bluuebunny/crossref_metadata_2025 huggingface dataset:
Solid‐Solution Alloy Nanoparticles of the Immiscible Iridium–Copper System with a Wide Composition Range for Enhanced Electrocatalytic Applications
Authors: Wang Fenglong , Kusada Kohei , Wu Dongshuang , Yamamoto Tomokazu , Toriyama Takaaki , Matsumura Syo , Nanba Yusuke , Koyama Michihisa , Kitagawa Hiroshi
Published: February 2018

For the first time, we synthesize solid‐solution alloy nanoparticles of Ir and Cu with a size of ca. 2 nm, despite Ir and Cu being immiscible in the bulk up to their melting over the whole composition range. We performed a systematic characterization on the nature of the IrxCu1−x solid‐solution alloys using powder X‐ray diffraction, scanning transmission electron microscopy coupled with energy‐dispersive X‐ray spectroscopy and X‐ray photoelectron spectroscopy. The results showed that the IrxCu1−x alloys had a face‐centered‐cubic structure; charge transfer from Cu to Ir occurred in the alloy nanoparticles, as the core‐level Ir 4f peaks shifted to lower energy region with the increase in Cu content. Furthermore, we observed that the alloying of Ir with Cu enhanced both the electrocatalytic oxygen evolution and oxygen reduction reactions. The enhanced activities could be attributed to the electronic interaction between Ir and Cu arising from the alloying effect at atomic‐level.
Catalytic Enantioselective Aza‐Benzoin Reactions of Aldehydes with 2H‐Azirines
Authors: Peng Qiupeng , Guo Donghui , Bie Jianbo , Wang Jian
Published: February 2018

The unprecedented enantioselective aza‐benzoin reaction of aldehydes with 2H‐azirines was developed by utilizing a chiral N‐heterocyclic carbene as the catalyst. A wide range of corresponding aziridines can be obtained in good yields with high enantioselectivities. The obtained optically active aziridines should be useful in the synthesis of other valuable molecules.
Nucleophilic Activation of Sulfur Hexafluoride: Metal‐Free, Selective Degradation by Phosphines
Authors: Buß Florenz , Mück‐Lichtenfeld Christian , Mehlmann Paul , Dielmann Fabian
Published: February 2018

The development of new methods for the chemical activation of the extremely inert greenhouse gas sulfur hexafluoride (SF6) not only is of current environmental interest, but also offers new opportunities for applications of SF6 as a reagent in organic synthesis. We herein report the first nucleophilic activation of SF6 by Lewis bases, namely by phosphines, which results either in its complete degradation to phosphine sulfides and difluorophosphoranes or in the selective conversion of SF6 into a bench‐stable, crystalline salt containing the SF5− anion. Quantum chemical calculations reveal a nucleophilic substitution mechanism (SN2) for the initial fluorine abstraction from SF6 by the phosphine. Furthermore, a scalable one‐pot procedure for the complete decomposition of SF6 into solid, nonvolatile products is presented based on cheap and commercially available starting materials.
Synthesis, spectroscopic properties, density functional theory calculations and nonlinear optical properties of novel complexes of 5‐hydroxy‐4,7‐dimethyl‐6‐(phenylazo)coumarin with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions
Authors: Abdel‐Latif Samir A. , Moustafa H.
Published: February 2018

5‐Hydroxy‐4,7‐dimethyl‐6‐(phenylazo)coumarin (L) has been synthesized and its novel complexes with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions have also been prepared and identified using various analytical tools. The complexes are octahedral binding via one/two oxygen, nitrogen atoms for 1:1 and 1:2 complexes and two/three coordinated water molecules. All the prepared solid complexes behave as neutral in dimethylformamide. The optimized structures of the studied complexes were theoretically investigated at the B3LYP/6‐311G** level. Molecular stability and bond strengths were investigated by applying natural bond orbital analysis. The geometries of the studied complexes are non‐planar as indicated from the values of dihedral angles. The global properties of hardness, global softness and electronegativity were computed. The calculated small energy gap between highest occupied and lowest unoccupied molecular orbital energies shows that charge transfer occurs within the complexes. The obtained total static dipole moment, mean polarizability, anisotropy of polarizability and mean first‐order hyperpolarizability (<β>) were compared with those of urea as a reference material. The results for <β> showed that the complexes are excellent candidates as nonlinear optical materials. The three‐dimensional plots of the molecular electrostatic potential for some selected complexes were investigated.
Calcium carbonate and wood reinforced hybrid PVC composites
Authors: Croitoru Catalin , Spirchez Cosmin , Cristea Daniel , Lunguleasa Aurel , Pop Mihai Alin , Bedo Tibor , Roata Ionut Claudiu , Luca Mihai Alexandru
Published: February 2018

In this article, poly(vinyl chloride) (PVC) sandwich‐structured hybrid composites with amorphous calcium carbonate and wood‐filled cores were obtained by compression molding. It has been determined that wood addition up to a weight ratio of 33% reported to the total filler amount is beneficial in improving both the inter‐filler and filler‐matrix interfacial adhesion, which alongside with the promoting of the amorphous PVC matrix crystallization is responsible for an increase up to 34% in the flexural strength of the composites, compared to unfilled PVC. The hybrid filled composites present up to 35% lower friction coefficients and up to 20% higher Brinell hardness values than the composites filled with calcium carbonate alone. Subsequently, wood addition determines an increase in the oxidation onset temperature for PVC and an increase with up to 20% in the sound and thermal‐insulative properties of the composites, compared to unfilled PVC. The dominating dispersive part of the composites surface energy aids in improving the mass and dimensional stability of the assembly to both water and dilute hydrochloric acid aqueous solutions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46317.
Thermal induced shape‐memory and self‐healing of segmented polyurethane containing diselenide bonds
Authors: Du Weining , Jin Yong , Pan Jiezhou , Fan Wuhou , Lai Shuangquan , Sun Xiaopeng
Published: February 2018

Herein, we synthesized a series of polyurethane copolymers (PUs) with poly(1,4‐butylene adipate) glycol as soft segment and 2,4‐toluene diisocyanate as well as extenders including 1,4‐butanediol and di(1‐hydroxyethylene) diselenide as hard segment. The chemical structure, thermal property, crystallization behavior, shape memory, and self‐healing performances of the PUs were systematically characterized by a series of experiments. It was found that the PU2 containing a higher diselenide component (∼33 mol %) exhibited both shape memory and self‐healing behaviors under a moderate temperature (∼57 °C). Meanwhile, the PUs showed a good repeatability of shape memory function, and their fixity and recovery ratios were all above 90%. Additionally, the dynamic exchangeable feature of diselenide bonding endues the PUs chains with an acceptable reprocessability and self‐healing performances, and the PU2 sample could be healed for five times by thermal treatment with the healing efficiencies above 70%. This work provides a heuristic perspective for the development of shape memory and self‐healing materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46326.
Switching From Reference Adalimumab to SB5 (Adalimumab Biosimilar) in Patients With Rheumatoid Arthritis
Authors: Weinblatt Michael E. , Baranauskaite Asta , Dokoupilova Eva , Zielinska Agnieszka , Jaworski Janusz , Racewicz Artur , Pileckyte Margarita , Jedrychowicz‐Rosiak Krystyna , Baek Inyoung , Ghil Jeehoon
Published: February 2018

Objective

The 24‐week equivalent efficacy and comparable safety results of the biosimilar SB5 and reference adalimumab (ADA) from the phase III randomized study in patients with moderate‐to‐severe rheumatoid arthritis (RA) have been reported previously. We undertook this transition study to evaluate patients who switched from ADA to SB5 or who continued to receive SB5 or ADA up to 52 weeks.

Methods

In this phase III study, patients were initially randomized 1:1 to receive SB5 or ADA (40 mg subcutaneously every other week). At 24 weeks, patients receiving ADA were rerandomized 1:1 to continue with ADA (ADA/ADA group) or to switch to SB5 (ADA/SB5 group) up to week 52; patients receiving SB5 continued with SB5 for 52 weeks (SB5 group). Efficacy, safety, and immunogenicity were evaluated up to 52 weeks.

Results

The full analysis set population consisted of 542 patients (269 in the SB5 group, 273 in the ADA overall group [patients who were randomized to receive ADA at week 0], 125 in the ADA/SB5 group, and 129 in the ADA/ADA group). The percentages of patients meeting the American College of Rheumatology 20%, 50%, or 70% improvement criteria (achieving an ACR20, ACR50, or ACR70 response) at week 24 were maintained after the transition from ADA to SB5, and these response rates were comparable across treatment groups throughout the study. ACR20 response rates ranged from 73.4% to 78.8% at week 52. Radiographic progression was minimal and comparable across treatment groups. The safety profile and the incidence of antidrug antibodies were comparable across treatment groups after transition.

Conclusion

SB5 was well tolerated over 1 year in patients with RA, with efficacy, safety, and immunogenicity comparable to those of ADA. Switching from ADA to SB5 had no treatment‐emergent issues such as increased adverse events, increased immunogenicity, or loss of efficacy.
Augmented Th17 Differentiation Leads to Cutaneous and Synovio‐Entheseal Inflammation in a Novel Model of Psoriatic Arthritis
Authors: Yang Lu , Fanok Melania H. , Mediero‐Munoz Aranzazu , Fogli Laura K. , Corciulo Carmen , Abdollahi Shahla , Cronstein Bruce N. , Scher Jose U. , Koralov Sergei B.
Published: February 2018

Objective

To introduce a novel preclinical animal model of psoriatic arthritis (PsA) in R26Stat3Cstopfl/fl CD4Cre mice, and to investigate the role of Th17 cytokines in the disease pathogenesis.

Methods

We characterized a novel murine model of Th17‐driven cutaneous and synovio‐entheseal disease directed by T cell–specific expression of a hyperactive Stat3 allele. By crossing R26Stat3Cstopfl/fl CD4Cre mice onto an interleukin‐22 (IL‐22)–knockout background or treating the mice with a neutralizing antibody against IL‐17, we interrogated how these Th17 cytokines could contribute to the pathogenesis of PsA.

Results

R26Stat3Cstopfl/fl CD4Cre mice developed acanthosis, hyperkeratosis, and parakeratosis of the skin, as well as enthesitis/tendinitis and periarticular bone erosion in different joints, accompanied by osteopenia. T cell–specific expression of a hyperactive Stat3C allele was found to drive the augmented Th17 response in these animals. Careful characterization of the mouse bone marrow revealed an increase in osteoclast progenitor (OCP) and RANKL‐producing cells, which contributed to the osteopenia phenotype observed in the mutant animals. Abrogation of the Th17 cytokines IL‐17 or IL‐22 improved both the skin and bone phenotype in R26Stat3Cstopfl/fl CD4Cre mice, revealing a central role of Th17 cells in the regulation of OCP and RANKL expression on stromal cells.

Conclusion

Perturbation of the IL‐23/Th17 axis instigates Th17‐mediated inflammation in R26Stat3Cstopfl/fl CD4Cre mice, leading to cutaneous and synovio‐entheseal inflammation and bone pathologic features highly reminiscent of human PsA. Both IL‐17A and IL‐22 produced by Th17 cells appear to play critical roles in promoting the cutaneous and musculoskeletal inflammation that characterizes PsA.
Copper‐Catalyzed Asymmetric Synthesis of Borylated cis‐Disubstituted Indolines
Authors: Li DingXi , Kim Jiwon , Yang Jung Woon , Yun Jaesook
Published: February 2018

A copper‐catalyzed, intramolecular borylative cyclization of vinyl arenes with imines is reported, which affords enantio‐enriched indolines as a single diastereomer under mild conditions. A benzylcopper species is generated by Cu‐Bpin addition to the alkene, which then acts as a nucleophile for intramolecular imine addition. The reaction is applicable to various vinyl arenes with an imine moiety at the ortho‐position, including heterocycles, for formation of borylated indolines in good yields and ee values up to 90 %.
Proneness to guilt, shame, and pride in children with Autism Spectrum Disorders and neurotypical children
Authors: Davidson Denise , Hilvert Elizabeth , Misiunaite Ieva , Giordano Michael
Published: February 2018

Self‐conscious emotions (e.g., guilt, shame, and pride) are complex emotions that require self‐reflection and self‐evaluation, and are thought to facilitate the maintenance of societal norms and personal standards. Despite the importance of self‐conscious emotions, most research has focused on basic emotion processing in children with Autism Spectrum Disorders (ASD). Therefore, in the present study, we used the Test of Self‐Conscious Affect for Children (TOSCA‐C) to assess proneness to, or propensity to experience, the self‐conscious emotions guilt, shame, and pride in children with ASD and neurotypical children. The TOSCA‐C is designed to capture a child's natural tendency to experience a given emotion across a range of everyday situations [Tangney, Stuewig, & Mashek, 2007]. We also assessed how individual characteristics contribute to the development of proneness to self‐conscious emotions, including theory of mind (ToM) and ASD symptomatology. In comparison to neurotypical children, children with ASD showed less proneness to guilt, although all children showed relatively high levels of proneness to guilt. Greater ToM ability was related to more proneness to guilt and authentic pride in children with ASD. Additionally, we found that children with ASD with more severe symptomatology were more prone to hubristic pride. Our results provide evidence of differences in proneness to self‐conscious emotions in children with ASD, as well as highlight important mechanisms contributing to how children with ASD may experience self‐conscious emotions. Autism Res 2018,11:883–892. ©2017 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

This research examined proneness to guilt, shame, and pride in children with Autism Spectrum Disorders (ASD) and neurotypical children. We found that children with ASD showed less proneness to guilt than neurotypical children. Better understanding of theory of mind was related to greater proneness to guilt and pride, but only for children with ASD. These findings are important because these complex emotions are linked with both positive and negative social behaviors towards others and oneself.
Ein innovatives Betonschalenbauverfahren in Anwendung: Herstellung der Wildbrücke AM2 mit PFHC
Authors: Kromoser Benjamin , Kollegger Johann , Kari Hannes , Gradenegger Karin , Ganster Martin
Published: February 2018

Fertiggestellte Betonschalen sind bei Auswahl einer geeigneten Geometrie ästhetische und wirtschaftliche Tragwerke, die mit einem Minimum an Material hohe Lasten abtragen und große Flächen überspannen können. Der hohe Aufwand für die Schalung führt zu hohen Kosten, die die Errichtung meist unwirtschaftlich machen. Am Institut für Tragkonstruktionen der TU Wien wurde in den vergangenen Jahren ein neues Betonschalenbauverfahren mit dem Namen Pneumatic Forming of Hardened Concrete (PFHC) entwickelt. Nach Durchlaufen eines straffen Entwicklungsprozesses, der zahlreiche Materialversuche, Zugversuche, Biegeversuche und auch Großversuche umfasste, wurde das Bauverfahren nun erstmals praktisch von den Österreichischen Bundesbahnen (ÖBB) im großen Maßstab für die Errichtung der Wildbrücke AM2 angewendet. Zuerst wurde eine Probeschale mit den Grundrissabmessungen 26,5 m × 19,1 m und einer Höhe von 4,2 m, die nun als Veranstaltungsüberdachung genutzt wird, gebaut. Anschließend wurde das Tragwerk der Brücke (Grundrissabmessungen 36,2 m × 38,7 m, Höhe 8,1 m) errichtet. Der erste, bereits in der vorigen Ausgabe veröffentlichte Teil des Beitrags fasst den Entwicklungsprozess zusammen und beschreibt den Einsatz digitaler Planungs‐ und Fertigungsmethoden für die Umsetzung des Projekts. Im zweiten Teil des Aufsatzes werden nun der gewählte Bauablauf, durchgeführte Versuche, ausgewählte Ausführungsdetails sowie das gewählte Messkonzept beschrieben.
The effect of a competitive strategy and green supply chain management on the financial and environmental performance of logistics service providers
Authors: Laari Sini , Töyli Juuso , Ojala Lauri
Published: February 2018

Despite the critical role of logistics service providers (LSPs) in improving the environmental sustainability of supply chains, there is still uncertainty about how LSPs can turn environmental management into competitive advantage. Based on a Finnish national logistics survey and financial reporting data from 266 LSPs, this article examines their competitive strategies and green supply chain management (GSCM), and tests their respective relationships with environmental and financial performance. Financial data are used to measure financial performance in a novel way. The findings indicate that leading LSPs with operational excellence and strong brands are more advanced in terms of GSCM than LSPs that do not excel in any competitive priority. GSCM practices are positively related to environmental performance, but not to financial performance. However, managers should not be discouraged by the apparent absence of short‐term financial benefits of GSCM practices, which in any case could enhance future differentiation opportunities.
Phase 1–3 of the cross‐cultural development of an EORTC questionnaire for the assessment of sexual health in cancer patients: the EORTC SHQ‐22
Authors: Oberguggenberger Anne Sophie , Nagele Eva , Inwald Elisabeth C. , Tomaszewski Krzysztof , Lanceley Anne , Nordin Andy , Creutzberg Carien L. , Kuljanic Karin , Kardamakis Dimitrios , Schmalz Claudia , Arraras Juan , Costantini Anna , Almont Thierry , Wei‐Chu Chie , Dehandschutter Sara , Winters Zoe , Greimel Elfriede ,   the EORTC Quality of Life Group
Published: February 2018

To develop and pretest an European Organization for the Research and Treatment of Cancer Sexual Health Questionnaire (EORTC SHQ‐22) for the assessment of physical, psychological, and social aspects of sexual health (SH) in male and female cancer patients and survivors. Questionnaire construction started with creating a list of relevant SH issues based on a comprehensive literature review. Issues were subsequently evaluated for relevance and prioritization by 78 healthcare professionals (HCP) and 107 patients from 12 countries during in‐depth interviews (phase 1). Extracted issues were operationalized into items (phase 2). Phase 3 focused on pretesting the preliminary questionnaire in a cross‐cultural patient sample (n = 171) using debriefing interviews. Psychometric properties were preliminary determined using a principal component analysis and Cronbach's alpha. We derived 53 relevant SH issues from the literature. Based on HCP and patient interviews, 22 of these 53 issues were selected and operationalized into items. Testing the preliminary 22‐item short questionnaire resulted in a change of wording in five items and two communication‐related items; no items were removed. Preliminary psychometric analysis revealed a two‐factor solution and 11 single items; both scales showed good reliability indicated by a Cronbach's alpha of 0.87 (sexual satisfaction) and 0.82 (sexual pain). Cross‐cultural pretesting of the preliminary EORTC SH questionnaire has indicated excellent applicability, patient acceptance, and comprehensiveness as well as good psychometric properties. The final development phase, that is psychometric validation (phase four) including large‐scale, cross‐cultural field testing of the EORTC SHQ‐22, has commenced.
Microsatellite instability status determined by next‐generation sequencing and compared with PD‐L1 and tumor mutational burden in 11,348 patients
Authors: Vanderwalde Ari , Spetzler David , Xiao Nianqing , Gatalica Zoran , Marshall John
Published: February 2018

Microsatellite instability (MSI) testing identifies patients who may benefit from immune checkpoint inhibitors. We developed an MSI assay that uses data from a commercially available next‐generation sequencing (NGS) panel to determine MSI status. The assay is applicable across cancer types and does not require matched samples from normal tissue. Here, we describe the MSI‐NGS method and explore the relationship of MSI with tumor mutational burden (TMB) and PD‐L1. MSI examined by PCR fragment analysis and NGS was compared for 2189 matched cases. Mismatch repair status by immunohistochemistry was compared to MSI‐NGS for 1986 matched cases. TMB was examined by NGS, and PD‐L1 was determined by immunohistochemistry. Among 2189 matched cases that spanned 26 cancer types, MSI‐NGS, as compared to MSI by PCR fragment analysis, had sensitivity of 95.8% (95% confidence interval [CI] 92.24, 98.08), specificity of 99.4% (95% CI 98.94, 99.69), positive predictive value of 94.5% (95% CI 90.62, 97.14), and negative predictive value of 99.2% (95% CI, 98.75, 99.57). High MSI (MSI‐H) status was identified in 23 of 26 cancer types. Among 11,348 cases examined (including the 2189 matched cases), the overall rates of MSI‐H, TMB‐high, and PD‐L1 positivity were 3.0%, 7.7%, and 25.4%, respectively. Thirty percent of MSI‐H cases were TMB‐low, and only 26% of MSI‐H cases were PD‐L1 positive. The overlap between TMB, MSI, and PD‐L1 differed among cancer types. Only 0.6% of the cases were positive for all three markers. MSI‐H status can be determined by NGS across cancer types. MSI‐H offers distinct data for treatment decisions regarding immune checkpoint inhibitors, in addition to the data available from TMB and PD‐L1.
A Neutral RuII Hydride Complex for the Regio‐ and Chemoselective Reduction of N‐Silylpyridinium Ions
Authors: Bähr Susanne , Oestreich Martin
Published: February 2018

A detailed experimental analysis of the 1,4‐selective reduction of pyridine with hydrosilanes catalyzed by a coordinatively unsaturated RuII thiolate complex is reported. The previously suggested intermediates, N‐silylpyridinium ions and a neutral RuII hydride, have been independently synthesized and do indeed participate in the catalytic cycle. The resting state is not the cationic RuII complex initially used as the catalyst but its pyridine‐coordinated congener. All RuII complexes, including the one resulting from hydrosilane activation, are in equilibrium with each other. The N‐silylated 1,4‐dihydropyridine together with the cationic RuII complex convert back into the corresponding N‐silylpyridinium ion and the neutral RuII hydride (retro‐hydrosilylation), followed by further backward reaction into the hydrosilane and the pyridine adduct of the cationic complex. These steps prove the overall reversibility of the transformation.
Aerobic Oxidation Catalysis by a Molecular Barium Vanadium Oxide
Authors: Lechner Manuel , Kastner Katharina , Chan Chee Jian , Güttel Robert , Streb Carsten
Published: February 2018

Aerobic catalytic oxidations are promising routes to replace environmentally harmful oxidants with O2 in organic syntheses. Here, we report a molecular barium vanadium oxide, [Ba4(dmso)14V14O38(NO3)] (={Ba4V14}) as viable homogeneous catalyst for a series of oxidation reactions in N,N‐dimethyl formamide solution under oxygen (8 bar). Starting from the model compound 9,10‐dihydroanthracene, we report initial dehydrogenation/ aromatization leading to anthracene formation; this intermediate is subsequently oxidized by stepwise oxygen transfer, first giving the mono‐oxygenated anthrone and then the di‐oxygenated target product, anthraquinone. Comparative reaction analyses using the Neumann catalyst [PV2Mo10O40]5− as reference show that oxygen diffusion into the reaction mixture is the rate‐limiting step, resulting in accumulation of the reduced catalyst species. This allows us to propose improved reactor designs to overcome this fundamental challenge for aerobic oxidation catalysis.
A Multifunctional Pincer Ligand for Cobalt‐Promoted Oxidation by N2O
Authors: Cook Brian J. , Chen Chun‐Hsing , Caulton Kenneth G.
Published: February 2018

The divalent cobalt complex of the diprotic pincer ligand bis‐pyrazolylpyridine, (H2L)CoCl2, is dehydrohalogenated twice by LiN(SiMe3)2 in the presence of PEt3 to give monomeric S=1/2 LCo(PEt3)2 (1), fully characterized in the solid‐state and solution as a square pyramidal monomer with a long axial Co−P bond. This 17‐electron species reacts in time of mixing with N2O to form L2Co2(μ‐OPEt3) (2)+3 OPEt3, the former the first example of phosphine oxide bridging two transition metals. The same products are formed from O2, and divalent cobalt persists even in the presence of excess oxidant. Species (2) catalyzes oxygen atom transfer (OAT) for generation of O=PEt3 from PEt3 from either N2O or O2. Bridging and terminal cobalt oxo intermediates are suggested, and the electron donor power, and potential redox activity of the dianionic pincer ligand is emphasized.
Tetrylones: An Intriguing Class of Monoatomic Zero‐valent Group 14 Compounds
Authors: Majhi Paresh Kumar , Sasamori Takahiro
Published: February 2018

Tetrylones (ylidones) represent a class of zero‐valent group 14 compounds with the general formula EL2 (E=C, Si, Ge, Sn, or Pb; L=neutral σ‐donating ligand), wherein the tetrel atom, E(0), possess its four valence electrons in the form of two electron lone pairs, and is moreover coordinated by two ligands (L) via donor‐acceptor interactions (L→E←L). This review focuses on the synthesis, structure, reactivity, and computational examination of the isolable heavier tetrylones (Si, Ge, Sn) that have been discovered recently. A comprehensive review on carbone chemistry is beyond the scope of this review. It should also be noted that tetrylones contain two different types of lone pairs, that is, one that exhibits p‐type and one that exhibits s‐type characteristics. Different behavior should thus be expected when these lone pairs react with Lewis acids.
Highly Efficient Photocatalytic System Constructed from CoP/Carbon Nanotubes or Graphene for Visible‐Light‐Driven CO2 Reduction
Authors: Fu Zi‐Cheng , Xu Rong‐Chen , Moore Joshua T. , Liang Fei , Nie Xiao‐Cun , Mi Chen , Mo Jiang , Xu Yong , Xu Quan‐Qing , Yang Zhi , Lin Zhe‐Shuai , Fu Wen‐Fu
Published: February 2018

Visible‐light‐driven conversion of CO2 to CO and high‐value‐added carbon products is a promising strategy for mitigating CO2 emissions and reserving solar energy in chemical form. We report an efficient system for CO2 transformation to CO catalyzed by bare CoP, hybrid CoP/carbon nanotubes (CNTs), and CoP/reduced graphene oxide (rGO) in mixed aqueous solutions containing a Ru‐based photosensitizer, under visible‐light irradiation. The in situ prepared hybrid catalysts CoP/CNT and CoP/rGO show excellent catalytic activities in CO2 reduction to CO, with a catalytic rates of up to 39 510 and 47 330 μmol h−1 g−1 in the first 2 h of reaction, respectively; a high CO selectivity of 73.1 % for the former was achieved in parallel competing reactions in the photoreduction of CO2 and H2O. A combination of experimental and computational studies clearly shows that strong interactions between CoP and carbon‐supported materials and partially adsorbed H2O molecules on the catalyst surface significantly improve CO‐generating rates.
Palladium‐Catalyzed Asymmetric Allylic Alkylation of 4‐Substituted Isoxazolidin‐5‐ones: Straightforward Access to β2,2‐Amino Acids
Authors: Nascimento de Oliveira Marllon , Arseniyadis Stellios , Cossy Janine
Published: February 2018

We report here an unprecedented and highly enantioselective palladium‐catalyzed allylic alkylation applied to 4‐substituted isoxazolidin‐5‐ones. Ultimately, the process provides a straightforward access to β2,2‐amino acids bearing an all‐carbon quaternary stereogenic center in great yields and a high degree of enantioselectivity.
Insights into the Target Interaction of Naturally Occurring Muraymycin Nucleoside Antibiotics
Authors: Koppermann Stefan , Cui Zheng , Fischer Patrick D. , Wang Xiachang , Ludwig Jannine , Thorson Jon S. , Van Lanen Steven G. , Ducho Christian
Published: February 2018

Muraymycins are a subclass of antimicrobially active uridine‐derived natural products. Biological data on several muraymycin analogues have been reported, including some inhibitory in vitro activities toward their target protein, the bacterial membrane enzyme MraY. However, a structure–activity relationship (SAR) study on naturally occurring muraymycins based on such in vitro data has been missing so far. In this work, we report a detailed SAR investigation on representatives of the four muraymycin subgroups A–D using a fluorescence‐based in vitro MraY assay. For some muraymycins, inhibition of MraY with IC50 values in the low‐picomolar range was observed. These inhibitory potencies were compared with antibacterial activities and were correlated to modelling data derived from a previously reported X‐ray crystal structure of MraY in complex with a muraymycin inhibitor. Overall, these results will pave the way for the development of muraymycin analogues with optimized properties as antibacterial drug candidates.
Regularity for Shape Optimizers: The Nondegenerate Case
Authors: Kriventsov Dennis , Lin Fanghua
Published: February 2018

We consider minimizers of

urn:x-wiley:0010-3640:media:cpa21743:cpa21743-math-0001

where F is a function strictly increasing in each parameter, and is the kth Dirichlet eigenvalue of Ω. Our main result is that the reduced boundary of the minimizer is composed of C1,α graphs and exhausts the topological boundary except for a set of Hausdorff dimension at most n – 3. We also obtain a new regularity result for vector‐valued Bernoulli‐type free boundary problems.© 2018 Wiley Periodicals, Inc.
From Synthesis of Amino Acids and Peptides to Enzymatic Catalysis: A Bottom‐Up Approach in Mechanochemistry
Authors: Bolm Carsten , Hernández José G.
Published: February 2018

Recently, chemical reactions induced or facilitated by mechanical energy have gained recognition in diverse areas of chemical synthesis. In particular, mechanosyntheses of amino acids and short peptides, along with their applications in catalysis, have revealed the high degree of stability of peptide bonds in environments of harsh mechanical stress. These observations quickly led to the recent interest in developing mechanochemical enzymatic reactions. Experimentally, manual grinding, ball‐milling techniques, and twin‐screw extrusion technology have proven valuable to convey mechanical forces into a chemical synthesis. These practices have enabled the establishment of more sustainable alternatives for chemical synthesis by reducing the use of organic solvents and waste production, thereby having a direct impact on the E‐factor of the chemical process. In this Minireview, the series of events that allowed the development of mechanochemical enzymatic reactions are described from a bottom‐up perspective.
Non‐loadbearing partitions of unfired clay masonry – Fire behaviour tests
Authors: Hartmann Raik , Burkert Toralf
Published: February 2018

Unfired clay masonry is the most frequently used construction type for residential buildings worldwide, but the long tradition of building with unfired clay masonry in Germany came to an end with the onset of industrialization.

The research project EGsL ”Unfired clay masonry: design and construction principles for a widespread use in residential building taking into account climatic conditions in temperate zones with Germany as example location“ is devoted to the preparation of basic principles based on the current state of knowledge about unfired clay as a building material in order to filter out design and construction principles for residential buildings of modern unfired clay masonry. It is assumed that unfired clay has a much better performance capability than is currently expected from the material.

The greatest suspicion about the structural safety of unfired clay buildings is based on the water susceptibility of unfired clay, since unfired clay loses its strength under the action of water. In order to improve confidence in the structural stability of residential buildings of unfired clay masonry, a display at the trade fair BAU 2017 showed the basis for an example application of important constructional joints of a theoretical building of unfired clay masonry.

As a follow‐up to this, the EGsL research project now intends to demonstrate the fire protection behaviour of unfired clay internal walls in order to ensure the structural stability of unfired clay buildings. The article reports on a first fire test on non‐loadbearing clay masonry walls and describes an example application of non‐loadbearing clay walls in the new Zinzendorf Gymnasium in Herrnhut.
Depressional wetlands affect watershed hydrological, biogeochemical, and ecological functions
Authors: Evenson Grey R. , Golden Heather E. , Lane Charles R. , McLaughlin Daniel L. , D'Amico Ellen
Published: February 2018

Depressional wetlands of the extensive U.S. and Canadian Prairie Pothole Region afford numerous ecosystem processes that maintain healthy watershed functioning. However, these wetlands have been lost at a prodigious rate over past decades due to drainage for development, climate effects, and other causes. Options for management entities to protect the existing wetlands, and their functions, may focus on conserving wetlands based on spatial location vis‐à‐vis a floodplain or on size limitations (e.g., permitting smaller wetlands to be destroyed but not larger wetlands). Yet the effects of such management practices and the concomitant loss of depressional wetlands on watershed‐scale hydrological, biogeochemical, and ecological functions are largely unknown. Using a hydrological model, we analyzed how different loss scenarios by wetland size and proximal location to the stream network affected watershed storage (i.e., inundation patterns and residence times), connectivity (i.e., streamflow contributing areas), and export (i.e., streamflow) in a large watershed in the Prairie Pothole Region of North Dakota, USA. Depressional wetlands store consequential amounts of precipitation and snowmelt. The loss of smaller depressional wetlands (<3.0 ha) substantially decreased landscape‐scale inundation heterogeneity, total inundated area, and hydrological residence times. Larger wetlands act as hydrologic “gatekeepers,” preventing surface runoff from reaching the stream network, and their modeled loss had a greater effect on streamflow due to changes in watershed connectivity and storage characteristics of larger wetlands. The wetland management scenario based on stream proximity (i.e., protecting wetlands 30 m and ~450 m from the stream) alone resulted in considerable landscape heterogeneity loss and decreased inundated area and residence times. With more snowmelt and precipitation available for runoff with wetland losses, contributing area increased across all loss scenarios. We additionally found that depressional wetlands attenuated peak flows; the probability of increased downstream flooding from wetland loss was also consistent across all loss scenarios. It is evident from this study that optimizing wetland management for one end goal (e.g., protection of large depressional wetlands for flood attenuation) over another (e.g., protecting of small depressional wetlands for biodiversity) may come at a cost for overall watershed hydrological, biogeochemical, and ecological resilience, functioning, and integrity.
YKOB: Participatory Sensing‐Based Road Condition Monitoring Using Smartphones Worn by Cyclist
Authors: TAKAHASHI JUNJI , KOBANA YUSUKE , ISOYAMA NAOYA , TOBE YOSHITO , LOPEZ GUILLAUME
Published: February 2018

We propose a novel road monitoring system named YKOB (Your Kinetic Observation Bike) based on participatory sensing. YKOB collects acceleration signals using smartphones worn by cyclists, and analyzes the collected signals to investigate road surface condition. When a bicycle passes on a bump or a dimple, its wheels vibrate. The vibrations are transmitted to the smartphone via the bicycle frame or the cyclist body, and registered as acceleration signals. Conversely, by analyzing the acceleration signals we can estimate the road surface condition. There are mainly two research issues in this system. The first issue is that the acceleration registered at the smartphone includes cyclist motion signal as well as road surface signal. The second issue is that it is necessary to distinguish abnormality of road surface from artificial differences in level, such as a difference between streets and sidewalks. We developed a signal separation algorithm based on independent component analysis to solve the first issue. We also developed a bump classification algorithm using real mother wavelet. These two proposed algorithms were evaluated with 640 trials in total of experimental data conducted by eight cyclists. The classification accuracy of 0.68 validates the simultaneous utilization of our proposed algorithms.
One‐Step In Situ Synthesis of Three‐Dimensional NiSb Thin Films as Anode Electrode Material for the Advanced Sodium‐Ion Battery
Authors: Dong Shihua , Li Caixia , Yin Longwei
Published: February 2018

A low‐cost, facile and highly efficient in situ solvothermal reaction has been developed for the first time to synthesize, by using a 3D Ni foam template, three‐dimensional nickel‐antimony (3D NiSb) thin films as anode electrode materials for use in sodium‐ion batteries (SIBs). The structure design and preparation have proved reasonable and efficient, leading to excellent electrochemical properties. At current densities of 100, 200 and 400 mA g–1, specific capacities of 643.8, 520.5 and 378.6 mA h g–1, respectively, could be obtained. Additionally, a specific capacity of 420 mA h g–1 could be achieved after 100 cycles at a current density of 100 mA g–1. This could be attributed to the special 3D binder‐free conductive network connecting the NiSb nanoparticles and the 3D contact area with the electrolyte, which is beneficial for the charge‐transfer kinetics and electrochemical performance. Moreover, the porous structure offers enough space to alleviate the volume changes and stress generated in the sodiation/desodiation process. Most importantly, the 3D porous Ni foam, as a support for NiSb nanoparticles, can effectively prevent the agglomeration of the NiSb and Na3Sb nanoparticles. Therefore, such a unique NiSb anode material may be of great significance in next‐generation energy storage devices.
Addition of Organozinc Reagents to Glycopyranosyl Cyanides: Access to Keto Ester‐C‐glycosides or Unsaturated Acyl‐C‐glycosides
Authors: Ella Obame Idriss , Ireddy Prathap , Guisot Nicolas E. S. , Nourry Arnaud , Saluzzo Christine , Dujardin Gilles , Dubreuil Didier , Pipelier Muriel , Guillarme Stéphane
Published: February 2018

Addition of Reformatsky‐type or allylic zinc reagents to 2,3,4,6‐tetra‐O‐benzylglycopyranosyl cyanides led to keto ester‐C‐glycosides or unsaturated acyl‐C‐glycosides in moderate to excellent yields in the galactose, glucose, and mannose series.
Anterior insular volume decrease is associated with dysfunction of the reward system in patients with chronic pain
Authors: Ikeda E. , Li T. , Kobinata H. , Zhang S. , Kurata J.
Published: February 2018

Background

Chronification of pain is associated with both anatomical and functional alterations of the brain. Alteration in regional grey matter volume might potentially be associated with modified activity of specific brain networks. In this cross‐sectional, observational study, we sought to identify brain regions with grey matter volume changes in patients with chronic pain and to reveal its significance by analysing alteration in functional connectivity from those regions. We further explored relevance of such alterations with psychometrics of chronic pain.

Methods

We recruited 23 patients with chronic pain and 17 age‐, gender‐matched healthy control subjects. After completing multiple psychophysical questionnaires, each subject underwent resting‐state functional magnetic resonance imaging and three‐dimensional anatomical imaging on a 3 Tesla magnetic resonance imaging scanner.

Results

Patients with chronic pain showed significant volume decrease at the right anterior insular cortex (p < 0.001) and the left middle cingulate cortex (p < 0.001) compared with healthy controls. They also showed decreased connectivity between the right anterior insular cortex and the left nucleus accumbens in negative association with the Pain Catastrophizing Scale (R2 = 0.20, p = 0.046) and the Beck's Depression Inventory scores (R2 = 0.24, p = 0.017).

Conclusions

Decreased grey matter volumes of those core regions for affective processing of pain might be a common cerebral feature shared by, at least some of, different aetiologies of chronic pain. Dysfunctional network between the anterior insular cortex and the nucleus accumbens might reflect affective and motivational disability involved in chronic pain. Such anatomical and functional profiles could potentially be part of a cerebral signature for chronification of pain.

Significance

This article illustrates decreased network activity of the reward system in association with insular cortical volume decrease in patients with chronic pain, and its close relationships with affective and cognitive morbidity of pain. Attenuation of brain's reward system involving cortical plastic changes might have a key role in chronification of pain.
Randomized double‐blind controlled study of bedtime low‐dose amitriptyline in chronic neck pain
Authors: Maarrawi J. , Abdel Hay J. , Kobaiter‐Maarrawi S. , Tabet P. , Peyron R. , Garcia‐Larrea L.
Published: February 2018

Background

Amitriptyline has well‐established efficacy in several chronic pain conditions. While optimal treatment for chronic neck pain (CNP) remains controversial, amitriptyline was not tested for CNP. We evaluated the effect of bedtime amitriptyline in the management of CNP.

Methods

A total of 220 patients suffering from idiopathic CNP were randomized to receive either placebo pill (n = 108) or 5 mg of amitriptyline (n = 112) at bedtime for 2 months. Primary outcome measure was visual analog scale (VAS) for pain. Secondary outcome measures were neck pain disability index (NPDI), Bergen Insomnia Score (BIS) and Hospital Anxiety and Depression Scale (HAD), measured before and at the end of 2 months of treatment, with the percentage of patient satisfaction measured at the end of follow‐up only.

Results

Eight of 112 patients (7.14%) in the amitriptyline group withdrew from the study because of intolerance. Amitriptyline group showed significantly lower VAS scores than placebo group (3.34 ± 1.45 vs. 6.12 ± 0.92; p < 0.0001), which corresponds to a 53.06 ± 20.29% of improvement from baseline pain as compared to 14.41 ± 11.05%, respectively (p < 0.0001). Similar significant improvements were observed with lesser extents for secondary outcome measures: NPDI, BIS, HAD‐A, HAD‐D and percentage of patient satisfaction.

Conclusion

Low‐dose amitriptyline is effective for the management of idiopathic CNP with few side effects and high patients’ satisfaction.

Significance

This randomized controlled trial is the first to show the effectiveness and tolerance of a medication, low‐dose amitriptyline, in managing idiopathic chronic neck pain and its related comorbidities. The optimal treatment of this condition was still controversial in the literature. It extends the indication of low‐dose amitriptyline to another chronic pain condition.
Self‐Humidified Pt Electrocatalyst Fabricated from Hydrophilic Molecules Coating with Enhanced Fuel Cell Performance
Authors: Xu Zejun , Ling Ying , Yang Zehui , Zhang Quan , Zhang Yunfeng , Cai Weiwei , Zhang Daohong
Published: February 2018

Catalyst layer is essential for fuel cell performance of polymer electrolyte fuel cells (PEFCs) since electrochemical reactions occur and triple phase boundary forms in catalyst layer. Here, we report a self‐humidified platinum (Pt) electrocatalyst, in which the Pt nanoparticles were coated by 2,7‐bis(3,4‐dihydroxyphenethyl)benzo[lmn][3,8]phenanthroline‐1,3,6,8‐tetraone (NPDA) and the surfaces of Pt nanoparticles are tuned to be hydrophilic, which could adsorb the generated water and enhanced the fuel cell performance under non‐humidified operation condition. Due to the hydrophilic surfaces of Pt nanoparticles, power density of self‐humidified Pt electrocatalyst rapidly reached the maximum power density (700 mW cm−2) without any humidification; in contrast, with hydrophobic surface, power density was only (525 mW cm−2). Meanwhile, the fabricated electrocatalyst exhibits higher durability and could work under real fuel cell operation condition for 18,000 h with only 9 % decay in electrochemical surface area.
Application of the patient rule induction method to detect hydrologic model behavioural parameters and quantify uncertainty
Authors: Shokri Ashkan , Walker Jeffrey P. , van Dijk Albert I. J. M. , Wright Ashley J. , Pauwels Valentijn R. N.
Published: February 2018

Finding an operational parameter vector is always challenging in the application of hydrologic models, with over‐parameterization and limited information from observations leading to uncertainty about the best parameter vectors. Thus, it is beneficial to find every possible behavioural parameter vector. This paper presents a new methodology, called the patient rule induction method for parameter estimation (PRIM‐PE), to define where the behavioural parameter vectors are located in the parameter space. The PRIM‐PE was used to discover all regions of the parameter space containing an acceptable model behaviour. This algorithm consists of an initial sampling procedure to generate a parameter sample that sufficiently represents the response surface with a uniform distribution within the “good‐enough” region (i.e., performance better than a predefined threshold) and a rule induction component (PRIM), which is then used to define regions in the parameter space in which the acceptable parameter vectors are located. To investigate its ability in different situations, the methodology is evaluated using four test problems. The PRIM‐PE sampling procedure was also compared against a Markov chain Monte Carlo sampler known as the differential evolution adaptive Metropolis (DREAMZS) algorithm. Finally, a spatially distributed hydrological model calibration problem with two settings (a three‐parameter calibration problem and a 23‐parameter calibration problem) was solved using the PRIM‐PE algorithm. The results show that the PRIM‐PE method captured the good‐enough region in the parameter space successfully using 8 and 107 boxes for the three‐parameter and 23‐parameter problems, respectively. This good‐enough region can be used in a global sensitivity analysis to provide a broad range of parameter vectors that produce acceptable model performance. Moreover, for a specific objective function and model structure, the size of the boxes can be used as a measure of equifinality.