bluuebunny/crossref_metadata_2025_split huggingface dataset:
Gender differences in acute and 30‐day outcomes after orbital atherectomy treatment of de novo, severely calcified coronary lesions
Authors: Kim Christopher Y. , Lee Arthur C. , Wiedenbeck Troy L. , Lee Michael S. , Chambers Jeff W. 
Published: September 2015

ObjectivesThe aim of this analysis is to evaluate potential differences according to gender in terms of acute and 30‐day clinical outcomes in patients enrolled in the ORBIT II trial with de novo, severely calcified coronary lesions treated with orbital atherectomy to facilitate stent delivery.BackgroundPrevious studies have shown an increased risk of safety events in females compared to males undergoing percutaneous coronary intervention.MethodsORBIT II, a prospective, nonrandomized, multicenter, single arm study conducted in the US evaluated the safety and efficacy of the coronary OAS to facilitate stent placement in de novo, severely calcified coronary lesions in 443 subjects (286 males and 157 females). The rate of major adverse cardiac events (MACE) defined as a composite of myocardial infarction, target vessel revascularization, and cardiac death was evaluated in‐hospital and 30‐days postprocedure. For this analysis, the ORBIT II safety and efficacy results were stratified by gender.ResultsAt baseline, females were significantly older than males and had a lower mean estimated glomerular filtration rate. Males had a higher rate of previous coronary artery bypass grafting and history of smoking. The rates of successful stent delivery and <50% residual stenosis were similar in males and females. In‐hospital and 30‐day MACE rates did not differ by gender.ConclusionsDespite females being older, having smaller arteries, and more renal dysfunction, preparation of severely calcified coronary lesions with orbital atherectomy to facilitate stent deployment results in similar rates of in‐hospital and 30‐day MACE, irrespective of gender. © 2015 Wiley Periodicals, Inc.
Decatungstate‐Photocatalyzed Si−H/C−H Activation in Silyl Hydrides: Hydrosilylation of Electron‐Poor Alkenes
Authors: Qrareya Hisham , Dondi Daniele , Ravelli Davide , Fagnoni Maurizio 
Published: September 2015

AbstractTetrabutylammonium decatungstate has been used for the photocatalytic activation of the Si−H bond in trisubstituted silanes and applied for the hydrosilylation of electron‐poor alkenes. The mechanism that occurs depends on the silyl hydride used, as supported by laser flash photolysis and EPR trapping experiments. Homolytic Si−H cleavage through a hydrogen atom transfer from the silane to the excited catalyst operates with dimethylphenylsilane and methyldiphenylsilane, for which the hydrosilylation yields were satisfactory. If we used tertiary silanes that have more labile Si−H bonds, such as triphenylsilane or tris(trimethylsilyl)silane, the reaction worked to some extent even under uncatalyzed conditions because of a radical chain reaction. Competition between C−H and Si−H cleavage was observed, however, if we used trialkylsilanes (e.g., triethylsilane). In favorable cases, the process was also efficient under flow conditions or if promoted by sunlight.
Copper Nanoparticles Stabilized in a Porous Chitosan Aerogel as a Heterogeneous Catalyst for C−S Cross‐coupling
Authors: Frindy Sana , el Kadib Abdelkrim , Lahcini Mohamed , Primo Ana , García Hermenegildo 
Published: September 2015

AbstractCu nanoparticles (NPs) embedded into chitosan fibrils act as a heterogeneous catalyst for the C−S coupling of aryl halides and thiophenol in toluene. The catalyst can be reused under optimal conditions with some activity decrease from the first to the second use. Characterization of the reused catalyst shows that Cu NPs do not undergo agglomeration. Cu‐chitosan is more active for aryl iodides than aryl bromides and chlorides. The presence of chitosan in a large excess is detrimental for the catalytic activity, probably because of the increase of solvent viscosity. It was found that halides formed as byproducts in the reaction act as a catalyst poison and may influence the extent of Cu leaching.
Water Oxidation Catalysis by Synthetic Manganese Oxides with Different Structural Motifs: A Comparative Study
Authors: Frey Carolin E. , Kurz Philipp 
Published: September 2015

AbstractManganese oxides are considered to be very promising materials for water oxidation catalysis (WOC), but the structural parameters influencing their catalytic activity have so far not been clearly identified. For this study, a dozen manganese oxides (MnOx) with various solid‐state structures were synthesised and carefully characterised by various physical and chemical methods. WOC by the different MnOx was then investigated with Ce4+ as chemical oxidant. Oxides with layered structures (birnessites) and those containing large tunnels (todorokites) clearly gave the best results with reaction rates exceeding 1250 ${{\rm{mmol}}_{{\rm{O}}_{\rm{2}} } }$ ${{\rm{mol}}_{{\rm{Mn}}}^{ - 1} }$ h−1 or about 50 μmolO2 m−2 h−1. In comparison, catalytic rates per mole of Mn of oxides characterised by well‐defined 3D networks were rather low (e.g., ca. 90 ${{\rm{mmol}}_{{\rm{O}}_{\rm{2}} } }$ ${{\rm{mol}}_{{\rm{Mn}}}^{ - 1} }$ h−1 for bixbyite, Mn2O3), but impressive if normalised per unit surface area (>100 ${{\rm{{\rm \mu} mol}}_{{\rm{O}}_{\rm{2}} } }$ m−2 h−1 for marokite, CaMn2O4). Thus, two groups of MnOx emerge from this screening as hot candidates for manganese‐based WOC materials: 1) amorphous oxides with tunnelled structures and the well‐established layered oxides; 2) crystalline MnIII oxides. However, synthetic methods to increase surface areas must be developed for the latter to obtain good catalysis rates per mole of Mn or per unit catalyst mass.
Robust Ordered Bundles of Porous Helical Nanotubes Assembled from Fully Rigid Ionic Benzene‐1,3,5‐tricarboxamides
Authors: Wu Xibo , Wang Daoliang , Chen Mingming , Wei Chengsha , Wei Shenghui , Huang Ningdong , Li Liangbin , Zhang Guobing 
Published: September 2015

AbstractSize‐controlled and ordered assemblies of artificial nanotubes are promising for practical applications; however, the supramolecular assembly of such systems remains challenging. A novel strategy is proposed that can be used to reinforce intermolecular noncovalent interactions to construct hierarchical supramolecular structures with fixed sizes and long‐range ordering by introducing ionic terminals and fully rigid arms into benzene‐1,3,5‐tricarboxamide (BTA) molecules. A series of similar BTA molecules with distinct terminal groups and arm lengths are synthesized; all form hexagonal bundles of helical rosette nanotubes spontaneously in water. Despite differences in molecular packing, the dimensions and bundling of the supramolecular nanotubes show almost identical concentration dependence for all molecules. The similarities of the hierarchical assemblies, which tolerate certain molecular irregularities, can extend to properties such as the void ratio of the nanotubular wall. This is a rational strategy that can be used to achieve supramolecular nanotubes in aqueous environments with precise size and ordering at the same time as allowing molecular modifications for functionality.
Controlled Chemical Derivatisation of Carbon Nanotubes with Imaging, Targeting, and Therapeutic Capabilities
Authors: Ménard‐Moyon Cécilia , Ali‐Boucetta Hanene , Fabbro Chiara , Chaloin Olivier , Kostarelos Kostas , Bianco Alberto 
Published: September 2015

AbstractIn drug delivery, carbon nanotubes (CNTs) hold a great potential as carriers because of their ability to easily cross biological barriers and be internalised into cells. Their high aspect ratio allows multi‐functionalisation and their development as a multimodal platform for targeted therapy. In this article, we report the controlled covalent derivatisation of triple‐functionalised CNTs with the anticancer drug gemcitabine, folic acid as a targeting ligand and fluorescein as a probe. The anticancer activity of gemcitabine was maintained after covalent grafting onto the CNTs. The functionalised nanotubes were internalised into both folate‐positive and negative cells, suggesting the passive diffusion of CNTs. Overall, our approach is versatile and offers a precise chemical control of the sidewall functionalisation of CNTs and the possibility to manoeuvre the types of functionalities required on the nanotubes for a multimodal therapeutic strategy.
Strongly Coupled Pt–Ni2GeO4 Hybrid Nanostructures as Potential Nanocatalysts for CO Oxidation
Authors: Ge Xin , Wang Xiao , Wang Zhuo , Yao Shuang , Feng Jing , Liu Dapeng , Song Shuyan , Zhang Hongjie 
Published: September 2015

AbstractA facile and low‐cost method has been developed to successfully fabricate 3D flower‐like and sphere‐like Ni2GeO4 nanostructures with tunable sizes and shapes. It is found that the hard template, polymethyl methacrylate (PMMA) nanopsheres, is essential to the formation of the final products. The as‐prepared nanostructures can serve as an outstanding support for Pt nanoparticles after surface modification with L‐lysine. In the catalytic test of CO oxidation, Pt–Ni2GeO4 nanoflowers exhibited much higher catalytic performance compared with Pt–Ni2GeO4 nanospheres, representing a typical size‐dependent catalytic property.
Metal‐Ion‐Triggered Exonuclease III Activity for the Construction of DNA Colorimetric Logic Gates
Authors: Gao Wan , Zhang Li , Liang Ru‐Ping , Qiu Jian‐Ding 
Published: September 2015

AbstractThe logic system is obtained by using a series of double‐stranded (ds) DNA templates with mismatched base pairs (T–T or C–C) and ion‐modulated exonuclease III (Exo III) activity, in which the Exo III cofactors, Hg2+ and Ag+ ions, are used as inputs for the activation of the respective scission of Exo III based on the formation of T–Hg2+–T or C–Ag+–C base pairs. Additionally, two kinds of signal probes are utilized to transduce the logic operations. One is the two split G‐rich DNA strands that are used to design the OR, AND, INHIBIT, and XOR gates, whereas the other is the self‐assembled split G‐quadruplex structure to construct NOR, NAND, IMPLICATION, and XNOR operations based on DNA hybridization and strand displacement. In the presence of hemin, the split G‐quadruplex biocatalyzes the formation of a colored product, which is an output signal for the different logic gates. Thus, we have constructed a complete set of colorimetric DNA logic gates based on the Exo III and split G‐quadruplex for the first time. In addition, we are able to effortlessly recognize the logic output signals by the naked eye and their simplicity and cost‐effective design is the most apparent feature for the logic gates developed in this work.
“Stripping” the Carbon Atom of Methyl Halide by a Cationic Holmium Complex: A Gas‐Phase Study
Authors: Zhou Shaodong , Schlangen Maria , Li Jilai , Wu Xiao‐Nan , Schwarz Helmut 
Published: September 2015

AbstractMechanistic aspects of an unusual reaction of [HoC6H4S]+ with CH3X (X=Cl, Br, I) have been investigated using Fourier‐transform ion cyclotron resonance mass spectrometry combined with density functional theory (DFT) calculations. In this thermal process, all four bonds of the methyl halides are cleaved.
Organic Photocatalytic Cyclization of Polyenes: A Visible‐Light‐Mediated Radical Cascade Approach
Authors: Yang Zhongbo , Li Han , Zhang Long , Zhang Ming‐Tian , Cheng Jin‐Pei , Luo Sanzhong 
Published: September 2015

AbstractA visible‐light‐mediated, organic photocatalytic stereoselective radical cascade cyclization of polyprenoids is described. The desired cascade cyclization products are achieved in good yields and high stereoselectivities with eosin Y as photocatalyst in hexafluoro‐2‐propanol. The catalyst system is also suitable for 1,3‐dicarbonyl compounds, which require only catalytic amounts of LiBr to promote the formation of the corresponding enols.
Short Convergent Synthesis of the Mycolactone Core Through Lithiation–Borylation Homologations
Authors: Brown Christopher A. , Aggarwal Varinder K. 
Published: September 2015

AbstractUsing iterative lithiation–borylation homologations, the mycolactone toxin core has been synthesized in 13 steps and 17 % overall yield. The rapid build‐up of molecular complexity, high convergence and high stereoselectivity are noteworthy features of this synthesis.
Synthesis of an Amphiphilic Bis‐Aqua Gd(OBETA) Complex for the Preparation of High‐Relaxivity Supramolecular Magnetic Resonance Imaging Probes
Authors: Negri Roberto , Carniato Fabio , Botta Mauro , Giovenzana Giovanni B. , Tei Lorenzo 
Published: September 2015

AbstractPrompted by the favourable relaxometric, thermodynamic and kinetic properties of the bis‐hydrated Gd(OBETA) (OBETA=2,2′‐oxybis(ethylamine)‐N,N,N′,N′‐tetraacetic acid) complex, a novel derivative tailored with an n‐hexadecyl chain was synthesised. The amphiphilic gadolinium complex was designed and prepared with the aim of obtaining high relaxivity supramolecular aggregates by self‐assembly in micelles and liposomes. Thus, lipidic nanoparticles were prepared and characterised by dynamic light scattering and 1H NMR relaxometry. Relaxivity values of up to 48.3 mm−1 s−1 (20 MHz and 298 K) were registered in liposomal aggregates. The binding to human serum albumin (HSA), evaluated both in terms of affinity and relaxometric properties of the supramolecular adduct, yielded exceptionally high relaxivity values (71.4 mm−1 s−1 at 30 MHz and 298 K).
Highly Efficient Organocatalyzed Conversion of Oxiranes and CO2 into Organic Carbonates
Authors: Sopeña Sergio , Fiorani Giulia , Martín Carmen , Kleij Arjan W. 
Published: September 2015

AbstractA binary catalyst system based on tannic acid/NBu4X (X=Br, I) is presented as a highly efficient organocatalyst at very low catalyst loading for the coupling of carbon dioxide and functional oxiranes to afford organic carbonates in good yields. The presence of multiple polyphenol fragments within the tannic acid structure is considered to be beneficial for synergistic effects that lead to higher stabilization of the catalyst structure during catalysis. The observed turnover frequencies (TOFs) exceed 200 h−1 and are among the highest reported to date for organocatalysts in this area of CO2 conversion. This organocatalyst system presents a useful, readily available, inexpensive, and, above all, reactive alternative for most of the metal‐based catalyst systems reported to date.
Intercalation of Lamellar Mineral Kaolinite with 2‐Picolinic Acid: Facile Preparation, Crystal Structure Optimization, and Proton Conductivity
Authors: Huang Xiao‐Qing , Yang Hao , Zhao Shun‐Ping , Liu Jian‐Lan , Ren Xiao‐Ming 
Published: September 2015

AbstractKaolinite intercalated with 2‐picolinic acid was prepared and characterized by scanning electron microscopy, powder X‐ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The proton conductivity (σ) of the material is 1.85 × 10–10 S cm–1 at 353 K and gradually increases to 1.7 × 10–7 S cm–1 at 393 K under N2 (anhydrous environment) with an activation energy of Ea = 1.93 eV, whereas σ = 1.56 × 10–7 S cm–1 under 80 % relative humidity at 353 K with Ea = 0.91 eV. The crystal structure optimized with the Cambridge Sequential Total Energy Package discloses the absence of a dense H‐bond network in the layer space of kaolinite, which explains the low proton conductivity and high proton transfer activation energy of the intercalated proton conductor.
From Cyclen to 12‐Crown‐4 Copper(II) Complexes: Exchange of Donor Atoms Improves DNA Cleavage Activity
Authors: Hormann Jan , van der Meer Margarethe , Sarkar Biprajit , Kulak Nora 
Published: September 2015

AbstractMacrocyclic CuII complexes with [NXOY] donor sets of different N/O ratios were synthesised resulting in a series ranging from cyclen (X = 4, Y = 0: 1) to 12‐crown‐4 (X = 0, Y = 4: 6) complexes. In order to elucidate the structure of the complexes UV/Vis spectroscopy and X‐ray crystallography were applied, focusing especially on the literature‐unknown compounds with regioisomeric [N2O2] and [NONO] donor sets (3, 4). The complexes were subjected to DNA cleavage experiments under reducing conditions and were also tested in the absence of a reducing agent. Although 3 and 6 were the most active DNA cleavers in the presence of reducing ascorbate, both of them and 4 also cleaved DNA (not hydrolytically) in its absence. This brings up questions regarding the cleavage mechanism. The present study is an expansion of our previously reported finding that heterosubstitution in macrocyclic ligands leads to changes in oxidative DNA cleavage activity of CuII complexes.
Aryl–F Bond Cleavage vs. C–E Reductive Elimination: Competitive Pathways of Metal–Ligand‐Cooperation‐Based E–H Bond Activation (E = N, S)
Authors: Scharf Adam , Goldberg Israel , Vigalok Arkadi , Vedernikov Andrei N. 
Published: September 2015

AbstractAn 8‐fluoroquinoline‐based dearomatized PNF‐pincer (Ar)PdII complex 1 reacts with N‐methylaniline to give an aromatized PNNH‐pincer complex, the product of the aromatic nucleophilic substitution of the PNF ligand fluorine atom. In contrast, the reaction between 1 and thiophenol leads exclusively to the Ar–S coupling product. Experimental and theoretical (DFT) studies suggest that both reactions proceed via substrate coordination and substrate‐to‐PNF hydrogen atom transfer through a metal–ligand cooperation mechanism to produce a PdII amide or sulfide intermediate. In the case of the amide, intramolecular nucleophilic substitution of the fluorine by the amide has a lower activation barrier than Ar–N coupling, whereas in the case of the phenylsulfide intermediate, Ar–S elimination is favored kinetically. Interestingly, for EtSH, both reaction pathways have similar activation energies, consistent with the experimentally observed formation of mixtures of products of both reactions. Overall, the DFT calculations support the feasibility of the Ar–E (E = N, S) coupling reactions via a metal–ligand cooperation mechanism.
Emulsifying triglycerides with dairy phospholipids instead of soy lecithin modulates gut lipase activity
Authors: Mathiassen Jakob Hovalt , Nejrup Rikke Guldhammer , Frøkiær Hanne , Nilsson Åke , Ohlsson Lena , Hellgren Lars I. 
Published: September 2015

A high energy supply and appropriate amount of polyunsaturated fatty acids is crucial for proper growth and development in neonates. The capacity for fatty acid absorption in newborns is however hampered due to an undeveloped pancreatic function combined with a low bile output. This seems in particular to limit fatty acid absorption in babies given infant formulas. Since interaction between the lipid droplet and the gastric and duodenal lipases occur through the hydrophobic/hydrophilic interface, the composition of the emulsifier may be crucial for efficient hydrolysis. We therefore determined hydrolytic rate of gastric lipase and pancreatic lipase, on their own or pancreatic lipase after gastric lipase on TAG droplets of similar size emulsified in either soy lecithin (SL) or in bovine milk phospholipids (MPL), more similar to human milk globule membrane lipids than soy lecithin. Gastric lipase activity was substantially higher on MPL‐emulsified particles, while SL emulsification caused a higher rate of pancreatic lipase hydrolysis, on particles that had not been pre‐treated with gastric lipase. MPL emulsification did however cause higher pancreatic lipase activity, when the particles had been pre‐treated with gastric lipase. The attenuating effect of MPL‐emulsification on pancreas lipase activity was validated in vivo in mice.Practical application: Our results show that the activity of gastric lipase, a key enzyme in lipid absorption in neonates, is highly dependent on the phospholipid composition of the surface layer on the emulsion droplets. We furthermore show that increasing gastric lipase activity by modifying the phospholipid composition on the droplet surface, also enhance the subsequent activity of the pancreatic lipase acting in the duodenum. This implies that it is possible to strategically design the surface layer of lipid droplets in infant formulas to maximize gastric lipase activity, and that this could improve total fatty acid absorption in formula‐fed neonates. This is of particular importance in the development of formula aimed at pre‐mature babies, but is also highly relevant for formulas for term‐born infants.Emulsifying corn oil in milk phospholipids rather than soy lecithin causes a substantial increase in gastric lipase activity (upper). The increased gastric lipase activity on the emulsion particles also causes a threefold increase in pancreatic lipase activity, when done in sequence of gastric lipase hydrolysis (lower). MPL = milk phospholipids, SL = soy lecithin, w/o GL = without gastric lipase pre‐treatment, w GL = with gastric lipase pre‐treatment.
Effects of a victim's response to an offender's apology: When the victim becomes the bad guy
Authors: Dhami Mandeep K. 
Published: September 2015

AbstractThe ‘apology‐acceptance’ script that may prevail during the victim–offender mediation process suggests that victims may feel obliged or pressured to accept an offender's offer of an apology. Violations of this expectation in terms of rejection of an apology or no recognition of it may influence the outcomes of mediation in several ways. Two experiments examined the effects of a victim's response to an offender's offer of a full apology on offenders' perceptions of the victim's response, emotional reactions, perceptions of the victim, attitudes towards the dispute and attitudes towards mediation. Experiment 1 compared the effects of a rejection, acceptance and no recognition of an apology, and Experiment 2 further investigated the effects of an acceptance versus no recognition of an apology. It was found that offenders who had their apology rejected considered the victim's response as least appropriate and were least satisfied by it. ‘Rejected’ offenders felt more anger towards the victim and had more negative impressions of the victim. Offenders who had their apology accepted felt more guilt and shame. They were, however, also more willing to reach an agreement and were more likely to perceive the conflict as being resolved. ‘Accepted’ offenders were also more likely to participate in mediation in the future and more willing to recommend mediation to others. The present research also demonstrated that no recognition of an apology has adverse effects similar to a rejection of an apology.
Emergent social identity and observing social support predict social support provided by survivors in a disaster: Solidarity in the 2010 Chile earthquake
Authors: Drury John , Brown Rupert , González Roberto , Miranda Daniel 
Published: September 2015

AbstractSurvivors of disasters commonly provide each other with social support, but the social‐psychological processes behind such solidarity behaviours have not been fully explicated. We describe a survey of 1240 adults affected by the 2010 Chile earthquake to examine the importance of two factors: observing others providing social support and social identification with other survivors. As expected, emotional social support was associated with social identification, which in turn was predicted by disaster exposure through common fate. Observing others' supportive behaviour predicted both providing emotional social support and providing coordinated instrumental social support. Expected support was a key mediator of these relationships and also predicted collective efficacy. There was also an interaction: social identification moderated the relationship between observing and providing social support. These findings serve to develop the social identity account of mass emergency behaviour and add value to disaster research by showing the relevance of concepts from collective action.