bluuebunny/crossref_metadata_2025_split huggingface dataset:
Self‐Integrated Porous Leaf‐like CuO Nanoplate Array‐Based Anodes for High‐Performance Lithium‐Ion Batteries
Authors: Li Zhi , Li Gangyong , Xu Wenyuan , Zhou Minjie , Xu Chenxi , Shi Mengting , Li Fangyi , Chen Liang , He Binhong 
Published: July 2018

AbstractDeveloping high‐energy‐density lithium‐ion batteries (LIBs) is of great significance for their wider commercialized application. The design of self‐integrated electrodes can be treated as a valid approach to achieve this goal. In this work, a facile and low‐cost wet chemical oxidation strategy is put forward to prepare self‐integrated porous leaf‐like CuO nanoplates on Cu foil substrates in situ. These nanoplates are then directly used as the anode for LIBs. The morphology, structure, and composition of the resultant CuO/Cu hybrid foils are characterized, and the relevant lithium storage properties of this anode are also investigated by using standard electrochemical tests. The results show that the CuO/Cu hybrid‐based anode possesses a porous leaf‐like morphology and self‐integrated architecture. Benefitting from this unique morphology and favorable architecture, the CuO/Cu hybrid‐based anode exhibits outstanding electrochemical performance, including excellent cycling stability and remarkable rate capability, demonstrating great potential in the application of high‐energy‐density LIBs.
Reversible Solution π‐Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical
Authors: Bonanno Nico M. , Poddutoori Prashanth K. , Sato Kazunobu , Sugisaki Kenji , Takui Takeji , Lough Alan J. , Lemaire Martin T. 
Published: July 2018

AbstractReversible solution π‐dimerization is observed in the stable neutral phenoxyl radical 2,6‐bis‐(8‐quinolylamino)‐4‐(tert‐butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π‐extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π‐dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.
Sustainable Heterogeneous Catalysts for CO2 Utilization by Using Dual Ligand ZnII/CdII Metal–Organic Frameworks
Authors: Parmar Bhavesh , Patel Parth , Kureshy Rukhsana I. , Khan Noor‐ul H. , Suresh Eringathodi 
Published: July 2018

AbstractTwo‐dimensional ZnII/CdII‐based dual ligand metal–organic frameworks (MOFs) {[M(CHDC)(L)]⋅H2O}n involving 4‐pyridyl carboxaldehyde isonicotinoylhydrazone (L) in combination with flexible 1,4‐cyclohexanedicarboxylic acid (H2CHDC) as linkers have been synthesized by adaptable synthetic protocols including a green mechanochemical (grinding) method. Characterization, chemical/thermal stability, phase purity, and solid‐state luminescent properties of both MOFs have been established by various analytical methods. Structural analysis revealed dimeric metal clusters composed of [M2(CHDC)2]n loops doubly pillared with L, generating a 2D framework. Both MOFs can be used as highly active solvent‐free binary catalysts for CO2 cycloaddition with epoxides in the presence of the co‐catalyst tetrabutylammonium bromide (TBAB) with good catalytic conversion in up to six catalytic cycles without significant loss of activity. The present investigation demonstrates the application of MOFs as efficient heterogeneous catalysts for CO2 utilization under moderate reaction conditions. Based on the single‐crystal X‐ray data, a probable mechanism for the cycloaddition reaction has also been proposed.
Electrolytes for Batteries with Earth‐Abundant Metal Anodes
Authors: Zhao Hongyang , Xu Jun , Yin Dandan , Du Yaping 
Published: July 2018

AbstractEarth‐abundant metal anodes have become one of the hottest topics in recent years. As alternatives to lithium metals, earth‐abundant metal anodes have significantly lower cost and higher energy density, but with unprecedented problems that cannot be solved by simply referring to experiences with lithium‐metal anodes. The electrolytes for these anodes greatly influence the overall performance, such as Coulombic efficiency, stability, and even the availability to become an anode. In this Minireview, some excellent state‐of‐art works on the electrolytes of energy‐storage systems with sodium‐, potassium‐, magnesium‐, calcium‐, and aluminum‐metal anodes are concisely summarized. The performance of these systems is highlighted by the rational design of the electrolyte and electrolyte/electrode interface.
Ping‐Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?
Authors: Nandi Ashim , Sucher Adam , Kozuch Sebastian 
Published: July 2018

AbstractIn a recent study, Scheiner designed a double‐germanium‐based fluoride receptor that binds the halogen by means of strong tetrel bonds (Chem. Eur. J. 2016, 22, 18850). In this system the F− binds to the germanium atoms in an asymmetric fashion, thereby producing a double‐well potential in which the fluoride can jump from one germanium to the other as in a ping‐pong game. Herein we prove through the use of computational tools that at cryogenic temperatures this rearrangement occurs by heavy‐atom quantum mechanical tunneling. The inductive strength of the substituents and the polarity of the solvent can modify the barrier and the tunneling rate. But the strongest effect is observed upon modification of the geometry of the molecule by specific substitutions that affect the barrier width, the most critical factor in a tunneling mechanism. We postulate two experimental tests, one by microwave spectroscopy and one by cryogenic NMR spectroscopy, that can prove the predicted fluoride tunneling.
Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N‐Halosuccinimide
Authors: Mukhopadhyay Sushobhan , Batra Sanjay 
Published: July 2018

AbstractA one‐pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N‐halosuccinimide (NXS) in DMF at room temperature under metal‐ and acid‐free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
Functionalization of Azapentabenzocorannulenes by Fivefold C−H Borylation and Cross‐Coupling Arylation: Application to Columnar Liquid‐Crystalline Materials
Authors: Nagano Taro , Nakamura Kimihiro , Tokimaru Yuki , Ito Shingo , Miyajima Daigo , Aida Takuzo , Nozaki Kyoko 
Published: July 2018

AbstractHerein, the one‐shot fivefold functionalization of azapentabenzocorannulenes by an iridium‐catalyzed fivefold C−H borylation reaction that exhibits excellent regioselectivity is reported. The borylated product can be used as a versatile synthetic intermediate for further derivatization via Suzuki–Miyaura cross‐coupling reactions. This fivefold borylation/arylation sequence was employed to synthesize liquid‐crystalline azapentabenzocorannulenes with five 3,4,5‐trialkoxyphenyl groups, which assemble into 1D hexagonal columnar structures over a wide temperature range. The present method expands the variety and utility of azapentabenzocorannulenes as promising π‐conjugated cores.
Iron‐Catalyzed Alkylation of Nitriles with Alcohols
Authors: Ma Wei , Cui Suya , Sun Huamin , Tang Weijun , Xue Dong , Li Chaoqun , Fan Juan , Xiao Jianliang , Wang Chao 
Published: July 2018

AbstractA general, efficient iron‐catalyzed α‐alkylation of nitriles with primary alcohols through a hydrogen‐borrowing pathway has been developed, allowing a wide variety of alkylated nitriles to be readily accessible. Detailed mechanistic studies suggest that the reaction proceeds via an olefin intermediate with the turnover rate limited by the hydrogenation of the olefin with an iron hydride. Apart from participating in the alkylation, the nitrile is found to play an important role in promoting the formation of and stabilizing the active catalytic species.
Automated Synthesis of (rac)‐, (R)‐, and (S)‐[18F]Epifluorohydrin and Their Application for Developing PET Radiotracers Containing a 3‐[18F]Fluoro‐2‐hydroxypropyl Moiety
Authors: Fujinaga Masayuki , Ohkubo Takayuki , Yamasaki Tomoteru , Zhang Yiding , Mori Wakana , Hanyu Masayuki , Kumata Katsushi , Hatori Akiko , Xie Lin , Nengaki Nobuki , Zhang Ming‐Rong 
Published: July 2018

AbstractTo introduce the 3‐[18F]fluoro‐2‐hydroxypropyl moiety into positron emission tomography (PET) radiotracers, we performed automated synthesis of (rac)‐, (R)‐, and (S)‐[18F]epifluorohydrin ([18F]1) by nucleophilic displacement of (rac)‐, (R)‐, or (S)‐glycidyl tosylate with 18F− and purification by distillation. The ring‐opening reaction of (R)‐ or (S)‐[18F]1 with phenol precursors gave enantioenriched [18F]fluoroalkylated products without racemisation. We then synthesised (rac)‐, (R)‐, and (S)‐ 2‐{5‐[4‐(3‐[18F]fluoro‐2‐hydroxypropoxy)phenyl]‐2‐oxobenzo[d]oxazol‐3(2H)‐yl}‐N‐methyl‐N‐phenylacetamide ([18F]6) as novel radiotracers for the PET imaging of translocator protein (18 kDa) and showed that (R)‐ and (S)‐[18F]6 had different radioactivity uptake in mouse bone and liver. Thus, (rac)‐, (R)‐, and (S)‐[18F]1 are effective radiolabelling reagents and can be used to develop PET radiotracers by examining the effects of chirality on their in vitro binding affinities and in vivo behaviour.
Microbiome Analyses for Toxicological Studies
Authors: Benjamino Jacquelynn , Beka Lidia , Graf Joerg 
Published: July 2018

AbstractMicrobiomes can be thought of as the integration of biotic and abiotic factors, including the microbial communities and the distinct physio‐chemical properties that are present in a habitat. The microbes within a microbiome can influence the chemical environment by degrading medications inside patients or contaminants in the environment, such as hydrocarbons released after the Deepwater Horizon oil spill. Identifying and monitoring the relative abundance of microbes can help to elucidate variations in their response to toxins and should be considered as a variable in statistical analyses. In addition, the presence of pathogenic microbes or toxin‐producing species could affect the observed toxicity of an environment. The protocols in this unit begin with the collection of samples, proceeds to sequencing of the bacterial DNA, and ends with an analysis of the bacterial community in light of environmental metadata. © 2018 by John Wiley & Sons, Inc.
Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia
Authors: Rorrer Julie , Pindi Suresh , Toste F. Dean , Bell Alexis T. 
Published: July 2018

AbstractLinear and branched ether molecules have attracted recent interest as diesel additives and lubricants that can be produced from biomass‐derived alcohols. In this study, tungstated zirconia was identified as a selective and green solid acid catalyst for the direct etherification of primary alcohols in the liquid phase, achieving ether selectivities of >94 % for C6–C12 linear alcohol coupling at 393 K. The length of linear primary alcohols (C6–C12) was shown to have a negligible effect on apparent activation energies for etherification and dehydration, demonstrating the possibility to produce both symmetrical and asymmetrical linear ethers. Reactions over a series of C6 alcohols with varying methyl branch positions indicated that substituted alcohols (2°, 3°) and alcohols with branches on the β‐carbon readily undergo dehydration, but alcohols with branches at least three carbons away from the ‐OH group are highly selective to ether. A novel model compound, 4‐hexyl‐1dodecanol, was synthesized and tested to further demonstrate this structure–activity relationship. Trends in the effects of alcohol structure on selectivity were consistent with previously proposed mechanisms for etherification and dehydration, and help to define possible pathways to selectively form ethers from biomass‐derived alcohols.
Multilayered, Bipolar, All‐Solid‐State Battery Enabled by a Perovskite‐Based Biphasic Solid Electrolyte
Authors: Shin Hyun‐Seop , Ryu Won‐Gyue , Park Min‐Sik , Jung Kyu‐Nam , Kim Hansung , Lee Jong‐Won 
Published: July 2018

AbstractThe use of solid electrolytes provides a technical solution to address the safety issues of lithium‐ion batteries and enables a bipolar design of high‐voltage and high‐energy battery modules. The bipolar design avoids unnecessary components and parts for packaging and electrical connection; therefore, it facilitates an increase in the volumetric energy density of the battery, while enabling easy build‐up of total output voltage. Herein, the design and construction of a multilayered, bipolar‐type, all‐solid‐state battery (ASSB) from a biphasic solid electrolyte (BSE) based on inorganic Li0.29La0.57TiO3 perovskite and poly(ethylene oxide) (PEO) are reported. A flexible and freestanding BSE membrane exhibits high Li+ conductivity of about 1.2×10−4 S cm−1, and shows enhanced electrochemical/thermal stability, in comparison to a PEO‐only solid electrolyte. A single‐layered ASSB assembled with a BSE shows promising electrochemical performance, as evidenced by a high reversible capacity of about 123 mA h g−1 and excellent cycling stability over 100 cycles. Furthermore, a proof‐of‐concept bipolar ASSB comprising three unit cells connected in series is constructed by using the BSE membrane and Al/Cu‐cladded bipolar plates. The bipolar ASSB shows high thermal stability and operates reversibly without any internal short circuit or current leakage during charge–discharge cycles; this demonstrates that BSEs provide a promising approach to the design and fabrication of bipolar ASSBs with improved safety and high energy density.
Bio‐available Solvent Cyrene: Synthesis, Derivatization, and Applications
Authors: Camp Jason E. 
Published: July 2018

AbstractThe development of green solvents is one of the key tenets of Green Chemistry as solvents account for the majority of waste stemming from the production of the chemicals on which we have all come to rely. An important class of solvents is the dipolar aprotics, which include N,N‐dimethylformamide (DMF) and N‐methyl‐2‐pyrrolidone (NMP). In addition to being derived from non‐renewable resources, these solvents are also under increased regulatory pressures that will limit their industrial applications. This Concept concerns the bio‐available solvent Cyrene (dihydrolevoglucosenone) as a potential replacement for toxic dipolar aprotic solvents. An emphasis is placed on examining the strengths and weaknesses of Cyrene as a solvent and is accomplished by looking at the synthesis, derivatization, and application in synthetic protocols of Cyrene. With respect to the Twelve Principles of Green Chemistry, this Concept describes a bio‐available solvent that should have a disruptive effect on the use of traditional industrial dipolar aprotic solvents.
Expression of p63 immunostaining in liquid‐based cytology (BD SurePath) of breast fine‐needle aspiration
Authors: Osugi Masumi , Kinoshita Kosei , Sugita Atsuro , Kito Katsumi , Maeda Toshiharu 
Published: July 2018

BackgroundWe performed p63 immunostaining to detect myoepithelial cells on BD SurePath liquid‐based cytology (LBC) slides and examined whether this improved the diagnostic accuracy in breast fine‐needle aspiration cytology (FNAC).MethodsWe examined the diagnostic accuracy using the LBC‐p63 immunostaining slides of 298 lesions obtained from July 2010 to August 2016.ResultsWe defined the cutoff values for malignancy as follows: (1) the percentage of p63+ cluster was <30%, (2) the percentage of p63+ single cells in cell clusters was <3%, (3) the number of p63+ single cells in the background was <20 when the total number of the cell clusters was <100, or the number was <120 when the total number was ≥100. The malignant lesions showed significantly lower values than the benign lesions in the percentage of p63+ clusters, the percentage of p63+ single cells in the clusters, and the number of p63+ single cells in the background (P < .001). The diagnostic values obtained only by Papanicolaou staining vs the improved values with LBC‐p63 immunostaining slides were as follows. Sensitivity, 88.3% to 99.0%; specificity, 89.1% to 99.0%; positive predictive value, 94.8% to 99.5%; negative predictive value, 77.4% to 97.8%; diagnostic accuracy, 88.6% to 99.0%, respectively.ConclusionThe diagnostic accuracy of breast FNAC was significantly improved by adding LBC‐p63 immunostaining.
Sediment microfabric records mass sedimentation of colonial cyanobacteria and extensive syndepositional metazoan reworking in Pliocene sapropels
Authors: Löhr Stefan C. , Kennedy Martin J. , George Simon C. , Williamson Robyn J. , Xu Huiyuan 
Published: July 2018

AbstractThe sapropel record of the eastern Mediterranean provides unique insight into the primary climatic, oceanographic, and biological drivers of organic carbon enrichment in marine sediments. The dominant source of organic matter, timing of oxygen depletion at the sea floor, and extent of metazoan reworking of these deposits remain unclear. These questions are addressed by combining microbeam imaging with bulk and molecular geochemical characterization of several Pliocene sapropels, revealing four microfacies which record distinct palaeoceanographic conditions, phytoplankton assemblages, and degrees of postdepositional reworking. The most organic‐rich, carbonate‐lean sapropel intervals consist of alternating 10–60‐μm‐thick organic and detrital mineral laminae. Petrographical features consistent with a pelagic origin, δ15N <−1.8 and the presence of 2α‐methylhopanes indicate that organic laminae formed by mass sedimentation of N‐fixing colonial cyanobacteria (Trichodesmium). The association of framboidal pyrite with organic laminae suggests that mass sedimentation led to the abrupt development of sea floor anoxia. Unlike similar Quaternary sapropels, no petrographic or biomarker evidence is found for a mat‐forming diatom contribution to these organic‐rich, laminated intervals. However, episodic mass sedimentation was not found to be a universal ingredient of sapropel formation. Carbonate‐lean, weakly laminated intervals contain >50 μm organomineral aggregates, interpreted as marine snow, whereas carbonate microfossil‐rich intervals record periods of nitrogen fixation and moderately increased primary production by a diverse assemblage of calcareous, organic‐walled, and siliceous plankton. The results presented here further show that burrowing by microscopic meiofauna impacted most sapropels, extending into seemingly laminated intervals below obvious disruption from burrowing macrofauna, indicating that metazoans influence organic carbon burial in oxygen‐depleted settings even where physical displacement of sediment is not visible.
Impact of pubertal timing and depression on error‐related brain activity in anxious youth
Authors: Peters Amy T. , Burkhouse Katie L. , Kujawa Autumn , Afshar Kaveh , Fitzgerald Kate D. , Monk Christopher S. , Hajcak Greg , Phan K. Luan 
Published: July 2018

AbstractAnxiety disorders are associated with enhanced error‐related negativity (ERN) across development but it remains unclear whether alterations in brain electrophysiology are linked to the timing of puberty. Pubertal timing and alterations of prefrontal and limbic development are implicated in risk for depression, but the interplay of these factors on the ERN–anxiety association has not been assessed. We examined the unique and interactive effects of pubertal timing and depression on the ERN in a sample of youth 10–19 years old with anxiety disorders (n = 30) or no history of psychopathology (n = 30). Earlier pubertal maturation was associated with an enhanced ERN. Among early, but not late maturing youth, higher depressive symptoms were associated with a reduced ERN. The magnitude of neural reactivity to errors is sensitive to anxiety, depression, and development. Early physical maturation and anxiety may heighten neural sensitivity to errors yet predict opposing effects in the context of depression.
Hair analysis can provide additional information in doping and forensic cases involving clostebol
Authors: Salomone Alberto , Gerace Enrico , Di Corcia Daniele , Alladio Eugenio , Vincenti Marco , Kintz Pascal 
Published: July 2018

AbstractClostebol is a synthetic anabolic androgenic steroid, with potential use as a performance‐enhancing drug if taken for long periods in order to produce the desired effect. Recently, the use of medications containing clostebol acetate has led to the suspension of several athletes in various sports. Previous studies have shown that urine can result positive in case of single intake of a banned substance, including unintentional consumption of steroids. In this context, a hair test can contribute to exculpation of athletes by demonstrating alternative administration or contamination. The development and validation of an ultra‐high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) method to detect clostebol and clostebol acetate in hair is hereby presented. Some real cases of athletes sanctioned for clostebol use, in which we analyzed hair samples to follow up investigations of doping control laboratories and obtain useful elements to understand the origin of clostebol intakes, and two forensic cases of anabolic drugs abuse, are also presented and discussed. In real head‐ and body‐hair samples, clostebol acetate could be detected in the low pg/mg range. As is typical of hair analysis, the interpretation of the quantitative findings may be challenging, and even more in sports owing to the lack of systematic studies. However, the results can be used to produce evidence contrary to any ruling issued against the athletes by the appropriate sports body, and possibly obtain a diminished sanction. Because the sports authorities do not make a distinction among circumstances or means of administration of anabolic compounds, athletes should be warned not to use clostebol‐containing medications.