bluuebunny/crossref_metadata_2025 huggingface dataset:
Metall‐Phosphor‐Trichalkogenide (MPCh3): von der Synthese zu aktuellen Energieanwendungen
Authors: Gusmão Rui , Sofer Zdenek , Pumera Martin
Published: October 2018

Aufgrund ihrer speziellen physikalischen und chemischen Eigenschaften stehen zweidimensionale (2D‐)Schichtmaterialien im Fokus der aktuellen materialwissenschaftlichen Forschung. Dies schließt Schichten ein, die aus einem einzelnen Element (Graphen, Phosphoren), zwei Elementen (Metall‐Dichalkogenide) oder mehreren Elementen bestehen. Die erstmals im späten 19. Jahrhundert synthetisierten Metall‐Phosphor‐Trichalkogenide (MPCh3 mit Ch=S, Se) bilden eine besondere Klasse von 2D‐Schichtmaterialien. MPCh3‐Verbindungen, die in den 1970er Jahren wegen ihres ungewöhnlichen Interkalationsverhaltens in Bezug auf ihre magnetischen Eigenschaften sowie als Sekundärelektroden in Lithium‐Batterien untersucht worden waren, wurden erst vor kurzem als 2D‐Nanomaterialien wiederentdeckt. Zahlreiche aktuelle Berichte über MPCh3 für die Wasserspaltungskatalyse und Energiespeicherung werden umfassend erörtert, wobei der Fokus auf der Synthese dieser Materialien und ihren wesentlichsten Eigenschaften liegt. Dieser Kurzaufsatz soll als Ausgangsbasis für die Erkundung solcher 2D‐Schichtmaterialien für elektrochemische Energieanwendungen dienen.
Palladium‐Catalyzed Enantioselective Addition of Chiral Metal Enolates to In Situ Generated ortho‐Quinone Methides
Authors: Göricke Fabian , Schneider Christoph
Published: October 2018

We describe herein a conceptually novel, cooperative Brønsted acid/base catalyzed process for the conjugate addition of cyclic β‐keto esters to ortho‐quinone methides both generated in situ. Upon hemiacetalization, densely functionalized chiral chromans with two adjacent quaternary and additionally a tertiary stereogenic center were obtained with very good diastereoselectivity (up to >95:5 d.r.) and typically excellent enantioselectivity (up to >99 % ee). The striking feature and key to success is the dual catalytic activation of both nucleophile and electrophile in two separate cycles with a single chiral catalyst.
Mannich‐type Reactions of Cyclic Nitrones: Effective Methods for the Enantioselective Synthesis of Piperidine‐containing Alkaloids
Authors: Lisnyak Vladislav G. , Lynch‐Colameta Tessa , Snyder Scott A.
Published: October 2018

Even though there are dozens of biologically active 2‐substituted and 2,6‐disubstituted piperidines, only a limited number of approaches exist for their synthesis. Herein is described two Mannich‐type additions to nitrones, one using β‐ketoacids under catalyst‐free conditions and another using methyl ketones in the presence of chiral thioureas, which can generate a broad array of such 2‐substituted materials, as well as other ring variants, in the form of β‐N‐hydroxy‐aminoketones. Both processes have broad scope, with the latter providing products with high enantioselectivity (up to 98 %). The combination of these methods, along with other critical steps, has enabled 8‐step total syntheses of the 2,6‐disubstituted piperidine alkaloids (−)‐lobeline and (−)‐sedinone.
Construction of Linear and Branched Tetraboranes by 1,1‐ and 1,2‐Diboration of Diborenes
Authors: Stennett Tom E. , Bertermann Rüdiger , Braunschweig Holger
Published: October 2018

Sterically unencumbered diborenes based on a benzylphosphine chelate undergo diboration reactions with bis(catecholato)diboron in the absence of a catalyst to yield tetraboranes. The symmetrical diborenes studied undergo 1,2‐diborations, whereas an unsymmetrical derivative was found to yield a triborylborane–phosphine adduct as the result of a formal 1,1‐diboration. A related borylborylene compound also underwent a 1,2‐diboration to produce a borylene–borane adduct.
Metal Phosphorous Trichalcogenides (MPCh3): From Synthesis to Contemporary Energy Challenges
Authors: Gusmão Rui , Sofer Zdenek , Pumera Martin
Published: October 2018

Owing to their unique physical and chemical properties, layered two‐dimensional (2D) materials have been established as the most significant topic in materials science for the current decade. This includes layers comprising mono‐element (graphene, phosphorene), di‐element (metal dichalcogenides), and even multi‐element. A distinctive class of 2D layered materials is the metal phosphorous trichalcogenides (MPCh3, Ch=S, Se), first synthesized in the late 1800s. Having an unusual intercalation behavior, MPCh3 were intensively studied in the 1970s for their magnetic properties and as secondary electrodes in lithium batteries, but fell from scrutiny until very recently, being 2D nanomaterials. Based on their synthesis and most significant properties, the present surge of reports related to water‐splitting catalysis and energy storage are discussed in detail. This Minireview is intended as a baseline for the anticipated new wave of researchers who aim to explore these 2D layered materials for their electrochemical energy applications.
Concise synthesis and antibacterial evaluation of novel 3‐(1,4‐disubstituted‐1,2,3‐triazolyl)uridine nucleosides
Authors: Tachallait Hamza , Bouyahya Abdelhakim , Talha Aicha , Bakri Youssef , Dakka Nadia , Demange Luc , Benhida Rachid , Bougrin Khalid
Published: October 2018

We report herein a simple and efficient synthesis of a new series of antibacterial uridine nucleosides. The strategy involved a sequential silylation/N‐glycosylation/N‐propargylation procedure of uracil 1 for preparing the dipolarophile 5 in good yield. A series of novel uridine‐[1,2,3]triazole nucleosides 6a–j were efficiently synthesized via the copper‐catalyzed azide–alkyne cycloaddition (CuAAC) from dipolarophile 5 with different selected azides. The reactions were carried out under both conventional and ultrasonic irradiation conditions. In general, improvements were observed when reactions were carried out under sonication. Their antibacterial potential has been evaluated by means of a micro‐dilution assay against either Gram‐positive or Gram‐negative bacteria. Compounds 6i and 6j have shown significant bactericidal activity against Staphylococcus aureus (MIC = 10 and 6 μM, respectively), and 6h against Escherichia coli (MIC = 8 μM). Moreover, antibacterial kinetic assays showed that 6i and 6j significantly reduced the S. aureus growth rate at the MIC concentration, after 6 h, compared to their deprotected analogs, 6k and 6l, respectively. Compound 6h also significantly reduced the growth of E. coli. These antibacterial effects may be related to the penetrating properties of these compounds, as revealed by the leakage of nucleic acids from the sensitive strains.
Sem: A Viking Age metalworking site in the southeast of Norway?
Authors: Gustavsen Lars , Kristiansen Monica , Nau Erich , Tafjord Bernt Egil
Published: October 2018

Evidence pertaining to Viking Age industry and trade is rarely encountered in the Norwegian archaeological record, although recent evidence suggests that sites of this character are more common than previously thought. Systematic metal detecting and large‐scale geophysical surveys carried out in Øvre Eiker in the southeast of Norway between 2014 and 2016 revealed a multiphase and complex settlement area, consisting of large pits potentially associated with metalworking. The evidence so far points to a site with far‐reaching contemporary connections, where objects were worked and exchanged. This short report aims to present the results from the work undertaken so far and to demonstrate how the complementary use of geophysical surveys and metal detection can add cultural‐historical depth to the site itself and to a little understood aspect of Early Medieval history.
Generation and Characterization of Anti–Citrullinated Protein Antibody–Producing B Cell Clones From Rheumatoid Arthritis Patients
Authors: Germar Kristine , Fehres Cynthia M. , Scherer Hans U. , van Uden Nathalie , Pollastro Sabrina , Yeremenko Nataliya , Hansson Monika , Kerkman Priscilla F. , van der Voort Ellen I. H. , Reed Evan , Maassen Hanna , Kwakkenbos Mark J. , Bakker Arjen Q. , Klareskog Lars , Malmström Vivianne , de Vries Niek , Toes René E. M. , Lundberg Karin , Spits Hergen , Baeten Dominique L.
Published: October 2018

Objective

Anti–citrullinated protein antibodies (ACPAs) are a hallmark of rheumatoid arthritis (RA). Aside from autoantibody production, the function of autoantigen‐specific B cells remains poorly understood in the context of this disease. This study set out to elucidate autoantigen‐specific B cell functions through the isolation and immortalization of unique citrullinated protein/peptide (CP)–reactive B cell clones from RA patients.

Methods

B cell clones from either the blood or synovial fluid of cyclic citrullinated peptide 2 (CCP2) antibody–positive RA patients were immortalized by genetic reprogramming with Bcl‐6 and Bcl‐xL. Enzyme‐linked immunosorbent assay and flow cytometry were used to identify CCP2‐reactive clones and to further characterize surface marker and cytokine expression as well as B cell receptor signaling competence. Global gene expression profiles were interrogated by RNA sequencing.

Results

Three unique CP‐reactive memory B cell clones were generated from the blood or synovial fluid of 2 RA patients. CP‐reactive memory B cells did not appear to be broadly cross‐reactive, but rather had a fairly restricted epitope recognition profile. These clones were able to secrete both pro‐ and antiinflammatory cytokines and had a unique surface profile of costimulatory molecules and receptors, including CD40 and C5a receptor type 1, when compared to non‐CP–reactive clones from the same patient. In addition, CP‐reactive clones bound citrullinated protein, but not native protein, and could mobilize calcium in response to antigen binding.

Conclusion

CP‐reactive memory B cells comprise a rare, seemingly oligoclonal population with restricted epitope specificity and distinct phenotypic and molecular characteristics suggestive of antigen‐presenting cells. Cloning by genetic reprogramming opens new avenues to study the function of autoreactive memory B cells, especially in terms of antigen processing, presentation, and subsequent T cell polarization.
Ultra‐Thin Coating and Three‐Dimensional Electrode Structures to Boosted Thick Electrode Lithium‐Ion Battery Performance
Authors: Li Jie , Gao Yan , Liang Xinhua , Park Jonghyun
Published: October 2018

This paper reports a multiscale controlled three‐dimensional (3D) electrode structure to boost the battery performance for thick electrode batteries with LiMn1.5Ni0.5O4 as cathode material, which exhibits a high areal capacity (3.5 mAh/cm2) along with a high specific capacity (130 mAh/g). This excellent battery performance is achieved by a new concept of cell electrode fabrication, which simultaneously controls the electrode structure in a multiscale manner to address the key challenges of the material. Particles with ultrathin conformal coating layers are prepared through atomic layer deposition followed by a nanoscale‐controlled, thermal diffusion doping. The particles are organized into a macroscale‐controlled 3D hybrid‐structure. This synergistic control of nano‐/macro‐structures is a promising concept for enhancing battery performance and its cycle life. The nanoscale coating/doping provides enhanced fundamental properties, including transport and structural properties, while the mesoscale control can provide a better network of the nanostructured elements by decreasing the diffusion path between. Electrochemical tests have shown that the synergistically controlled electrode exhibits the best performance among non‐controlled and selectively‐controlled samples, in terms of specific capacity, areal capacity, and cycle life.
Stahl‐ und textilbewehrte Vorsatzschalen von Sandwichwänden unter thermischen Einwirkungsgrößen
Authors: Bert Christopher , Fischer Oliver
Published: October 2018

Im Rahmen eines durch die Forschungsinitiative Zukunft Bau des Bundesministeriums für Umwelt, Naturschutz, Bau und Reaktorsicherheit (BMUB) geförderten Vorhabens des Lehrstuhls für Massivbau der Technischen Universität München (TUM) werden an Sandwichwänden mit unterschiedlichen Vorsatzschalen unter Variation von zahlreichen Randbedingungen systematische thermische Untersuchungen durchgeführt.

Sandwichfassaden werden bisher vor allem aus Stahlbeton mit Vorsatzschalendicken zwischen etwa 70 und 100 mm ausgeführt. Die erforderliche Dicke ergibt sich hierbei unter anderem aus den einzuhaltenden Betondeckungen, um den Bewehrungsstahl dauerhaft vor Korrosion zu schützen. Aktuelle Entwicklungen ermöglichen z. B. durch textilbewehrte Betone sehr flexibel formbare Vorsatzschalen, die aufgrund der korrosionsbeständigen textilen Bewehrung und der hohen Festigkeiten mit Vorsatzschalendicken von gerade einmal 20–30 mm auskommen. Im Hinblick auf diese Entwicklung ist das Ziel des o.g. Forschungsvorhabens, die für die Bemessung maßgebenden Temperaturgrößen und ‐gradienten sowohl numerisch als auch experimentell nachzuweisen und geeignete Nachweisformate für die Praxis bereitzustellen. Neben diversen numerisch gestützten Analysen wird das Temperaturverhalten von großformatigen Vorsatzschalen mit 30 und 80 mm Dicke in einem in‐situ Naturversuch über eine gesamte Wetterperiode (365 Tage) untersucht. Ergänzende experimentelle Untersuchungen im Labor mittels einer eigens entwickelten multifunktionalen Klimakammer (Simulation verschiedenster Wetterszenarien) schließen das Vorhaben ab.
Große Stabdurchmesser und hohe Bewehrungsgrade
Authors: Schoening Janna , Hegger Josef
Published: October 2018

Der Neuvorschlag für Eurocode 2 enthält keine Zusatzregeln für den Einsatz von großen Stabdurchmessern, während Stabdurchmesser > ∅ 32 mm derzeit nach Eurocode 2 nur unter Einhaltung von Zusatzregeln verwendet werden dürfen. Die Zusatzregeln wurden für ∅ 40 mm Bewehrungsstäbe im Rahmen von zwei umfangreichen Versuchsprogrammen an insgesamt drei Forschungsstellen untersucht. Nach den Versuchen mit ∅ 40 mm Bewehrungsstäben wurden verstärkt auch Versuche an ∅ 28 mm Stäben durchgeführt, um den Übergang der Bemessungs‐ und Konstruktionsregeln zu herkömmlichen Stabdurchmessern bestimmen zu können. In diesem Artikel werden die an der RWTH Aachen University durchgeführten Versuche zum Verbundtragverhalten mit Hilfe von Beam‐End‐Versuchen, Vierpunkt‐Biegeversuchen mit Übergreifungen und Endverankerungen beschrieben. Die Versuchsergebnisse zeigen, dass einige Zusatzregeln entfallen können. Im Anschluss wird eine Datenbankauswertung verschiedener Bemessungsansätze für die erreichbare Stahlspannung in Verankerungen und Übergreifungen beschrieben. Die Bemessungsansätze zur Ermittlung der erforderlichen Verankerungs‐ und Übergreifungslängen werden anhand einer Versuchsdatenbank verglichen.
Chemical profiling by LC–MS/MS and HPLC fingerprint combined with chemometrics and simultaneous determination of 16 characteristic ingredients for the quality consistency evaluation of Shaoyao‐Gancao Decoction
Authors: Lu Pengfei , Chen Yong , Tan Manliang , Wu Yongjiang
Published: October 2018

In this paper, to evaluate the effect of the region of origin on the quality consistency of Shaoyao‐Gancao Decoction (SGD), the SGD fingerprint was developed for the first time. Chemometric methods including similarity analysis, hierarchical clustering analysis and principal component analysis were employed to study the quality consistency of SGD. Meanwhile, high‐performance liquid chromatography coupled with electrospray ionization quadrupole time‐of‐flight mass spectrometry was applied for comprehensive analysis of SGD and 93 compounds were tentatively characterized. Furthermore, a high‐performance liquid chromatography method with multi‐wavelength switching for simultaneous determination of 16 characteristic ingredients comprising gallic acid, oxypaeniflorin, albiflorin, paeoniflorin, liquiritin apioside, liquiritin, isoliquiritin apioside, galloylpaeoniflorin, 1,2,3,4,6‐penta‐O‐galloyl‐d‐galactopyranose (PGG), ononin, isoliquiritin, liquiritigenin, benzoylpaeoniflorin, glycyrrhizic acid, isoliquiritigenin and formononetin, was established. All 16 analytes show excellent linearity (R2 ≥ 0.9990) with recoveries ranging from 96.58 to 104.61% and limits of detection and quantification of 0.022–0.291 and 0.037–0.635 μg/mL, respectively. Finally, it was successfully applied to determine 15 batches of SGD. The results of our research indicate that different regions of origin have a significant effect on the quality consistency of SGD, and its fingerprint combined with chemometrics and multi‐ingredient determination comprise an efficient and reliable approach for quality consistency evaluation.
Prostate cancer survivors: Risk and mortality in second primary cancers
Authors: Chattopadhyay Subhayan , Zheng Guoqiao , Hemminki Otto , Försti Asta , Sundquist Kristina , Hemminki Kari
Published: October 2018

To assess etiological and clinical consequences of second primary cancers (SPCs) in prostate cancer (PC) patients, we followed newly diagnosed patients to identify men who were diagnosed with a SPC and recorded their causes of death. We used the Swedish Family‐Cancer Database to assess relative risks (RRs) and causes of death in SPCs until the year 2015 in patients with a PC diagnosis between 2001 and 2010. Among a total of 4.26 million men, 76 614 were diagnosed with PC at the median age of 71 years. Among them, 8659 (11.3%) received a subsequent diagnosis of SPC after a median follow‐up of 4 years. The most common SPCs were colorectal, skin, bladder, and lung cancers, melanoma, and non‐Hodgkin lymphoma. The ranking was almost identical with first cancers among elderly men in Sweden. The RR for SPCs in prostate‐specific antigen—detected PC was approximately equal to RR in other PC. Mortality patterns of PC patients were distinct depending on the presence or absence of SPC. Among patients with SPC, 47.8% died as a result of the corresponding SPC, followed by other causes (22.2%) and PC (18.1%). For patients without SPC, PC and non‐neoplastic causes almost matched each other as the main causes of death (48.5% and 47.8%). The results suggest that SPCs appear autonomous from primary PC and reflect incidence and mortality of first cancers in general. SPC was the most common cause of death in patients with SPC; close to half of the patients died due to SPC. For improved survival in PC patients, prevention and early detection of SPCs would be important, and the present results suggest that risk factors for SPC in PC are the same as those for first cancer in general.
Stability of Heat Transfer Nanofluids – A Review
Authors: Mukherjee Sayantan , Mishra Purna Chandra , Chaudhuri Paritosh
Published: October 2018

Nanofluids are suspension of highly conductive nano‐sized particles in conventional fluids that may be applicable as ultrafast cooling agent to extend the thermal performance of cooling devices. However, before considering the feasibility as coolant for high heat flux components, a thorough investigation of the long‐term stability of nanofluids is of paramount importance. Preparation of extremely stable nanofluids has become one of the main technical challenges. The present contribution aims to summarize the recent developments in the preparation, characterization, and stabilization of nanofluids based on the information available in literatures. Lastly, existing needs and attainable solution to challenges, leading to the upcoming research in the development of highly stable nanofluids, are discussed.
Ethanol from Biomass Hydrolysates by Efficient Fermentation of Glucose and Xylose – A Review
Authors: Nosrati‐Ghods Nosaibeh , Harrison Susan T. L. , Isafiade Adeniyi J. , Tai Siew L.
Published: October 2018

Fermentation performance of these biomass hydrolysates is limited by the lack of industrially suitable organisms to convert both glucose and xylose efficiently. To resolve this issue, several methods have been suggested, e.g., co‐cultivation of two or more species, engineering strains for enhanced substrate utilization, and use of sequential culture. Challenges of co‐culture include slower xylose fermentation due to varying affinities for oxygen, lower ethanol tolerance of xylose‐fermenters, and catabolite repression. Although successful engineering of microorganisms is demonstrated, there is limitation in understanding of the metabolic pathways regulations. Alternatively, sequential batch culture was suggested, but its productivity needs to be improved. Optimizing process conditions, e.g. process configuration, immobilization technique, cell type, enables improved yield and productivity. This paper reviews the approaches and conditions sought to improve glucose and xylose conversion from lignocellulosic hydrolysates to ethanol, with specific emphasis on microbial systems used to maximize biomass resource efficiency, ethanol yield, and productivity.
Induction of remission in autoimmune polyglandular syndrome type three (APS III): An old drug with new perspectives
Authors: Allam Magdy Mohamed , Elzawawy Hanaa Tarek Hussein
Published: October 2018

Key Clinical Message

The autoimmune polyglandular syndrome is a sequential chain of autoimmune events. Whenever diagnosed, the clinician's target should be induction of remission and if possible hindering its progression especially if associated with refractory vitiligo, resistant Grave's, or unexplained hyperglycemia in T1DM. Azathioprine could be used for induction of remission in autoimmune polyglandular syndrome type three especially with vitiligo and autoimmune thyroiditis.
Nivolumab‐induced severe acute kidney injury with a long latent phase in a patient with non‐small‐cell lung cancer: A case report
Authors: Uchida Naohiro , Tsuji Seijiro , Fujita Kohei , Koizumi Mitsuteru , Moriyoshi Koki , Mio Tadashi
Published: October 2018

Key Clinical Message

In the treatment of immunotherapy with immune checkpoint inhibitors, we often experience immune‐related adverse event which manifest most frequently as a skin disorder, and very rarely as a renal disorder. In our manuscript, we report the case of a 71‐year‐old man with nivolumab‐induced severe acute kidney injury (AKI) in which the time from treatment initiation to the onset of AKI was the longest among the previously reported cases (377 days). Prolonged follow‐up is therefore warranted to detect late‐onset AKI.
Ruthenium(II)biscarboxylate‐Catalyzed Hydrogen‐Isotope Exchange by Alkene C−H Activation
Authors: Bechtoldt Alexander , Ackermann Lutz
Published: October 2018

Ruthenium(II) biscarboxylate catalysis enabled efficient hydrogen isotope exchange of acrylic C−H bonds with user‐friendly D2O. The C−H labelling was characterized by excellent positional selectivity and a broad functional group tolerance. The deuteration was successfully conducted on 55 mmol scale with TONs of >1000, while mechanistic studies provided insights into ruthenium(II) oxidase catalysis. The obtained deuterated alkenes enabled the synthesis of labeled standards for mass spectrometry of irradiated foodstuffs.
Syngas Methanation over Spray‐Granulated Ni/Al2O3 Catalyst in a Laboratory Transport‐Bed Reactor
Authors: Liu Jiao , Cui Dianmiao , Yu Jian , Su Fabing , Xu Guangwen
Published: October 2018

Syngas methanation in a laboratory transport‐bed reactor has been performed. It was found that the CO conversion over the granular Ni/Al2O3 catalyst only slightly increased with the rise of aeration gas velocity for the recycling valve but severely decreased due to decreased gas residence time in the reactor. The effect of increasing the temperature of the recycled catalyst on the CO conversion at atmospheric pressure was also studied. Both the experimental temperature rise along the transport‐bed reactor and the estimated heat balance involving reactions verified the high heat‐transfer efficiency and its technical superiority for syngas methanation.
Process Design and Operating Strategies for a Continuous Vaporization System for Purifying Organic Hole‐Transport Materials
Authors: Kim Jin , Park Kiho , Jin Seokgeun , Yang Dae Ryook
Published: October 2018

A continuous vaporization system for the purification of organic hole‐transport materials is proposed to enhance the production rate. A detailed configuration to change a conventional batch process into a continuous one was suggested. The operating strategies of the continuous process were determined from experimental results. Fundamental experiments concerning liquid flow rate through a vertical pipe and product shape were performed. The liquid flow was successfully predicted by using the Hagen‐Poiseuille equation with a correction factor, and a suitable tube design could be estimated to obtain a droplet product. Moreover, an operating temperature window was suggested for uniform shape and size of the final product. This study will be useful for improved process efficiency and successful operation of this process.
3D Mixing Dynamics in T‐Jet Mixers
Authors: Sultan M. Ashar , Pardilhó Sara L. , Brito Margarida S. C. A. , Fonte Cláudio P. , Dias Madalena M. , Lopes José C. B. , Santos Ricardo J.
Published: October 2018

The dynamic flow field in T‐jet mixers is characterized by means of 3D computational fluid dynamics simulations. The main goal of this work is to identify and discuss the chaotic flow regime in T‐jet reactors and the parameters that enable this flow regime, namely, the critical Reynolds number and design parameters of these mixers. The 3D chaotic flow regime that occurs in T‐jet mixers is described herein with unprecedented detail regarding the mixing scales, flow dynamics, and coherent structures. The mixing scales are proven to be set by the mixer dimensions. The chaotic flow regime in T‐jets is of practical interest due to its capability to promote very fast mixing, although descriptions in the literature are scarce.
Rapid Hydrogen Peroxide Decomposition Using a Microreactor
Authors: Sun Bing , Zhu Hongwei , Jin Yan , Qiao Kun , Xu Wei , Jiang Jie
Published: October 2018

The rapid decomposition of hydrogen peroxide (H2O2) is often desired in the cleanup of excess H2O2 when it is used as an oxidant. Although the decomposition process has been studied in batch reactors, it has never been performed before in a fixed‐bed microreactor with residence time on the scale of seconds. With enhanced mass and heat transfer in microreactors, higher H2O2 decomposition efficiency compared to batch reactors was obtained. A variety of parameters including length of microchannels, flow rate, solvent composition, and gas pressure were examined carefully and a first‐order kinetic model was established. Within a few seconds, more than 70 % of the H2O2 was decomposed successfully. The challenge of catalyst passivation was discussed as well.
Efficient Electrocatalytic Oxygen Evolution at Extremely High Current Density over 3D Ultrasmall Zero‐Valent Iron‐Coupled Nickel Sulfide Nanosheets
Authors: Cheng Xiaodi , Lei Chaojun , Yang Jian , Yang Bin , Li Zhongjian , Lu Jianguo , Zhang Xingwang , Lei Lecheng , Hou Yang , Ostrikov Kostya (Ken)
Published: October 2018

Nonprecious water oxidation electrocatalysts that perform well at high current densities are among the key enabling drivers of renewable energy technologies. Herein, we report a novel strategy to produce 3D ultrasmall zero‐valent iron‐coupled nickel sulfides nanosheets (Fe0−NixSy) hybrid on self‐supported conductive Ni foam (denoted as Fe0−NixSy/NF) through a robust single‐step gas–solid reaction. In this 3D hybrid, the Fe0−NixSy nanosheets with a length of approximately 400 nm and an average thickness of 33 nm are uniformly grown on the Ni foam. Benefiting from the unique 3D hierarchical structure and synergistic effect between Fe0 and NixSy, the 3D Fe0−NixSy/NF hybrid shows an excellent electrocatalytic activity towards oxygen evolution reaction (OER) at extremely high current densities in basic media. The current densities of 1000 and 1500 mA cm−2 are achieved at low potentials of 1.57 and 1.60 V, respectively, thus meeting the expected OER standards for industrial applications. These overpotentials of the 3D Fe0−NixSy/NF hybrid are the lowest among all previously reported nickel‐sulfide‐based electrocatalysts, and are even superior compared to state‐of‐the‐art Ir/C catalysts. We further demonstrate that the integration of the 3D Fe0−NixSy/NF electrocatalyst as both anode and cathode with a silicon photovoltaic cell enables highly active and sustainable solar‐driven overall water splitting.
Coupling Ultrasound to the Electro‐Oxidation of Methyl Paraben Synthetic Wastewater: Effect of Frequency and Supporting Electrolyte
Authors: Dionisio Dawany , Motheo Artur J. , Sáez Cristina , Canizares Pablo , Rodrigo Manuel A.
Published: October 2018

In this paper, electrooxidation of methyl paraben (MeP) is studied by electrolysis only and electrolysis coupled with sonolysis, using a diamond electrode. Complete mineralization of MeP was achieved for both processes, in chloride and sulfate media. Results showed that, although the oxidation of pollutant is faster in the presence of chloride, the mineralization is favored in sulfate medium. Ultrasound irradiation enhanced the removal of organic matter due to the activation of oxidant species in both supporting electrolytes. Moreover, the formation of chlorine gas in the chloride containing medium improves the ultrasound cavitation effect, promoting faster depletion of the total organic carbon in the first hour of treatment. Regarding the formation of more toxic products, all possible organochlorinated intermediates were removed, since complete mineralization was attained in less than 5 hours. Ultrasonic coupling to the electrolysis process accelerates the destruction of the intermediates and delays the formation of perchlorate, which only begins after the complete removal of the total organic carbon. Low and high ultrasound frequencies were evaluated and were found to produce different effects of cavitation, which affect the electrolysis in different ways. The final result will be a balance between these effects and thus, an optimum frequency can be established for different systems.
A Dynamically Stabilized Single‐Nickel Electrocatalyst for Selective Reduction of Oxygen to Hydrogen Peroxide
Authors: Wang Tingting , Zeng Zhongming , Cao Lingyun , Li Zhe , Hu Xuefu , An Bing , Wang Cheng , Lin Wenbin
Published: October 2018

On‐location electrochemical generation of H2O2 is of great current interest. Herein, selective two‐electron reduction of O2 to H2O2 by a single [NiII(H2O)6]2+ cation that is dynamically associated with a negatively charged metal–organic layer (MOL) by hydrogen bonding and coulombic interactions is reported. In contrast, NiII centers covalently immobilized on the MOL reduce O2 to H2O in a four‐ electron process. Oxygen adsorption by [NiII(H2O)6]2+ followed by two‐electron reduction generates neutral [NiII(H2O)4(OH)(OOH)]0, which momentarily disconnects from the negatively charged MOL to avoid the injection of additional electrons. Release of H2O2 from [NiII(H2O)4(OH)(OOH)]0 regenerates [NiII(H2O)6]2+, which regains affinity to the MOL. Such dynamically associated NiII single‐metal electrocatalysts ensure high selectivity and represent a new strategy for generating selective catalysts for electrochemical production of important chemicals.
Tuning the Photophysical Properties of Symmetric Squarylium Dyes: Investigation on the Halogen Modulation Effects
Authors: Chen Weiben , Zhang Simeng , Dai Gaole , Chen Ying , Li Miao , Zhao Xiaoyu , Chen Yulan , Chen Long
Published: October 2018

A series of symmetric squarylium dyes (SQDPA‐X) with different halogen (X=F, Cl, Br, I) substituents have been developed. The photophysical properties could be facilely tuned by the halogen modulation effects. The strategy of incorporating different halogen substitutions into AIE active luminogens enables a facile approach for exploring new intriguing organic fluorescent dyes.
12/10‐Helix in Mixed β‐Peptides Alternating Bicyclic and Acyclic β‐Amino Acids: Probing the Relationship between Bicyclic Side Chain and Helix Stability
Authors: Simon Matthieu , Milbeo Pierre , Liu Hongtao , André Christophe , Wenger Emmanuel , Martinez Jean , Amblard Muriel , Aubert Emmanuel , Legrand Baptiste , Calmès Monique
Published: October 2018

12/10‐Helices constitute suitable templates that can be used to design original structures. Nevertheless, they often suffer from a weak stability in polar solvents because they exhibit a mixed hydrogen‐bond network resulting in a small macrodipole. In this work, stable and functionalizable 12/10‐helices were developed by alternating a highly constrained β2, 3, 3‐trisubstituted bicyclic amino acid (S)‐1‐aminobicyclo[2.2.2]octane‐2‐carboxylic acid ((S)‐ABOC) and an acyclic substituted β‐homologated proteinogenic amino acid (l‐β3‐hAA). Based on NMR spectroscopic analysis, it was shown that such mixed β‐peptides display well‐defined right‐handed 12/10‐helices in polar, apolar, and chaotropic solvents; that are, CD3OH, CDCl3, and [D6]DMSO, respectively. The stability of the hydrogen bonds forming the C10 and C12 pseudocycles as well as the benefit provided by the use of the constrained bicyclic ABOC versus typical acyclic β‐amino acids sequences when designing 12/10‐helix were investigated using NH/ND NMR exchange experiments and DFT calculations in various solvents. These studies showed that the β3‐hAA/(S)‐ABOC helix displayed a more stable hydrogen‐bond network through specific stabilization of the C10 pseudocycles involving the bridgehead NH of the ABOC bicyclic scaffold.
Three‐Stage Aromaticity Switching in Boron(III) and Phosphorus(V) N‐Fused p‐Benziporphyrin
Authors: Idec Aneta , Pawlicki Miłosz , Latos‐Grażyński Lechosław
Published: October 2018

Insertion of PCl3 or PhBCl2 into 5,10,15,20‐tetraaryl‐p‐benziporphyrin prompted an intramolecular fusion affording anti‐aromatic phosphorus(V) and non‐aromatic boron(III) complexes of two N‐fused dihydro‐p‐benziporphyrin isomers. These macrocycles are classified as carbatriphyrin due to the common [CNN] coordination. A sequence of direct transformations, triggered by protonation or two‐electron redox processes, afforded a set of three mutually convertible N‐fused p‐benziporphyrinoids, with distinct anti‐aromatic, non‐aromatic, and aromatic spectroscopic features.
Disaccharide‐Based Anionic Amphiphiles as Potent Inhibitors of Lipopolysaccharide‐Induced Inflammation
Authors: Borio Alessio , Holgado Aurora , Garate Jose Antonio , Beyaert Rudi , Heine Holger , Zamyatina Alla
Published: October 2018

Despite significant advances made in the last decade in the understanding of molecular mechanisms of sepsis and in the development of clinically relevant therapies, sepsis remains the leading cause of mortality in intensive care units with increasing incidence worldwide. Toll‐like receptor 4 (TLR4)—a transmembrane pattern‐recognition receptor responsible for propagating the immediate immune response to Gram‐negative bacterial infection—plays a central role in the pathogenesis of sepsis and chronic inflammation‐related disorders. TLR4 is complexed with the lipopolysaccharide (LPS)‐sensing protein myeloid differentiation‐2 (MD‐2) which represents a preferred target for establishing new anti‐inflammatory treatment strategies. Herein we report the development, facile synthesis, and biological evaluation of novel disaccharide‐based TLR4⋅MD‐2 antagonists with potent anti‐endotoxic activity at micromolar concentrations. A series of synthetic anionic glycolipids entailing amide‐linked β‐ketoacyl lipid residues was prepared in a straightforward manner by using a single orthogonally protected nonreducing diglucosamine scaffold. Suppression of the LPS‐induced release of interleukin‐6 and tumor necrosis factor was monitored and confirmed in human immune cells (MNC and THP1) and mouse macrophages. Structure–activity relationship studies and molecular dynamics simulations revealed the structural basis for the high‐affinity interaction between anionic glycolipids and MD‐2, and highlighted two compounds as leads for the development of potential anti‐inflammatory therapeutics.
Effect of PIN diode nonlinearity on decoupler circuits in magnetic resonance imaging surface coils
Authors: Ganti Aasrith , Ortiz Timothy , Wynn Tracy A. , Lin Jenshan , Duensing Randy
Published: October 2018

Decoupler circuits are the primary circuits used to maintain safety and image quality in switching magnetic resonance imaging (MRI) surface coils. Decoupler circuits predominantly employ PIN diodes as a switch and their performance is most commonly calculated on the bench at DC and low power RF conditions. The effects of high‐power RF on PIN diode decoupler circuits are not usually measured. Experiments at high RF power levels reveal a decrease in the impedance of a typical decoupler as the PIN diode operates in the nonlinear region, effectively increasing the ON‐resistance of the PIN diode. The constraints that dictate the start of nonlinearities are studied, and ways to control these nonlinearities are presented. Furthermore, this work is used as a basis to extend and improve upon previous work that established figure of merit (FOM) for PIN diode decouplers. This study is a comprehensive guide for MRI coil designers who face the task of designing decoupler circuits for surface coils and are looking for tools to accurately estimate the dynamic impedance of the circuit over the course of an MRI sequence.
Renal cell carcinoma and pathologic nodal disease: Implications for American Joint Committee on Cancer staging
Authors: Yu Kai‐Jie , Keskin Sarp K. , Meissner Matthew A. , Petros Firas G. , Wang Xuemei , Borregales Leonardo D. , Gu Cindy , Tamboli Pheroze , Matin Surena F. , Wood Christopher G. , Karam Jose A.
Published: October 2018

Background

Lymph node (LN) metastases are associated with poor outcomes for patients with renal cell carcinoma (RCC). This study compared the survival outcomes of patients with stage III, node‐positive disease (pT123N1M0) and patients with stage III, node‐negative disease (pT3N0M0).

Methods

A database of 4652 patients with RCC of any histological subtype treated with surgery at The University of Texas MD Anderson Cancer Center from 1993 to 2012 was retrospectively assessed. A total of 115 patients with pT123N1M0 disease, 274 patients with pT3N0M0 disease, and 523 patients with pT123N0/xM1 disease were included. Overall survival (OS) and cancer‐specific survival (CSS) were estimated and compared between each cohort.

Results

Median OS and CSS times were significantly better for pT3N0M0 patients than pT123N1M0 patients (OS, 10.2 vs 2.4 years, P < .0001; CSS, not reached vs 2.8 years, P < .0001). Similar median OS and CSS times were noted for pT123N1M0 and pT123N0/xM1 patients (OS, 2.4 vs 2.4 years; P = .62; CSS, 2.8 vs 2.4 years; P = .10). In a multivariate analysis, tumor grade (hazard ratio [HR] for OS, 2.47; P < .0001; HR for CSS, 2.99; P < .0001) and pathologic LN involvement (HR for OS, 2.44; P < .0001; HR for CSS, 2.85; P < .0001) were associated with worse OS and CSS.

Conclusions

Among RCC patients classified with stage III disease, those with pT123N1M0 disease had significantly worse survival than those with pT3N0M0 disease. OS and CSS were similar for patients with pT123N1M0 disease and patients with pT123N0/xM1 disease (stage IV). If validated, these findings suggest that RCC patients with nodal disease should be reclassified as having stage IV disease.
Analyzing Integrin‐Dependent Adhesion
Authors: Mould A. Paul
Published: October 2018

In this unit, methods for the analysis of integrin‐dependent adhesion are described. Two major types of assays are commonly used for this analysis. The first are cell adhesion assays. A key application of this type of assay is to identify which integrin(s) mediate cell‐substrate interactions; a comprehensive list of antibodies suitable for this purpose is detailed. The second are solid‐phase assays in which purified integrins and integrin ligands are used. These assays can be used, e.g., to measure apparent affinities of integrins for different ligands and IC50 values of pharmacological inhibitors. Curr. Protoc. Cell Biol. 53:9.4.1‐9.4.17. © 2018 by John Wiley & Sons, Inc.
Cognitive decision engine based on binary particles swarm optimization with non‐linear decreasing inertia weight
Authors: Shi Chengzhuo , Dou Zheng , Sangaiah Arun Kumar , Wang Jin
Published: October 2018

In this paper, a multi‐carrier cognitive decision engine based on a binary particle swarm optimization with a non‐linear decreasing inertia‐weight (NDI‐BPSO) is presented. Our main goal is to solve the optimization problem of transmitter parameters in different wireless communication modes for cognitive radio systems (CRSs), especially for the transmitter in communication systems based on the environment sensing. In the new algorithm, the multi‐carrier cognitive decision engine based on an NDI‐BPSO algorithm can mitigate the local extreme points effectively and reduce the oscillation phenomenon in the process of optimization. We apply the NDI‐BPSO to the cognitive orthogonal frequency division multiplexing (OFDM) system to determine the best parameters to obtain good performances in different communication modes. The simulation results show that the proposed multi‐objective cognitive decision engine, which has a high fitness value and strong robustness for different communication modes, is better than the existing engines. The novel NDI‐BPSO algorithm achieves the objective of parameter optimization effectively.
A methodology for cost‐benefit analysis of information security technologies
Authors: Zeng Wen
Published: October 2018

Although information security technologies (such as digital rights management products) have been proven effective and successful in protecting the confidentiality of sensitive information by providing access control, these technologies have not been widely adopted and used to their potential. One reason for this could be that cost and benefit of these products have not been analyzed in a systematic and quantitative manner to date. As a result, companies do not have an established procedure to evaluate the cost and benefit of implementing these products. In this document, the benefits of implementing a digital rights management product in enterprises are quantified using stochastic Petri nets models and are compared with the security needs of a corporation and potential costs incurred by the implementation process. An evaluating procedure for implementing these products is established. This procedure has the potential to be used to improve the ability of a corporation to make sensible security investment decisions.
Oxacycle‐Fused [1]Benzothieno[3,2‐b][1]benzothiophene Derivatives: Synthesis, Electronic Structure, Electrochemical Properties, Ionisation Potential, and Crystal Structure
Authors: Mohankumar Meera , Chattopadhyay Basab , Hadji Rachid , Sanguinet Lionel , Kennedy Alan R. , Lemaur Vincent , Cornil Jérôme , Fenwick Oliver , Samorì Paolo , Geerts Yves
Published: October 2018

The molecular properties of [1]benzothieno[3,2‐b][1]benzothiophene (BTBT) are vulnerable to structural modifications, which in turn are determined by the functionalization of the backbone. Hence versatile synthetic strategies are needed to discover the properties of this molecule. To address this, we have attempted heteroatom (oxygen) functionalization of BTBT by a concise and easily scalable synthesis. Fourfold hydroxy‐substituted BTBT is the key intermediate, from which the compounds 2,3,7,8‐bis(ethylenedioxy)‐[1]benzothieno[3,2‐b][1]benzothiophene and 2,3,7,8‐bis(methylenedioxy)‐[1]benzothieno[3,2‐b][1]benzothiophene are synthesized. The difference in ether functionalities on the BTBT scaffold influences the ionisation potential values substantially. The crystal structure reveals the transformation of the herringbone motif in bare BTBT towards π‐stacked columns in the newly synthesized derivatives. The results are further justified by the simulated HOMO levels of the model compound.
Thermal Conversion of MOF@MOF: Synthesis of an N‐Doped Carbon Material with Excellent ORR Performance
Authors: Zhang Mengxin , Wu Dan , Ye Yingxiang , Wu Ling , Yao Zizhu , Ma Xiuling , Wang Lihua , Zhang Zhangjing , Xiang Shengchang
Published: October 2018

Here we propose a new strategy in which two isomorphic metal−organic frameworks (MOFs) [FJU‐40‐H (a) and FJU‐40‐NH2 (b)] are used to construct the core‐shell material MOF@MOF. This strategy based on nitrogen doping and specific surface has resulted in an N‐doped porous carbon (NPC) material in a one‐step thermal treatment in N2 atmosphere; this material displays high catalytic activity for the oxygen reduction reaction (ORR). The materials were analyzed by SEM, XPS, Raman, specific surface area, pore size distribution and electrochemical measurements. It was found that NPC derived from the core‐shell MOF@MOF can provide excellent catalytic ORR performance exceeding that of the single MOF. The onset potential is NPC‐b@a‐4h (−0.068 V)>NPC‐a@b‐4h (−0.075 V)>NPC‐a‐4h (−0.109 V)>NPC‐b‐4h (−0.113 V). Moreover, the results also show that the performance of NPC‐b@a (n=4.15) is better than that of NPC‐a@b (n=3.32), which means the different nitrogen content of ligands inside and outside of the core affects the ORR properties.
Enabling Reversible (De)Lithiation of Aluminum by using Bis(fluorosulfonyl)imide‐Based Electrolytes
Authors: Qin Bingsheng , Jeong Sangsik , Zhang Huang , Ulissi Ulderico , Vieira Carvalho Diogo , Varzi Alberto , Passerini Stefano
Published: October 2018

Aluminum, a cost‐effective and abundant metal capable of alloying with Li up to around 1000 mAh g−1, is a very appealing anode material for high energy density lithium‐ion batteries (LIBs). However, despite repeated efforts in the past three decades, reports presenting stable cycling performance are extremely rare. This study concerns recent findings on the highly reversible (de)lithiation of a micro‐sized Al anode (m‐Al) by using bis(fluorosulfonyl)imide (FSI)‐based electrolytes. By using this kind of electrolyte, m‐Al can deliver a specific capacity over 900 mAh g−1 and superior Coulombic efficiency (96.8 %) to traditional carbonate‐ and glyme‐based electrolytes (87.8 % and 88.1 %, respectively), which represents the best performance ever obtained for an Al anode without sophisticated structure design. The significantly improved electrochemical performance, which paves the way to realizing high‐performance Al‐based high energy density LIBs, can be attributed the peculiar solid–electrolyte interphase (SEI) formed by the FSI‐containing electrolyte.
Solar Photothermal Electrodes for Highly Efficient Microbial Energy Harvesting at Low Ambient Temperatures
Authors: Wang Yi , Zhou Lihua , Luo Xiaoshan , Zhang Yaping , Sun Jian , Ning Xun‐an , Yuan Yong
Published: October 2018

Temperature is an important parameter for the performance of bioelectrochemical systems (BESs). Energy‐intensive bulk water heating has been usually employed to maintain a desired temperature for the BESs. This study concerns a proof‐of‐concept of a light‐to‐heat photothermal electrode for solar heating of a local electroactive biofilm in a BES for efficient microbial energy harvesting at low temperatures as a replacement for bulk water heating approaches. The photothermal electrode was prepared by coating Ti3C2Tx MXene sunlight absorber onto carbon felt. The as‐prepared photothermal electrode could efficiently raise the local temperature of the bioelectrode to approximately 30 °C from low bulk water temperatures (i.e., 10, 15, and 20 °C) under simulated sunlight illumination. As a result, highly efficient microbial energy could be harvested from the low‐temperature BES equipped with a photothermal electrode without bulk water heating. This study represents a new avenue for the design and fabrication of electrodes for temperature‐sensitive electrochemical and biological systems.