided by wetlands in Galveston Bay, Texas, USA, under the Intergovernmental Panel on Climate Change (IPCC) A1B max (0.69 m) sea level rise scenario. Built exclusively upon the output produced during the Sea Level Affecting Marshes Model 6 (SLAMM 6) exercise for the Galveston Bay region, this study showed that fresh marsh and salt marsh present a steady decline from 2009 (initial condition) to 2100. Fresh marsh was projected to undergo the biggest changes, with the loss of approximately 21% of its extent between 2009 and 2100 under the A1B max scenario. The percentages of change for salt marsh were less prominent at approximately 12%. This trend was also shown in the values of selected ecosystem services (disturbance regulation, waste regulation, recreation, and aesthetics) provided by these habitats. An ordinary least squares regression was used to calculate the monetary value of the selected ecosystem services provided by salt marsh and fresh marsh in 2009, and in 2050 and 2100 under the A1B max scenario. The value of the selected services showed potential monetary losses in excess of US$40 million annually in 2100, compared to 2009 for fresh marsh and more than $11 million for salt marsh. The estimates provided here are only small portions of what can be lost due to the decrease in habitat extent, and they highlight the need for protecting not only built infrastructure but also natural resources from sea level rise. Integr Environ Assess Manag 2017;13:431–443. © 2016 SETAC

Key Points

Fresh marsh was projected to decrease by 21% between 2009 and 2100. The percentages of change for salt marsh were less prominent at approximately 12%. Ecosystem services values decreased more than US$40 million/y for fresh marsh. Ecosystem services values decreased more than $11 million/y for salt marsh.
Green Oxidation Process in the Synthesis of LLM‐105 with H2O2/Peroxotungstate System and its Theoretical Study
Authors: Zhu Jie , Zhao Xue‐Jing , Wang Peng‐Cheng , Lu Ming
Published: June 2016

A new catalytic system was developed and applied to the oxidation reactions involved in the synthesis of LLM-105, in which protonated peroxotungstate combining chitosan was used as catalyst. With H2O2 as oxidant, good to excellent yields could be achieved in the synthesis of pyrazine‐1‐oxide, 2,6‐dimethoxypyrazine‐1‐oxide, 2,6‐dichloropyrazine‐1‐oxide, and 2‐chloro‐6‐methoxypyrazine‐1‐oxide without any addition of trifluoracetic acid, which provided a significant exploration toward novel and environmentally benign synthetic route for LLM-105. Theoretical studies were also carried out with Gaussian 03 to evaluate the oxidation process. All of the calculated data matched well with our experimental results.
Synthesis and Antibacterial Activity Evaluation of Novel (E)‐4‐(4‐((arylidene)amino)phenoxy)coumarin Derivatives
Authors: Chen Mei‐Hang , Tang Bang‐Cheng , Zhang Xun , Shu Hua
Published: June 2016

A series of novel (E)‐4‐(4‐((arylidene)amino)phenoxy)coumarin derivatives were synthesized from 4‐hydroxycoumarin in three step reactions, and their antibacterial activities against Xanthomonas oryzae pv. oryzae (Xoo) and Xanthomonas citri subsp. Citri (Xcc) in vitro were evaluated. Result found that most of the target compounds exhibited pronounced antibacterial activities. Among the target compounds, 3f, 3g, 3h, 3i, 3j, 3n, 3o, and 3p exhibited excellent antibacterial activities against Xoo, with EC50 values of 143.9, 127.4, 133.8, 145.8, 138.4, 116.9, 134.6, and 121.8 µg/mL, respectively, which were better than that of thiadiazole copper (203.6 µg/mL). Moreover, compounds 3f, 3g, 3h, 3i, 3j, 3n, 3o, and 3p showed good antibacterial activities against Xcc, with EC50 values of 118.4, 126.3, 117.2, 105.3, 102.3, 95.2, 96.0, and 88.2 µg/mL, respectively, which were similar to that of thiadiazole copper (138.3 µg/mL).
Synthesis and Investigation of Mixed μ‐Opioid and δ‐Opioid Agonists as Possible Bivalent Ligands for Treatment of Pain
Authors: Vardanyan Ruben S. , Cain James P. , Haghighi Saghar Mowlazadeh , Kumirov Vlad K. , McIntosh Mary I. , Sandweiss Alexander J. , Porreca Frank , Hruby Victor J.
Published: June 2016

Several studies have suggested functional association between μ‐opioid and δ‐opioid receptors and showed that μ‐activity could be modulated by δ‐ligands. The general conclusion is that agonists for the δ‐receptor can enhance the analgesic potency and efficacy of μ‐agonists. Our preliminary investigations demonstrate that new bivalent ligands constructed from the μ‐agonist fentanyl and the δ‐agonist enkephalin‐like peptides are promising entities for creation of new analgesics with reduced side effects for treatment of neuropathic pain. A new superposition of the mentioned pharmacophores led to novel μ‐bivalent/δ‐bivalent compounds that demonstrate both μ‐opioid and δ‐opioid receptor agonist activity and high efficacy in anti‐inflammatory and neuropathic pain models with the potential of reduced unwanted side effects.
Logistic regression analysis of drought persistence in East China
Authors: Meng Lei , Ford Trent , Guo Ying
Published: June 2016

East China (EC) has experienced a number of severe droughts in recent decades. Understanding the characteristics of droughts and their persistence will provide operational guidelines for water resource management and agricultural production. This study uses a logistic regression model to measure the probability of drought occurrence in the current season given the previous season's Standardized Precipitation Index (SPI) and Southern Oscillation Index (SOI) as well as drought persistence. Results reveal large spatial and seasonal variations in the relationship between the previous season's SPI and the drought occurrence probability in a given season. The drought persistence averaged over the entire study area for all the four seasons is approximately 34% with large variations from season to season and from region to region. The East and Northeast regions have the largest summer drought persistence (∼40%) and lowest fall drought persistence (∼28%). The spatial pattern in winter and spring drought persistence is dissimilar with stronger winter and weaker spring drought persistence in the Southwest and Northeast relative to other regions. Logistic regression analysis indicates a stronger negative relationship in summer‐to‐fall (or between fall drought occurrence and summer SPI) than other inter‐season relationships. Most of the stations with significant relationships in summer‐to‐fall lie in the East and the southern part of the North region. Significant negative relationships in winter–spring and fall–winter are primarily located on the western portion of the study area. A significant negative spring–summer relationship exists in the North region. Further, spring drought occurrence has a statistically significant positive relationship with winter SOI in the Southeast. Fall drought occurrence and summer SOI are negatively correlated in the northwest portion of EC (i.e. the border of North and Southwest regions). Overall, this study demonstrates that the impact of previous season SPI and SOI on current season drought varies substantially from region to region and from season to season. This study also shows stronger drought persistence in summer than in other seasons. In other words, the probability of fall drought occurrence is closely related to summer moisture conditions in the EC.