bluuebunny/crossref_metadata_2025 huggingface dataset:
Stabilization of Single Metal Atoms on Graphitic Carbon Nitride
Authors: Chen Zupeng , Mitchell Sharon , Vorobyeva Evgeniya , Leary Rowan K. , Hauert Roland , Furnival Tom , Ramasse Quentin M. , Thomas John M. , Midgley Paul A. , Dontsova Dariya , Antonietti Markus , Pogodin Sergey , López Núria , Pérez‐Ramírez Javier
Published: January 2017

Graphitic carbon nitride (g‐C3N4) exhibits unique properties as a support for single‐atom heterogeneous catalysts (SAHCs). Understanding how the synthesis method, carrier properties, and metal identity impact the isolation of metal centers is essential to guide their design. This study compares the effectiveness of direct and postsynthetic routes to prepare SAHCs by incorporating palladium, silver, iridium, platinum, or gold in g‐C3N4 of distinct morphology (bulk, mesoporous and exfoliated). The speciation (single atoms, dimers, clusters, or nanoparticles), distribution, and oxidation state of the supported metals are characterized by multiple techniques including extensive use of aberration‐corrected electron microscopy. SAHCs are most readily attained via direct approaches applying copolymerizable metal precursors and employing high surface area carriers. In contrast, although post‐synthetic routes enable improved control over the metal loading, nanoparticle formation is more prevalent. Comparison of the carrier morphologies also points toward the involvement of defects in stabilizing single atoms. The distinct metal dispersions are rationalized by density functional theory and kinetic Monte Carlo simulations, highlighting the interplay between the adsorption energetics and diffusion kinetics. Evaluation in the continuous three‐phase semihydrogenation of 1‐hexyne identifies controlling the metal–carrier interaction and exposing the metal sites at the surface layer as key challenges in designing efficient SAHCs.
Rhodium‐Catalyzed Asymmetric Hydrogenation of Tetrasubstituted Cyclic Enamides: Efficient Access to Chiral Cycloalkylamine Derivatives
Authors: Li Xiuxiu , You Cai , Yang Hailong , Che Jinteng , Chen Pengyu , Yang Yusheng , Lv Hui , Zhang Xumu
Published: January 2017

An efficient rhodium‐catalyzed asymmetric hydrogenation of challenging tetrasubstituted cyclic enamides has been developed, affording cyclic chiral amides with high yields and excellent enantioselectivities (up to 99% yield and >99% ee). This novel methodology provides an efficient and concise synthetic route to chiral cycloalkylamines with two contiguous stereogenic centers. The potential utility of this protocol in the synthesis of bioactive molecules is also disclosed.

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Evaluating predictors of lead exposure for activities disturbing materials painted with or containing lead using historic published data from U.S. workplaces
Authors: Locke Sarah J. , Deziel Nicole C. , Koh Dong‐Hee , Graubard Barry I. , Purdue Mark P. , Friesen Melissa C.
Published: January 2017

Objectives

We evaluated predictors of differences in published occupational lead concentrations for activities disturbing material painted with or containing lead in U.S. workplaces to aid historical exposure reconstruction.

Methods

For the aforementioned tasks, 221 air and 113 blood lead summary results (1960–2010) were extracted from a previously developed database. Differences in the natural log‐transformed geometric mean (GM) for year, industry, job, and other ancillary variables were evaluated in meta‐regression models that weighted each summary result by its inverse variance and sample size.

Results

Air and blood lead GMs declined 5%/year and 6%/year, respectively, in most industries. Exposure contrast in the GMs across the nine jobs and five industries was higher based on air versus blood concentrations. For welding activities, blood lead GMs were 1.7 times higher in worst‐case versus non‐worst case scenarios.

Conclusions

Job, industry, and time‐specific exposure differences were identified; other determinants were too sparse or collinear to characterize. Am. J. Ind. Med. 60:189–197, 2017. © 2017 Wiley Periodicals, Inc.
Olefin Insertion into a Pd–F Bond: Catalyst Reactivation Following β‐F Elimination in Ethylene/Vinyl Fluoride Copolymerization
Authors: Wada Shinji , Jordan Richard F.
Published: January 2017

The discrete (phosphinoarenesulfonate)Pd fluoride complex (POBp,OMe)PdF(lutidine), where POBp,OMe=(2‐MeOC6H4)(2‐{2,6‐(MeO)2C6H3}C6H4)(2‐SO3‐5‐MeC6H3)P, inserts vinyl fluoride (VF) to form (POBp,OMe)PdCH2CHF2(lutidine) and inserts multiple ethylene (E) units to generate polyethylene that contains −CH2F chain ends. These results provide strong evidence that the −CHF2 and −CH2F chain ends in E/VF copolymer generated by (phosphinoarenesulfonate)PdR catalysts form by β‐F elimination of Pd(β‐F‐alkyl) species, VF or E insertion of the resulting (PO)PdF species, and subsequent chain growth. These results also imply that β‐F elimination is not an important catalyst deactivation reaction in this system.
An Exonuclease III‐Powered, On‐Particle Stochastic DNA Walker
Authors: Qu Xiangmeng , Zhu Dan , Yao Guangbao , Su Shao , Chao Jie , Liu Huajie , Zuo Xiaolei , Wang Lihua , Shi Jiye , Wang Lianhui , Huang Wei , Pei Hao , Fan Chunhai
Published: January 2017

DNA‐based machines have attracted rapidly growing interest owing to their potential in drug delivery, biocomputing, and diagnostic applications. Herein, we report a type of exonuclease III (Exo III)‐powered stochastic DNA walker that can autonomously move on a spherical nucleic acid (SNA)‐based 3D track. The motion is propelled by unidirectional Exo III digestion of hybridized DNA tracks in a burnt‐bridge mechanism. The operation of this Exo III‐propelled DNA walker was monitored in real time and at the single‐particle resolution using total internal reflection fluorescence microscopy (TIRF). We further interrogated the morphological effect of the 3D track on the nuclease activity, which suggested that the performance of the DNA walker was critically dependent upon the DNA density and the track conformation. Finally, we demonstrated potential bioanalytical applications of this SNA‐based stochastic DNA walker by exploiting movement‐triggered cascade signal amplification.
Kohlenstoff‐Kohlenstoff‐Bindungsbildung in einem schwachen Ligandenfeld: Nutzung von Open‐Shell‐Übergangsmetallkatalysatoren der ersten Übergangsperiode
Authors: Chirik Paul J.
Published: January 2017

Übergangsmetallkatalysatoren auf Basis der reichlich vorhandenen Metalle der ersten Übergangsperiode zeigen herausragende Eigenschaften in C‐C‐Bindungsbildungsreaktionen. So stellen Eisen‐ und Cobaltdihalogenid‐Komplexe von Aryl‐substituierten Bis(imino)pyridinen, die durch Alkylaluminiumreagentien aktiviert werden, hochaktive Katalysatoren für die Polymerisation von Ethylen dar. Eisen‐ und Cobalt‐Alkylkomplexe mit offener Koordinationsschale (Open‐Shell‐Komplexe) wurden synthetisiert, die als Einzelkomponenten‐Katalysatoren für die Olefin‐Polymerisation agieren. Ebenso wurden reduzierte Eisen‐ und Cobalt‐Distickstoff‐Komplexe mit Bis(imino)pyridin‐Liganden gefunden, die eine einzigartige [2+2]‐Cycloaddition unaktivierter terminaler Alkene herbeiführen. Untersuchungen der Elektronenstruktur weisen auf Open‐Shell‐Intermediate hin, die sich von den herkömmlichen metallorganischen Starkfeld‐Komplexen, die bisher als Katalysatoren für C‐C‐Bindungsbildungen verwendet wurden, deutlich abgrenzen.
Au/La2Ti2O7 Nanostructures Sensitized with Black Phosphorus for Plasmon‐Enhanced Photocatalytic Hydrogen Production in Visible and Near‐Infrared Light
Authors: Zhu Mingshan , Cai Xiaoyan , Fujitsuka Mamoru , Zhang Junying , Majima Tetsuro
Published: January 2017

Efficient utilization of solar energy is a high‐priority target and the search for suitable materials as photocatalysts that not only can harvest the broad wavelength of solar light, from UV to near‐infrared (NIR) region, but also can achieve high and efficient solar‐to‐hydrogen conversion is one of the most challenging missions. Herein, using Au/La2Ti2O7 (BP‐Au/LTO) sensitized with black phosphorus (BP), a broadband solar response photocatalyst was designed and used as efficient photocatalyst for H2 production. The optimum H2 production rates of BP‐Au/LTO were about 0.74 and 0.30 mmol g−1 h−1 at wavelengths longer than 420 nm and 780 nm, respectively. The broad absorption of BP and plasmonic Au contribute to the enhanced photocatalytic activity in the visible and NIR light regions. Time‐resolved diffuse reflectance spectroscopy revealed efficient interfacial electron transfer from excited BP and Au to LTO which is in accordance with the observed high photoactivities.
Molecular Polygons Probe the Role of Intramolecular Strain in the Photophysics of π‐Conjugated Chromophores
Authors: Wilhelm Philipp , Vogelsang Jan , Poluektov Georgiy , Schönfelder Nina , Keller Tristan J. , Jester Stefan‐Sven , Höger Sigurd , Lupton John M.
Published: January 2017

π‐Conjugated segments, chromophores, are the electronically active units of polymer materials used in organic electronics. To elucidate the effect of the bending of these linear moieties on elementary electronic properties, such as luminescence color and radiative rate, we introduce a series of molecular polygons. The π‐system in these molecules becomes so distorted in bichromophores (digons) that these absorb and emit light of arbitrary polarization: any part of the chain absorbs and emits radiation with equal probability. Bending leads to a cancellation of transition dipole moment (TDM), increasing excited‐state lifetime. Simultaneously, fluorescence shifts to the red as radiative transitions require mixing of the excited state with vibrational modes. However, strain can become so large that excited‐state localization on shorter units of the chain occurs, compensating TDM cancellation. The underlying correlations between shape and photophysics can only be resolved in single molecules.
An S‐Oxygenated [NiFe] Complex Modelling Sulfenate Intermediates of an O2‐Tolerant Hydrogenase
Authors: Lindenmaier Nils J. , Wahlefeld Stefan , Bill Eckhard , Szilvási Tibor , Eberle Christopher , Yao Shenglai , Hildebrandt Peter , Horch Marius , Zebger Ingo , Driess Matthias
Published: January 2017

To understand the molecular details of O2‐tolerant hydrogen cycling by a soluble NAD+‐reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S‐oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen‐inhibited [NiFe] active site. This compound and its non‐S‐oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S‐oxygenated intermediates in hydrogenases and similar enzymes.
Removal of Multiple Contaminants from Water by Polyoxometalate Supported Ionic Liquid Phases (POM‐SILPs)
Authors: Herrmann Sven , De Matteis Laura , de la Fuente Jesús M. , Mitchell Scott G. , Streb Carsten
Published: January 2017

The simultaneous removal of organic, inorganic, and microbial contaminants from water by one material offers significant advantages when fast, facile, and robust water purification is required. Herein, we present a supported ionic liquid phase (SILP) composite where each component targets a specific type of water contaminant: a polyoxometalate‐ionic liquid (POM‐IL) is immobilized on porous silica, giving the heterogeneous SILP. The water‐insoluble POM‐IL is composed of antimicrobial alkylammonium cations and lacunary polyoxometalate anions with heavy‐metal binding sites. The lipophilicity of the POM‐IL enables adsorption of organic contaminants. The silica support can bind radionuclides. Using the POM‐SILP in filtration columns enables one‐step multi‐contaminant water purification. The results show how multi‐functional POM‐SILPs can be designed for advanced purification applications.
Determining Electrochemical Surface Stress of Single Nanowires
Authors: Wang Hui , Shan Xiaonan , Yu Hui , Wang Yan , Schmickler Wolfgang , Chen Hong‐Yuan , Tao Nongjian
Published: January 2017

Electrochemical surface stress is important in nanomaterials because of their large surface‐to‐volume ratios, which lead to unique mechanical and electrocatalytic properties, but directly measuring this quantity has been challenging. Here we report on experimental determination of the surface stress, and associated electrochemical processes of a single gold nanowire with an optical imaging technique. We show that surface stress changes linearly and reversibly with the potential between 0 and 0.8 V versus Ag/AgCl, but abruptly with large hysteresis, associated with the oxidation and reduction of the nanowire, between 0.8 and 1.5 V. The potential derivative of the surface stress closely resembles the cyclic voltammograms. We described the observations in terms of anion adsorption and surface oxidation/reduction. This work demonstrates a new approach to study electrochemical processes and the associated surface stress changes of nanomaterials.
Mononuclear Clusterfullerene Single‐Molecule Magnet Containing Strained Fused‐Pentagons Stabilized by a Nearly Linear Metal Cyanide Cluster
Authors: Liu Fupin , Wang Song , Gao Cong‐Li , Deng Qingming , Zhu Xianjun , Kostanyan Aram , Westerström Rasmus , Jin Fei , Xie Su‐Yuan , Popov Alexey A. , Greber Thomas , Yang Shangfeng
Published: January 2017

Fused‐pentagons results in an increase of local steric strain according to the isolated pentagon rule (IPR), and for all reported non‐IPR clusterfullerenes multiple (two or three) metals are required to stabilize the strained fused‐pentagons, making it difficult to access the single‐atom properties. Herein, we report the syntheses and isolations of novel non‐IPR mononuclear clusterfullerenes MNC@C76 (M=Tb, Y), in which one pair of strained fused‐pentagon is stabilized by a mononuclear cluster. The molecular structures of MNC@C76 (M=Tb, Y) were determined unambiguously by single‐crystal X‐ray diffraction, featuring a non‐IPR C2v(19138)‐C76 cage entrapping a nearly linear MNC cluster, which is remarkably different from the triangular MNC cluster within the reported analogous clusterfullerenes based on IPR‐obeying C82 cages. The TbNC@C76 molecule is found to be a field‐induced single‐molecule magnet (SMM).
A 11‐Steps Total Synthesis of Magellanine through a Gold(I)‐Catalyzed Dehydro Diels–Alder Reaction
Authors: McGee Philippe , Bétournay Geneviève , Barabé Francis , Barriault Louis
Published: January 2017

We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)‐catalyzed dehydro Diels–Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this AuI‐catalyzed cycloaddition was further demonstrated by accomplishing a 11‐steps total synthesis of (±)‐magellanine.
Carbon–Carbon Bond Formation in a Weak Ligand Field: Leveraging Open‐Shell First‐Row Transition‐Metal Catalysts
Authors: Chirik Paul J.
Published: January 2017

Unique features of earth‐abundant transition‐metal catalysts are reviewed in the context of catalytic carbon–carbon bond‐forming reactions. Aryl‐substituted bis(imino)pyridine iron and cobalt dihalide compounds, when activated with alkyl aluminum reagents, form highly active catalysts for the polymerization of ethylene. Open‐shell iron and cobalt alkyl complexes have been synthesized that serve as single‐component olefin polymerization catalysts. Reduced bis(imino)pyridine iron and cobalt dinitrogen compounds have also been discovered that promote the unique [2+2] cycloaddition of unactivated terminal alkenes. Studies of the electronic structure support open‐shell intermediates, a deviation from traditional strong‐field organometallic compounds that promote catalytic C−C bond formation.
High‐temperature tensile behavior at different crosshead speeds during loading of glass fiber‐reinforced polymer composites
Authors: Mahato Kishore Kumar , Dutta Krishna , Ray Bankim Chandra
Published: January 2017

The present study evaluates on the static tensile behavior of glass fiber reinforced polymer (GFRP) composites at 50% and 70% volume fractions of reinforcement tested at room (25 °C), 70 °C, 90 °C, and 110 °C temperatures with 1, 10, 100, 500, and 1000 mm/min crosshead speeds to investigate the impact of high temperature on the mechanical properties and different dominating failures modes. The experimental results reveal that with increase in crosshead speeds the tensile strength of the composite is increasing. The effect of crosshead speeds and temperature with changing fiber volume fractions affects the GFRP composite. Although both the composite systems are found to be crosshead speed sensitive. Crosshead speed sensitivity seems to be more unpredictable at high temperature and at high crosshead speed. Furthermore, it appears to be more unprecedented nature of fluctuation with high fiber volume fraction. The crucial parameters required during the materials designing in various structural components were evaluated and modelled with the help of Weibull constitutive model. The fractography analyses were done to identify the various dominating failure modes in the GFRP composite. There was no significant change found in the glass transition temperatures (Tg) of both the composite system when exposed to different temperature environments. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44715.
Silver‐ and gold‐labeled colloidal and crosslinked glycopolymers based on glycyl glycosynthons and maleic anhydride copolymers for lectin binding
Authors: Samoilova Nadezhda A. , Krayukhina Maria A. , Babushkina Tatyana A. , Yamskov Igor A. , Likhosherstov Leonid M. , Piskarev Vladimir E.
Published: January 2017

A simple, convenient, and inexpensive technique for preparing lectin‐specific nanogold‐ and silver‐labeled colloidal and crosslinked neoglycoconjugates, based on maleic anhydride copolymers, was developed. Water‐soluble nanogold‐ and silver‐labeled glyconanoparticles were obtained in two steps: (1) introduction of free N‐acetyl‐D‐glucosamine or glycyl‐spacered glycosynthons—β‐N‐glycyl‐N‐acetyl‐D‐glucosamine or β‐N‐glycyl‐lactose—into poly(ethylene‐alt‐maleic anhydride) or poly(N‐vinylpyrrolidone‐alt‐maleic anhydride) and (2) labeling in situ the thus‐obtained glycopolymers with gold or silver nanoparticles. Lectin sorbents were synthesized from glycyl‐spacered glycosynthons and spherical, granulated, crosslinked maleic anhydride copolymers in an aqueous system without any condensing agents. Thus, maleic anhydride copolymer was used solely, without any preliminary modification of the polymer, as a matrix for crosslinking, for specific ligand binding, and as metal nanoparticles as a stabilizing cover. The resulting colloidal gold or silver glyconanoparticles were used as lectin sensors (in a dot‐blot analysis of lectins) and as crosslinked neoglycoconjugates for lectin sorption studies. The corresponding gold‐ or silver‐labeled water‐soluble glyconanoparticles and crosslinked neoglycoconjugates manifested high activity and specificity in all tests with a series of β‐D‐GlcNAc‐specific and β‐D‐Gal‐specific lectins. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44718.
Influence of precursor film microstructure on properties of HDPE microporous membranes prepared by stretching
Authors: Yadegari Ali , Morshedian Jalil , Khonakdar Hossein‐Ali , Wagenknecht Udo , Heinrich Gert
Published: January 2017

Oriented HDPE films having a stacked lamellar morphology were prepared to develop microporous membranes through cast film extrusion followed by stretching. Applying higher draw ratios (DR) and annealing the cast films improved crystal alignments remarkably. It was shown the improvement in c‐axis orientation upon annealing was more significant for the films prepared with lower DR. Furthermore, applying Raman spectroscopy, the amorphous mass fraction of the films was obtained. Subsequently, considering a three‐phase structure (i.e., crystal, amorphous and interphase), the interphase content of the films was also determined. A distinct DR dependence of the interphase content was noticed. It was observed that in addition to crystal perfection upon annealing, the amorphous phase fraction was also decreased due to possibly increase in free volume, promoting lamellar separation and cavitation during the subsequent stretching step. SEM images of the membranes surfaces as well as their normalized water vapor transmission rate (WVTR) values indicated a more uniform pore formation and increased permeability with DR. Furthermore, it was found that lower interphase content in the films with higher DR favors lamellar separation. However, permeability in the stretched precursor films with DR higher than a certain level (DR = 93) was not improved significantly. Moreover, crystallinity and crystal orientation of produced membranes were investigated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44725.
A Dual Role of Upper Zone of Growth Plate and Cartilage Matrix–Associated Protein in Human and Mouse Osteoarthritic Cartilage: Inhibition of Aggrecanases and Promotion of Bone Turnover
Authors: Stock Michael , Menges Stefanie , Eitzinger Nicole , Geßlein Maria , Botschner Renate , Wormser Laura , Distler Alfiya , Schlötzer‐Schrehardt Ursula , Dietel Katharina , Distler Jörg , Beyer Christian , Gelse Kolja , Engelke Klaus , Koenders Marije I. , van den Berg Wim , von der Mark Klaus , Schett Georg
Published: January 2017

Objective

Cartilage damage and subchondral bone changes are closely connected in osteoarthritis. Nevertheless, how these processes are interlinked is, to date, incompletely understood. This study was undertaken to investigate the mechanistic role of a cartilage‐derived protein, upper zone of growth plate and cartilage matrix–associated protein (UCMA), in osteoarthritis‐related cartilage and bone changes.

Methods

UCMA expression was assessed in healthy and osteoarthritic human and mouse cartilage. For analysis of cartilage and bone changes, osteoarthritis was induced by destabilization of the medial meniscus (DMM) in wild‐type (WT) and Ucma‐deficient mice. UCMA–collagen interactions, the effect of UCMA on aggrecanase activity, and the impact of recombinant UCMA on osteoclast differentiation were studied in vitro.

Results

UCMA was found to be overexpressed in human and mouse osteoarthritic cartilage. DMM‐triggered cartilage changes, including increased structural damage, proteoglycan loss, and chondrocyte cell death, were aggravated in Ucma‐deficient mice compared to WT littermates, thereby demonstrating the potential chondroprotective effects of UCMA. Moreover, UCMA inhibited ADAMTS‐dependent aggrecanase activity and directly interacted with cartilage‐specific collagen types. In contrast, osteoarthritis‐related bone changes were significantly reduced in Ucma‐deficient mice, showing less pronounced osteophyte formation and subchondral bone sclerosis. Mechanistically, UCMA directly promoted osteoclast differentiation in vitro.

Conclusion

UCMA appears to link cartilage with bone changes in osteoarthritis by supporting cartilage integrity as an endogenous inhibitor of aggrecanases while also promoting osteoclastogenesis and subchondral bone turnover. Thus, UCMA represents an important link between cartilage and bone in osteoarthritis.
Immune‐Array Analysis in Sporadic Inclusion Body Myositis Reveals HLA–DRB1 Amino Acid Heterogeneity Across the Myositis Spectrum
Authors: Rothwell Simon , Cooper Robert G. , Lundberg Ingrid E. , Gregersen Peter K. , Hanna Michael G. , Machado Pedro M. , Herbert Megan K. , Pruijn Ger J. M. , Lilleker James B. , Roberts Mark , Bowes John , Seldin Michael F. , Vencovsky Jiri , Danko Katalin , Limaye Vidya , Selva‐O'Callaghan Albert , Platt Hazel , Molberg Øyvind , Benveniste Olivier , Radstake Timothy R. D. J. , Doria Andrea , De Bleecker Jan , De Paepe Boel , Gieger Christian , Meitinger Thomas , Winkelmann Juliane , Amos Christopher I. , Ollier William E. , Padyukov Leonid , Lee Annette T. , Lamb Janine A. , Chinoy Hector ,   for the Myositis Genetics Consortium
Published: January 2017

Objective

Inclusion body myositis (IBM) is characterized by a combination of inflammatory and degenerative changes affecting muscle. While the primary cause of IBM is unknown, genetic factors may influence disease susceptibility. To determine genetic factors contributing to the etiology of IBM, we conducted the largest genetic association study of the disease to date, investigating immune‐related genes using the Immunochip.

Methods

A total of 252 Caucasian patients with IBM were recruited from 11 countries through the Myositis Genetics Consortium and compared with 1,008 ethnically matched controls. Classic HLA alleles and amino acids were imputed using SNP2HLA.

Results

The HLA region was confirmed as the most strongly associated region in IBM (P = 3.58 × 10−33). HLA imputation identified 3 independent associations (with HLA–DRB1*03:01, DRB1*01:01, and DRB1*13:01), although the strongest association was with amino acid positions 26 and 11 of the HLA–DRB1 molecule. No association with anti–cytosolic 5′‐nucleotidase 1A–positive status was found independent of HLA–DRB1*03:01. There was no association of HLA genotypes with age at onset of IBM. Three non‐HLA regions reached suggestive significance, including the chromosome 3 p21.31 region, an established risk locus for autoimmune disease, where a frameshift mutation in CCR5 is thought to be the causal variant.

Conclusion

This is the largest, most comprehensive genetic association study to date in IBM. The data confirm that HLA is the most strongly associated region and identifies novel amino acid associations that may explain the risk in this locus. These amino acid associations differentiate IBM from polymyositis and dermatomyositis and may determine properties of the peptide‐binding groove, allowing it to preferentially bind autoantigenic peptides. A novel suggestive association within the chromosome 3 p21.31 region suggests a role for CCR5.
Cocatalyst‐Free Hybrid Ionic Liquid (IL)‐Based Porous Materials for Efficient Synthesis of Cyclic Carbonates through a Cooperative Activation Pathway
Authors: Jayakumar Sanjeevi , Li He , Zhao Yaopeng , Chen Jian , Yang Qihua
Published: January 2017

Cocatalyst‐free ionic liquid (IL)‐based porous polymers (Px‐Vy‐OHzR) functionalized with an intermolecular hydroxyl group were prepared by means of radical copolymerization of 1‐butyl‐3‐vinylimidazolium bromide, (4‐vinylphenyl)methanol (VBzOH), and divinylbenzene (DVB) under solvothermal conditions. As the ratio of 4‐vinylphenylmethanol in the initial mixture increased, the content of the hydroxyl groups in the polymer increased from 3.35 to 5.35 mmol g−1 and the Brunauer–Emmett–Teller (BET) surface area of the polymer decreased sharply from 365 to 2.5 m2 g−1. In the carbonation of CO2 and epoxides, the turnover frequency (TOF) of Px‐Vy‐OHzR increased gradually from 25 to 67 h−1 as the OH ratio increased irrespective of the sharp decrease in BET surface area, which suggests the existence of a cooperative activation effect between OH and ILs. To obtain a high OH content while still maintaining a high BET surface area, hybrid porous materials (SBA‐[VxOHy]R‐n) were prepared by means of copolymerization of 1‐ethyl‐3‐vinylimidazolium bromide and 4‐vinylphenylmethanol in the mesopores of SBA‐15. SBA‐[VxOHy]R‐n was more active than its polymer counterpart (TOF: 188 versus 71 h−1) in the cycloaddition of CO2 with propyl oxide owing to the combined effect of the high BET surface area and the high OH content. The hybridization of mesoporous materials with polymers represents an efficient strategy for the preparation of high‐performance solid catalysts for chemical transformations.
A General Strategy to Enhance the Performance of Dye‐Sensitized Solar Cells by Incorporating a Light‐Harvesting Dye with a Hydrophobic Polydiacetylene Electrolyte‐Blocking Layer
Authors: Desta Mekonnen Abebayehu , Liao Chia‐Wei , Sun Shih‐Sheng
Published: January 2017

A unique strategy to suppress charge recombination effectively and enhance light harvesting in dye‐sensitized solar cells (DSSCs) is demonstrated by the design of a new dipolar organic dye functionalized with a diacetylene unit, which is capable of undergoing a photoinduced crosslinking reaction to generate a hydrophobic polydiacetylene layer. The polydiacetylene layer serves as an electrolyte‐blocking layer that effectively blocks the approach of the oxidized redox mediator and suppresses the dark current, and also plays a role in light harvesting owing to efficient energy transfer to the dipolar dyes. A 15 % efficiency improvement was achieved on going from the monomer dye (JSC=13.5 mA cm−2, Voc=0.728 V, fill factor=0.73, η=7.17 %) to the crosslinked dye (JSC=14.9 mA cm−2, Voc=0.750 V, fill factor=0.74, η=8.27 %) under AM 1.5 conditions.
Nachweis der Ankertragfähigkeit auf Grundlage faseroptischer Messtechnik
Authors: Kindler Arne , Schaller Maria‐Barbara , Glötzl Jürgen
Published: January 2017

Die heute gängigen Dauerüberwachungen (Ankermonitoring) von Ankern basieren überwiegend auf dem Einsatz von Ankerkraftmessdosen. Die Erfahrungen der letzten Jahrzehnte haben jedoch gezeigt, dass die Zuverlässigkeit der Anzeige über die Zeit verloren geht. Darüber hinaus bedingt der Einsatz von Ankerkraftmessdosen eine zusätzliche Bauhöhe am Ankerkopf. Andere Mess‐ und Prüfverfahren wie z. B. die herkömmlichen Lichtwellenleitersensoren bedingen einen Abgleich mit einem unbelasteten Lichtwellenleiter und geben nur punktuelle Aussagen über das Tragverhalten wieder. Weiterhin kommt hinzu, dass die gewonnenen Aussagen interpretiert werden müssen, um den Zustand der Verankerung beurteilen zu können. Im folgenden Beitrag wird über erste Ergebnisse eines Ankermonitorings auf der Basis von ortsverteilten Messungen einer in den Verpresskörper eingebetteten Glasfaser berichtet. Das neue Messkonzept basiert auf der Rayleigh‐Technologie und dient der Prüfung des Tragverhaltens des Ankers sowie der Prüfung des Verpresskörperzustands bei betonschädigenden Grundwässern. Aufgrund der Wirtschaftlichkeit der eingesetzten Glasfaser ist die Ausbildung von redundanten Messsystemen nicht mit hohen Kosten verbunden. Hinsichtlich der Langlebigkeit der Glasfasern kann auf Erfahrungen aus der Telekommunikation zurückgegriffen werden.
Acetylated tau in Alzheimer's disease: An instigator of synaptic dysfunction underlying memory loss
Authors: Tracy Tara E. , Gan Li
Published: January 2017

Pathogenesis in tauopathies involves the accumulation of tau in the brain and progressive synapse loss accompanied by cognitive decline. Pathological tau is found at synapses, and it promotes synaptic dysfunction and memory deficits. The specific role of toxic tau in disrupting the molecular networks that regulate synaptic strength has been elusive. A novel mechanistic link between tau toxicity and synaptic plasticity involves the acetylation of two lysines on tau, K274, and K281, which are associated with dementia in Alzheimer's disease (AD). We propose that an increase in tau acetylated on these lysines blocks the expression of long‐term potentiation at hippocampal synapses leading to impaired memory in AD. Acetylated tau could inhibit the activity‐dependent recruitment of postsynaptic AMPA‐type glutamate receptors required for plasticity by interfering with the postsynaptic localization of KIBRA, a memory‐associated protein. Strategies that reduce the acetylation of tau may lead to effective treatments for cognitive decline in AD.
The Discovery of Novel Protein Tyrosine Phosphatase ε Inhibitors Using a High‐throughput Screening Approach
Authors: Yun Hye‐Yeoung , Ku Bonsu , Lee Hye Seon , Shin Ho‐Chul , Park Jun‐Beom , Kim Chang Hyen , Kim Seung Jun
Published: January 2017

Protein tyrosine phosphatase epsilon (PTPε) is important for signal transduction in osteoclasts, and is considered to be an attractive drug target for the treatment of osteoporosis. We identified 11 potent PTPε inhibitors based on three chemical scaffolds through the high‐throughput screening of a chemical library. As these compounds are structurally diverse with high bioavailability, they warrant further investigation in the near future. The discovery of these inhibitors and the relationship between their structure and inhibitory activity toward PTPε is discussed in detail.
Docking‐based In Silico Screening for Identification of Micromolar Inhibitors of Tropomyosin‐related Kinase A from Natural Origin
Authors: Kim Daehyun , Park Jung Youl , Kim Ji‐Hyun
Published: January 2017

Tropomyosin‐related kinase A (TrkA) serves as a promising target protein for the development of anticancer medicines. We report new TrkA inhibitors of natural origin identified from the structure‐based virtual and biochemical screening. A proper molecular hydration term was implemented into the original free energy function to perform virtual screening with an improved accuracy. As a consequence, four natural TrkA inhibitors were found with IC50
values ranging from 3 to 70 μM. The good biochemical efficacies and structural simplicities of these new inhibitors signifies that they deserve to be further studied for optimization of the anticancer activity through the structure–activity relationship analysis. The detailed analysis of binding modes indicates that the micromolar biochemical efficacy of the new inhibitors could be achieved by the simultaneous establishment of multiple hydrogen bonds and hydrophobic interactions in the ATP‐binding site of TrkA.
Associations between pathologic tumor features and preadjuvant therapy cognitive performance in women diagnosed with breast cancer
Authors: Koleck Theresa A. , Bender Catherine M. , Sereika Susan M. , Ryan Christopher M. , Ghotkar Puja , Brufsky Adam M. , Jankowitz Rachel C. , McAuliffe Priscilla F. , Clark Beth Z. , Conley Yvette P.
Published: January 2017

Intertumor heterogeneity has been proposed as a potential mechanism to account for variability in cognitive performance in women diagnosed with breast cancer. The purpose of this study was to explore associations between variation in pathologic tumor features (PTFs) and variability in preadjuvant therapy cognitive performance in postmenopausal women newly diagnosed with early‐stage breast cancer. Participants (N = 329) completed a comprehensive battery of neuropsychological tests to evaluate cognitive performance after primary surgery but prior to initiation of adjuvant anastrozole±chemotherapy. PTF data were abstracted from medical records. Robust multiple linear regression models were fit to estimate associations between individual PTFs and the cognitive function composite domain scores. All models controlled for age, estimated intelligence, and levels of depressive symptoms, anxiety, fatigue, and pain. Diagnosis of a HER2‐positive tumor contributed to poorer verbal (b = −0.287, P = 0.018), visual (b = −0.270, P = 0.001), and visual working (b = −0.490, P < 0.001) memory performance compared to diagnosis of a HER2‐negative tumor. Similarly, as HER2 immunohistochemistry classification score increased, verbal (b = −0.072, P = 0.093), visual (b = −0.081, P = 0.003), and visual working (b = −0.170, P < 0.001) memory performance score decreased. Associations with performance were also noted between location, focality/centricity, hormone receptor expression, cellular proliferation (i.e., Ki67), and Oncotype DX® Breast Cancer Assay Recurrence Score®.) Our results suggest that certain PTFs related to more aggressive tumor phenotypes or inferior breast cancer prognosis may be implicated in poorer preadjuvant therapy cognitive performance. Follow‐up studies that include a cognitive assessment before primary surgery should be conducted to further delineate the role of intertumor heterogeneity on cognitive performance.
BEX3 contributes to cisplatin chemoresistance in nasopharyngeal carcinoma
Authors: Gao Wei , Li John Zeng‐Hong , Chen Si‐Qi , Chu Chiao‐Yun , Chan Jimmy Yu‐Wai , Wong Thian‐Sze
Published: January 2017

Nasopharyngeal carcinoma (NPC) can develop cisplatin‐resistant phenotype. Research has revealed that enriched in cancer stem cell population is involved in developing cisplatin‐resistant phenotype. CD271 is a candidate stem cell maker in head and neck cancers. The CD receptor does not possess any enzymatic property. Signal transduction function of CD271 is mediated by the cellular receptor‐associated protein. Our data showed that Brain‐expressed X‐linked 3 (BEX3), a CD271 receptor‐associated protein, was overexpressed in NPC. BEX3 overexpression was a unique event in cancer developed in the head and neck regions, especially NPC. BEX3 expression was inducible by cisplatin in NPC. In cisplatin‐resistant NPC xenograft, treatment with nontoxic level of cisplatin led to a remarkable increase in BEX3 level. High BEX3 expression was accompanied with high octamer‐binding transcription factor 4 (OCT4) expression in cisplatin‐resistant NPC. To confirm the inducing role of BEX3 on OCT4 expression, we knockdown BEX3 using siRNA and compared the expression of OCT4 with mock transfectants. Suppressing BEX3 transcripts led to a significant reduction in OCT4. In addition, targeting BEX3 using shRNA could increase the sensitivity of NPC cells to cisplatin. In summary, our results indicated a unique functional role of BEX3 in mediating the sensitivity of NPC cells to cisplatin. Targeting or blocking BEX3 activity might be useful in reversing the cisplatin‐resistant phenotype in NPC.
The Maintenance of Traditional and Technological Forms of Post‐Adoption Contact
Authors: Greenhow Sarah , Hackett Simon , Jones Christine , Meins Elizabeth
Published: January 2017

Openness in adoption practice now often includes post‐adoption contact with the adopted child's birth family. Traditionally, indirect and direct contact has been supported and mediated by professionals following the adoption of children from the public care system in the UK. However, more recently, the widespread growth in the use of digital technologies has made it possible for both adopted children and birth relatives to search and contact one another through the use of sites such as Facebook without professional support. This practice has been called ‘virtual contact’. Using data from interviews with 11 adoptive parents and six adopted young people, who had experienced virtual contact, it is suggested that virtual contact works well when it is successfully integrated with the maintenance of more traditional methods of contact but can present risks when introduced without prior contact. Implications for practice are discussed in terms of how virtual contact can become a positive addition to adoption practices by utilising integrated methods of openness through which adoptive relationships can be maintained. Copyright © 2017 John Wiley & Sons, Ltd.

‘Use of digital technologies has made it possible for both adopted children and birth relatives to search and contact one another… without professional support’

Key Practitioner Messages

Technology, used to supplement existing relationships with birth relatives, can be successful within a climate ofintegrated opennesswhere traditional and technological methods of contact are used.

Prior ‘traditional’ contact can assist in the development of relationships and boundaries before moving to virtual contact.

‘Out of the blue’ virtual contact, without prior connections, can be challenging and present risks.

Integrated openness may not work well for all individuals and it is necessary to assess the appropriateness and value of all relationships irrespective of the methods of contact.
Practical and General Manganese‐Catalyzed Carbonylative Coupling of Alkyl Iodides with Amides
Authors: Li Yahui , Zhu Fengxiang , Wang Zechao , Rabeah Jabor , Brückner Angelika , Wu Xiao‐Feng
Published: January 2017

A selective manganese‐catalyzed carbonylative transformation of alkyl iodides and amides was developed. A variety of imides were prepared in moderate to good yields. Alkyl bromides could also be applied by in situ treatment with NaI to give the corresponding alkyl iodides. Notably, no additives or expensive ligands were required here. As the first example of the carbonylative coupling of alkyl iodides with amides, the simple reaction conditions and the advantages of a manganese catalyst make this new general procedure more attractive and practical than conventional techniques. Mechanistically, control experiments and electron paramagnetic resonance spectroscopy studies were also performed, and the radical nature of this new process was proven.
Time Series Extended Finite‐State Machine‐Based Relevance Vector Machine Multi‐Fault Prediction
Authors: Zhou Zi-Qian , Zhu Qun-Xiong , Xu Yuan
Published: January 2017

Fault prediction means to detect faults that can occur in the future. While most studies focus on predicting one fault at a time, multi‐fault prediction is more practical for industrial processes as multiple faults can cause much more damage than a single one. A time series extended finite‐state machine (TS‐EFSM)‐based relevance vector machine (RVM) approach is proposed for multi‐fault prediction. Time lags and correlation coefficients between the process variables and process states are determined. Then, a variable and a state dependence diagram based on the correlation coefficients is established with the EFSM. Furthermore, the RVM is applied to identify parameters for the sake of better prediction accuracy and shorter testing times. With the prediction parameters, faults can be predicted using the aforementioned TS‐EFSM state transitions.
Regioselectivity Change in the Organocatalytic Enantioselective (3+2) Cycloaddition with Nitrones through Cooperative Hydrogen‐Bonding Catalysis/Iminium Activation
Authors: Prieto Liher , Juste‐Navarro Veronica , Uria Uxue , Delso Ignacio , Reyes Efraim , Tejero Tomas , Carrillo Luisa , Merino Pedro , Vicario Jose L.
Published: January 2017

The reaction of nitrones with enals through iminium activation can be modulated by using cooperative hydrogen‐bonding catalysis to induce the participation of a nitrone ylide (C‐N‐C) instead of the classical C‐N‐O dipole. As a consequence, N‐hydroxypyrrolidines are obtained, rather than the expected isoxazolidines. The reaction proceeds smoothly and high enantioselectivities are observed in all cases. By using the appropriate substrate, polysubstituted pyrrolidines incorporating quaternary stereocenters can be efficiently prepared.
Synthesis and Oxidation of a Paddlewheel‐Shaped Rhodium/Antimony Complex Featuring Pyridine‐2‐Thiolate Ligands
Authors: Wächtler Erik , Oro Luis A. , Iglesias Manuel , Gerke Birgit , Pöttgen Rainer , Gericke Robert , Wagler Jörg
Published: January 2017

The paddlewheel‐shaped complex [Sb(μ‐pyS)4Rh]2 (1) (pyS−= 2‐S‐C5H4N−) was synthesized from [Rh(pyS)(cod)]2 (cod=1,5‐cyclooctadiene) and Sb(pyS)3. Upon oxidation with ONMe3, the complex [(μ‐O)Sb(μ‐pyS)3Rh(κ2‐pyS)]2 (2) is formed. Both 1 and 2 form dimers and feature short Rh−Sb bonds and bridging pyS ligands. 121Sb Mössbauer spectro‐ scopy and computational studies were employed to elucidate the Rh−Sb bonding in 1 and 2. Both covalent (Rh−Sb, X‐type Sb ligand) and dative (Rh→Sb, Z‐type; Rh←Sb L‐type Sb ligand) interactions have to be considered for the description of their bonding situations.
Triarylmethane Dyes for Artificial Repellent Cotton Fibers
Authors: Montagut Ana Maria , Gálvez Erik , Shafir Alexandr , Sebastián Rosa María , Vallribera Adelina
Published: January 2017

Families of new hydrophobic and/or oleophobic triarylmethane dyes possessing long hydrocarbon or polyfluorinated chains have been prepared. When covalently grafted on to cotton fabric, these dyes give rise to a new type of colored superhydrophobic fibers.
Small Molecule Activation with N,NR‐MIC Platinum Complexes
Authors: Jin Hanpeng , Mück‐Lichtenfeld Christian , Hepp Alexander , Stephan Douglas W. , Hahn F. Ekkehardt
Published: January 2017

The reaction of platinum complex trans‐[1] bearing an N,NEt‐imidazolide ligand with bis(diphenylphosphino)ethane (dppe) or bis(dicyclohexylphosphino)ethane (dchpe) yields the dinuclear MIC complexes [2]I2 or the mononuclear MIC complex [3]I, respectively. Whereas dinuclear [2]I2 does not react with elemental hydrogen, the mononuclear complex [3]I splits elemental hydrogen under mild reaction conditions with formation of hydride complex [4]I and N‐ethylimidazole. Dinuclear complex [3]I activates CS2 with formation of complex [5]I featuring the CS2 molecule bound through the carbon atom to the MIC nitrogen atom and one sulfur atom coordinating to the platinum center.
Profiles and Risk Assessment of Heavy Metals in Great Rift Lakes, Kenya
Authors: Yang Yuyi , Wei Liangfu , Cui Lili , Zhang Miaomiao , Wang Jun
Published: January 2017

Heavy metal pollution in surface water of four lakes (Naivasha, Elementaita, Nakuru, and Bogoria) of the Great Rift Valley in Kenya, East Africa was investigated in this study. Eight heavy metals including chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), lead (Pb), cadmium (Cd), and mercury (Hg) were determined using inductively coupled plasma‐mass spectrometer (ICP‐MS). Among the tested heavy metals, Cd and Hg were detected in all surface water samples. The concentrations of Cr, Cd, Ni, and Pb were relatively lower than those of other metals in the four lakes. Results of Kohonen self‐organizing map indicated that all the sampling sites in four lakes of the Great Rift Valley in Kenya could be classified into three different groups based on the heavy metal pollution. Lake Naivasha and Nakuru had characteristics of low concentrations of Cr, Ni, Cu, As, and Hg. Lake Bogoria was characterized by high levels of Ni, Cu, Cd, and Hg, and low levels of Pb, Cr, Zn, and As. Lake Elementaita showed characteristics of high concentrations of As and Hg and low concentrations of Pb, Ni, Cu, and Cd. Source identification using principal component analysis (PCA) indicated that anthropogenic factor played an increasingly important role in the heavy metal pollution of four lakes of the Great Rift Valley in Kenya, East Africa. Analysis of non‐carcinogenic health risks of heavy metals indicated Hg and As in Lake Elementaita and Hg in Lake Bogoria may pose adverse health effects to local residents via ingestion route.