bluuebunny/crossref_metadata_2025 huggingface dataset:
Bimetallic and Plasmonic Ag–Au on TiO2 for Solar Water Splitting: An Active Nanocomposite for Entire Visible‐Light‐Region Absorption
Authors: Patra Kshirodra K. , Gopinath Chinnakonda S.
Published: September 2016

The current study demonstrates a potential method for maximum utilization of the entire visible light region of the solar spectrum by designing a plasmonic‐metals semiconductor composite. A combination of Ag+Au nanoclusters would broaden the visible‐light absorption at least between 400 and 650 nm. This hypothesis was evaluated through solar water splitting (SWS) activity of Au–TiO2, Ag–TiO2, and Ag on Au‐TiO2 (AgAuT) composites. AgAuT bimetallic nanocomposite shows the maximum apparent quantum yield of 3.3 % with hydrogen generation (718 μmol h.g−1) from aqueous methanol, and overall water splitting activity (7 μmol g.h−1, AQY=0.04 %) under one sun conditions. Enhanced photocatalytic activity of AgAuT is partly attributed to the formation of hot electrons. A thin layer of Ag coating on Au particles leads to a core–shell morphology with Au in the core. Fermi level equilibration between metal and titania, and Schottky junction formation are directly demonstrated. The strong electronic interaction between Ag and Au, and with TiO2 is evident from its electron rich character and confirmed by Raman spectroscopy, X‐ray photoelectron spectroscopy, photoluminescence, and high‐resolution TEM measurements. Electronic factors seem to be responsible for the high rate of hydrogen production.
Seawater‐Based Biocatalytic Strategy: Stereoselective Reductions of Ketones with Marine Yeasts
Authors: Serra Immacolata , Guidi Benedetta , Burgaud Gaetan , Contente Martina L. , Ferraboschi Patrizia , Pinto Andrea , Compagno Concetta , Molinari Francesco , Romano Diego
Published: September 2016

The large consumption of freshwater in fermentations and bio‐transformations is a matter of concern for the sustainability of many bio‐processes. The use of seawater to perform bio‐processes is a sustainable alternative. In this work, we used marine yeasts from deep‐sub‐seafloor sediments grown in seawater as bio‐catalysts to perform the stereoselective reduction of different ketones, and the bio‐transformations were accomplished in seawater as well. Strains of Meyerozyma guilliermondii and Rhodotorula mucilaginosa were able to reduce different aromatic ketones with high molar conversions and moderate‐to‐high enantioselectivity with no significant differences between bio‐catalysis performed in seawater and freshwater. Finally, the selected marine yeasts were used for the reduction of key intermediates in seawater for the synthesis of molecules of pharmaceutical interest (desogestrel, norgestrel, gestodene, pramipexole).
Hydrogenation of Carbonyl Derivatives with a Well‐Defined Rhenium Precatalyst
Authors: Wei Duo , Roisnel Thierry , Darcel Christophe , Clot Eric , Sortais Jean‐Baptiste
Published: September 2016

The first efficient and general rhenium‐catalyzed hydrogenation of carbonyl derivatives was developed. The key to the success of the reaction was the use of a well‐defined rhenium complex bearing a tridentate diphosphinoamino ligand as the catalyst (0.5 mol %) at 70 °C in the presence of H2 (30 bar). The mechanism of the reaction was investigated by DFT(PBE0‐D3) calculations.
Nanoparticle Surface Coverage Controls the Speciation of Electrochemically Generated Chlorine
Authors: Kraikaew Pitchnaree , Tanner Eden E. L. , Sokolov Stanislav V. , Batchelor‐McAuley Christopher , Holter Jennifer , Young Neil P. , Compton Richard G.
Published: September 2016

Cyclic voltammetry is used to investigate the oxidation of chloride on platinum nanoparticles. The electrochemical response of the nanoparticles drop‐cast onto a glassy carbon electrode is compared to that recorded at a platinum macroelectrode. The use of “nano”‐ and “macro”‐scale Pt reveals different ratios of the electrochemically formed products, chlorine (Cl2) and the trichloride (Cl3−) anion. This difference in the speciation is attributed to the chloride oxidation being a surface‐reaction‐limited process. For the situation in which there are a limited number of active sites available on the electrode, owing to low nanoparticle surface coverages, the sub‐diffusion‐limited currents result in higher chloride concentrations adjacent to the electrochemical interface. This excess chloride at the interface leads to the formation of the trichloride anion. The effect of surface oxide formation towards the chloride oxidation is also examined on both electrodes. Formation of platinum oxide serves to inhibit the rate of chloride oxidation.
Formation of a Nonlinear Optical Host–Guest Hybrid Material by Tight Confinement of LDS 722 into Aluminophosphate 1D Nanochannels
Authors: Sola‐Llano Rebeca , Martínez‐Martínez Virginia , Fujita Yasuhiko , Gómez‐Hortigüela Luis , Alfayate Almudena , Uji‐i Hiroshi , Fron Eduard , Pérez‐Pariente Joaquín , López‐Arbeloa Iñigo
Published: September 2016

In this work, hemicyanine dye LDS 722 is encapsulated into the 1D elliptical nanochannels of MgAPO‐11 aluminophosphate by a crystallization inclusion method. The synthesis of the hybrid material has been optimized through a systematic variation of the crystallization conditions in order to obtain pure and large crystals (around 20 μm×30 μm) suitable for optical applications. The tight fitting between the molecular size of the guest dye and the pore dimensions of the host has favored a rigid planar conformation of the dye, restricting its inherent flexibility, which is confirmed by molecular simulations. Consequently, the encapsulation of LDS 722 into MgAPO‐11 has led to an astonishing enhancement of the fluorescence with respect to the dye into MgAPO‐5, with slightly larger cylindrical channels, and with respect to the dye in solution. Moreover, the perfect alignment of LDS 722 (dye with intrinsic nonlinear‐optical properties) along the channels of MgAPO‐11 has revealed attractive second‐order nonlinear properties, such as second harmonic generation, proven through microscopy measurements in single crystals.
Skeletal Rearrangement in the ZnII‐Catalyzed [4+2]‐Annulation of Disubstituted N‐Hydroxy Allenylamines with Nitrosoarenes to Yield Substituted 1,2‐Oxazinan‐3‐one Derivatives
Authors: Sharma Pankaj , Liu Rai‐Shung
Published: September 2016

This work reports zinc‐catalyzed [4+2]‐annulation reactions of disubstituted N‐hydroxy allenylamines with nitrosoarenes to afford substituted 1,2‐oxazinan‐3‐ones with a skeletal rearrangement. This annulation is applicable to a reasonable scope of allenylamines and nitrosoarenes. Our control experiments indicate that nitrosobenzene can also implement this annulation through a radical annulation path, but with poor efficiency. Zn(OTf)2 or AgOTf greatly improves the efficiency of this [4+2]‐annulation; the effect of these metal species is discussed in detail.
Sublimable Cationic Iridium(III) Complexes with 1,10‐Phenanthroline Derivatives as Ancillary Ligands for Highly Efficient and Polychromic Electroluminescence
Authors: Ma Dongxin , Zhang Chen , Qiu Yong , Duan Lian
Published: September 2016

A novel series of four sublimable cationic iridium(III) complexes have been prepared with 1,10‐phenanthroline derivatives as ancillary ligands and the same negative counter‐ion, tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate, which has a large steric hindrance and widely dispersed charges, thereby increasing the ionic radii, reducing the electrostatic interaction, and thus improving the volatility. Their structural, photophysical, electrochemical, and thermal properties have been fully characterized. Upon excitation, these compounds show polychromic emission varying from green to orange in solution, which are blue‐shifted in the solid state to different extents due to π–π conjugate effects in the ancillary ligands and the resulting molecular aggregation. OLEDs fabricated by vacuum evaporation deposition demonstrated desirable device performance with high efficiency and brightness, exhibiting various electroluminescent colors dependent upon doping concentration.
A Stable Bis(benzocyclobutadiene)‐Annelated Tetraazapentacene Derivative
Authors: Biegger Philipp , Schaffroth Manuel , Tverskoy Olena , Rominger Frank , Bunz Uwe H. F.
Published: September 2016

Biphenylene‐2,3‐dione is a powerful reagent to build up cyclobutadiene‐containing azapolyheterocycles. The target structures are formed in high yields through classical condensation of suitable aromatic diamines with the biphenylenedione. To achieve the title compound, the biphenylenedione is coupled with a diaminobenzothiadiazole derivative. Reductive cleavage of the thiadiazole ring and subsequent condensation with the biphenylenedione gives the title compound in which a central tetraazapentacene is flanked by two benzocyclobutadiene units. This compound is stable despite its extended π‐system and its optical features are blueshifted in comparison to those of the symmetrical tetraazapentacene.
Radical Reactions Induced by Visible Light in Dichloromethane Solutions of Hünig's Base: Synthetic Applications and Mechanistic Observations
Authors: Böhm Alexander , Bach Thorsten
Published: September 2016

β‐(3‐Iodopropoxy)‐substituted α,β‐unsaturated lactams, lactones, and cycloalkenones (eight examples) underwent reductive radical reactions in a dichloromethane solution of N,N‐diisopropylethylamine (Hünig's base) upon irradiation with visible light (λ=419 nm). Apart from plain reduction reactions (hydro‐de‐iodination), a significant degree of cyclization was observed in three cases. In parallel to the conversion of the substrates, the formation of intensely colored by‐products was observed. Based on mass spectrometric evidence and upon comparison with known compounds, the by‐products were identified as cyanine dyes. Their formation supports the hypothesis that irradiation of dichloromethane solutions of Hünig's base leads to the formation of radicals, which in turn can either initiate a radical reaction or combine with cyanine precursors. It was shown by deuterium‐labelling experiments, that one equivalent of dichloromethane is incorporated into the cyanine dyes and that the reductive quenching of radical intermediates is at least partially due to hydrogen abstraction from the solvent. As a consequence, a reductive cyclization of the starting materials is favored in CD2Cl2 solutions as shown for two β‐(3‐iodopropoxy)‐substituted tetronates, which underwent in dichloromethane almost exclusive reduction, but gave predominantly the cyclization products in CD2Cl2.
The Evolution of the Total Synthesis of Rocaglamide
Authors: Zhou Zhe , Dixon Darryl D. , Jolit Anais , Tius Marcus A.
Published: September 2016

The complex flavagline, (−)‐rocaglamide, possesses a synthetically intriguing tricyclic scaffold with five contiguous stereocenters and also exhibits potent anticancer, anti‐inflammatory and insecticidal activity. This full account details distinct approaches to (±)‐ and (−)‐rocaglamide utilizing Brønsted acid catalyzed and asymmetric Pd0‐catalyzed Nazarov chemistry developed in our laboratory, respectively. The successful asymmetric synthesis revealed unforeseen mechanistic complexity that required adjusting our strategy to overcome an unanticipated racemization process, an unusual reversible ring‐cleavage step and a very facile trialkylsilyl group migration.
Globale und regionale Klimapolitik
Authors: Huckestein Brigitta , Breiner Timo
Published: September 2016

Der Klimawandel ist eine globale Herausforderung. Globale Vereinbarungen erreichen bisher aber nicht das Ziel, den Klimawandel auf 2°C bis 1,5°C zu begrenzen. Es fehlt an Maßnahmen mit weltweiter Gültigkeit – wie dies beispielsweise ein globaler Preis auf Treibhausgasemissionen darstellen würde. Die chemische Industrie leistet durch ihre Produkte und innovative Produktionsprozesse wertvolle Beiträge zum Klimaschutz. Damit sie jedoch ihr Innovationspotenzial weiter ausschöpfen kann, bedarf es geeigneter politischer Rahmenbedingungen – regional und global. Maßnahmen der EU sollten die effizientesten Produzenten im Vergleich zu ihren internationalen Wettbewerbern nicht benachteiligen.
Ein Wirkstoff gegen Malaria aus der Natur: Artemisinin
Authors: Eckhardt Katrin , Zeller Klaus‐Peter , Siehl Hans‐Ullrich , Berger Stefan , Sicker Dieter
Published: September 2016

Artemisinin, ein ungewöhnliches tetracyclisches, endoperoxidisches Sesquiterpen ist ein wegen der überragenden Wirkung gegen den Malariaparasiten außergewöhnlich intensiv erforschter, bioaktiver Naturstoff. Seine chinesische Entdeckerin Tu Youyou erhielt dafür 2015 den Nobelpreis für Medizin. Als Malariawirkstoff ist sein Potential aber nicht ausgeschöpft. Wir setzen die beiden ChiuZ‐Beiträge von 2014 über Artemisinin fort und beschreiben die Isolierung von Artemisinin aus Blättern des Einjährigen Beifußes. Wir präsentieren und interpretieren den kompletten Satz analytischer Spektren zur Strukturzuordnung. Hintergrundinformationen ergänzen das Bild.
Effect of Partially Fluorinated N‐Alkyl‐Substituted Piperidine‐2‐carboxamides on Pharmacologically Relevant Properties
Authors: Vorberg Raffael , Trapp Nils , Zimmerli Daniel , Wagner Björn , Fischer Holger , Kratochwil Nicole A. , Kansy Manfred , Carreira Erick M. , Müller Klaus
Published: September 2016

The modulation of pharmacologically relevant properties of N‐alkyl‐piperidine‐2‐carboxamides was studied by selective introduction of 1–3 fluorine atoms into the n‐propyl and n‐butyl side chains of the local anesthetics ropivacaine and levobupivacaine. The basicity modulation by nearby fluorine substituents is essentially additive and exhibits an exponential attenuation as a function of topological distance between fluorine and the basic center. The intrinsic lipophilicity of the neutral piperidine derivatives displays the characteristic response noted for partially fluorinated alkyl groups attached to neutral heteroaryl systems. However, basicity decrease by nearby fluorine substituents affects lipophilicities at neutral pH, so that all partially fluorinated derivatives are of similar or higher lipophilicity than their non‐fluorinated parents. Aqueous solubilities were found to correlate inversely with lipophilicity with a significant contribution from crystal packing energies, as indicated by variations in melting point temperatures. All fluorinated derivatives were found to be somewhat more readily oxidized in human liver microsomes, the rates of degradation correlating with increasing lipophilicity. Because the piperidine‐2‐carboxamide core is chiral, pairs with enantiomeric N‐alkyl groups are diastereomeric. While little response to such stereoisomerism was observed for basicity or lipophilicity, more pronounced variations were observed for melting point temperatures and oxidative degradation.
Comprehensive cellular‐resolution atlas of the adult human brain
Authors: Ding Song‐Lin , Royall Joshua J. , Sunkin Susan M. , Ng Lydia , Facer Benjamin A.C. , Lesnar Phil , Guillozet‐Bongaarts Angie , McMurray Bergen , Szafer Aaron , Dolbeare Tim A. , Stevens Allison , Tirrell Lee , Benner Thomas , Caldejon Shiella , Dalley Rachel A. , Dee Nick , Lau Christopher , Nyhus Julie , Reding Melissa , Riley Zackery L. , Sandman David , Shen Elaine , van der Kouwe Andre , Varjabedian Ani , Write Michelle , Zollei Lilla , Dang Chinh , Knowles James A. , Koch Christof , Phillips John W. , Sestan Nenad , Wohnoutka Paul , Zielke H. Ronald , Hohmann John G. , Jones Allan R. , Bernard Amy , Hawrylycz Michael J. , Hof Patrick R. , Fischl Bruce , Lein Ed S.
Published: September 2016

Detailed anatomical understanding of the human brain is essential for unraveling its functional architecture, yet current reference atlases have major limitations such as lack of whole‐brain coverage, relatively low image resolution, and sparse structural annotation. We present the first digital human brain atlas to incorporate neuroimaging, high‐resolution histology, and chemoarchitecture across a complete adult female brain, consisting of magnetic resonance imaging (MRI), diffusion‐weighted imaging (DWI), and 1,356 large‐format cellular resolution (1 µm/pixel) Nissl and immunohistochemistry anatomical plates. The atlas is comprehensively annotated for 862 structures, including 117 white matter tracts and several novel cyto‐ and chemoarchitecturally defined structures, and these annotations were transferred onto the matching MRI dataset. Neocortical delineations were done for sulci, gyri, and modified Brodmann areas to link macroscopic anatomical and microscopic cytoarchitectural parcellations. Correlated neuroimaging and histological structural delineation allowed fine feature identification in MRI data and subsequent structural identification in MRI data from other brains. This interactive online digital atlas is integrated with existing Allen Institute for Brain Science gene expression atlases and is publicly accessible as a resource for the neuroscience community. J. Comp. Neurol. 524:3127–3481, 2016. © 2016 The Authors The Journal of Comparative Neurology Published by Wiley Periodicals, Inc.
Hybrid Synchronization of two complex delayed dynamical networks with nonidentical topologies and mixed coupling
Authors: Li Baocheng
Published: September 2016

In this article, we study a new hybrid synchronization scheme for two different delayed dynamical networks with nonidentical topologies and mixed coupling. Based on Barbalat lemma and Schur complement lemma, some hybrid synchronization criteria are achieved via the open‐loop‐plus‐pinning adaptive control strategy. Two numerical examples with two types of node dynamics illustrate the effectiveness of the proposed synchronous criteria. © 2016 Wiley Periodicals, Inc. Complexity 21: 470–482, 2016
Platinum Cubic Nanoframes with Enhanced Catalytic Activity and Durability Toward Oxygen Reduction
Authors: Park Jinho , Wang Helan , Vara Madeline , Xia Younan
Published: September 2016

We report the synthesis and electrocatalytic properties of Pt cubic nanoframes with ultrathin ridges less than 2 nm in thickness. The nanoframes were synthesized through site‐selected deposition of Pt onto the corner and edge sites of Pd nanocubes, followed by selective removal of the Pd cores via chemical etching. The Br− ions chemisorbed on the side faces of a Pd nanocube played a critical role in enabling the siteselected deposition. In addition, the kinetics of deposition and the diffusion of Pt adatoms was optimized by carefully controlling the injection rate of the Pt precursor and the reaction temperature, respectively, to obtain the frame‐like structure. When benchmarked against a commercial Pt/C comprised of Pt particles 2–3 nm in size, the Pt frame/C catalyst exhibited not only enhanced mass activity toward oxygen reduction, but also substantially improved catalytic durability. In an accelerated durability test, the Pt frame/C catalyst showed a mass activity more than 6× greater than for the Pt/C reference after 20 000 cycles of repeated potential sweeping. This improvement can be largely attributed to the frame‐like structure, which is unique in suppressing both the detachment and aggregation of catalytic particles owing to the significantly enhanced interaction with carbon support.
Mass cytometry panel optimization through the designed distribution of signal interference
Authors: Takahashi Chikara , Au‐Yeung Amelia , Fuh Franklin , Ramirez‐Montagut Teresa , Bolen Chris , Mathews William , O'Gorman William E.
Published: September 2016

Mass cytometry is capable of measuring more than 40 distinct proteins on individual cells making it a promising technology for innovating biomarker discovery. However, in order for this potential to be fully realized, best practices in panel design need to be further defined in order to achieve consistency and reproducibility in data analysis. Of particular importance are controls that reveal, and panel design principles that mitigate the effects of signal interference or overlap. We observed a disparity between the staining profiles of two noncompeting anti‐ integrin β7 mAbs and hypothesized that signal interference was responsible. A mass‐minus‐one (MMO) control was applied and demonstrated that signal overlap caused the perceived interclonal discrepancy in β7 expression. Panel redesign in consideration of mass‐cytometry specific interference dynamics dramatically improved concordance between both mAbs by redistributing background signals caused by overlap. These studies visualize how signal overlap can complicate mass cytometry data interpretation and demonstrate how the rational distribution of interference can greatly improve panel design and data quality. © 2016 International Society for Advancement of Cytometry
A Novel Flow Cytometric Method for the Simultaneous Detection of Antibodies Against Platelet, Lymphocyte, And Neutrophil
Authors: Suh Myung Chul , Suh Jang Soo , Won Dong Il
Published: September 2016

Background

Platelet or neutrophil antibodies (Ab) detected by an indirect method need to be further investigated to confirm that they are HLA (lymphocyte)‐specific. This can only be determined by the assessment of lymphocytes from the same donor. We have developed an improved flow cytometric method for the simultaneous detection of Abs against three distinct cell types (platelets, lymphocytes, and neutrophils) in a single suspension.

Methods

We prepared white blood cell (WBC) suspensions using an overlay procedure. To enhance the retrieval of the three cell types during flow cytometry, the acquisition time was divided into two periods, platelet phase and WBC phase, and a different live acquisition gate was applied to each phase. The sample/control ratio of mean fluorescence intensity (MFI) was measured for each cell type.

Results

The number of cells in the starting cell suspension and the retrieved cell numbers of the three cell types were sufficient to detect their cognate antibodies. There was no significant difference between the MFI ratios observed in the current protocol and those from the conventional method (P > 0.05), and positive correlations were found (P < 0.05) for all three cell types. Each positive control serum with a specific set of Abs showed the typical comprehensive reaction pattern to the three cell types. Based on such patterns, 47% (14/30) of the patient sera that reacted with platelets were demonstrated to be due to anti‐HLA Abs without platelet Abs.

Conclusions

Our method could enhance both interpretation accuracy of the diagnostic test results and laboratory efficiency. As an increased reaction with platelets is commonly due to anti‐HLA Abs, the reactivity of the lymphocytes from the same donor should also be tested, which can be routinely done by using our protocol. © 2016 International Clinical Cytometry Society
Using Computerized Cytomorphometry to Distinguish between Benign and Malignant Cases in Thyroid Fine‐Needle Aspiration Cytology
Authors: Celik Zeliha Esin , Altinay Serdar , Kilinc Fahriye , Arslan Nur , Yilmaz Burcu Sanal , Karabagli Pınar , Ugurluoglu Ceyhan
Published: September 2016

Background

Only a small number of studies on computerized cytomorphometry have been performed for thyroid FNAC. The present study aimed to determine the usefulness of computerized cytomorphometry methods to further classify thyroid lesions as benign or malignant and to compare the practicability and value of using Papanicolaou (Pap) and Giemsa stains in thyroid FNAC by evaluating their association to various cytologic nuclear parameters.

Methods

Fifty‐eight thyroid lesions diagnosed by FNAC and categorized according to the Bethesda system for reporting thyroid cytopathology were evaluated in terms of various cytologic nuclear parameters, including nuclear area (NA), nuclear perimeter (NP), nuclear density (ND), long nuclear diameter (LND), and short nuclear diameter (SND). The Pap‐ and Giemsa‐stained slides were examined separately.

Results

In the malignant cases, NA, NP, LND, and SND were higher than in the benign cases for both the Pap and Giemsa stains. NA, NP, LND, and SND were higher in Giemsa than Pap for both the benign and malignant groups. Statistically significant differences were detected between the benign and malignant cases in the AUS category.

Conclusions

Computerized cytomorphometry is useful in distinguishing between benign and malignant lesions in thyroid FNAC. The measurement of cytologic nuclear parameters in cases suggestive of AUS may be useful for the probable classification of cases as benign or malignant. Although further studies are needed, in nuclear morphometric assessment of thyroid FNAC, Giemsa staining may be more useful and valuable than the Pap stain because of its association with various cytologic nuclear parameters. Diagn. Cytopathol. 2016;44:902–911. © 2016 Wiley Periodicals, Inc.
Efficient Electromagnetic Analysis for Cryptographic Module on the Frequency Domain
Authors: HAYASHI YU‐ICHI , HOMMA NAOFUMI , MIZUKI TAKAAKI , AOKI TAKAFUMI , SONE HIDEAKI
Published: September 2016

An efficient analysis method in the frequency domain for the extraction of information under the degradation of signal‐to‐noise ratio (SNR) is proposed. When the electromagnetic emission from the cryptographic module on the hardware is analyzed, the electromagnetic fields caused by operation on the other modules interfere to the electromagnetic field from the cryptographic module. Therefore, the amount of the measured data required for the extraction of information under the condition of degraded SNR increases and the analysis for this increase in data needs additional computation time. In order to accelerate the analysis under the degradation of SNR, we focus on only the processing of analysis target data. Furthermore, the signal of information and noises is separated with the analysis on the frequency domain. The proposed method is examined through experiments.
Load Balancing of Processing Servers for Cloud Control System
Authors: OHNISHI NAOYA , TAKANAKA TOORU , NAKATANI HIROSHI
Published: September 2016

When a large‐scale disaster occurs in control systems for social infrastructure, field equipment and control programs of the control systems might be lost. We have proposed the control system that operates control processing on cloud servers for rapid recovery from a disaster. This paper proposes architecture for cloud control system and a method for balancing the processing load of cloud servers. We examine the response time of the control processing operated by the cloud control system built on Amazon Web Services.
Threshold Fluence for Femtosecond Laser Nanoablation for Metals
Authors: HASHIDA MASAKI , MIYASAKA YASUHIRO , NISHII TAKAYA , SHIMIZU MASAHIRO , INOUE SHUNSUKE , SAKABE SHUJI
Published: September 2016

Femtosecond laser nanoablation of Ti by short‐pulse laser irradiation (800 nm/40 fs) is studied in the laser fluence range of 0.07 J/cm2 to 0.5 J/cm2. To determine the ablation threshold, the ablation rate dependence on laser fluence is precisely measured. Multishot ablation threshold of titanium is found to be 0.074 J/cm2 in which value is good agreement with that reported previously by other group. To discuss the ablation mechanism, all the ablation thresholds for metals previously published are plotted as a function of work function and melting temperature. We found that the ablation thresholds correlated with work function of metals. Experimental data suggested that the femtosecond laser ablation is mainly due to multiphoton absorption and optical field ionization.
Transfer Methods of PZT Thin Capacitor to Flexible Polymer by Self‐Assembled Monolayers
Authors: MIZUNO YUKI , BYUN IKJOO , KIM BEOMJOON , ICHIKI MASAAKI
Published: September 2016

This paper describes the fabrication method that a lead zirconate titanate (PZT) thin film capacitor, which is formed on a Si substrate by metal organic decomposition (MOD), can be easily transferred to flexible polymer (polydimenthylsiloxane; PDMS) without additional chemical contamination. The thin film capacitor is composed of sandwich structure of PZT between two metal layers. To embed the capacitor structure in the polymer substrate by dry peel‐off process, three kinds of self‐assembled monolayers (SAMs) were investigated for adhesion or antiadhesion layer between metal, polymer, and Si substrate, respectively. Also, the MOD's annealing process with SAMs for PZT lamination was investigated. As a result, the PZT capacitors of 1 μm thickness with a perovskite structure were successfully transferred and embedded in PDMS substrate. These results will be useful for fabricating MEMS devices and integration technology of electrical device to a polymer substrate such as capacitors in three‐dimensional integration or for flexible electronics.
Diversity of Polyoxometalate‐Based Copper Compounds Obtained from the Same Reaction System
Authors: Buvailo Halyna I. , Makhankova Valeriya G. , Kokozay Vladimir N. , Zatovsky Igor V. , Omelchenko Irina V. , Shishkina Svitlana V. , Zabierowski Piotr , Matoga Dariusz , Jezierska Julia
Published: September 2016

Two simple pathways using metallic copper or copper salts are proposed for the synthesis of hybrid compounds under mild conditions. A variety of Strandberg‐ and mixed‐metal Keggin‐based products, namely, (NH4)5n{[Cu(en)2][PMo8V4O40]}n·9nH2O (1), (NH4)4n{[Cu(en)(H2O)][P2Mo5O23]}n·3.5nH2O (2), (NH4)7[PMo8V4O40]·17H2O (3) and (NH4)2n{[Cu(en)2][Cu(en)(H2O)][P2Mo5O23]}n·3nH2O (4), were isolated upon the variation of the composition of the reaction system. A rare four‐substituted [PMo8V4O40]7– Keggin anion was obtained. The influence of the vanadium source [V2O5, NH4VO3 or (NH4)2V6O16] and the copper precursor (copper powder vs. copper salts) on the nature of the resulting products was studied. An ex situ electron paramagnetic resonance (EPR) spectroscopy study revealed the formation of VIV and CuII centres in the reaction mixture during Cu0 dissolution. The obtained compounds possess electrocatalytic activity in the reduction of iodate and nitrite anions, and a carbon‐paste electrode modified with 4 exhibited a linear current response to l‐cysteine. Furthermore, 4 demonstrated rapid and almost complete adsorption of a cationic dye.
Application of Isocyanides as Amide Surrogates in the Synthesis of Diverse Isoindolin‐1‐one Derivatives by a Palladium‐Catalyzed Tandem Carboxamidation/Hydroamidation Reaction
Authors: Pathare Ramdas S , Sharma Shivani , Elagandhula Sathish , Saini Vaishali , Sawant Devesh M , Yadav Monika , Sharon Ashoke , Khan Shahnawaz , Pardasani Ram T
Published: September 2016

The rapid synthesis of the isoindolinone skeleton has been accomplished by a palladium‐catalyzed one‐pot tandem process, which consists of an isocyanide insertion/hydration (carboxamidation) and 5‐exo‐dig cycloisomerization (hydroamidation) reaction sequence that afforded the products in good to excellent yields. Preliminary mechanistic studies of this sequential C–C/C–O/C–N bond formation process suggests that the carboxamidation step is palladium‐dependent, whereas the hydroamidation step is solely mediated by the base and is driven by the electrophilicity of the alkyne.
Functionalization of Reduced Graphene Oxide with β‐cyclodextrin Modified Palladium Nanoparticles for the Detection of Hydrazine in Environmental Water Samples
Authors: Sakthinathan Subramanian , Kubendhiran Subbiramaniyan , Chen Shen‐Ming , Sireesha Pedaballi , Karuppiah Chelladurai , Su Chaochin
Published: September 2016

A sensitive and selective hydrazine sensor was developed by β‐cyclodextrin modified palladium nanoparticles decorated reduced graphene oxide (PdNPs‐β‐CD/rGO) nanocomposite. The PdNPs‐β‐CD/rGO hybrid material was prepared by simple electrochemical method. The hydrophobic cavity of β‐CD ineracts with palladium nanoparticles by hydrophobic interaction and further it is uniformly assembled on the rGO surface through hydrogen bond formation, which is clearly confirmed by FT‐IR, FESEM and TEM. The high electrocatalytic activity of hydrazine oxidation was observed at −0.05 V (vs. Ag/AgCl) on PdNPs‐β‐CD/rGO modified electrode; due to the excellent stabilization, high catalytic activity and large surface area of the PdNPs‐β‐CD/rGO composite. The PdNPs‐β‐CD/rGO fabricated hydrazine sensor exhibited an excellent analytical performance, including high sensitivity (1.95 μA μM−1 cm−2), lower detection limit (28 nM) and a wide linear range (0.05 to 1600 μM). We also demonstrated that the PdNPs‐β‐CD/rGO nanocomposite modified electrode is a highly selective and sensitive sensor towards detection of hydrazine among the various interfering species. Hence, the proposed hydrazine sensor is able to determine hydrazine in different water samples.
Electrochemically Controlled Ion‐exchange Property of Carbon Nanotubes/Polypyrrole Nanocomposite in Various Electrolyte Solutions
Authors: Choi Daiwon , Zhu Chengzhou , Fu Shaofang , Du Dan , Engelhard Mark H. , Lin Yuehe
Published: September 2016

The electrochemically controlled ion‐exchange properties of multi‐wall carbon nanotube (MWNT)/electronically conductive polypyrrole (PPy) polymer composite in the various electrolyte solutions have been investigated. The ion‐exchange behavior, rate and capacity of the electrochemically deposited polypyrrole with and without carbon nanotube (CNT) were compared and characterized using cyclic voltammetry (CV), chronoamperometry (CA), electrochemical quartz crystal microbalance (EQCM), X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It has been found that the presence of carbon nanotube backbone resulted in improvement in ion‐exchange rate, stability of polypyrrole, and higher anion loading capacity per PPy due to higher surface area, electronic conductivity, porous structure of thin film, and thinner film thickness providing shorter diffusion path. Chronoamperometric studies show that electrically switched anion exchange could be completed more than 10 times faster than pure PPy thin film. The anion selectivity of CNT/PPy film is demonstrated using X‐ray photoelectron spectroscopy (XPS).
Bayesian inference for nonstationary marginal extremes
Authors: Randell D. , Turnbull K. , Ewans K. , Jonathan P.
Published: September 2016

We propose a simple piecewise model for a sample of peaks‐over‐threshold, nonstationary with respect to multidimensional covariates, and estimate it using a carefully designed and computationally efficient Bayesian inference. Model parameters are themselves parameterized as functions of covariates using penalized B‐spline representations. This allows detailed characterization of non‐stationarity extreme environments. The approach gives similar inferences to a comparable frequentist penalized maximum likelihood method, but is computationally considerably more efficient and allows a more complete characterization of uncertainty in a single modelling step. We use the model to quantify the joint directional and seasonal variation of storm peak significant wave height at a northern North Sea location and estimate predictive directional–seasonal return value distributions necessary for the design and reliability assessment of marine and coastal structures.
Effects of mulching accumulator straw on growth and cadmium accumulation of Cyphomandra betacea seedlings
Authors: He Jing , Lin Lijin , Ma Qianqian , Liao Ming'an , Wang Xun , Liang Dong , Xia Hui , Lai Yunsong , Tang Yi , Chen Shengxiang , Wang Li
Published: September 2016

Mulching with the straws of Trifolium repens, Conyza canadensis and Stellaria media increased the root, stem, leaf, shoot and whole‐plant biomasses of Cyphomandra betacea seedlings under cadmium (Cd) stress compared with the control, increased the chlorophyll a, chlorophyll b, total chlorophyll and carotinoid contents, and improved superoxide dismutase, peroxidase, and catalase activities. However, the straw of Eclipta prostrata decreased the biomass, photosynthetic pigment content and antioxidant enzyme activity of Cyphomandra betacea seedlings under Cd stress compared with the control. Mulching with the straws of Trifolium repens, Eclipta prostrate, and Stellaria media increased the Cd contents in roots, stems, leaves, and shoots of Cyphomandra betacea seedlings compared with control, while the straw of Conyza canadensis decreased the Cd content. Therefore, mulching with Conyza canadensis can promote the growth of Cyphomandra betacea seedlings, and decrease their Cd accumulation, which benefits the safe production of Cyphomandra betacea. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 366–371, 2017
The viability of design and operation of the air injection well for improvement In Situ repair capacity in landfill
Authors: Liu Lei , Ma Jun , Xue Qiang , Zeng Gang , Zhao Ying
Published: September 2016

The rationality of air injection well for operation parameter design is important for effective repair and safety of aeration systems in landfills. On the basis of the literature, the operating results of the air injection systems used in field sites were summarized, and the key design parameters were addressed. The operation and assessment of aeration systems were presented. First, the behavior of oxygen transport was caused by the characteristics of the pore media in the waste body. A mathematical model was needed to address the spatial–temporal evolutions of oxygen concentration in landfill. The optimum design method of gas injection well should be developed to elevate the oxygen content at maximum level across the field site, applying to most landfills. Second, an effective leachate exchange and recirculation plan should be developed to ensure sustained aerobic reaction in full scale. Some experiences of leachate discharge in field sites were presented. Third, the relationship between oxygen consumption and stability indicators should be determined to create an effective aeration plan. This function will help evaluate the reliability of aeration systems. This study provides evidence for the design, construction, operation, and effectiveness assessment of air injection well in repair engineering of landfills. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 412–419, 2017
A research about Beijing's carbon emissions based on the IPSO‐BP model
Authors: Wen Lei , Liu Yanjun
Published: September 2016

The problem of CO2 emissions, as an important factor of air pollution, attracts broad attention. For the purpose of pollution prevention, this paper would establish a reasonable model to study Beijing's impacting factors of carbon emissions and carry out future forecast. This paper use the non‐inertia weight coefficient and particle mutation particle swarm optimization (PSO) algorithm to optimize the initial connection weights and thresholds of the traditional BP neural network, and establish a BP neural network model based on the improved PSO. Through empirical analysis of carbon emissions and its driven factors in Beijing city from 1978 to 2012, IPSO‐BP is found to be a good method to make carbon emissions' forecast as it can improve the global optimization ability of traditional IPSO and BP algorithm. The results also can contribute to the local government's policy related decision‐making to make control of carbon emissions. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 428–434, 2017
A Meta‐analysis on the neural basis of planning: Activation likelihood estimation of functional brain imaging results in the Tower of London task
Authors: Nitschke Kai , Köstering Lena , Finkel Lisa , Weiller Cornelius , Kaller Christoph P.
Published: September 2016

The ability to mentally design and evaluate series of future actions has often been studied in terms of planning abilities, commonly using well‐structured laboratory tasks like the Tower of London (ToL). Despite a wealth of studies, findings on the specific localization of planning processes within prefrontal cortex (PFC) and on the hemispheric lateralization are equivocal. Here, we address this issue by integrating evidence from two different sources of data: First, we provide a systematic overview of the existing lesion data on planning in the ToL (10 studies, 211 patients) which does not indicate any evidence for a general lateralization of planning processes in (pre)frontal cortex. Second, we report a quantitative meta‐analysis with activation likelihood estimation based on 31 functional neuroimaging datasets on the ToL. Separate meta‐analyses of the activation patterns reported for Overall Planning (537 participants) and for Planning Complexity (182 participants) congruently show bilateral contributions of mid‐dorsolateral PFC, frontal eye fields, supplementary motor area, precuneus, caudate, anterior insula, and inferior parietal cortex in addition to a left‐lateralized involvement of rostrolateral PFC. In contrast to previous attributions of planning‐related brain activity to the entire dorsolateral prefrontal cortex (dlPFC) and either its left or right homolog derived from single studies on the ToL, the present meta‐analyses stress the pivotal role specifically of the mid‐dorsolateral part of PFC (mid‐dlPFC), presumably corresponding to Brodmann Areas 46 and 9/46, and strongly argue for a bilateral rather than lateralized involvement of the dlPFC in planning in the ToL. Hum Brain Mapp 38:396–413, 2017. © 2016 Wiley Periodicals, Inc.
Hypoxia‐driven Hif2a coordinates mouse liver regeneration by coupling parenchymal growth to vascular expansion
Authors: Kron Philipp , Linecker Michael , Limani Perparim , Schlegel Andrea , Kambakamba Patryk , Lehn Jean‐Marie , Nicolau Claude , Graf Rolf , Humar Bostjan , Clavien Pierre‐Alain
Published: September 2016

Interaction between sinusoidal endothelial cells and hepatocytes is a prerequisite for liver function. Upon tissue loss, both liver cell populations need to be regenerated. Repopulation occurs in a coordinated pattern, first through the regeneration of parenchyme (hepatocytes), which then produces vascular endothelial growth factor (VEGF) to enable the subsequent angiogenic phase. The signals that instruct hepatocytes to induce timely VEGF remain unidentified. Given that liver is highly vascularized, we reasoned that fluctuations in oxygenation after tissue loss may contribute to the coordination between hepatocyte and sinusoidal endothelial cell proliferation. To prevent drops in oxygen after hepatectomy, mice were pretreated with inositol trispyrophosphate (ITPP), an allosteric effector of hemoglobin causing increased O2 release from heme under hypoxic conditions. ITPP treatment delayed liver weight gain after hepatectomy. Comparison with controls revealed the presence of a hypoxic period around the peak of hepatocyte mitosis. Inhibition of hypoxia led to deficient hepatocyte mitosis, suppressed the regenerative Vegf wave, and abrogated the subsequent reconstruction of the sinusoidal network. These ITPP effects were ongoing with the reduction in hepatocellular hypoxia inducible factor 2a (Hif2a). In contrast, Hif1a was unaffected by ITPP. Hif2a knockdown phenocopied all effects of ITPP, including the mitotic deficiencies, Vegf suppression, and angiogenic failure. Conclusions: Oxygen is a key regulator of liver regeneration. Hypoxia—inherent to the expansion of parenchyme—activates Hif2a to couple hepatocyte mitosis with the angiogenic phase. Hif2a acts as a safeguard to initiate sinusoidal reconstruction only upon successful hepatocyte mitosis, thereby enforcing a timely order onto cell type‐specific regeneration patterns. These findings portray the hypoxia‐driven Hif2a‐Vegf axis as a prime node in coordinating sinusoidal endothelial cell‐hepatocyte crosstalk during liver regeneration. (Hepatology 2016;64:2198‐2209).
The cystic fibrosis transmembrane conductance regulator controls biliary epithelial inflammation and permeability by regulating Src tyrosine kinase activity
Authors: Fiorotto Romina , Villani Ambra , Kourtidis Antonis , Scirpo Roberto , Amenduni Mariangela , Geibel Peter J. , Cadamuro Massimiliano , Spirli Carlo , Anastasiadis Panos Z. , Strazzabosco Mario
Published: September 2016

In the liver, the cystic fibrosis (CF) transmembrane conductance regulator (CFTR) regulates bile secretion and other functions at the apical membrane of biliary epithelial cells (i.e., cholangiocytes). CF‐related liver disease is a major cause of death in patients with CF. CFTR dysfunction affects innate immune pathways, generating a para‐inflammatory status in the liver and other epithelia. This study investigates the mechanisms linking CFTR to toll‐like receptor 4 activity. We found that CFTR is associated with a multiprotein complex at the apical membrane of normal mouse cholangiocytes, with proteins that negatively control Rous sarcoma oncogene cellular homolog (Src) activity. In CFTR‐defective cholangiocytes, Src tyrosine kinase self‐activates and phosphorylates toll‐like receptor 4, resulting in activation of nuclear factor kappa‐light‐chain‐enhancer of activated B cells and increased proinflammatory cytokine production in response to endotoxins. This Src/nuclear factor kappa‐light‐chain‐enhancer of activated B cells‐dependent inflammatory process attracts inflammatory cells but also generates changes in the apical junctional complex and loss of epithelial barrier function. Inhibition of Src decreased the inflammatory response of CF cholangiocytes to lipopolysaccharide, rescued the junctional defect in vitro, and significantly attenuated endotoxin‐induced biliary damage and inflammation in vivo (Cftr knockout mice). Conclusion: These findings reveal a novel function of CFTR as a regulator of toll‐like receptor 4 responses and cell polarity in biliary epithelial cells; this mechanism is pathogenetic, as shown by the protective effects of Src inhibition in vivo, and may be a novel therapeutic target in CF‐related liver disease and other inflammatory cholangiopathies. (Hepatology 2016;64:2118‐2134).
Characterization of the Specificity, Functionality, and Durability of Host T‐Cell Responses Against the Full‐Length Hepatitis E Virus
Authors: Brown Anthony , Halliday John S. , Swadling Leo , Madden Richie G. , Bendall Richard , Hunter Jeremy G. , Maggs James , Simmonds Peter , Smith Donald B. , Vine Louisa , McLaughlin Cara , Collier Jane , Bonsall David , Jeffery Katie , Dunachie Susanna , Klenerman Paul , Izopet Jacques , Kamar Nassim , Dalton Harry R. , Barnes Eleanor
Published: September 2016

The interplay between host antiviral immunity and immunopathology during hepatitis E virus (HEV) infection determines important clinical outcomes. We characterized the specificity, functionality, and durability of host T‐cell responses against the full‐length HEV virus and assessed a novel “Quantiferon” assay for the rapid diagnosis of HEV infection. Eighty‐nine volunteers were recruited from Oxford, Truro (UK), and Toulouse (France), including 44 immune‐competent patients with acute HEV infection, 18 HEV‐exposed immunosuppressed organ‐transplant recipients (8 with chronic HEV), and 27 healthy volunteers. A genotype 3a peptide library (616 overlapping peptides spanning open reading frames [ORFs] 1‐3) was used in interferon‐gamma (IFN‐γ) T‐cell ELISpot assays. CD4+/CD8+ T‐cell subsets and polyfunctionality were defined using ICCS and SPICE analysis. Quantification of IFN‐γ used whole‐blood stimulation with recombinant HEV‐capsid protein in the QuantiFERON kit. HEV‐specific T‐cell responses were detected in 41/44 immune‐competent HEV exposed volunteers (median magnitude: 397 spot‐forming units/106 peripheral blood mononuclear cells), most frequently targeting ORF2. High‐magnitude, polyfunctional CD4 and CD8+ T cells were detected during acute disease and maintained to 12 years, but these declined over time, with CD8+ responses becoming more monofunctional. Low‐level responses were detectable in immunosuppressed patients. Twenty‐three novel HEV CD4+ and CD8+ T‐cell targets were mapped predominantly to conserved genomic regions. QuantiFERON testing demonstrated an inverse correlation between IFN‐γ production and the time from clinical presentation, providing 100% specificity, and 71% sensitivity (area under the receiver operator characteristic curve of 0.86) for HEV exposure at 0.3 IU/mL. Conclusion: Robust HEV‐specific T‐cell responses generated during acute disease predominantly target ORF2, but decline in magnitude and polyfunctionality over time. Defining HEV T‐cell targets will be important for the investigation of HEV‐associated autoimmune disease. (Hepatology 2016;64:1934‐1950).