bluuebunny/crossref_metadata_2025 huggingface dataset:
Diamond‐Based All‐Carbon Photodetectors for Solar‐Blind Imaging
Authors: Lin Chao‐Nan , Lu Ying‐Jie , Yang Xun , Tian Yong‐Zhi , Gao Chao‐Jun , Sun Jun‐Lu , Dong Lin , Zhong Fang , Hu Wei‐Da , Shan Chong‐Xin
Published: May 2018

Single‐crystalline diamond wafers are synthesized, and all‐carbon solar‐blind photodetectors are constructed based on the diamond with interdigitated graphite as electrodes. The graphite electrodes are made by laser‐induced graphitization of the diamond. The peak responsivity of the photodetector is 21.8 A W−1, and detectivity is 1.39 × 1012 cm Hz1/2 W−1 when the bias voltage is 50 V, it is noted that both of these are among the best values ever reported for diamond‐based photodetectors. The photodetectors are employed as the sensing pixels in an imaging system, and a clear image is obtained, which is the first report on solar‐blind imaging of diamond photodetectors. The results reported in this paper provide a facile approach to high‐performance diamond solar‐blind photodetectors and their applications in solar‐blind imaging, thus may address a significant step toward the preparation and application of diamond photodetectors.
Organic Solvent and Surfactant Free Fluorescent Organic Nanoparticles by Laser Ablation of Aggregation‐Induced Enhanced Emission Dyes
Authors: Lim Chang‐Keun , Popov Anton A. , Tselikov Gleb , Heo Jeongyun , Pliss Artem , Kim Sehoon , Kabashin Andrei V. , Prasad Paras N.
Published: May 2018

Less toxic and highly fluorescent nanoparticles are in high demand to image biological events and early‐stage disease. A strategy to fabricate highly fluorescent organic nanoparticles by laser ablation of aggregation‐induced enhanced emission (AIE) luminophores, which are free of any organic solvent and surfactant, is presented. As these dyes provide no concentration quenching, the increased number of photoluminescent molecules in a nanoparticle produces bright fluorescence even with their small size (<2 nm), making them highly suitable for intracellular uptake and imaging for a variety of biomedical applications. The design and synthesis of a new AIE luminophore, DCEtDCS, are reported and its photoluminescent quantum yield enhancement up to 58% in the aggregated state is demonstrated. Extremely stable nanoparticles of this luminophore with a narrow size distribution, by laser ablation in water are reported and its superior optical properties that are comparable to quantum dots are verified. The highly negative surface charge of these nanoparticles impedes cellular uptake, but when the surface is coated with chitosan, a cationic polymer, intracellular uptake in microglia is achieved. The strategy provides a novel tool to produce in water, ultrasmall and surfactant‐free highly fluorescent organic nanoparticles suitable for biomedical applications.
Large‐Area Lasing and Multicolor Perovskite Quantum Dot Patterns
Authors: Lin Chun Hao , Zeng Qingji , Lafalce Evan , Yu Shengtao , Smith Marcus J. , Yoon Young Jun , Chang Yajing , Jiang Yang , Lin Zhiqun , Vardeny Zeev Valy , Tsukruk Vladimir V.
Published: May 2018

Herein, a novel orthogonal lithography process is reported to pattern all‐inorganic perovskite CsPbX3 (X = Cl, Br, I) quantum dot (QD) arrays which cannot be patterned with traditional approaches. This approach involves a combination of fluorinated polymer and solvent to resolve issues of polar–nonpolar solvent constraints thus enabling the fabrication of complex patterns with high optical gain and multicolor emission. This approach is utilized to fabricate high‐resolution large‐area arrays of microdisk lasers and multicolor (binary and ternary emission) pixels. The optical cavity modes of CsPbBr3 QD microdisk lasers are readily controlled by tuning the disk size, where the mode spacing decreases while the number of modes increases with increasing disk diameter. Finally, the versatility of this approach for the integration of environmentally sensitive QDs with different emission signatures and composition on the same chip, while achieving high‐density, high‐resolution large‐area QD arrays with multicolor pixels, is demonstrated.
Visible‐Light‐Mediated Dearomatization/Cyanation Cascade Reaction of Indoles: Access to Highly Functionalized Spiro‐γ‐lactam Indolines with Two Contiguous Sterically Congested Quaternary Carbon Stereocenters
Authors: Wang Qiang , Qu Yi , Xia Qing , Song Hongjian , Song Haibin , Liu Yuxiu , Wang Qingmin
Published: May 2018

A protocol for visible‐light‐induced radical dearomatization/cyanation cascade reaction of indole derivatives is reported. This protocol provides straightforward access to gem‐difluorinated and cyanated 3,3’‐spirocyclic indolines with moderate to excellent diastereoselectivity and permits the construction of two contiguous sterically congested quaternary carbon stereocenters.

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Asymmetric Synthesis of Fused Bicyclic N,O‐ and O,O‐Acetals via Cascade Reaction by Gold(I)/N,N′‐Dioxide‐Nickel(II) Bimetallic Relay Catalysis
Authors: Hu Bowen , Li Jun , Cao Weidi , Lin Qianchi , Yang Jian , Lin Lili , Liu Xiaohua , Feng Xiaoming
Published: May 2018

An efficient catalytic asymmetric cyclization/inverse‐electron‐demand hetero‐Diels‐Alder cascade reaction of β,γ‐unsaturated α‐ketoesters with alkyl amides or alcohols were accomplished. The process was based on the utilization bimetallic catalyst system with achiral gold(I) catalyst and chiral N,N′‐dioxide/Ni(II) catalyst, delivering a variety of fused bicyclic N,O‐acetals or O,O‐acetals in up to 99% yield and 99% ee with >19:1 dr under mild reaction conditions. Based on the control experiments and previous studies, a possible reaction pathway of bimetallic relay catalysis cascade reactions was presented.

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The relationship between organizational policies and practices and work limitations among hospital patient care workers
Authors: Sparer Emily H. , Boden Leslie I. , Sorensen Glorian , Dennerlein Jack T. , Stoddard Anne , Wagner Gregory R. , Nagler Eve M. , Hashimoto Dean M. , Hopcia Karen , Sabbath Erika L.
Published: May 2018

Objective

We examined relationships between organizational policies and practices (OPPs) (safety practices, ergonomic practices, and people‐oriented culture) and work limitations in a sample of hospital workers.

Methods

We used the 6‐item Work Limitations Questionnaire (WLQ) to assess workers’ perceptions of health‐related work limitations. Self‐reported OPPs and the WLQ were collected from workers in Boston, Massachusetts (n = 1277). We conducted random‐intercept multi‐level logistic regression models for each OPP using stepwise selection of covariates.

Results

As the unit‐average ergonomic practice score increased by one, the odds of a worker reporting work limitations decreased by approximately 39% (P‐value = 0.018), adjusted for job title, age, and body mass index. A similar relationship existed for people‐oriented culture (P‐value = 0.038). The association between safety practices and work limitations was similar, but not statistically significant.

Conclusions

This study demonstrated the importance of workplace OPPs. OPPs that promote positive and supportive environments and that foster improvements in ergonomics may help reduce work limitations.
Solvent Effects on the Actinic Step of Donor–Acceptor Stenhouse Adduct Photoswitching
Authors: Lerch Michael M. , Di Donato Mariangela , Laurent Adèle D. , Medved' Miroslav , Iagatti Alessandro , Bussotti Laura , Lapini Andrea , Buma Wybren Jan , Foggi Paolo , Szymański Wiktor , Feringa Ben L.
Published: May 2018

Donor–acceptor Stenhouse adducts (DASAs) are negative photochromes that switch with visible light and are highly promising for applications ranging from smart materials to biological systems. However, the strong solvent dependence of the photoswitching kinetics limits their application. The nature of the photoswitching mechanism in different solvents is key for addressing the solvatochromism of DASAs, but as yet has remained elusive. Here, we employ spectroscopic analyses and TD‐DFT calculations to reveal changing solvatochromic shifts and energies of the species involved in DASA photoswitching. Time‐resolved visible pump‐probe spectroscopy suggests that the primary photochemical step remains the same, irrespective of the polarity and protic nature of the solvent. Disentangling the different factors determining the solvent‐dependence of DASA photoswitching, presented here, is crucial for the rational development of applications in a wide range of different media.
Access to the Bis‐benzene Cobalt(I) Sandwich Cation and its Derivatives: Synthons for a “Naked” Cobalt(I) Source?
Authors: Meier Stefan C. , Holz Albina , Kulenkampff Jan , Schmidt Alexei , Kratzert Daniel , Himmel Daniel , Schmitz Dominik , Scheidt Ernst‐Wilhelm , Scherer Wolfgang , Bülow Christine , Timm Martin , Lindblad Rebecka , Akin Scott T. , Zamudio‐Bayer Vicente , von Issendorff Bernd , Duncan Michael A. , Lau J. Tobias , Krossing Ingo
Published: May 2018

The synthesis and structural characterization of the hitherto unknown parent Co(bz)2+ (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO5+ salt, or directly from Co2(CO)8 and a Ag+ salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(ORF)4]− and [F{Al(ORF)3}2]− {RF=C(CF3)3} and the solvent ortho‐difluorobenzene (o‐DFB). The magnetic properties of Co(bz)2+ were measured and compared in the condensed and gas phases. The weakly bound Co(o‐dfb)2+ salts are of particular interest for the preparation of further CoI salts, for example, the structurally characterized low‐coordinate 12 valence electron Co(PtBu3)2+ and Co(NHC)2+ salts.
Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active‐Metal‐Template Synthesis of [2]Rotaxanes
Authors: Alcântara Arthur F. P. , Fontana Liniquer A. , Rigolin Vitor H. , Andrade Yuri F. S. , Ribeiro Marcos A. , Barros Wdeson P. , Ornelas Catia , Megiatto Jackson D.
Published: May 2018

A CoII/porphyrinate‐based macrocycle in the presence of a 3,5‐diphenylpyridine axial ligand functions as an endotopic ligand to direct the assembly of [2]rotaxanes from diazo and styrene half‐threads, by radical‐carbene‐transfer reactions, in excellent 95 % yield. The method reported herein applies the active‐metal‐template strategy to include radical‐type activation of ligands by the metal‐template ion during the organometallic process which ultimately yields the mechanical bond. A careful quantitative analysis of the product distribution afforded from the rotaxane self‐assembly reaction shows that the CoII/porphyrinate subunit is still active after formation of the mechanical bond and, upon coordination of an additional diazo half‐thread derivative, promotes a novel intercomponent C−H insertion reaction to yield a new rotaxane‐like species. This unexpected intercomponent C−H insertion illustrates the distinct reactivity brought to the CoII/porphyrinate catalyst by the mechanical bond.
Stabilising Peptoid Helices Using Non‐Chiral Fluoroalkyl Monomers
Authors: Gimenez Diana , Aguilar Juan A. , Bromley Elizabeth H. C. , Cobb Steven L.
Published: May 2018

Stability towards protease degradation combined with modular synthesis has made peptoids of considerable interest in the fields of chemical biology, medicine, and biomaterials. Given their tertiary amide backbone, peptoids lack the capacity to hydrogen‐bond, and as such, controlling secondary structure can be challenging. The incorporation of bulky, charged, or chiral aromatic monomers can be used to control conformation but such building blocks limit applications in many areas. Through NMR and X‐ray analysis we demonstrate that non‐chiral neutral fluoroalkyl monomers can be used to influence the Kcis/trans equilibria of peptoid amide bonds in model systems. The cis‐isomer preference displayed is highly unprecedented given that neither chirality nor charge is used to control the peptoid amide conformation. The application of our fluoroalkyl monomers in the design of a series of linear peptoid oligomers that exhibit stable helical structures is also reported.
Radical trans‐Hydroboration of Alkynes with N‐Heterocyclic Carbene Boranes
Authors: Shimoi Masaki , Watanabe Takashi , Maeda Katsuhiro , Curran Dennis P. , Taniguchi Tsuyoshi
Published: May 2018

Hydroboration of internal alkynes with N‐heterocyclic carbene boranes (NHC‐boranes) occurs to provide stable NHC (E)‐alkenylboranes upon thermolysis in the presence of di‐tert‐butyl peroxide. The E isomer results from an unusual trans‐hydroboration, and the E/Z selectivity is typically high (90:10 or greater). Evidence suggests that this hydroboration occurs by a radical‐chain reaction involving addition of an NHC‐boryl radical to an alkyne to give a β‐NHC‐borylalkenyl radical. Ensuing hydrogen abstraction from the starting NHC‐borane provides the product and returns the starting NHC‐boryl radical. Experiments suggest that the observed trans‐selectivity results from kinetic control in the hydrogen‐transfer reaction.
Nobler than the Noblest: Noncubic Gold Microcrystallites
Authors: Mettela Gangaiah , Kouser Summayya , Sow Chaitali , Pantelides Sokrates T. , Kulkarni Giridhar U.
Published: May 2018

Conventional gold comprising the cubic lattice is universally known for its stability. However, well known to chemists and metallurgists, this nobility is challenged by reagents such as aqua regia, which dissolve gold to form a salt solution. Among metals, mercury blends with gold to form amalgam, otherwise transition metals such as copper tend to interact with gold surfaces in electrochemical media. Herein, we report a combined experimental and theoretical investigation of the stability of Au microcrystallites bearing unconventional crystal lattices that exhibit enhanced stability towards Hg and aqua regia and practically no interaction with Cu during electroless plating. The unconventional gold is undoubtedly nobler.
Synthesis and Biological Evaluation of the Antimicrobial Natural Product Lipoxazolidinone A
Authors: Mills Jonathan J. , Robinson Kaylib R. , Zehnder Troy E. , Pierce Joshua G.
Published: May 2018

Natural products have historically been a major source of antibiotics and therefore novel scaffolds are constantly of interest. The lipoxazolidinone family of marine natural products, with an unusual 4‐oxazolidinone heterocycle at their core, represents a new scaffold for antimicrobial discovery; however, questions regarding their mechanism of action and high lipophilicity have likely slowed follow‐up studies. Herein, we report the first synthesis of lipoxazolidinone A, 15 structural analogues to explore its active pharmacophore, and initial resistance and mechanism of action studies. These results suggest that 4‐oxazolidinones are valuable scaffolds for antimicrobial development and reveal simplified lead compounds for further optimization.
Directed Remote Lateral Metalation: Highly Substituted 2‐Naphthols and BINOLs by In Situ Generation of a Directing Group
Authors: Patel Jignesh J. , Laars Marju , Gan Wei , Board Johnathan , Kitching Matthew O. , Snieckus Victor
Published: May 2018

A general synthesis of highly substituted 2‐naphthols based on a new carbanionic reaction sequence is demonstrated. The reaction exploits the dual nature of lithium bases consisting of consecutive ring opening of readily available coumarins with either LiNEt2 or LiNiPr2 into Z‐cinnamamides, thus generating a directing group in situ and allowing, by conformational freedom, a lateral directed remote metalation for ring closure to give the aryl 2‐naphthols in good to excellent yields. These transformations can be combined to provide a more efficient one‐pot process. Mechanistic insight into the remote lateral metalation step, demonstrating the requirement of Z‐cinnamamide, is described. Application of this methodology to the synthesis of highly substituted 3,3′‐diaryl BINOL ligands is also reported.
Nano‐Saturn: Experimental Evidence of Complex Formation of an Anthracene Cyclic Ring with C60
Authors: Yamamoto Yuta , Tsurumaki Eiji , Wakamatsu Kan , Toyota Shinji
Published: May 2018

An anthracene cyclic hexamer was synthesized by the coupling reaction as a macrocyclic hydrocarbon host. This disk‐shaped host included a C60 guest in 1:1 ratio to form a Saturn‐type supramolecular complex in solution and in crystals. X‐ray analysis unambiguously revealed that the guest molecule was accommodated in the middle of the host cavity with several CH⋅⋅⋅π contacts. The association constant Ka determined by NMR titration measurements was 2.3×103 L mol−1 at 298 K in toluene. The structural features and the role of CH⋅⋅⋅π interactions are discussed with the aid of DFT calculations.
Ab Initio Emulsion Atom‐Transfer Radical Polymerization
Authors: Lorandi Francesca , Wang Yi , Fantin Marco , Matyjaszewski Krzysztof
Published: May 2018

Stable latexes of poly(meth)acrylates with predetermined molecular weights, narrow molecular‐weight distributions, and controlled architecture were prepared by true ab initio emulsion atom‐transfer radical polymerization. Water‐soluble (macro)initiators in combination with a hydrophilic catalyst, Cu/tris(2‐pyridylmethyl)amine, initiated the polymerization in the aqueous phase. The catalyst strongly interacted with the surfactant sodium dodecyl sulfate (SDS), thereby tuning the polymerization within nucleated hydrophobic polymer particles. Long‐term stable latexes were obtained, even with SDS loading below 3 wt % relative to monomer. Block and gradient copolymers were prepared in situ. The reaction volume and solid content were successfully increased to 100 mL and 40 vol %, respectively, thus suggesting facile scale‐up of this technique. The proposed setup could be integrated in existing industrial plants used for emulsion polymerization.
trans‐Carbocarbonation of Internal Alkynes through a Formal anti‐Carbopalladation/C−H Activation Cascade
Authors: Reding Andreas , Jones Peter G. , Werz Daniel B.
Published: May 2018

An intramolecular Pd‐catalyzed cascade reaction is presented that consists of a formal anti‐carbopalladation of a C−C triple bond followed by C−H activation. As a result, oligocyclic ring systems with an embedded tetrasubstituted double bond are formed. The key to success in affording the trans geometry of the emerging double bond are alkyne units with residues that must not undergo β‐hydride elimination (e.g., t‐butyl or silyl groups). Silyl groups proved to be a perfect handle to further convert the tetrasubstituted alkenes. The evaluation of kinetic data with a deuterium‐labeled compound and X‐ray analyses of trapped intermediates provided additional insight into the catalytic cycle.
Polymer complexes. LXXI. Spectroscopic studies, thermal properties, DNA binding and antimicrobial activity of polymer complexes
Authors: Diab M.A. , El‐Sonbati A.Z. , Morgan Sh.M. , El‐Mogazy M.A.
Published: May 2018

Polymer complexes of Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) were prepared by the reaction of 3‐allyl‐5‐[(4‐nitrophenylazo)]‐2‐thioxothiazolidine‐4‐one (HL) with metal ions. The structure of polymer complexes was characterized by elemental analysis, IR, UV–Vis spectra, X‐ray diffraction analysis, magnetic susceptibility, conductivity measurements and thermal analysis. Reaction of HL with Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) ions (acetate or chloride) give polymer complexes (1–5) with general stoichiometric [M(L)(O2CCH3)(H2O)2]n (where L = anionic of HL and M = Co(II) (1) or Ni(II) (2)), [Mn(HL)2(OCOCH3)2]n (3), [Cr(L)2(Cl)(H2O)]n (4) and [Cd(HL)(O2CCH3)2]n (5). The value of HOMO–LUMO energy gap (ΔE) for forms (A‐C) of monomer (HL) is 2.529, 2.296 and 2.235 eV, respectively. According to ΔE value, compound has minimum ΔE is the more stable, so keto hydrazone form (C) is more stable than the other forms (azo keto form (A), azo enol form (B)). The interaction between HL, polymer complexes of Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) with Calf thymus DNA showed hypochromism effect. The HL and its polymer complexes were tested against some bacterial and fungal species. The results showed that the Cr(III) polymer complex (4) has more antibacterial activity than HL and polymer complexes (1–3 and 5) against Bacillus subtilis, Staphylococcus aureus and Salmonella typhimurium.
Volatiles and Tendency of Radical Formation of Cold‐Pressed Brazil Nut Oil During Ambient Storage
Authors: Sartori Alan G. de O. , Sampaio Geni R. , Bastos Deborah H. M. , Regitano d'Arce Marisa A. B. , Skibsted Leif H.
Published: May 2018

Cold‐pressed Brazil nut oil (BNO) is a value‐added nontimber forest coproduct of market interest, despite the lack of knowledge about its ambient storage stability. The objective of the present study was to investigate oxidative changes in BNO stored in clear and brown glass bottles under retail conditions with a focus on monitoring for the first time the formation of volatile aroma compounds (VAC), the depletion of tocopherol analogs, and the tendency of radical formation. VAC, whose formation continuously increased and correlated with storage time, were detected using headspace‐solid‐phase microextraction‐gas chromatography–mass spectrometry. Depletion of tocopherols was more pronounced for the oil stored in clear glass bottles and the content loss was higher for alpha‐tocopherol than for gamma‐tocopherol. Furthermore, the tendency of radical formation was detected using a spin‐trapping electron spin resonance spectroscopy method, which was demonstrated to be a simpler, faster, and less sample‐demanding tool to monitor the oxidative status of BNO stored under retail conditions and its results significantly correlated with those obtained using traditional methods for the determination of primary oxidation products. However, the simultaneous measurement of key off‐flavor volatiles is recommended for samples with unknown history.
Sonocrystallization of a Tristearin‐Free Fat
Authors: Kadamne Jeta V. , Moore Maria , Akoh Casimir C. , Martini Silvana
Published: May 2018

The objective of this study was to fractionate a purified interesterified fat to eliminate tristearin (SSS) and to evaluate the crystallization behavior of the tristearin‐free fat. The fractionated sample was crystallized with and without the application of high‐intensity ultrasound (HIU) by supercooling the sample at 2 °C. In the absence of SSS, the crystallization process was driven by low‐melting‐point triacylglycerols (TAG) such as OSS and OOS (O, oleic; S, stearic acid). There were no differences observed in the crystallinity in the sample based on the solid fat content (P > 0.05) along with any microstructural differences. In addition, an increase in the enthalpy of melting was observed upon sonication, indicating higher crystallinity (P < 0.05). Stronger intramolecular forces were formed in the sonicated samples as evidenced by increased viscoelastic parameters such as the elastic modulus (G′) and storage modulus (G″) (P < 0.05). G′ values increased from 138.25 ± 41.30 to 939.73 ± 277.45 Pa while the G″ values increased from 39.15 ± 8.98 to 149.77 ± 16.00 Pa (P < 0.05). Change in viscosity was not observed as a consequence of sonication (P > 0.05). This study showed that HIU was effective in changing the crystallization behavior of SSS‐free fats with low‐melting TAG.
Synthesis of waterborne polyurethane containing alkoxysilane side groups: Study on spacer linkages
Authors: Li Qi , Ye Jun , Qiu Teng , Guo Longhai , He Lifan , Li Xiaoyu
Published: May 2018

Environmentally friendly waterborne polyurethanes (WPUs) modified by moisture‐curable alkoxysilane have been much studied nowadays. In this work, a new diol‐bearing pendant urea‐propyl trimethoxysilane (APD‐Si) was synthesized and used as the chain extender in the preparation of a silicone‐modified WPU dispersion. Both the formation of hybrid networks based on the condensation of trimethoxysilane groups and the enhanced microphase separation of the hard and soft segments have been found to rely on the strong hydrogen‐bonding capability of the urea‐containing spacers, which link the alkoxysilane groups with the backbone of WPU. Because of the synergism of chemically bonded silsesquioxane and physically hydrogen bonded hard domains serving as crosslinking points, the mechanical properties of the hybrid films of WPU are improved, especially the modulus and yield strength. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46628.
Laser transmission welding of poly(lactic acid) and polyamide66/sepiolite nanocomposites
Authors: Navas‐Martos Francisco J. , Yebra‐Rodríguez África , La Rubia M. Dolores
Published: May 2018

Influence of sepiolite nanoclay on the properties of the resulting join between poly(lactic acid) (PLA) and different Polyamide66 (PA66)/nanoclay nanocomposites was studied in this work. Six different polymer nanocomposites based on PA66 were manufactured through a melt compounding process by adding a fixed 1.64 wt % of a commercial IR absorber additive and the respective weight percentages of sepiolite to the polymer matrix. Several nanocomposite/PLA joints were finally performed by means of the transmission laser welding technology and the resulting weldings were characterized in terms of mechanical properties by performing peeling and shearing tests. Furthermore, both welded and mechanically tested samples were also analyzed by scanning electron microscopy in order to study the morphology of the weld seam. The results of the performed tests show that the addition of sepiolite to the PA66 improves the welding performance only in those cases in which the percentage of sepiolite of the nanocomposites is higher than 5 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2018,135, 46638.
Long‐term studies on PVC membranes used in tunnels
Authors: Londschien Martin , Bonnet Martin
Published: May 2018

Building tunnels places very high demands on the durability of all materials used. However, up to now only very few real long‐term studies on waterproofing membranes used in tunnels have been carried out. Samples from soft poly(vinyl chloride) membranes with diverse ages of over 40 years were taken during refurbishment programs to ensure safety in various Swiss tunnels. The results of gel permeation chromatography as well as measurements of the plasticizer and gel content showed that all of the membranes have very low polymer degradation or, respectively, none detectable crosslinking of the polymer. The main change determined was the decrease in plasticizer content and the resulting increase in stiffness of the membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46689.
Oxygenates from the Electrochemical Reduction of Carbon Dioxide
Authors: Feng Guanghui , Chen Wei , Wang Baiyin , Song Yanfang , Li Guihua , Fang Jianhui , Wei Wei , Sun Yuhan
Published: May 2018

Electrochemical reduction of carbon dioxide (CO2) driven by renewable electricity to give chemicals and fuels is considered an ideal approach that can alleviate both carbon emission and energy tension stress. High‐value chemicals such as oxygenates can be effectively produced from the electroreduction of CO2, and this is highly attractive to promote the economy and applicability of CO2 utilization. This review focuses on recent advancements in the electrochemical reduction of CO2 to formic acid, methanol, ethanol, acetic acid, and other oxygenates. The principles of the process, influencing factors, and typical catalysts are summarized. On the basis of the aforementioned discussions, we present future prospects for further development of the electroreduction of CO2 to oxygenates.
Atomic and Molecular Layer Deposition for Superior Lithium‐Sulfur Batteries: Strategies, Performance, and Mechanisms
Authors: Sun Qian , Lau Kah Chun , Geng Dongsheng , Meng Xiangbo
Published: May 2018

Lithium‐sulfur (Li−S) batteries hold great promise for powering future electric vehicles, given their high theoretical specific energy of 2600 Wh/kg and low cost. However, the commercialization of Li−S batteries is being hindered by several serious technical challenges including the corrosion of lithium metal anodes, the formation of lithium dendrites, the shuttle effect of lithium polysulfides, the decomposition of electrolyte, and low conductivity of sulfur and lithium sulfide. In the past decade, atomic layer deposition (ALD) as a new research thrust has been demonstrated to be a very effective technique in dramatically improving the performance of lithium‐ion batteries (LIBs), featuring many unique advantages in fabricating sub‐nano to nanoscale inorganic films. Stimulated by ALD's benefits, recently more and more research efforts have been reported in ALD for addressing the technical issues of Li−S batteries and show very promising outcomes. Analogous to ALD, molecular layer deposition (MLD) is a thin‐film technique exclusively for polymeric films. Some of the latest studies have uncovered that MLD is an alternative tool for tackling the challenges of Li−S batteries with exceptional effectiveness. In this review, for the first time, we systematically summarized the progresses of both ALD and MLD in developing superior Li−S batteries, covering their technical strategies, resulting performance, and the underlying mechanisms. In terms of the functionalities of ALD and MLD in Li−S batteries, we focus our discussion in two main complementary aspects: (i) surface coatings and (ii) electrode designs.
Reward ignorant modeling of dynamic treatment regimes
Authors: Wallace Michael P. , Moodie Erica E. M. , Stephens David A.
Published: May 2018

Personalized medicine optimizes patient outcome by tailoring treatments to patient‐level characteristics. This approach is formalized by dynamic treatment regimes (DTRs): decision rules that take patient information as input and output recommended treatment decisions. The DTR literature has seen the development of increasingly sophisticated causal inference techniques that attempt to address the limitations of our typically observational datasets. Often overlooked, however, is that in practice most patients may be expected to receive optimal or near‐optimal treatment, and so the outcome used as part of a typical DTR analysis may provide limited information. In light of this, we propose considering a more standard analysis: ignore the outcome and elicit an optimal DTR by modeling the observed treatment as a function of relevant covariates. This offers a far simpler analysis and, in some settings, improved optimal treatment identification. To distinguish this approach from more traditional DTR analyses, we term it reward ignorant modeling, and also introduce the concept of multimethod analysis, whereby different analysis methods are used in settings with multiple treatment decisions. We demonstrate this concept through a variety of simulation studies, and through analysis of data from the International Warfarin Pharmacogenetics Consortium, which also serve as motivation for this work.
Including cannabinoids in the treatment of painful schwannomatosis
Authors: Iorno Vittorio , Roberto Anna , Colantonio Laura Brigitta , Landi Laura , Corli Oscar
Published: May 2018

A 47‐year‐old man, affected by Schwannomatosis, presented a very severe pain (10/10, NRS) with paroxysmal shooting episodes, allodynia, paresthesia, and dysesthesia; in parallel, the patient had lost weight (from 70 to 49 kg) and experienced fatigue and deep depression. The previous pain prescription, including opioids and antineutopathic drugs, was fully ineffective. We progressively substituted this therapy with 15 drops, 3 times/daily, of THC/CBD in a concentration ratio 5:1, equal to 15 mg of active substance each time, reaching improvement in pain intensity (6/10) and in several other aspects as mood and quality of life
Cortical brain structure and sexual orientation in adult females with bipolar disorder or attention deficit hyperactivity disorder
Authors: Abé Christoph , Rahman Qazi , Långström Niklas , Rydén Eleonore , Ingvar Martin , Landén Mikael
Published: May 2018

Background

Nonheterosexual individuals have higher risk of psychiatric morbidity. Together with growing evidence for sexual orientation‐related brain differences, this raises the concern that sexual orientation may be an important factor to control for in neuroimaging studies of neuropsychiatric disorders.

Methods

We studied sexual orientation in adult psychiatric patients with bipolar disorder (BD) or ADHD in a large clinical cohort (N = 154). We compared cortical brain structure in exclusively heterosexual women (HEW, n = 29) with that of nonexclusively heterosexual women (nHEW, n = 37) using surface‐based reconstruction techniques provided by FreeSurfer.

Results

The prevalence of nonheterosexual sexual orientation was tentatively higher than reported in general population samples. Consistent with previously reported cross‐sex shifted brain patterns among homosexual individuals, nHEW patients showed significantly larger cortical volumes than HEW in medial occipital brain regions.

Conclusion

We found evidence for a sex‐reversed difference in cortical volume among nonheterosexual female patients, which provides insights into the neurobiology of sexual orientation, and may provide the first clues toward a better neurobiological understanding of the association between sexual orientation and mental health. We also suggest that sexual orientation is an important factor to consider in future neuroimaging studies of populations with certain mental health disorders.
Building organizational resilience through sensemaking: The case of climate change and extreme weather events
Authors: Tisch Daniel , Galbreath Jeremy
Published: May 2018

Resilience to increasingly frequent extreme weather events from climate change is of concern in many industries, especially those in the agricultural sector. This qualitative study utilizes interviews with 38 dairy farmers in New Zealand, observations recorded on site and archival documents to examine retention–enactment–selection sensemaking microprocesses thematically, and to show how sensemaking enables and constrains resilience. We found that farmers have achieved organizational resilience to extreme weather patterns during the decade to 2014 that is benign to belief in climate change; that adaptation to climate change can be anticipatory; and that social relationships in rural communities are instrumental to building organizational resilience. The implication for farmers and policy‐makers is that resilience can be built by local members of rural communities in places that are familiar to them—a phenomenon we introduce as “community sensegiving.” Future research directions using place‐based research approaches and sensemaking concepts to build resilience are offered.
The effect of automatic assessment on novice programming: Strengths and limitations of existing systems
Authors: Ullah Zahid , Lajis Adidah , Jamjoom Mona , Altalhi Abdulrahman , Al‐Ghamdi Abdullah , Saleem Farrukh
Published: May 2018

Computer programming is always of high concern for students in introductory programming courses. High rates of failure occur every semester due to lack of adequate skills in programming. No student can become a programmer overnight because such learning requires proper guidance as well as consistent practice with the programming exercises. The role of instructors in the development of students' learning skills is crucial in order to provide feedback on their errors and improve their knowledge accordingly. On the other hand, due to the large number of students, instructors are also overloading themselves to focus on each individual student's errors. To address these issues, researchers have developed numerous Automatic Assessment (AA) systems that not only evaluate the students' programs but also provide instant feedback on their errors as well as abridge the workload of the instructors. Due to the large pool of existing systems, it is difficult to cover each and every system in one study. Therefore, this paper provides a comprehensive overview of some of the existing systems based on the three‐analysis approaches: dynamic, static, and hybrid. Moreover, this paper aims to discuss the strengths and limitations of these systems and suggests some potential recommendations regarding the AA specifications for novice programming, which may help in standardizing these systems.
The significant influence of having children on the postoperative prognosis of patients with nonsmall cell lung cancer: A propensity score‐matched analysis
Authors: Takamori Shinkichi , Tagawa Tetsuzo , Toyokawa Gouji , Ueo Hiroki , Shimokawa Mototsugu , Kinoshita Fumihiko , Matsubara Taichi , Kozuma Yuka , Haratake Naoki , Akamine Takaki , Katsura Masakazu , Takada Kazuki , Hirai Fumihiko , Shoji Fumihiro , Okamoto Tatsuro , Oda Yoshinao , Maehara Yoshihiko
Published: May 2018

The aim of this study was to elucidate the relationship between family‐associated factors and the postoperative prognosis in patients with nonsmall cell lung cancer (NSCLC). Additionally, we investigated whether having children was associated with the postoperative maintenance of the nutritional status. We selected 438 NSCLC patients who had undergone curative lung resection between 2004 and 2011 at Kyushu University (Fukuoka, Japan), whose family‐associated factors were available. Nutritional indices, including the prognostic nutritional index (PNI), were used to estimate the change in the nutritional status for 1 year after surgery. A propensity score analysis was conducted after adjusting the following variables: sex, age, smoking history, performance status, pathological stage, and histological type. Three hundred patients (68.5%) had both children and partners. Forty‐nine patients (11.2%) only had children, and 56 (12.8%) patients only had a partner. Thirty‐three patients (7.5%) did not have a partner or children. The overall survival (OS) and disease‐free survival (DFS) of the partner‐present and partner‐absent patients did not differ to a statistically significant extent (P = .862 and P = .712, respectively). However, childless patients showed significantly shorter OS and DFS in comparison with patients with children (P = .005 and P = .002, respectively). The postoperative exacerbation of PNI was significantly greater in childless patients than in patients with children (P = .003). These results remained after propensity score matching. Childless patients had a significantly poorer postoperative prognosis than those with children. Surgeons caring for childless NSCLC patients should be aware of the poorer postoperative outcomes in this population.
Prevention of cisplatin‐induced hearing loss in children: Informing the design of future clinical trials
Authors: Minasian Lori M. , Frazier A. Lindsay , Sung Lillian , O’Mara Ann , Kelaghan Joseph , Chang Kay W. , Krailo Mark , Pollock Brad H. , Reaman Gregory , Freyer David R.
Published: May 2018

Cisplatin is an essential chemotherapeutic agent in the treatment of many pediatric cancers. Unfortunately, cisplatin‐induced hearing loss (CIHL) is a common, clinically significant side effect with life‐long ramifications, particularly for young children. ACCL05C1 and ACCL0431 are two recently completed Children’s Oncology Group studies focused on the measurement and prevention of CIHL. The purpose of this paper was to gain insights from ACCL05C1 and ACCL0431, the first published cooperative group studies dedicated solely to CIHL, to inform the design of future pediatric otoprotection trials. Use of otoprotective agents is an attractive strategy for preventing CIHL, but their successful development must overcome a unique constellation of methodological challenges related to translating preclinical research into clinical trials that are feasible, evaluate practical interventions, and limit risk. Issues particularly important for children include use of appropriate methods for hearing assessment and CIHL severity grading, and use of trial designs that are well‐informed by preclinical models and suitable for relatively small sample sizes. Increasing interest has made available new funding opportunities for expanding this urgently needed research.
Preliminary experience with a novel Multisensor algorithm for heart failure monitoring: The HeartLogic index
Authors: Santini Luca , Mahfouz Karim , Schirripa Valentina , Danisi Nicola , Leone Michelangelo , Mangone Gloria , Campari Monica , Valsecchi Sergio , Ammirati Fabrizio
Published: May 2018

Key Clinical Message

We report the first case of a patient in whom an implantable cardioverter‐defibrillator (ICD) endowed with HeartLogic, a novel algorithm for heart failure (HF) monitoring, was implanted in clinical practice. The good temporal association between HeartLogic index threshold crossings and HF hospitalizations confirms the high sensitivity in detecting gradual worsening of HF.
Is black tar heroin use associated with wound botulism? A report of two Hispanic patients
Authors: Qureshi Ihtesham A. , Qureshi Mohtashim A. , Vellipuram Anantha‐Ramana , Kassar Darine
Published: May 2018

Key Clinical Message

Wound botulism is a potentially lethal condition that can cause paralysis. Its association with black tar heroin is a well‐established fact. It is essential to alert clinicians in recognizing the patients with history of injection drug abuse presenting with clinical features of botulism early on admission for prompt diagnosis and treatment.
Coupling of Epoxides and Lactones by Cationic Indium Catalysts To Form Functionalized Spiro‐Orthoesters
Authors: Jung Hyuk‐Joon , Chang Chen , Yu Insun , Aluthge Dinesh C. , Ebrahimi Tannaz , Mehrkhodavandi Parisa
Published: May 2018

We prepared a cationic indium catalyst for the conversion of epoxides and lactones into spiro‐orthoesters (SOEs), a family of expanding monomers. The cationic indium alkyl complexes [(NNiO)In(CH2SiMe3)(S)][B{3,5‐(CF3)2C6H3}4] (2⋅Solv; H(NNiO)=2,4‐dicumyl‐6‐({[2‐(dimethylamino)cyclohexyl]imino}methyl)phenol, S=OEt2 or THF) were synthesized and fully characterized. The reaction of ϵ‐caprolactone with 1,2‐epoxy‐7‐octene resulted in the formation of 2‐(hex‐5‐en‐1‐yl)‐1,4,6‐trioxaspiro[4.6]undecane (SOE1) with full conversion of both components. We extended the substrate scope to five‐ and six‐membered lactones as well as to a number of functionalized epoxides. The reactivity of the SOEs was explored.
Asymmetric Supercapacitor Based on Chemically Coupled Hybrid Material of Fe2O3‐Fe3O4 Heterostructure and Nitrogen‐Doped Reduced Graphene Oxide
Authors: Mallick Sourav , Jana Partha Pratim , Raj C. Retna
Published: May 2018

The synthesis of a novel chemically coupled hybrid material based on Fe2O3‐Fe3O4 heterostructure and nitrogen‐doped reduced graphene oxide (N‐rGO) for the development of high performance supercapacitor devices is demonstrated. The chemically coupled hybrid material is synthesized in a one‐pot method under hydrothermal condition, resulting in the formation of crystalline α‐Fe2O3 and poorly crystalline/amorphous Fe3O4. The Fe2O3‐Fe3O4 particles have an average size of 30–50 nm. Chemical integration of Fe2O3‐Fe3O4 with N‐rGO through Fe‐O−C bonds is achieved. The chemical coupling of N‐rGO with pseudocapacitive Fe2O3‐Fe3O4 enhances the overall performance of the composite. Two asymmetric supercapacitor devices using the hybrid material either as positive or negative electrode are fabricated. The supercapacitive behaviour is evaluated in terms of specific capacitance, energy density, power density and cycling stability, showing excellent performance. The asymmetric device based on hybrid material as the positive and activated carbon as the negative electrode, delivers a specific capacitance of 111.95 F g−1 at 0.8 A g−1 with an energy density of 44.93 Wh kg−1. The supercapacitor has excellent cycling stability with a capacitance retention of >92 % even after 10000 extensive charge‐discharge cycles. The all‐solid‐state asymmetric supercapacitor device is fabricated using gel electrolyte. Solid‐state devices connected in series successfully light up 29 LEDs.
Simple Microwave‐Assisted Synthesis of Delafossite CuFeO2 as an Anode Material for Sodium‐Ion Batteries
Authors: Youn Duck Hyun , Choi Yo Han , Kim Jun‐Hyuk , Han Sungmin , Heller Adam , Mullins C. Buddie
Published: May 2018

A simple synthesis of microcrystalline delafossite CuFeO2 is reported. Rhombohedral CuFeO2 0.7–2.5 μm crystals were obtained by heating an aqueous solution of Fe(NO3)3, Cu(NO3)2, and propionaldehyde to 180 °C for 2 h in a microwave oven, which enables the synthesis of the CuFeO2 microcrystals with significantly reduced heating time at a mild temperature. The electrode made with the delafossite CuFeO2 discharged at 0.01 V and charged at 1.5 V vs Na+/Na and retained a reversible capacity of 240 mAh g−1 at a specific current of 0.1 Ag−1 after 200 cycles. The delafossite CuFeO2 microcrystals could be a potential anode material for sodium‐ion batteries considering the simple synthetic method and acceptable reversible capacity compared to other nanostructured anode materials.
Donor–Donor′–Acceptor Triads Based on [3.3]Paracyclophane with a 1,4‐Dithiafulvene Donor and a Cyanomethylene Acceptor: Synthesis, Structure, and Electrochemical and Photophysical Properties
Authors: Sako Katsuya , Hasegawa Tomoya , Onda Hiroyuki , Shiotsuka Michito , Watanabe Motonori , Shinmyozu Teruo , Tojo Sachiko , Fujitsuka Mamoru , Majima Tetsuro , Hirao Yasukazu , Kubo Takashi , Iwanaga Tetsuo , Toyota Shinji , Takemura Hiroyuki
Published: May 2018

Donor–donor′–acceptor triads (1, 2), based on [3.3]paracyclophane ([3.3]PCP) as a bridge, with electron‐donating properties (D′) using 1,4‐dithiafulvene (DTF; TTF half unit) as a donor and dicyanomethylene (DCM; TCNE half unit) or an ethoxycarbonyl‐cyanomethylene (ECM) as an acceptor were designed and synthesized. The pulse radiolysis study of 1 a in 1,2‐dichloroethane allowed the clear assignment of the absorption bands of the DTF radical cation (1 a.+), whereas the absorption bands due to the DCM radical anion could not be observed by γ‐ray radiolysis in 2‐methyltetrahydrofuran rigid glass at 77 K. Electrochemical oxidation of 1 a first generates the DTF radical cation (1 a.+), the absorption bands of which are in agreement with those observed by a pulse radiolysis study, followed by dication (1 a2+). The ESR spectrum of 1 a.+ showed a symmetrical signal with fine structure and an ESR simulation predicted that the spin of 1 a.+ is delocalized over S and C atoms of the DTF moiety and the central C atom of the trimethylene bridge bearing the DTF moiety. Pulse radiolysis, ESR, and electrochemical studies indicate that the DTF radical cation of 1 a.+ is more stable than that of 6.+, and the latter shows a strong tendency to dimerize. This result indicates that the [3.3]PCP moiety as a bridge can stabilize the DTF radical cation more than the 1,3‐diphenylpropane moiety because of kinetic stability due to its rigid structure and the weak electronic interaction of DTF and DCM moieties through [3.3]PCP.
Progress, Mechanisms and Applications of Liquid‐Metal Catalyst Systems
Authors: Liang Shu‐Ting , Wang Hong‐Zhang , Liu Jing
Published: May 2018

Among the significant growths of liquid metal (LM) research achieved over the past few years, the field of LM as catalysts offers promising opportunities for material scientists to exploit, and thus, burgeoning progress has been made. This article presents an overview of recent progress in developing LM catalysis, which spans from liquid‐phase catalysts, photocatalysts, heterogeneous catalysts, and bimetallic catalysts, to catalysts based on liquid‐metal/metal‐oxide (LM/MO) frameworks. The different types, preparation methods, and typical applications of LM catalysts are classified and reviewed. Typical catalytic applications of LM systems discussed include the growth of graphene films/nanoribbons/carbon nanotube, photocatalytic degradation of CR or PFOA/splitting of H2O/reduction of CO2, and catalytic reactions like butane or acetylene dehydrogenation, methanol steam reforming, and reduction of potassium ferricyanide. The prospects, future trends, and challenges of LM catalysts are also mentioned.