bluuebunny/crossref_metadata_2025 huggingface dataset:
Achieving the impossible: a review of magic-based interventions and their effects on wellbeing
Authors: Wiseman Richard , Watt Caroline
Published: December 2018

Research has demonstrated that involvement with mainstream performing arts, such as music and dance, can boost wellbeing. This article extends this work by reviewing little-known research on whether learning magic tricks can have an equally beneficial effect. We first present an historic overview of several magic-based interventions created by magicians, psychologists and occupational therapists. We then identify the potential benefits of such interventions, and review studies that have attempted to systematically assess these interventions. The studies have mostly revealed beneficial outcomes, but much of the work is of poor methodological quality (involving small numbers of participants and no control group), and has tended to focus on clinical populations. Finally, we present guidelines for future research in the area, emphasizing the need for more systematic and better-controlled studies.
Marmelada de Santa Luzia: análise da potencialidade de Luziânia e região para uma indicação geográfica
Authors: Aveni Alessandro , Mello Andrei Simão de , Cordeiro Fabio Lima , Saldanha Daniela Soares Couto , Carvalho Debora Mendes
Published: December 2018

O presente trabalho relata uma pesquisa exploratória desenvolvida com visitas de campo e pesquisa bibliográfica, com o objetivo de analisar elementos para viabilidade de pedido de registro de Indicação Geográfica para o produto Marmelada de Santa Luzia em Luziânia (GO). A análise realizada teve como base os dispositivos legais pertinentes ao tema e apresenta um breve esboço histórico do surgimento do produto na região, demonstra as características de produção que envolvem saberes locais e identifica diversos elementos que denotam como o produto é popularmente conhecido, ou seja, que comprovam a sua notoriedade e boa fama. Conclui-se que o produto apresenta potencial para registro de uma Indicação Geográfica na modalidade de Indicação de Procedência, mas que estudos técnicos e econômicos mais aprofundados são necessários para obtenção do registro perante o INPI.
Prospecção‌ ‌Tecnológica‌ ‌de‌ ‌Patentes‌ ‌Sobre‌ ‌Cultivos‌ ‌de‌ ‌Microalgas‌ ‌Visando‌ ‌à‌ ‌Produção‌ ‌de‌ ‌ Biodiesel‌ ‌
Authors: Santos Camila Cristina Andrade dos , Queiroz Luciano Matos , Perelo Louisa Wessels , Andrade Emerson Sales
Published: December 2018

O modelo insustentável do uso intensivo de combustíveis fósseis tem impulsionado o desenvolvimento de pesquisas cujo objetivo prioritário é a obtenção de alternativas mais limpas e financeiramente viáveis. Dentre essas alternativas, insere-se o biodiesel produzido a partir da biomassa obtida mediante o cultivo de microalgas. Essa pesquisa realizou um estudo prospectivo de patentes sobre o cultivo de microalgas para a produção de biodiesel utilizando o código do Sistema Cooperativo de Classificação de Patentes (CCP), C12N1/12 combinado com C12P7/649, como melhor estratégia de busca, chegando a um total de 309 patentes, agrupadas em 103 famílias. Os resultados refletiram que essa tecnologia se encontra em plena difusão, havendo maior número de depósitos e depositantes nos Estados Unidos da América, China e Coreia do Sul, e que os principais depositantes ainda são as pessoas físicas.
Overview of non‐coding mutations in chronic lymphocytic leukemia
Authors: Spina Valeria , Rossi Davide
Published: December 2018

Chronic lymphocytic leukemia (CLL) is the most frequent leukemia type in which the genetic alterations influencing the clinico‐biological course are not entirely understood. CLL has a heterogeneous course, with some patients showing an indolent course and others experiencing an aggressive course. Whole‐genome sequencing and whole‐exome sequencing studies identified recurrently mutated genes in CLL and profiled its clonal evolution patterns. However, more recent whole‐genome sequencing studies also identified variants in non‐coding sequences of the CLL genome, revealing important lesions outside the protein‐coding regions. Here we describe the most representative non‐coding lesion of the CLL genome, including lesions in the 3′‐UTR region of NOTCH1 which result in the truncation of the NOTCH1 protein PEST domain, and non‐coding mutations in an enhancer region on chromosome 9p13 which result in reduced expression of the PAX5 transcription factor. In addition, we describe the role of microRNA in CLL, in particular the miR15a/miR16‐1 microRNA recurrently affected by deletions of chromosome 13q14. Together, new findings in non‐coding genome genetic lesions provide a more complete portrait of the genomic landscape of CLL with clinical implications.
20% Efficient Perovskite Solar Cells with 2D Electron Transporting Layer
Authors: Zhao Xiaojuan , Liu Shuangshuang , Zhang Haitao , Chang Sheng‐Yung , Huang Wenchao , Zhu Bowen , Shen Yan , Shen Cai , Wang Deyu , Yang Yang , Wang Mingkui
Published: December 2018

Herein, a 2D SnS2 electron transporting layer is reported via self‐assembly stacking deposition for highly efficient planar perovskite solar cells, achieving over 20% power conversion efficiency under AM 1.5 G 100 mW cm−2 light illumination. To the best of the authors' knowledge, this represents the highest efficiency that has so far been reported for perovskite solar cells using a 2D electron transporting layer. The large‐scaled 2D multilayer SnS2 sheet structure triggers a heterogeneous nucleation over the perovskite precursor film. The intermolecular Pb⋅⋅⋅S interactions between perovskite and SnS2 could passivate the interfacial trap states, which suppress charge recombination and thus facilitate electron extraction for balanced charge transport at interfaces between electron transporting layer/perovskite and hole transporting layer/perovskite. This work demonstrates that 2D materials have great potential for high‐performance perovskite solar cells.
Controlled Doping of Wafer‐Scale PtSe2 Films for Device Application
Authors: Xu Hu , Zhang Haima , Liu Yawen , Zhang Simeng , Sun Yangye , Guo Zhongxun , Sheng Yaochen , Wang Xudong , Luo Chen , Wu Xing , Wang Jianlu , Hu Weida , Xu Zihan , Sun Qingqing , Zhou Peng , Shi Jing , Sun Zhengzong , Zhang David Wei , Bao Wenzhong
Published: December 2018

Semiconductive transition metal dichalcogenides (TMDs) have been considered as next generation semiconductors, but to date most device investigations are still based on microscale exfoliation with a low yield. Wafer scale growth of TMDs has been reported but effective doping approaches remain challenging due to their atomically thick nature. This work reports the synthesis of wafer‐scale continuous few‐layer PtSe2 films with effective doping in a controllable manner. Chemical component analyses confirm that both n‐doping and p‐doping can be effectively modulated through a controlled selenization process. The electrical properties of PtSe2 films have been systematically studied by fabricating top‐gated field effect transistors (FETs). The device current on/off ratio is optimized in two‐layer PtSe2 FETs, and four‐terminal configuration displays a reasonably high effective field effect mobility (14 and 15 cm2 V−1 s−1 for p‐type and n‐type FETs, respectively) with a nearly symmetric p‐type and n‐type performance. Temperature dependent measurement reveals that the variable range hopping is dominant at low temperatures. To further establish feasible application based on controllable doping of PtSe2, a logic inverter and vertically stacked p–n junction arrays are demonstrated. These results validate that PtSe2 is a promising candidate among the family of TMDs for future functional electronic applications.
High Performance Roll‐to‐Roll Produced Fullerene‐Free Organic Photovoltaic Devices via Temperature‐Controlled Slot Die Coating
Authors: Na Seok‐In , Seo You‐Hyun , Nah Yoon‐Chae , Kim Seok‐Soon , Heo Hyojung , Kim Jueng‐Eun , Rolston Nicholas , Dauskardt Reinhold H. , Gao Mei , Lee Youngu , Vak Doojin
Published: December 2018

Solution‐processed organic photovoltaics (OPVs) have continued to show their potential as a low‐cost power generation technology; however, there has been a significant gap between device efficiencies fabricated with lab‐scale techniques—i.e., spin coating—and scalable deposition methods. Herein, temperature‐controlled slot die deposition is developed for the photoactive layer of OPVs. The influence of solution and substrate temperatures on photoactive films and their effects on power conversion efficiency (PCE) in slot die coated OPVs using a 3D printer‐based slot die coater are studied on the basis of device performance, molecular structure, film morphology, and carrier transport behavior. These studies clearly demonstrate that both substrate and solution temperatures during slot die coating can influence device performance, and the combination of hot substrate (120 °C) and hot solution (90 °C) conditions result in mechanically robust films with PCE values up to 10.0% using this scalable deposition method in air. The efficiency is close to that of state‐of‐the‐art devices fabricated by spin coating. The deposition condition is translated to roll‐to‐roll processing without further modification and results in flexible OPVs with PCE values above 7%. The results underscore the promising potential of temperature‐controlled slot die coating for roll‐to‐roll manufacturing of high performance OPVs.
A Stretchable Ionic Diode from Copolyelectrolyte Hydrogels with Methacrylated Polysaccharides
Authors: Lee Hae‐Ryung , Woo Jaesung , Han Seok Hee , Lim Seung‐Min , Lim Sungsoo , Kang Yong‐Woo , Song Won Jun , Park Jae‐Man , Chung Taek Dong , Joo Young‐Chang , Sun Jeong‐Yun
Published: December 2018

As the demand for soft and flexible devices steadily increases, the ionic applications demonstrated with gel materials have come under the spotlight. Here, stretchable and wearable ionic diodes (SIDs) made from polyelectrolyte hydrogels are introduced. Polyelectrolyte hydrogels are mechanically modified using methacrylated polysaccharides while preserving the ion‐permselectivity of poly(sulfopropyl acrylate) potassium salt (PSPA) and poly([acrylamidopropyl]trimethylammonium chloride) (PDMAPAA‐Q), forming ionic copolymers. Then, SIDs composed of polyelectrolyte copolymer hydrogels are fabricated in VHB substrates as a stretchable and transparent insulating layer which is engraved by a laser. The SIDs show rectifying behaviors beyond the stretch of 3 with the aid of perfect adhesion between hydrogels and elastomeric substrates, and preserve their rectifications over hundreds of cycles. The operation of the SID is visualized by a wearable ionic circuit which rectifies ionic currents and lightens the LED under the forward bias during finger movements.
Biomimetic Supertough and Strong Biodegradable Polymeric Materials with Improved Thermal Properties and Excellent UV‐Blocking Performance
Authors: Zhang Xiao , Liu Weifeng , Yang Dongjie , Qiu Xueqing
Published: December 2018

The preparation of biodegradable polymeric materials with both great strength and toughness remains a huge challenge. The natural spider silk exhibits a combined super high tensile strength and high fracture toughness (150–190 J g−1), attributing to the hierarchically assembled nanophase separation and the densely organized sacrificial hydrogen bonds confined in the nanoscale granules. Herein, inspired by natural spider silk, a facile strategy is reported for the preparation of nanostructured biomimetic polymeric material by incorporating biomass‐derived lignosulfonic acid (LA) as interspersed nanoparticles into a biodegradable poly(vinyl alcohol) (PVA) matrix. The fabricated PVA/LA nanocomposite film exhibits the world's highest toughness of 172 (±5) J g−1 among the PVA materials, as well as a powerful tensile strength of 98.2 MPa and a large breaking strain of 282%. The outstanding performance is attributed to the strain‐induced scattering of LA nanoparticles in the PVA matrix and the strong intermolecular sacrificial hydrogen bonds confined in the interphase. Moreover, after introducing the easily available green biomass LA, the prepared biomimetic polymer films show excellent ultraviolet‐blocking performance and good thermal stability. As both PVA and LA are biodegradable, this work presents an innovative design strategy for fully biodegradable robust polymeric materials with integrated strength and toughness.
Biocompatible Soft Fluidic Strain and Force Sensors for Wearable Devices
Authors: Xu Siyi , Vogt Daniel M. , Hsu Wen‐Hao , Osborne John , Walsh Timothy , Foster Jonathan R. , Sullivan Sarah K. , Smith Vincent C. , Rousing Andreas W. , Goldfield Eugene C. , Wood Robert J.
Published: December 2018

Fluidic soft sensors have been widely used in wearable devices for human motion capturing. However, thus far, the biocompatibility of the conductive liquid, the linearity of the sensing signal, and the hysteresis between the loading and release processes have limited the sensing quality as well as the applications of these sensors. In this paper, silicone based strain and force sensors composed of a novel biocompatible conductive liquid (potassium iodide and glycerol solution) are introduced. The strain sensors exhibit negligible hysteresis up to 5 Hz, with a gauge factor of 2.2 at 1 Hz. The force sensors feature a novel multifunctional layered structure, with microcylinder‐filled channels to achieve high linearity, low hysteresis (5.3% hysteresis at 1 Hz), and good sensitivity (100% resistance increase at a 5 N load). The sensors' gauge factors are stable at various temperatures and humidity levels. These biocompatible, low hysteresis, and high linearity sensors are promising for safe and reliable diagnostic devices, wearable motion capture, and compliant human–computer interfaces.
Ultrathin MoO3 Layers in Composite Metal Electrodes: Improved Optics Allow Highly Efficient Organic Light‐Emitting Diodes
Authors: Li Yungui , Tang Zheng , Hänisch Christian , Will Paul‐Anton , Kovačič Milan , Hou Ji‐Ling , Scholz Reinhard , Leo Karl , Lenk Simone , Reineke Sebastian
Published: December 2018

Molybdenum trioxide (MoO3) has been investigated as a seeding and energy‐level modification layer for ultrathin metal electrode in organic light‐emitting diodes (OLEDs). However, the optical effect of this interlayer has not been addressed so far. In this article, the influence of the thin MoO3 layer for bottom emitting OLEDs is thoroughly investigated. It is noted that a thin MoO3 layer has a substantial impact on the device performance through inducing a synergistic effect of suppressing the nonradiative surface plasmon polariton (SPP) modes and modulating the cavity resonance. In presence of MoO3 layer, the SPP mode is suppressed from 400 to 520 nm. Moreover, introducing a thin MoO3 layer reduces the reflectance of the Au/Ag electrode, resulting in a decreased destructive resonance in devices. These combined effects enable to build highly efficient OLEDs, with the external quantum efficiency and luminous efficacy of two‐unit stacked white OLEDs reaching 38.8% and 53.9 lm W−1 at 1000 cd m−2, when substrate and air modes are extracted. The efficiency is about 1.9 times higher compared to the one without MoO3 layer. The result provides insights into indium tin oxide free optoelectronic devices, as well as light extraction strategy and color purity manipulations for OLEDs.
Optimized Electrolyte Loading and Active Film Thickness for Sandwich Polymer Light‐Emitting Electrochemical Cells
Authors: Diethelm Matthias , Grossmann Quirin , Schiller Andreas , Knapp Evelyne , Jenatsch Sandra , Kawecki Maciej , Nüesch Frank , Hany Roland
Published: December 2018

Effects of ion concentration and active layer thickness play a critical role on the performance of light‐emitting electrochemical cells. Expanding on a pioneering materials system comprising the super yellow (SY) polymer and the electrolyte trimethylolpropane ethoxylate (TMPE)/Li+CF3SO3−, it is reported that a slightly lowered salt concentration and layer thickness result in a substantial efficiency increase, and that this increase is confined to a narrow concentration and thickness range. For a film thickness of 70 nm, a blend ratio SY:TMPE:Li+CF3SO3− = 1:0.075:0.0225, and a current of 7.7 mA cm−2 the current efficacy is 11.6 cd A−1, on a par with SY light‐emitting diodes. The optimized salt content can be explained by increased exciton quenching at higher concentrations and hindered carrier injection and conduction at lower concentrations, while the optical dependence on the layer thickness is due to weak microcavity effects. A comprehensive optical modeling study is presented, which includes the doping‐induced changes of the refractive indices and self‐absorption losses due the emission–absorption overlap of intrinsic and doped SY. The analysis indicates either a thickness‐independent emitter position (EP) close to the anode or a thickness‐dependent EP, shifted to the cathode for increased thicknesses.
Manipulating Terahertz Plasmonic Vortex Based on Geometric and Dynamic Phase
Authors: Zang XiaoFei , Zhu YiMing , Mao ChenXi , Xu WeiWei , Ding HongZhen , Xie JingYa , Cheng QingQing , Chen Lin , Peng Yan , Hu Qing , Gu Min , Zhuang SongLin
Published: December 2018

Electromagnetic waves carrying orbital angular momentum (OAM), namely, vortex beams, have a plethora of applications ranging from rotating microparticles to high‐capacity data transmissions, and it is a continuing trend in manipulating OAM with higher degrees of freedom. Here, an approach to control terahertz (THz) near‐field plasmonic vortex based on geometric and dynamic phase is proposed and experimentally demonstrated. By locally tailoring the orientation angle (geometric phase) and radial position (dynamic phase) of aperture arrays embedded in an ultrathin gold film, the excited surface waves can be flexibly engineered to form both spin‐independent and spin‐dependent THz plasmonic vortex field distributions, resulting in multi‐degree of freedom for controlling OAM of THz surface plasmon polaritons (SPPs). Arbitrary OAM values of THz plasmonic vortex and coherent superposition between two OAM states are investigated based on near‐field scanning terahertz microscopy (NSTM) system. The proposed approach provides unprecedented freedom to modulate THz near‐field plasmonic vortex, which will have potential applications in THz communications and quantum information processing.
Nanoscale Bacteria‐Enabled Autonomous Drug Delivery System (NanoBEADS) Enhances Intratumoral Transport of Nanomedicine
Authors: Suh SeungBeum , Jo Ami , Traore Mahama A. , Zhan Ying , Coutermarsh‐Ott Sheryl L. , Ringel‐Scaia Veronica M. , Allen Irving C. , Davis Richey M. , Behkam Bahareh
Published: December 2018

Cancer drug delivery remains a formidable challenge due to systemic toxicity and inadequate extravascular transport of nanotherapeutics to cells distal from blood vessels. It is hypothesized that, in absence of an external driving force, the Salmonella enterica serovar Typhimurium could be exploited for autonomous targeted delivery of nanotherapeutics to currently unreachable sites. To test the hypothesis, a nanoscale bacteria‐enabled autonomous drug delivery system (NanoBEADS) is developed in which the functional capabilities of the tumor‐targeting S. Typhimurium VNP20009 are interfaced with poly(lactic‐co‐glycolic acid) nanoparticles. The impact of nanoparticle conjugation is evaluated on NanoBEADS' invasion of cancer cells and intratumoral transport in 3D tumor spheroids in vitro, and biodistribution in a mammary tumor model in vivo. It is found that intercellular (between cells) self‐replication and translocation are the dominant mechanisms of bacteria intratumoral penetration and that nanoparticle conjugation does not impede bacteria's intratumoral transport performance. Through the development of new transport metrics, it is demonstrated that NanoBEADS enhance nanoparticle retention and distribution in solid tumors by up to a remarkable 100‐fold without requiring any externally applied driving force or control input. Such autonomous biohybrid systems could unlock a powerful new paradigm in cancer treatment by improving the therapeutic index of chemotherapeutic drugs and minimizing systemic side effects.
Interfacial Scaffolding Preparation of Hierarchical PBA‐Based Derivative Electrocatalysts for Efficient Water Splitting
Authors: Wang Yueqing , Ma Jizhen , Wang Jun , Chen Si , Wang Huaisheng , Zhang Jintao
Published: December 2018

The development of highly efficient and durable electrocatalysts is crucial for overall water splitting. Herein, the in situ scaffolding formation of 3D Prussian blue analogues (PBAs) on a variety of 2D or 1D metal hydroxides/oxides to fabricate hierarchical nanostructures is first demonstrated. Typically, cobalt hydroxide or oxide nanoarrays are used as the precursor and structural oriented template for the subsequent growth of 3D PBA nanocubes. The mechanism study reveals that the interfacial scaffolding process can be reversibly controlled via the in situ ion exchange process with adjusting coordination ions. Thus, the facile, versatile strategy can extend to successfully fabricate a variety of hierarchical PBA‐based nanostructures including on cobalt fluoride hydroxide, copper hydroxide, monometal or bimetal nickel–cobalt hydroxides, cobalt oxide, and manganese oxide nanosheets with structural tailor‐ability and chemical diversity. More interestingly, the metal nitride derivatives obtained via controlled calcination process exhibit good electrocatalytic activity for water splitting with low overpotentials, and remarkable durability for 1200 h, thanks to the superior intrinsic activity of bimetal nature and the scrupulous hierarchical structure. This versatile strategy provides a paradigm for rational design of PBA‐based functional nanomaterials, which is highly promising in energy conversion, storage, and electrocatalytic fields.
Introduction of d‐Amino Acids in Minimalistic Peptide Substrates by an S‐Adenosyl‐l‐Methionine Radical Epimerase
Authors: Vagstad Anna L. , Kuranaga Takefumi , Püntener Salome , Pattabiraman Vijaya R. , Bode Jeffrey W. , Piel Jörn
Published: December 2018

Post‐translational modifying enzymes from the S‐adenosyl‐l‐methionine (AdoMet) radical superfamily garner attention due to their ability to accomplish challenging biochemical reactions. Among them, a family of AdoMet radical epimerases catalyze irreversible l‐ to d‐amino acid transformations of diverse residues, including 18 sites in the complex sponge‐derived polytheonamide toxins. Herein, the in vitro activity of the model epimerase OspD is reported and its catalytic mechanism and substrate flexibility is investigated. The wild‐type enzyme was capable of leader‐independent epimerization of not only the stand‐alone core peptide, but also truncated and cyclic core variants. Introduction of d‐amino acids can drastically alter the stability, structure, and activity of peptides; thus, epimerases offer opportunities in peptide bioengineering.
Multi‐Light‐Responsive Quantum Dot Sensitized Hybrid Micromotors with Dual‐Mode Propulsion
Authors: María Hormigos Roberto , Jurado Sánchez Beatriz , Escarpa Alberto
Published: December 2018

CdS quantum dots/C60 tubular micromotors with chemical/multi‐light‐controlled propulsion and “on‐the‐fly” acceleration capabilities are described. In situ growth of CdS quantum dots on the outer fullerene layer imparts this layer with light‐responsive properties in connection to inner Pt, Pd or MnO2 layers. This is the first time that visible light is used to drive bubble‐propelled tubular micromotors. The micromotors exhibit a broad absorption range from 320 to 670 nm and can be wirelessly controlled by modulating light intensity and peroxide concentration. The built‐in accelerating optical system allows for the control of the velocity over the entire UV/Vis light spectra by modulating the catalyst surface chemistry. The light‐responsive properties have been also exploited to accelerate the chemical dealloying and propulsion of micromotors containing a Cu/Pd layer. Such dual operated hybrid micromotors hold considerable promise for designing smart micromachines for on‐demand operations, motion‐based sensing, and enhanced cargo transportation.
Orientation of an Amphiphilic Copolymer to a Lamellar Structure on a Hydrophobic Surface and Implications for CO2 Capture Membranes
Authors: Park Cheol Hun , Lee Jae Hun , Jung Jung Pyo , Lee Wooseop , Ryu Du Yeol , Kim Jong Hak
Published: December 2018

The structural orientation of an amphiphilic crystalline polymer to a highly ordered microphase‐separated lamellar structure on a hydrophobic surface is presented. It is formed by the surface graft polymerization of poly(ethylene glycol)behenyl ether methacrylate onto poly(trimethylsilyl) propyne in the presence of allylamine. In particular, allylamine plays a pivotal role in controlling the crystalline phase, configuration, and permeation properties. The resulting materials are effectively used to improve the CO2 capture property of membranes. Upon the optimization of the reaction conditions, a high CO2 permeability of 501 Barrer and a CO2/N2 ideal selectivity of 77.2 are obtained, which exceed the Robeson upper bound limit. It is inspiring to surpass the upper bound limit via a simple surface modification method.
Carbon‐Supported Divacancy‐Anchored Platinum Single‐Atom Electrocatalysts with Superhigh Pt Utilization for the Oxygen Reduction Reaction
Authors: Liu Jing , Jiao Menggai , Mei Bingbao , Tong Yuxin , Li Yuping , Ruan Mingbo , Song Ping , Sun Gongquan , Jiang Luhua , Wang Ying , Jiang Zheng , Gu Lin , Zhou Zhen , Xu Weilin
Published: December 2018

Maximizing the platinum utilization in electrocatalysts toward oxygen reduction reaction (ORR) is very desirable for large‐scale sustainable application of Pt in energy systems. A cost‐effective carbon‐supported carbon‐defect‐anchored platinum single‐atom electrocatalysts (Pt1/C) with remarkable ORR performance is reported. An acidic H2/O2 single cell with Pt1/C as cathode delivers a maximum power density of 520 mW cm−2 at 80 °C, corresponding to a superhigh platinum utilization of 0.09 gPt kW−1. Further physical characterization and density functional theory computations reveal that single Pt atoms anchored stably by four carbon atoms in carbon divacancies (Pt‐C4) are the main active centers for the observed high ORR performance.
Enantiospecific Synthesis of ortho‐Substituted 1,1‐Diarylalkanes by a 1,2‐Metalate Rearrangement/anti‐SN2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence
Authors: Rubial Belén , Collins Beatrice S. L. , Bigler Raphael , Aichhorn Stefan , Noble Adam , Aggarwal Varinder K.
Published: December 2018

The one‐pot sequential coupling of benzylamines, boronic esters, and aryl iodides has been investigated. In the presence of an N‐activator, the boronate complex formed from an ortho‐lithiated benzylamine and a boronic ester undergoes stereospecific 1,2‐metalate rearrangement/anti‐SN2′ elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ‐selective allylic Suzuki–Miyaura cross‐coupling to generate 1,1‐diarylalkanes. When enantioenriched α‐substituted benzylamines are employed, the corresponding 1,1‐diarylalkanes are formed with high stereospecificity.
Synthesis of C−C Bonded Two‐Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid–Liquid Interface
Authors: Zhou Deng , Tan Xianyang , Wu Huimin , Tian Lihong , Li Ming
Published: December 2018

Synthesis of free‐standing two‐dimensional (2D) conjugated covalent organic framework (COF) films linked by C−C bonds is highly desirable. Now a very simple and mild strategy has been developed to synthesize them by Suzuki polymerization on a water–toluene interface in a refrigerator. The versatility of this strategy was confirmed by the successful synthesis of two different 2D‐COF films: a porous graphene and a porphyrin‐contained 2D‐COF. Both 2D‐COF films have large lateral size and their crystalline domains were visualized by high resolution TEM. Based on the wide compatibility of Suzuki reaction, our breakthrough work opened a door for the synthesis of various 2D conjugated COF films. For application studies, the porous graphene exhibits a good carrier mobility, which is much higher than −C=N− linked 2D COF films and a good catalytic activity for hydrogen evolution reaction, which is comparable with nitrogen‐ or phosphorus‐doped graphene.
Oxidative Addition to Palladium(0) Made Easy through Photoexcited‐State Metal Catalysis: Experiment and Computation
Authors: Kancherla Rajesh , Muralirajan Krishnamoorthy , Maity Bholanath , Zhu Chen , Krach Patricia E. , Cavallo Luigi , Rueping Magnus
Published: December 2018

Visible‐light induced, palladium catalyzed alkylations of α,β‐unsaturated acids with unactivated alkyl bromides are described. A variety of primary, secondary, and tertiary alkyl bromides are activated by the photoexcited palladium metal catalyst to provide a series of olefins at room temperature under mild reaction conditions. Mechanistic investigations and density functional theory (DFT) studies suggest that a photoinduced inner‐sphere mechanism is operative in which a barrierless, single‐electron transfer oxidative addition of the alkyl halide to Pd0 is key for the efficient transformation.
PIII‐Chelation‐Assisted Indole C7‐Arylation, Olefination, Methylation, and Acylation with Carboxylic Acids/Anhydrides by Rhodium Catalysis
Authors: Qiu Xiaodong , Wang Panpan , Wang Dingyi , Wang Minyan , Yuan Yu , Shi Zhuangzhi
Published: December 2018

Rhodium‐catalyzed C7‐selective decarbonylative arylation, olefination, and methylation of indoles with carboxylic acids or anhydrides by C−H and C−C bond activation have been developed. Furthermore, C7‐acylation products can also be generated selectively at a lower reaction temperature in the developed system. The key to the high reactivity and regioselectivity of this transformation is the appropriate choice of an indole N‐PtBu2 chelation‐assisted group. This method has many advantages, including easy access and removal of the directing group, the use of cheap and widely available coupling agents, no requirement of an external ligand or oxidant, a broad substrate scope, high efficiency, and the formation of a sole regioisomer.
Design, synthesis and characterization of tin‐based cancer chemotherapy drug entity: In vitro DNA binding, cleavage, induction of cancer cell apoptosis by triggering DNA damage‐mediated p53 phosphorylation and molecular docking
Authors: Esmail Sabah Ahmed Abdo , Shamsi Manal , Chen Tianfeng , Al‐asbahy Waddhaah M.
Published: December 2018

A new organotin complex derived from propyl gallate and 1,10‐phenanthroline was designed, synthesized and characterized using spectroscopic and elemental analytical methods. The underlying mechanisms of the anticancer action of the tin complex were further elucidated by evaluating its in vitro DNA interaction and the regulating signaling pathways. Our results showed that the tin complex could effectively activate DNA strand breaks in MCF‐7 cells in a dose‐dependent manner after cellular internalization. Phosphorylation of a DNA damage marker, histone H2A.X (Ser139), was thus upregulated in treated cells. Additionally, our results indicate that p53 is phosphorylated in response to DNA damage, and that this phosphorylation may be involved in the subsequent induction and activation of p53. In vitro DNA binding of the complex in Tris–HCl buffer was studied using various biophysical methods, revealing that the tin complex binds to DNA non‐covalently via electrostatic interaction. The higher Kb value of the complex suggested greater DNA binding propensity. Further, to evaluate the mode of action at the molecular level, interaction studies of the tin complex with nucleotide (5′‐GMP) were carried out. The complex exhibits DNA cleavage activity with supercoiled pBR322 in the presence of different activators. The complex cleaves DNA efficiently via oxidative cleavage pathway. Molecular docking studies were performed to understand the binding mode of the tin complex with DNA (PDB ID: 1BNA).
Text Mining for Personalized Knowledge Extraction From Online Support Groups
Authors: Bandaragoda Tharindu Rukshan , De Silva Daswin , Alahakoon Damminda , Ranasinghe Weranja , Bolton Damien
Published: December 2018

The traditional approach to health care is being revolutionized by the rapid adoption of patient‐centered healthcare models. The successful transformation of patients from passive recipients to active participants is largely attributed to increased access to healthcare information. Online support groups present a platform to seek and exchange information in an inclusive environment. As the volume of text on online support groups continues to grow exponentially, it is imperative to improve the quality of retrieved information in terms of relevance, reliability, and usefulness. We present a text‐mining approach that generates a knowledge extraction layer to address this void in personalized information retrieval from online support groups. The knowledge extraction layer encapsulates an ensemble of text‐mining techniques with a domain ontology to interpose an investigable and extensible structure on hitherto unstructured text. This structure is not limited to personalized information retrieval for patients, as it also imparts aggregates for crowdsourcing analytics by healthcare researchers. The proposed approach was successfully trialed on an active online support group consisting of 800,000 posts by 72,066 participants. Demonstrations for both patient and researcher use cases accentuate the value of the proposed approach to unlock a broad spectrum of personalized and aggregate knowledge concealed within crowdsourced content.
Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance
Authors: Wei Qi , Ge Bang‐Di , Zhang Jing , Sun Ai‐Huan , Li Jin‐Hua , Han Song‐De , Wang Guo‐Ming
Published: December 2018

Through regulating the pH values, a series of iodo‐argentate/cuprate hybrids, [Me3(4‐TPT)]4[Ag6I18] (1, Me3(4‐TPT)=N,N′,N′′‐trimethyl‐2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine), [Me3(4‐TPT)][M5I8] (M=Ag/2, Cu/2 a), [Me3(3‐TPT)][M5I8] (Me3(3‐TPT)=N,N′,N′′‐trimethyl‐2,4,6‐tris(3‐pyridyl)‐1,3,5‐triazine, M=Ag/3, Cu/4), which exhibit adjustable structural variations with different dimensional structures, have been obtained under solvothermal conditions. They are directed by two types of in situ N‐alkylation TPT‐derivatives (Me3(4‐TPT) for 1/2/2 a and Me3(3‐TPT) for 3/4) and represent the isolated units (1), 1D polymeric chain (4), 2D layered structures (2/2 a, 3) based on diverse metal iodide clusters. These compounds possess reducing band gaps as compared with the bulk β‐AgI and CuI and belong to potential semiconductor materials. Iodocuprates feature highly efficient photocatalytic activity in the sunlight‐induced degradation of organic dyes. The detailed study on the possible photocatalytic mechanism, including radical trapping tests and theoretical calculations, reveals that the N‐alkylation TPT moieties contribute to the narrow semiconducting behavior and effectively inhibit the recombination of photogenerated electron‐hole pairs, which result in an excellent visible‐light‐induced photocatalytic performance.
Water‐Soluble Pillar[n]arene Mediated Supramolecular Self‐Assembly: Multi‐Dimensional Morphology Controlled by Host Size
Authors: Liu Yamin , Shi Kejia , Ma Da
Published: December 2018

We report tunable supramolecular self‐assemblies formed by water‐soluble pillar[n]arenes (WPns, n=5–7) and bipyridinium‐azobenzene guests. Nanoscale or microscale morphology of self‐assemblies in water was controlled by the host size of WPn. Supramolecular self‐assemblies could undergo morphology conversion under irradiation with UV light.
Use of generally recognized as safe or dietary compounds to inhibit buprenorphine metabolism: potential to improve buprenorphine oral bioavailability
Authors: Maharao Neha , Venitz Jurgen , Gerk Phillip M.
Published: December 2018

The present study evaluated the potential of five generally recognized as safe (GRAS) or dietary compounds (α‐mangostin, chrysin, ginger extract, pterostilbene and silybin) to inhibit oxidative (CYP) and conjugative (UGT) metabolism using pooled human intestinal and liver microsomes. Buprenorphine was chosen as the model substrate as it is extensively metabolized by CYPs to norbuprenorphine and by UGTs to buprenorphine glucuronide. Chrysin, ginger extract, α‐mangostin, pterostilbene and silybin were tested for their inhibition of the formation of norbuprenorphine or buprenorphine glucuronide in both intestinal and liver microsomes. Pterostilbene was the most potent inhibitor of norbuprenorphine formation in both intestinal and liver microsomes, with IC50 values of 1.3 and 0.8 μM, respectively, while α‐mangostin and silybin most potently inhibited buprenorphine glucuronide formation. The equipotent combination of pterostilbene and ginger extract additively inhibited both pathways in intestinal microsomes. Since pterostilbene and ginger extract showed potent CYP and/or UGT inhibition of buprenorphine metabolism, their equipotent combination was tested to assess the presence of synergistic inhibition. However, because the combination showed additive inhibition, it was not used while performing IVIVE analysis. Based on quantitative in vitro–in vivo extrapolation, pterostilbene (21 mg oral dose) appeared to be most effective in improving the mean predicted Foral and AUC∞PO of buprenorphine from 3 ± 2% and 340 ± 330 ng*min/ml to 75 ± 8% and 36,000 ± 25,000 ng*min/ml, respectively. At a 10‐fold lower dose of pterostilbene, the predicted buprenorphine Foral approximated sublingual bioavailability (~35%) and showed a 2–4 fold reduction in the variability around the predicted AUC∞PO of buprenorphine. These results demonstrate the feasibility of using various GRAS/dietary compounds to inhibit substantially the metabolism by CYP and UGT enzymes to achieve higher and less variable oral bioavailability. This inhibitor strategy may be useful for drugs suffering from low and variable oral bioavailability due to extensive presystemic oxidative and/or conjugative metabolism.
The first example of fluorescence of the solid individual compounds of Eu2+ ion: EuCl2, EuI2, EuBr2
Authors: Galimov D.I. , Bulgakov R.G.
Published: December 2018

Fluorescence (FL) from Eu2+ ion solid individual compounds was observed for the first time using the examples EuCl2, EuI2 and EuBr2. Fluorescence was detected at excitation by ultraviolet (UV) light from powdered samples of Eu (II) halides at room temperature (RT) in an argon atmosphere. In air, FL of all Eu2+ compounds studied was stable, and intensity persisted for weeks. Depending on the nature of the halide anion and due to a nephelauxetic effect, the position of the maxima in the FL spectra underwent a red shift in the series: EuCl2 (409 nm) < EuBr2 (428 mm) < EuI2 (432 nm). The lifetimes of the excited states of the Eu2+* ions for EuI2, EuCl2 and EuBr2 were 355, 76 and 54 ns, respectively.
Quantification of three triterpenic acids in dried rosemary using HPLC‐fluorescence detection and 4‐(4,5‐diphenyl‐1H‐imidazole‐2‐yl)benzoyl chloride derivatization
Authors: Wada Mitsuhiro , Tojoh Yui , Nakamura Shinichi , Mutoh Junpei , Kai Hisahiro , Matsuno Koji , Nakashima Kenichiro
Published: December 2018

Functional triterpenic acids such as ursolic acid (UA), oleanolic acid (OA) and betulinic acid (BA) are representative ingredients in rosemary that may have health benefits. UA, OA and BA in rosemary extracts were derivatized with 4‐(4,5‐diphenyl‐1H‐imidazole‐2‐yl)benzoyl chloride (DIB‐Cl) and detected using HPLC‐fluorescence (FL). Dried rosemary (50 mg) was ground, added to 3 ml of ethanol, sonicated for 40 min, then the sample solution was added to a mixture of 1% trimethylamine and 1 mM DIB‐Cl in acetonitrile. The mixture was settled for 5 min at room temperature, then the DIB‐triterpenic acid derivatives were separated using a Wakopak Handy ODS column (250 × 4.6 mm, 6 μm) eluted with 25 mM acetate buffer (pH 4.5)/methanol/acetonitrile (= 8:10:82 v/v/v%). The fluorescence intensity of the eluent was monitored at 365 (λex) and 490 nm (λem) and the maximum retention time of the derivatives was 30 min. Calibration curves constructed using rosemary extract spiked with standards showed good linearity (r ≥ 0.997) in the range 2.5–100 ng/ml. The detection limits at 3σ for internal BA, UA and OA peaks in rosemary extract were 0.2, 0.4 and 0.5 ng/ml, respectively. This method was used to quantify BA, UA and OA in commercially available dried rosemary products.
Computerized anatomy of the distal radius and its relevance to volar plating, research, and teaching
Authors: Gehweiler Dominic , Teunis Teun , Varjas Viktor , Kerstan Dirk , Gueorguiev Boyko , Kamer Lukas , Noser Hansrudi
Published: December 2018

Distal radius fractures are common and fracture patterns and fixation can be complex. Computerized anatomy evaluation (CAE) might offer non‐invasive and enhanced anatomy assessment that might help with implant selection and placement and screw length determination. Our goal was to test the accuracy of two CAE methods for anatomical volar plate positioning and screw lengths measurement of the distal radius. We included 56 high‐resolution peripheral quantitative computed tomography scans of intact, human distal radii. Plates were placed manually onto 3D printed models (method 1), which was compared with automated computerized plate placement onto the 3D computer models (method 2). Subsequently, screw lengths were determined digitally for both methods. Screw lengths evaluations were compared via Bland–Altman plots. Both CAE methods resulted in identical volar plate selection and in anatomical plate positioning. For screw length the concordance correlation coefficient was ≥0.91, the location shift ≤0.22 mm, and the scale shift ≤0.16. The differences were smaller than ±1 mm in all samples. Both CAE methods allow for comparable plate positioning and subsequent screw length measurement in distal radius volar plating. Both can be used as a non‐invasive teaching environment for volar plate fixation. Method 2 even offers fully computerized assessments. Future studies could compare our models to other anatomical areas, post‐operative volar plate positioning, and model performance in actual distal radius fracture instead of intact radii. Clin. Anat. 32:361–368, 2019. © 2018 The Authors. Clinical Anatomy published by Wiley Periodicals, Inc. on behalf of American Association of Clinical Anatomists.
Superficial siderosis due to filum terminale tumor: An uncommon cause of cranial nerve dysfunction
Authors: Campion Tom , Arfeen Farrukh , Adams Ashok
Published: December 2018

Key Clinical Message

If superficial siderosis is suspected based on clinical presentation, susceptibility weighted imaging should be undertaken in addition to standard MRI sequences as it is more sensitive than T2 weighted imaging. Once diagnosed, imaging of the entire brain and spine must be undertaken to assess for an underlying cause.
The Impact of a College Career Course on Students’ Career Decision States
Authors: Miller Adam K. , Osborn Debra S. , Sampson James P. , Peterson Gary W. , Reardon Robert C.
Published: December 2018

The college experience for many students is marked by challenges and concerns surrounding educational and career choices. These challenges and concerns may be reflected in a student’s career decision state, or the extent that one is certain, satisfied, and clear about one’s career goals. This study examines students’ career decision states at the beginning and at the end of a career course intervention. The article concludes with a discussion of the implications of the findings for further practice and research.
Thixotropic Behavior of Oil‐in‐Water Emulsions Stabilized with Ethoxylated Amines at Low Shear Rates
Authors: Grecco Zanotti Maria Augusta , Gonçalves dos Santos Ronaldo
Published: December 2018

Oil‐in‐water (O/W) emulsification is a lubricating pipeline method based on the reduction of the energy frictional loss produced during viscous flow. The flow behavior of heavy O/W emulsions formulated with nonionic surfactants is described. The effects of pH and salinity of the aqueous phase on droplet diameter, stability, and apparent viscosity of O/W emulsions were evaluated. The low‐shear Couette flow of O/W emulsions displayed intense shear‐thinning and thixotropic behavior. Thixotropy was associated to the droplet deformation energy caused by shear rate changes. The droplet deformation and alignment led to the apparent viscosity reduction compared to the fluid at rest. Thixotropic behavior is supposed to balance between the breakdown and recovery of droplet ordered structures. Emulsion formulation parameters were influenced by the aqueous phase pH, enabling to manage the emulsion properties. The droplet mean diameter of < 18 µm resulted in very stable emulsions.
Comparison of Electrospun Carbon−Carbon Composite and Commercial Felt for Their Activity and Electrolyte Utilization in Vanadium Redox Flow Batteries
Authors: Fetyan Abdulmonem , Schneider Jonathan , Schnucklake Maike , El‐Nagar Gumaa A. , Banerjee Rupak , Bevilacqua Nico , Zeis Roswitha , Roth Christina
Published: December 2018

Invited for this month's cover picture is the joint project between the groups of Prof. Christina Roth (Freie Universität Berlin, Germany) and Dr. Roswitha Zeis (Helmholtz Institute Ulm, Germany). The cover image shows electrospun nanofibers used as the electrode in a vanadium redox flow battery. Read the full text of the Article at 10.1002/celc.201801128.
Dramatically Enhanced Li‐Ion Storage of ZnO@C Anodes through TiO2 Homogeneous Hybridization
Authors: Liu Zhengbo , Ji Shaomin , Xu Xijun , Hu Renzong , Liu Jiangwen , Liu Jun
Published: December 2018

Amorphous nanoparticles of ZnO and TiO2 embedded in carbon nanocages (AZT⊂CNCs) were successfully synthesized through a simple annealing process of TiO2‐coated zeolitic imidazolate framework‐8 (ZIF‐8). In the current anode of AZT⊂CNCs, tiny ZnO and TiO2 nanoparticles were uniformly distributed in the carbon matrix (carbon nanocages), which could effectively buffer the volume expansion of electroactive ZnO and provide excellent electric conductivity. After fully investigating the electrochemical performance of the AZT⊂CNCs samples obtained with different additive amounts of tetrabutyl orthotitanate (TBOT) for TiO2 coating, it has been found that AZT‐30 (0.1 g ZIF‐8 with 30 mL TBOT) shows the best cycle stability (510 mA h g−1 after 350 cycles at 200 mA g−1) and a superior rate capability (610 mA h g−1 after 3500 cycles at 2 A g−1). The greatly enhanced Li‐ion storage performance could be ascribed to the fact that the introduction of amorphous TiO2 could activate the reversible lithiation/delithiation reaction of ZnO during the charge/discharge process.
Synthesis and Structure Determination of SCM‐15: A 3D Large Pore Zeolite with Interconnected Straight 12×12×10‐Ring Channels
Authors: Luo Yi , Smeets Stef , Wang Zhendong , Sun Junliang , Yang Weimin
Published: December 2018

A new germanosilicate zeolite named SCM‐15 (Sinopec Composite Material No. 15), the first zeolite containing a 3‐dimensional (3D) channel system with interconnected 12‐, 12‐, and 10‐ring channels (pore sizes: 6.1×7.2, 6.1×7.4, and 5.2×5.9 Å), has been synthesized using neutral 4‐pyrrolidinopyridine as organic structure‐directing agents (OSDAs). Its structure has been determined by combining single‐crystal electron diffraction (SCED) and synchrotron powder X‐ray diffraction (SPXD) data. The unique open framework structure of SCM‐15 is related to that of FOS‐5 (BEC), ITQ‐7 (ISV), PKU‐16 (POS), ITQ‐26 (IWS), ITQ‐21, Beta polymorph B, and SU‐78B, since all these framework structures can be constructed from similar chains which are connected through shared 4‐ring or double 4‐ring (d4r) units. Based on this relation, six topologically reasonable 3D large or extra‐large pore hypothetical zeolites are predicted.