bluuebunny/crossref_metadata_2025_split huggingface dataset:
Imidazolyl‐Naphthalenediimide‐Based Threading Intercalators of DNA
Authors: Suseela Y. V. , Das Shubhajit , Pati Swapan K. , Govindaraju T. 
Published: September 2016

AbstractIntercalation by threading is anticipated to feature in DNA‐binding molecules for developing DNA‐targeted diagnostics and therapeutics. We investigated the role of an imidazolyl moiety in threading intercalators of DNA by employing a number of imidazolyl–naphthalenediimide conjugates. Threading intercalation was studied by UV spectroscopy, competitive binding fluorescent dye displacement, circular dichroism, isothermal calorimetry, and computational analysis. NIm6 was found to be a strong candidate, with good half‐life, as revealed by dissociation kinetic analysis. Computational studies supported intercalation of the naphthalene core between base pairs and binding of the imidazolyl moieties in the adjacent grooves (threading mechanism) through electrostatic and hydrogen‐bonding interactions. The interaction of the positively charged imidazolium moieties with the negatively charged phosphate backbone of DNA contributed to the favorable enthalpy change, as revealed by the experimental and computational data. Threading intercalation by NIm6 caused significant retardation of DNA in an electrophoretic mobility shift assay. The biological significance of potent imidazolyl naphthalenediimide conjugates was demonstrated by the inhibition of topo‐ isomerase I activity and cytotoxicity against HeLa cells.
Juvenile animal cruelty and firesetting behaviour
Authors: Baglivio Michael T. , Wolff Kevin T. , DeLisi Matt , Vaughn Michael G. , Piquero Alex R. 
Published: September 2016

AbstractBackgroundThere is a view that young people presenting with an animal cruelty and firesetting combination represent a uniquely risky group, but prior work has relied on samples with insufficient power.Research questionWhat is the prevalence of the co‐occurrence of animal cruelty and firesetting behaviour among young delinquents? What other features correlate with this?MethodsWe measured the prevalence of animal cruelty and firesetting among 292,649 juvenile offenders and used rare events logistic regression to examine demographic, criminal, mental health and family histories as correlates.ResultsThe prevalence of animal cruelty was 0.59%, accounting for 1732 young people, and of firesetting 1.56% (n = 4553). The co‐occurrence of these behaviours was rare: 0.17% (n = 498), but approximately twice that expected by chance based on the prevalence of each behaviour individually (0.59% × 1.56% = 0.009%). Rates were higher in males, older youths and Whites. Among historical variables, criminal history was the strongest correlate, followed by mental health problems, then familial and individual indicators.ConclusionsAs only male gender and being a victim of sexual abuse increased the odds of evidencing both animal cruelty and firesetting behaviour substantially above the odds for each behaviour individually, there thus appears to be little that is unique to the co‐occurrence. Our findings suggest that sensitivity to the occurrence of each is the best way forward, with rather familiar assessments and interventions offering some hope of reducing these seriously damaging behaviours. Copyright © 2016 John Wiley & Sons, Ltd.
Enhanced Electrokinetics of C−C Bond Splitting during Ethanol Oxidation by using a Pt/Rh/Sn Catalyst with a Partially Oxidized Pt and Rh Core and a SnO2 Shell
Authors: Yang Guangxing , Frenkel Anatoly I. , Su Dong , Teng Xiaowei 
Published: September 2016

AbstractDirect ethanol fuel cells (DEFCs) are a promising technology for generating electricity through the electro‐oxidation of liquid ethanol. Its implementation requires the development of anode catalysts capable of producing CO2 and yielding 12‐electron transfer through breaking the C−C bond of ethanol. Here, we presented comprehensive studies of the electrokinetics of CO2 generation on Pt/Rh/Sn ternary catalysts. Our studies showed that the triphasic PtRhOx–SnO2 catalysts with a partially oxidized Pt and Rh core and a SnO2 shell, validated by X‐ray absorption analyses and scanning transmission electron microscope‐electron energy loss spectroscopy line scans, coincided with a 2.5‐fold increase in the CO2 generation rate towards ethanol oxidation reaction, compared with the biphasic PtRh‐SnO2 catalysts with a metallic PtRh alloy core and commercial Pt. These studies provided insight into the design of a new genre of electrocatalysts with a partially oxidized noble metal.
Orthogonal Palladium‐Catalyzed Direct C−H Bond Arylation of Heteroaromatics with Aryl Halides
Authors: Théveau Laure , Schneider Cédric , Fruit Corinne , Hoarau Christophe 
Published: September 2016

AbstractTransition metal‐catalyzed direct C−H bond functionalization of heterocycles with halo(het)arenes has received considerable attention as synthetic alternative to standard cross‐coupling reactions regarding step‐ and atom‐economy in the preparation of heteroarylmetals intermediates and better chemo‐selectivity towards standard organic functions such as aldehyde, ketone, ester, cyanide, and amide. An additional major and poorly highlighted interest of such methodology is its unparalleled ability to open the chemical space of functionalization of heterocycles towards challenging unprecedented sites. This Review gives an overview of the advances in challenging orthogonal direct C−H arylation of heterocycles related to the wide variety of catalytic C−H bond metalation processes, most of them evaluated by DFT calculations.
Ammonia Decomposition over Nickel Catalysts Supported on Rare‐Earth Oxides for the On‐Site Generation of Hydrogen
Authors: Okura Kaname , Okanishi Takeou , Muroyama Hiroki , Matsui Toshiaki , Eguchi Koichi 
Published: September 2016

AbstractAmmonia decomposition has attracted the interest of many researchers as a promising process for the on‐site generation of H2. In this study, Ni catalysts supported on various rare‐earth oxides were prepared by the impregnation method and employed for ammonia decomposition. The Ni/Y2O3 catalyst exhibited the best performance among the samples investigated. The reaction kinetics study indicated that most of rare‐earth oxide supports were effective for the alleviation of the hydrogen inhibition phenomenon in the decomposition reaction. The desorption behavior of hydrogen has revealed that the amount of hydrogen atoms adsorbed strongly on the Ni surface up to high temperatures was relatively small in the case of Ni/Y2O3. Furthermore, for Ni/Y2O3 the optimal Ni loading was 40 wt % in terms of the catalytic activity because of the appropriate Ni dispersion.
Highly Active and Coke‐Tolerant Hierarchical Mordenite Catalysts Synthesized by Recrystallization for the Isopropylation of Naphthalene
Authors: Lee Young Hye , Kim Won Yong , Park Hunmin , Choi Yo Han , Lee Jae Sung 
Published: September 2016

AbstractIn the isopropylation of naphthalene for the production of 2,6‐naphthalenedicarboxylate, the monomer of polyethylene naphthalate plastic, a shape‐selective mordenite (MOR) zeolite catalyst provides the best selectivity for the desired 2,6‐diisopropylnaphthalene. However, the small pore size of the zeolite limits the naphthalene conversion and lowers the stability because of pore‐mouth blocking by coke. We discovered that these problems could be mitigated by synthesizing a micro‐meso hierarchical pore structure in the MOR zeolite by the recrystallization of MOR with cetyltrimethylammonium bromide as a mesopore‐forming surfactant. The recrystallized catalysts allow the facile diffusion of bulky molecules through connected meso‐ and micropores to and from active catalytic sites located in the small MOR pores. Relative to microporous MOR, the hierarchical MOR catalyst demonstrated a greatly enhanced activity, stability, and coke tolerance, and the intrinsic high shape selectivity of MOR for 2,6‐diisopropylnaphthalene was maintained. Mild desilication enlarged the pore volume and formed additional acid sites to increase the activity further.
A Simple and Versatile Approach for the Fabrication of Paper‐Based Nanocatalysts: Low Cost, Easy Handling, and Catalyst Recovery
Authors: Montiel Laura , Delgado Jorge A. , Novell Marta , Andrade Francisco J. , Claver Carmen , Blondeau Pascal , Godard Cyril 
Published: September 2016

AbstractA versatile method for the preparation of efficient and reusable nanocatalysts involving the painting of a commercial filter paper with a Pd@CNT (CNT=carbon nanotubes) ink was herein explored. The resulting paper‐based material provided excellent results in the semihydrogenation of alkynes and alkynols and could be recycled at least five times without loss of activity or selectivity.
Zirconium Oxide Supported Palladium Nanoparticles as a Highly Efficient Catalyst in the Hydrogenation–Amination of Levulinic Acid to Pyrrolidones
Authors: Zhang Jian , Xie Bin , Wang Liang , Yi Xianfeng , Wang Chengtao , Wang Guoxiong , Dai Zhifeng , Zheng Anmin , Xiao Feng‐Shou 
Published: September 2016

AbstractThe selective hydrogenation–amination of levulinic acid into pyrrolidones is regarded as one of the most important reactions to transform biomass‐derived lignocellulose feedstocks into valuable chemicals. Here we report on ZrO2‐supported Pd nanoparticles as a highly active, chemoselective, and reusable catalyst for the hydrogenation–amination of levulinic acid with H2 and various amines under mild reaction conditions. The Pd/ZrO2 catalyst exhibited a marked increase in activity compared with conventional Pd catalysts and a significant enhancement in pyrrolidone selectivity. The excellent catalytic performances are reasonably attributed to the ZrO2 support, which has strong Lewis acidity to enhance the hydrogenation–amination reaction and hinder side reactions.
Ligand‐Promoted Palladium‐Catalyzed C−H Acetoxylation of Simple Arenes
Authors: Valderas Carolina , Naksomboon Kananat , Fernández‐Ibáñez M. Ángeles 
Published: September 2016

AbstractThe palladium‐catalyzed C−H oxidation of simple arenes is an attractive strategy to obtain phenols, which have many applications in the fine chemicals industry. Although some advances have been made in this research area, low reactivity and selectivity are, in general, observed. This report describes a new catalytic system for the efficient C−H acetoxylation of simple arenes based on Pd(OAc)2 and a pyridinecarboxylic acid ligand.
Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?
Authors: Engesser Tobias A. , Friedmann Christian , Martens Arthur , Kratzert Daniel , Malinowski Przemysław J. , Krossing Ingo 
Published: September 2016

AbstractA series of gold acetonitrile complexes [Au(NCMe)2]+[WCA]− with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO]+[WCA]− in acetonitrile ([WCA]−=[GaCl4]−, [B(CF3)4]−, [Al(ORF)4]−; RF=C(CF3)3). In the crystal structures, the [Au(NCMe)2]+ units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C−N stretching frequencies of [Au(NCMe)2]+ units). An attempt to prepare [Au(L)2]+ units, even with less weakly basic solvents like CH2Cl2, led to decomposition of the [Al(ORF)4]− anion and formation of [NO(CH2Cl2)2]+[F(Al(ORF)3)2]−. All nitrosyl reagents [NO]+[WCA]− were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO]+[B(CF3)3CN]− was prepared. Its reaction with gold unexpectedly produced [Au(NCMe)2]+[Au(NCB(CF3)3)2]−, in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF3)3)2]− behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe)2]+ cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe)2]+[Al(ORF)4]−, is facile and, for example, [Au(PPh3)(NCMe)]+[Al(ORF)4]− can be selectively generated. This reactivity opens the possibility to generate various [AuL1L2]+[Al(ORF)4]− salts through consecutive ligand‐exchange reactions that offer access to a huge variety of AuI complexes for gold catalysis.
Aseptic Zero Discharge Fluid Dynamic Gauging for Measuring the Thickness of Soft Layers on Surfaces
Authors: Wang Shiyao , Schlüter Florian , Gottschalk Nathalie , Scholl Stephan , Wilson D. Ian , Augustin Wolfgang 
Published: September 2016

AbstractA bench‐top device that can be used to perform fluid dynamic gauging measurements of soft solid layers with zero net liquid discharge and potentially under aseptic (closed system) conditions is demonstrated. Test results are presented for Newtonian liquids with a range of viscosities: deionized water, sucrose solutions, glycerol/water solutions and paraffin oil. The experimental data for discharge coefficient Cd against clearance/nozzle throat diameter gave good agreement with CFD simulations and literature. The influence of surface roughness was studied by making measurements on a series of commercial sandpapers. The rough surfaces gave rise to systematic differences in Cd from those obtained with smooth substrates. Careful calibration is required when gauging rough surfaces.
Direct Correlation between Molecular Cross‐linking and Macroscopic Mechanical Properties for Green Solids of Deoxyribonucleic Acids
Authors: Morimitsu Yuma , Matsuno Hisao , Ohta Noboru , Sekiguchi Hiroshi , Tanaka Keiji 
Published: September 2016

AbstractDouble‐stranded deoxyribonucleic acids (DNAs) were intermolecularly cross‐linked using 2,5‐hexanedione under reductive amination conditions in aqueous phase. Cross‐linking points between DNAs were directly observed by atomic force microscopy in conjunction with a conventional gel electrophoresis analysis. While DNA chains near cross‐linking points were denatured, DNA chains not near cross‐linking points maintained B‐form double strands. A transparent and self‐supported film of cross‐linked DNA (DNA‐c) was obtained by a simple solvent‐casting method. The tensile properties of DNA‐c films were much better than those of non‐cross‐linked DNA (DNA‐n) films due to the presence of the cross‐linking portions. Structural analyses based on wide‐angle X‐ray diffraction measurements revealed that the reorientation of DNA‐c was remarkably restricted by the introduction of cross‐linking points.
Free Energy of Bare and Capped Gold Nanoparticles Permeating through a Lipid Bilayer
Authors: Mhashal Anil R. , Roy Sudip 
Published: September 2016

AbstractHerein, we study the permeation free energy of bare and octane‐thiol‐capped gold nanoparticles (AuNPs) translocating through a lipid membrane. To investigate this, we have pulled the bare and capped AuNPs from bulk water to the membrane interior and estimated the free energy cost. The adsorption of the bare AuNP on the bilayer surface is energetically favorable but further loading inside it requires energy. However, the estimated free‐energy barrier for loading the capped AuNP into the lipid membrane is much higher compared to bare AuNP. We also demonstrate the details of the permeation process of bare and capped AuNPs. Bare AuNP induces the curvature in the lipid membrane whereas capped AuNP creates an opening in the interacting monolayer and get inserted into the membrane. The insertion of capped AuNP induces a partial unzipping of the lipid bilayer, which results in the ordering of the local lipids interacting with the nanoparticle. However, bare AuNP disrupts the lipid membrane by pushing the lipid molecules inside the membrane. We also analyze pore formation due to the insertion of capped AuNP into the membrane, which results in water molecules penetrating the hydrophobic region.
Two‐Step Mechanochromic Luminescence of N,N′‐Bis‐Boc‐3,3′‐di(pyren‐1‐yl)‐2,2′‐biindole
Authors: Ito Suguru , Yamada Takeshi , Asami Masatoshi 
Published: September 2016

AbstractDespite recent advances in the development of mechanochromic luminescent organic molecules, the mechano‐responsive properties of intramolecularly stacked fluorophores are not well documented. Herein, the synthesis and emission properties of three N,N′‐bis‐Boc‐3,3′‐diaryl‐2,2′‐biindole (Boc=tert‐butoxycarbonyl) derivatives as a new class of solid‐state emissive fluorophores are described. For a 3,3′‐dipyrenyl derivative in the crystalline state, partial intramolecular stacking of the dipyrenyl groups was observed, which results in a two‐step mechanochromic luminescence from blue (λem=462 nm) to green (λem=516 nm) and yellow (λem=535 nm).
S‐Adenosyl Methionine in the Therapy of Depression and Other Psychiatric Disorders
Authors: Karas Kuželički Nataša 
Published: September 2016

ABSTRACT

Preclinical Research

S‐adenosyl methionine (SAM) is a major methyl donor and as such exerts its influence on CNS function through methylation reactions, such as methylation of several catecholamine moiety‐containing neurotransmitters, epigenetic changes through methylation of DNA, RNA, RNA‐binding proteins and histones, and phospholipid methylation. Based on available evidence, SAM is currently recommended as a next‐step (second‐line) treatment option following inadequate treatment response to a first‐line antidepressant. It shows significant promise in the treatment of pediatric and perinatal depression, as well as Alzheimer's disease, but to make this a recommendation further clinical trials are needed. SAM is safe to use in most patients, but is contraindicated in those with bipolar disorder. Concerns considering the possible increase of homocysteine levels (and cardiovascular complications) due to long‐term SAM therapy need to be further addressed in clinical trials taking into account individual`s ability to metabolize homocysteine and his/her folate status. Drug Dev Res 77 : 336–346, 2016. © 2016 Wiley Periodicals, Inc.
Bridging two scholarly islands enriches both: COI DNA barcodes for species identification versus human mitochondrial variation for the study of migrations and pathologies
Authors: Thaler David S. , Stoeckle Mark Y. 
Published: September 2016

AbstractDNA barcodes for species identification and the analysis of human mitochondrial variation have developed as independent fields even though both are based on sequences from animal mitochondria. This study finds questions within each field that can be addressed by reference to the other. DNA barcodes are based on a 648‐bp segment of the mitochondrially encoded cytochrome oxidase I. From most species, this segment is the only sequence available. It is impossible to know whether it fairly represents overall mitochondrial variation. For modern humans, the entire mitochondrial genome is available from thousands of healthy individuals. SNPs in the human mitochondrial genome are evenly distributed across all protein‐encoding regions arguing that COI DNA barcode is representative. Barcode variation among related species is largely based on synonymous codons. Data on human mitochondrial variation support the interpretation that most – possibly all – synonymous substitutions in mitochondria are selectively neutral. DNA barcodes confirm reports of a low variance in modern humans compared to nonhuman primates. In addition, DNA barcodes allow the comparison of modern human variance to many other extant animal species. Birds are a well‐curated group in which DNA barcodes are coupled with census and geographic data. Putting modern human variation in the context of intraspecies variation among birds shows humans to be a single breeding population of average variance.
Fifteen‐year trends in the management of cardiogenic shock and associated 1‐year mortality in elderly patients with acute myocardial infarction: the FAST‐MI programme
Authors: Aissaoui Nadia , Puymirat Etienne , Juilliere Yves , Jourdain Patrick , Blanchard Didier , Schiele François , Guéret Pascal , Popovic Batric , Ferrieres Jean , Simon Tabassome , Danchin Nicolas 
Published: September 2016

AbstractAimsAlhough cardiogenic shock (CS) after acute myocardial infarction (AMI) is more common in elderly patients, information on the epidemiology of these patients is scarce. This study aimed to assess the trends in prevalence, characteristics, management, and outcomes of elderly patients admitted with CS complicating AMI between 1995 and 2010, using data from the FAST‐MI programme.Methods and resultsWe analysed the incidence and 1‐year mortality of CS in four nationwide French surveys carried out 5 years apart from 1995 to 2010, including consecutive AMI patients over 1‐month periods. Among the 10 610 patients, 3389 were aged ≥75 years, of whom 9.9% developed CS. The prevalence of CS decreased in elderly patients from 11.6% in 1995 to 6.7% in 2010 (P = 0.02). Over the 15‐year period, the characteristics of elderly patients with CS changed, with more diabetes, hypertension, and hypercholesterolaemia. The use of PCI increased markedly in elderly patients with and without CS, reaching 51% and 59%, respectively, in 2010. In addition, medical therapy also evolved, with more patients receiving antithrombotic agents, beta‐blockers, and statins. Over time, 1‐year mortality decreased by 32% among elderly patients with CS but remained high (59% in 2010). ST‐segmet elevation myocardial infarction and previous AMI were independent correlates of increased 1‐year death, while study period was associated with decreased mortality (2010 vs, 1995: hazard ratio 0.40, 95% confidence interval 0.27–0.61, P < 0.001), along with early use of PCI.ConclusionCardiogenic shock in elderly patients with AMI remains a major clinical concern. However, 1‐year mortality declined in these patients, a decrease potentially mediated by broader use of PCI and the improvement of global patient management.
Analytical Approach for Evaluation of Lithium‐Ion Battery Cells
Authors: Wagner Sebastian , Oberland Alexander , Turek Thomas 
Published: September 2016

AbstractA new method for evaluation of battery cells containing porous thin‐layer electrodes is developed. For this purpose, a typical concept of chemical reaction engineering to classify reactors by dimensionless characteristic values is used. Therefore, the system of equations describing the porous electrodes in a battery cell is transferred to dimensionless notation and corresponding dimensionless properties are developed. The required kinetic data are measured with the help of electrochemical test cells. A complete set of parameters for the description of the lithium‐ion battery is determined and the characteristic properties for the chosen example are calculated and analyzed. Finally, the performance of the anode and cathode using lithium manganese oxide and surface‐modified graphite as active materials is compared with the aid of the newly developed dimensionless parameters.