bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Evaluation of Titanocenes in Ionic Liquids with Non‐coordinating and Coordinating Anions and Application for NH3 Synthesis
Authors: Katayama Akira , Inomata Tomohiko , Ozawa Tomohiro , Masuda Hideki 
Published: September 2017

AbstractRedox behaviors of monomeric and dimeric titanocenes, [Cp2TiCl2] (1) and [(Cp2TiCl)2] (2), were investigated in two different types of ionic liquid (IL) with non‐coordinating and coordinating anions, 1‐butyl‐1‐methylpyrrolidinium tris(pentafluoroethyl)‐ trifluorophosphate (Pyr4FAP) and 1‐butyl‐1‐methylpyrrolidinium triflate (Pyr4OTf), respectively. UV‐vis/NIR spectra obtained during the electrochemical reduction of 1 revealed that it was converted to 2 in the ILs through the formation of [Cp2TiCl] (3). In Pyr4OTf, 3 was coordinated with the OTf anion in the η1‐O mode, during the electrochemical reductions of Ti(IV/III) process, whereas 3 was not coordinated by the FAP anion in Pyr4FAP. Additionally, electrochemical NH3 synthesis was carried out in a solid polymer electrolyte cell by using a gas diffusion electrode coated with Pyr4FAP or Pyr4OTf containing titanocenes. The electrochemical reduction using 2 in Pyr4FAP at −1.5 V (vs. Ag/AgCl) gave a high yield (34 % at 29.9 C) of NH3 per Ti ion. The electrochemical reduction using 1 in Pyr4OTf gave a 6.8 % yield of NH3 per Ti ion at 20 °C. These findings indicate that the use of an IL with a non‐coordinating anion such as FAP contributes to the coordination and reduction of N2 to titanocenes.
Bending Monolayer Artificial Muscle
Authors: Otero Toribio F. , Valero Laura 
Published: September 2017

AbstractA bending electro‐chemo‐mechanical monolayer artificial muscle is presented and characterized. A transversal cross‐linking gradient attained during the film electropolymerization is proposed as the origin of the reaction‐driven muscular action. Each unit of charge consumed per unit of polymer weight gives the largest angular displacement described in the literature. This oversimplified polymeric motor for engineering applications saves extra energy required to bend and trail inactive layers from bilayer or multilayer classical structures.
Elucidation of the Reaction Behavior of Silicon Negative Electrodes in a Bis(fluorosulfonyl)amide‐Based Ionic Liquid Electrolyte
Authors: Yamaguchi Kazuki , Domi Yasuhiro , Usui Hiroyuki , Sakaguchi Hiroki 
Published: September 2017

AbstractExcellent cycling performance of an electrode composed of silicon alone was achieved in a bis(fluorosulfonyl)amide (FSA)‐based electrolyte, with a high discharge capacity of 950 mA h g−1 observed even at the 500th cycle. To elucidate the reaction behavior of the Si electrode in an FSA‐based ionic liquid electrolyte, we investigated the change in the cross‐sectional morphology of the Si‐active material layer, the distribution of Li in the layer, and the crystallinity of Si on the electrode surface. By cross‐sectional scanning electron microscopy, we confirmed that the electrode thickness increased with the cycle number. The increase in thickness was less noticeable in the FSA‐based electrolyte than in an organic electrolyte. An elemental analysis of the electrode material revealed that a film derived from the electrolyte was formed not only on the surface but also inside of the electrode. Soft X‐ray emission spectroscopy demonstrated that the distribution of Li in the FSA‐based electrolyte was more uniform for the cross‐section of the cycled electrode compared to that in an organic electrolyte. The results of Raman spectroscopy indicated that domains of amorphous Si were homogeneously distributed on the electrode surface in the FSA‐based electrolyte. The uniform distribution of the lithiation−delithiation reaction should help to suppress disintegration of the active material layer.
Experimental and Computational Studies of the Structure of Sulfonimidoyl Vinyllithiums
Authors: Giesen Alexander Walter , Raabe Gerhard , Runsink Jan , Gais Hans‐Joachim 
Published: September 2017

AbstracttBuCH=C(Li)S(O)(NSO2Tol)Ph⋅L (L=2THF, TMEDA) (1⋅L) in THF solution is a monomer with a C−Li bond according to NMR spectroscopy and cryoscopy. It was identified as CIP through the scalar 13C,6Li coupling and 6Li,{1H} NOE experiments. The CIP has a six‐membered C‐Li‐O‐S‐N‐S chelate ring structure. 6Li,1H FUCOUP and 6Li,1H HMQC NMR experiments of 1⋅TMEDA revealed a scalar 6Li,1H coupling across the Li−C=C−H bonds. According to the NMR data the π‐bond of 1⋅L is polarized by the negative charge of the anionic C atom. tBuCH=C(Li)S(O)(NMe)Ph (2⋅L) is most likely also a monomer with a C−Li bond. According to 6Li,{1H} NOE experiments it has a four‐membered C‐Li‐N‐S chelate ring structure. 13C NMR spectroscopy showed the C−Li bonds of 1⋅L and 2⋅L to be fluxional. 1H NMR spectroscopy and 1D TOCSY experiments of Ph2C=C(Li)S(O)(NSO2Tol)Ph revealed topomerization of the phenyl groups, which is attributed to a fast positional exchange of the Li atom and the sulfonimidoyl group. The fluxionality of the C−Li bond and the interchange of the Li atom and the sulfonimidoyl group at the anionic C atom of sulfonimidoyl vinyllithiums, which result in a low configurational stability, most likely involve the formation of O,Li and N,Li CIPs through heterolysis of the C−Li bond. Ab initio calculation of MeCH=C(Li)S(O)(NMe)Ph yielded an energy minimum structure with a C−Li bond, a four‐membered C‐Li‐N‐S chelate ring and a strongly expanded C=C−Li bond angle. According to calculation of MeCH=C(Li)S(O)(NMe)Ph, [MeCH=CS(O)(NMe)Ph]− and MeCH=C(H)S(O)(NMe)Ph deprotonation is not accompanied by a shortening of the C−S bond. Ab initio calculation of MeCH=C(Li)S(O)(NSO2Me)Ph gave a structure with a C−Li bond and a six‐membered C‐Li‐O‐S‐N‐S chelate ring. 6Li,1H NOE experiments and cryoscopy of LiCH2S(O)(NSO2Tol)Ph (3) revealed a monomeric CIP with a C−Li bond. The CIP has a six‐membered C‐Li‐O‐S‐N‐S chelate ring structure found in polymeric 3 in the crystal.
An Explosive Bomb‐Inspired Method to Prepare Collapsed and Ruptured Fe2O3/Nitrogen‐Doped Carbon Capsules as Catalyst Support
Authors: Wu Jie , Zhang Hui , Feng Yan , Zhang Xiao , Yao Tongjie , Lian Yongfu 
Published: September 2017

AbstractCompared with integrated capsules, ruptured ones have better mass diffusion and transport properties due to large gaps in the shells. However, most studies focus on integrated capsules, whereas little attention has been paid to the ruptured counterparts. Herein, an explosive bomb‐inspired method was employed to prepare collapsed and ruptured Fe2O3/nitrogen‐doped carbon (CR‐Fe2O3/NC) capsules by using polystyrene (PS) nanoparticles (NPs) as a hard template, and polypyrrole (PPy) with embedded Prussian blue (PB) NPs as the shell. During pyrolysis, PB is converted into Fe2O3, and PPy is carbonized to form NC. Importantly, the PS core decomposes into gas molecules, leading to high pressure inside of the capsule, which explodes the thin shell into pieces. The roles of shell thickness and amount of Fe2O3 on determining the spherical or collapsed, and integrated or ruptured morphology were revealed. Taking advantage of structural merits, including large gaps, thin shells, low density, and high surface area, CR‐Fe2O3/NC capsules were used as supports for Pd NPs. These capsules exhibited better catalytic activity than that of integrated ones. Due to the magnetic properties, they could be reused at least five times.
Theoretical Evidence for the Utilization of Low‐Valent Main‐Group Complexes as Rare‐Synthon Equivalents
Authors: Benedek Zsolt , Orbán Balázs , Szilvási Tibor 
Published: September 2017

AbstractWe examine by the means of computational chemistry the ability of two phosphasilenes to transfer the phosphinidene moiety to four double bonded organic functional groups (>C=C<, ‐N=N‐, >C=O, and >C=S) in the presence of different bulky ligands. We show that large bulky groups in the reactants can sterically prohibit the otherwise favored association of reactants and phosphasilenes and instead a new phosphinidene transfer reaction can occur. We find that the transfer reaction mechanism is generally present independent from the functional group and by introducing large enough trimethylsilyl or tert‐butyl‐dimethylsilyl ligands it can be used to transfer phosphinidene to organic functional groups such as thioformaldehydes or diazenes, respectively. We propose that by exploiting the complex bonding nature of low‐valent main group complexes they can act as synthetic equivalents of hitherto unknown very reactive synthons. We encourage experimentalists to explore the reactivity of their main‐group complexes by varying the size of the bulky substituents on the reactants that can result in new unexpected chemistry.
Supramolecular Synthon Approach in Developing Anti‐Inflammatory Topical Gels for In Vivo Self‐Delivery
Authors: Roy Rajdip , Dastidar Parthasarathi 
Published: September 2017

AbstractA new series of tertiary‐butyl ammonium (TBA) salts of various nonsteroidal anti‐inflammatory drugs (NSAIDs) have been synthesized and characterized. Nearly 90 % of the NSAID‐derived primary ammonium monocarboxylate (PAM) salts displayed remarkable gelation ability with various solvents including methyl salicylate. Single crystal X‐ray diffraction data (SXRD) revealed the existence of 1D PAM synthon in the gelator salts. Structure–property correlation studies based on SXRD and powder X‐ray diffraction (PXRD) data established the presence of the 1D PAM synthon in the bulk salts as well as in the corresponding xerogels. A parallel series of salts derived from TRIS (2‐amino‐2‐(hydroxymethyl)‐1,3‐propanediol) and the same set of NSAIDs displayed poor gelation ability; only 33 % of the salts in the series displayed gelation ability. A few selected gelator salts of both TBA and TRIS were found to be biocompatible (MTT assay with RAW 264.7 cell line) and two of the selected salts (FLR.TBA and FLR.TRIS) possessed anti‐inflammatory properties equal to the parent drug FLR (flurbiprofen). Finally a methyl salicylate topical gel derived from FLR.TRIS was successfully delivered in a self‐delivery fashion to treat inflamed skin conditions in the mice model. Histological studies of the dorsal tissues of the untreated and treated mice clearly demonstrated the effect of topical gels in such treatment.
Stereospecific Winding of Polycyclic Aromatic Hydrocarbons into Trinacria Propellers
Authors: Mosca Dario , Stopin Antoine , Wouters Johan , Demitri Nicola , Bonifazi Davide 
Published: September 2017

AbstractInvited for the cover of this issue is the group of Bonifazi at the University of Cardiff and their collaborators from University of Namur (Belgium) and Elettra, Synchrotron Trieste (Italy). The image depicts the propeller‐like conformation of their newly synthesized molecular system that, thanks to the peculiar aromatic‐embracing folding, resembles the shape of the Sicilian Trinacria symbol, as demonstrated by its X‐ray single‐crystal structure. Read the full text of the article at 10.1002/chem.201702032.
Changes in parameters of right ventricular function with cardiac resynchronization therapy
Authors: Sharma Abhishek , Lavie Carl J. , Vallakati Ajay , Garg Akash , Goel Sunny , Lazar Jason , Fonarow Gregg C. 
Published: September 2017

BackgroundStudies have shown that cardiac resynchronization therapy (CRT) significantly improves right ventricle (RV) size and function in patients with heart failure (HF).HypothesisCRT does not lead to improvement in RV function independent of baseline clinical variables.MethodsA systematic search of studies published between 1966 to August 31, 2015 was conducted using Pub Med, CINAHL, Cochrane CENTRAL and the Web of Science databases. Studies reporting tricuspid annular plane systolic excursion (TAPSE) or RV basal strain or RV long axis diameter or RV short axis diameter or RV fractional area change (FAC), before and after CRT, were identified. A meta‐analysis was performed using random effects with inverse variance method to determine the pooled mean difference in various parameters of RV function after CRT. Meta‐regression analysis was performed to test the relationship between change in various parameters of RV functions after CRT and covariates‐ age, QRS duration, and left ventricular ejection fraction (LVEF).ResultsThirteen studies (N=1541) were selected for final analysis. CRT therapy led to statistically significant increases in TAPSE [1.21 (95% CI 0.55‐1.86; p<0.001)], RV FAC [2.26 (95% CI 0.50‐4.01; p<0.001)] and basal strain [2.82 (95% CI 0.59‐5.05; p<0.001)] and statistically significant decreases in mean RV long axis diameter [‐2.94 (95% CI ‐5.07‐ ‐0.82; p=0.005)] and short axis diameter [‐1.39 (95% CI ‐2.10‐ ‐0.67; p=0.876)] after a mean follow up period of 9 months. However, after meta‐regression analysis for age, QRS duration, and baseline LVEF as covariates, there was no significant improvement in any of the parameters of RV function after CRT.ConclusionThere was a statistically significant improvement in TAPSE, RV basal strain, RV fractional area, RV long axis and short axis with CRT. However, improvement in these echocardiographic parameters of RV function after CRT was not independent of baseline clinical variables but statistically dependent on age, QRS duration and baseline LVEF.
Diagnostic accuracy of serum antibodies to human papillomavirus type 16 early antigens in the detection of human papillomavirus–related oropharyngeal cancer
Authors: Dahlstrom Kristina R. , Anderson Karen S. , Field Matthew S. , Chowell Diego , Ning Jing , Li Nan , Wei Qingyi , Li Guojun , Sturgis Erich M. 
Published: September 2017

BACKGROUNDBecause of the current epidemic of human papillomavirus (HPV)–related oropharyngeal cancer (OPC), a screening strategy is urgently needed. The presence of serum antibodies to HPV‐16 early (E) antigens is associated with an increased risk for OPC. The purpose of this study was to evaluate the diagnostic accuracy of antibodies to a panel of HPV‐16 E antigens in screening for OPC.METHODSThis case‐control study included 378 patients with OPC, 153 patients with nonoropharyngeal head and neck cancer (non‐OPC), and 782 healthy control subjects. The tumor HPV status was determined with p16 immunohistochemistry and HPV in situ hybridization. HPV‐16 E antibody levels in serum were identified with an enzyme‐linked immunosorbent assay. A trained binary logistic regression model based on the combination of all E antigens was predefined and applied to the data set. The sensitivity and specificity of the assay for distinguishing HPV‐related OPC from controls were calculated. Logistic regression analysis was used to calculate odds ratios with 95% confidence intervals for the association of head and neck cancer with the antibody status.RESULTSOf the 378 patients with OPC, 348 had p16‐positive OPC. HPV‐16 E antibody levels were significantly higher among patients with p16‐positive OPC but not among patients with non‐OPC or among controls. Serology showed high sensitivity and specificity for HPV‐related OPC (binary classifier: 83% sensitivity and 99% specificity for p16‐positive OPC).CONCLUSIONSA trained binary classification algorithm that incorporates information about multiple E antibodies has high sensitivity and specificity and may be advantageous for risk stratification in future screening trials. Cancer 2017;123:4886‐94. © 2017 American Cancer Society.
Biomolecule‐Enabled Chiral Assembly of Plasmonic Nanostructures
Authors: Lee Hye‐Eun , Ahn Hyo‐Yong , Lee Jaehun , Nam Ki Tae 
Published: September 2017

AbstractThe field of chiral plasmonics has received increasing attention in various areas of nanoscience due to the unprecedented light‐matter interactions and promising optical applications. Chiral arrangement of nanoparticles is one of the strategies employed for fabrication of chiral nanostructures. These arrays exhibit collective chirality, where the chiroptical properties are governed by the geometrical parameters with nanometer precision. In this regard, the self‐assembly of biomolecules, such as peptides, DNA, and macromolecules, and their integration with plasmonic building blocks, can provide a route for the design and production of chiral plasmonic assemblies. In this Focus Review, we highlight biomolecule‐assisted methods for the chiral assembly of plasmonic nanostructures with emphasis on of the types of biomolecules and the geometry of the resulting assemblies. We present an overview of recent achievements in chiral plasmonic assemblies and provide perspectives for future directions in the field of chiral plasmonics.
Distinct seasonal migration patterns of Japanese native and non‐native genotypes of common carp estimated by environmental DNA
Authors: Uchii Kimiko , Doi Hideyuki , Yamanaka Hiroki , Minamoto Toshifumi 
Published: September 2017

AbstractUnderstanding behavioral differences between intraspecific genotypes of aquatic animals is challenging because we cannot directly observe the animals underwater or visually distinguish morphologically similar counterparts. Here, we tested a new monitoring tool that uses environmental DNA (eDNA), an assemblage of DNA in environmental water, to specifically detect Japanese native and introduced non‐native genotypes of common carp (Cyprinus carpio) in Lake Biwa, Japan, and estimated differences between the two genotypes in the use of inland habitats. We monitored the ratios of native and non‐native single nucleotide polymorphism alleles of a mitochondrial locus of common carp in a lagoon connected to Lake Biwa for 3 years using eDNA. We observed seasonal dynamics in the allele frequency showing that the native genotype frequency peaked every spring, suggesting that native individuals migrated to the lagoon for spawning and then returned to the main lake, whereas non‐native individuals tended to stay in the lagoon. The estimated migration patterns corresponded with the estimates of a previous study, which were based on commercial fish catch data. Our findings suggest that eDNA‐based monitoring can be useful tool for addressing intraspecific behavioral differences underwater.
Skin denervation does not alter cortical potentials to surface concentric electrode stimulation: A comparison with laser evoked potentials and contact heat evoked potentials
Authors: La Cesa S. , Di Stefano G. , Leone C. , Pepe A. , Galosi E. , Alu F. , Fasolino A. , Cruccu G. , Valeriani M. , Truini A. 
Published: September 2017

AbstractBackgroundIn the neurophysiological assessment of patients with neuropathic pain, laser evoked potentials (LEPs), contact heat evoked potentials (CHEPs) and the evoked potentials by the intraepidermal electrical stimulation via concentric needle electrode are widely agreed as nociceptive specific responses; conversely, the nociceptive specificity of evoked potentials by surface concentric electrode (SE‐PREPs) is still debated.MethodsIn this neurophysiological study we aimed at verifying the nociceptive specificity of SE‐PREPs. We recorded LEPs, CHEPs and SE‐PREPs in eleven healthy participants, before and after epidermal denervation produced by prolonged capsaicin application. We also used skin biopsy to verify the capsaicin‐induced nociceptive nerve fibre loss in the epidermis.ResultsWe found that whereas LEPs and CHEPs were suppressed after capsaicin‐induced epidermal denervation, the surface concentric electrode stimulation of the same denervated skin area yielded unchanged SE‐PREPs.ConclusionThe suppression of LEPs and CHEPs after nociceptive nerve fibre loss in the epidermis indicates that these techniques are selectively mediated by nociceptive system. Conversely, the lack of SE‐PREP changes suggests that SE‐PREPs do not provide selective information on nociceptive system function.SignificanceCapsaicin‐induced epidermal denervation abolishes laser evoked potentials (LEPs) and contact heat evoked potentials (CHEPs), but leaves unaffected pain‐related evoked potentials by surface concentric electrode (SE‐PREPs). These findings suggest that unlike LEPs and CHEPs, SE‐PREPs are not selectively mediated by nociceptive system.
Tapioca Biofilm Containing Nitrogen‐doped Titanium Dioxide Nanoparticles for Electrochemical Detection of 17‐β Estradiol
Authors: Mauruto de Oliveira Gabriela C. , P. de Palma Elisangela , Kunita Marcos H. , Antigo Medeiros Roberta , de Matos Roberto , Francisco Kelly Roberta , Janegitz Bruno C. 
Published: September 2017

AbstractA novel sensor architecture based on thin film of tapioca decorated within nitrogen‐doped titanium dioxide (N‐TiO2) nanoparticles is reported. The nanostructures were characterized by scanning electron microscope, transmission electron microscope, X‐rays diffraction and voltammetric techniques. The proposed electrode was used for detection of low concentrations of 17‐β estradiol in without purification step, which was investigated by using linear sweep adsorptive stripping voltammetry. Under optimal conditions, the analytical curve was linear over a 17β‐estradiol concentration range of 9.9×10−6 to 1.4×10−5 mol L−1, with a detection limit of 1.7×10−7 mol L−1. The tapioca and N‐TiO2 nanoparticles homogeneous film was applied for detection of 17‐β‐estradiol in tap water and synthetic urine samples, which presented satisfactory results.
A pediatric structural MRI analysis of healthy brain development from newborns to young adults
Authors: Levman Jacob , MacDonald Patrick , Lim Ashley Ruyan , Forgeron Cynthia , Takahashi Emi 
Published: September 2017

AbstractAssessment of healthy brain maturation can be useful toward better understanding natural patterns of brain growth and toward the characterization of a variety of neurodevelopmental disorders as deviations from normal growth trajectories. Structural magnetic resonance imaging (MRI) provides excellent soft‐tissue contrast, which allows for the assessment of gray and white matter in the developing brain. We performed a large‐scale retrospective analysis of 993 pediatric structural brain MRI examinations of healthy subjects (n = 988, aged 0–32 years) imaged clinically at 3 T, and extracted a wide variety of measurements such as white matter volumes, cortical thickness, and gyral curvature localized to subregions of the brain. All extracted structural biomarkers were tested for their correlation with subject age at time of imaging, providing measurements that may assist in the assessment of neurological maturation. Additional analyses were also performed to assess gender‐based differences in the brain at a variety of developmental stages, and to assess hemispheric asymmetries. Results add to the literature by analyzing a realistic distribution of healthy participants imaged clinically, a useful cohort toward the investigation and creation of diagnostic tests for a variety of pathologies as aberrations from healthy growth trajectories. The next generation of diagnostic tests will be responsible for identifying pathological conditions from populations of healthy clinically imaged individuals. Hum Brain Mapp 38:5931–5942, 2017. © 2017 Wiley Periodicals, Inc.