bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Ketimide Ligand is Not Just an Inert Spectator: Heteroallene Insertion Reactivity of an Actinide–Ketimide Linkage in a Thorium Carbene Amide Ketimide Complex
Authors: Lu Erli , Lewis William , Blake Alexander J. , Liddle Stephen T. 
Published: July 2014

AbstractThe ketimide anion R2CN− is an important class of chemically robust ligand that binds strongly to metal ions and is considered ideal for supporting reactive metal fragments due to its inert spectator nature; this contrasts with R2N− amides that exhibit a wide range of reactivities. Here, we report the synthesis and characterization of a rare example of an actinide ketimide complex [Th(BIPMTMS){N(SiMe3)2}(NCPh2)] [2, BIPMTMS=C(PPh2NSiMe3)2]. Complex 2 contains ThCcarbene, ThNamide and ThNketimide linkages, thereby presenting the opportunity to probe the preferential reactivity of these linkages. Importantly, reactivity studies of 2 with unsaturated substrates shows that insertion reactions occur preferentially at the ThNketimide bond rather than at the ThCcarbene or ThNamide bonds. This overturns the established view that metal‐ketimide linkages are purely inert spectators.
Targetable Phosphorescent Oxygen Nanosensors for the Assessment of Tumor Mitochondrial Dysfunction By Monitoring the Respiratory Activity
Authors: Wang Xiao‐Hui , Peng Hong‐Shang , Yang Lin , You Fang‐Tian , Teng Feng , Hou Ling‐Ling , Wolfbeis Otto S. 
Published: July 2014

AbstractCellular respiration is a worthwhile criterion to evaluate mitochondrial dysfunction by measuring the dissolved oxygen. However, most of the existing sensing strategies merely report extracellular (ec‐) or intracellular (ic‐) O2 rather than intramitochondrial (im‐) O2. Herein we present a method to assess tumor mitochondrial dysfunction with three phosphorescent nanosensors, which respond to ec‐, ic‐, and im‐O2. Time‐resolved luminescence is applied to determine the respective oxygen consumption rates (OCRs) under varying respiratory conditions. Data obtained for the OCRs and on (intra)cellular O2 gradients demonstrate that mitochondria in tumor cells are distinctly less active than those of healthy cells, resulting from restrained glucose utilization of and physical injury to the mitochondria. We believe that such a site‐resolved sensing strategy can be applied to numerous other situations, for example to evaluate the adverse effects of drug candidates.
Cyclizing Radical Carboiodination, Carbotelluration, and Carboaminoxylation of Aryl Amines
Authors: Hartmann Marcel , Studer Armido 
Published: July 2014

AbstractRadical carboiodination of various aryl amines is reported. Aryl diazonium salts, generated in situ from the corresponding aryl amines, are reacted with Bu4NI to provide the corresponding aryl radicals which undergo 5‐exo or 6‐exo cyclization. Iodine abstraction eventually affords the carboiodinated products in good to excellent yields. If TEMPO is added, the cascade provides the cyclized carboaminoxylation products. Running the reaction in the presence of PhTeTePh affords the phenyltellurated cyclized products.
Development of CN Coupling Using Mechanochemistry: Catalytic Coupling of Arylsulfonamides and Carbodiimides
Authors: Tan Davin , Mottillo Cristina , Katsenis Athanassios D. , Štrukil Vjekoslav , Friščić Tomislav 
Published: July 2014

AbstractReported herein is the mechanochemical synthesis of sulfonyl guanidines, a family of molecules which are relevant as pharmaceuticals and herbicides, by direct coupling of sulfonamides and aromatic or aliphatic carbodiimides. Attempts to conduct the coupling in solution have either failed or given very low conversions, thus demonstrating mechanochemistry as the necessary component for the discovery of this synthetic strategy.
“CLASSIC NMR”: An In‐Situ NMR Strategy for Mapping the Time‐Evolution of Crystallization Processes by Combined Liquid‐State and Solid‐State Measurements
Authors: Hughes Colan E. , Williams P. Andrew , Harris Kenneth D. M. 
Published: July 2014

AbstractA new in‐situ NMR strategy (termed CLASSIC NMR) for mapping the evolution of crystallization processes is reported, involving simultaneous measurement of both liquid‐state and solid‐state NMR spectra as a function of time. This combined strategy allows complementary information to be obtained on the evolution of both the solid and liquid phases during the crystallization process. In particular, as crystallization proceeds (monitored by solid‐state NMR), the solution state becomes more dilute, leading to changes in solution‐state speciation and the modes of molecular aggregation in solution, which are monitored by liquid‐state NMR. The CLASSIC NMR experiment is applied here to yield new insights into the crystallization of m‐aminobenzoic acid.
Hybrid silica generated In situ in polyurethane‐based composites
Authors: Heck Cesar A. , Giacomolli Diego A. , Livotto Paolo R. , dos Santos João Henrique Z. , Wolf Carlos R. 
Published: July 2014

ABSTRACTA series of composites of commercial polyurethane (PU) and hybrid silica have been prepared by the sol‐gel process through the in situ synthesis of hybrid silica in a solution of dichloromethane. Mechanical properties, small angle x‐ray scattering (SAXS) and differential scanning calorimetry measurements were performed to evaluate the effects that hybrid silica has on the properties of the resulting PU composites. A series of 13 different organosilane differing in polarity and alkyl chain length has been employed. Compared with pristine PU, composites bearing hybrid silicas were more likely to exhibit reductions in the yield stress and increase in the elongation at break. Samples also showed a negligible variation in the glass transition temperature and a reduction in the ΔCp. The enthalpy of the crystallization process showed a trend towards reduction. Based on the SAXS measurements, the composites showed a small reduction in the interdomain spacing, an increase in the degree of phase separation and a tendency towards reduction in the size of the interphase thickness between domains. These results can be better explained as being caused by the volume of the organic group from the organosilane rather than by the chemical interaction of the organic group with the PU organic moieties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41157.
Mechanical properties and thermostability of polyimide/mesoporous silica nanocomposite via effectively using the pores
Authors: Ye Xiangyuan , Wang Jinqing , Xu Ye , Niu Lengyuan , Fan Zengjie , Gong Peiwei , Ma Limin , Wang Honggang , Yang Zhigang , Yang Shengrong 
Published: July 2014

ABSTRACTSeries of polyimide (PI)/mesoporous silica nanospheres (MSNs) nanocomposite films with different contents of MSNs were successfully prepared via a simple wet impregnation method. The morphologies, microstructures, mechanical properties, transmittance, and thermal properties of the prepared PI and the PI/MSNs nanocomposite films were investigated in detail. As a result, the thermal stability and mechanical performances of PI were obviously improved by incorporating MSNs into PI. The tensile stress and Young's modulus of the nanocomposite film with 5 wt % MSNs were raised up to 97.65 MPa and 2220.06 MPa, which are greatly higher than the values of 82.51 MPa and 1440.86 MPa for the pure PI film. Experimental results confirmed that the designed polymerization tactic, which occurred in the pores of the MSNs, facilitated to enhance the mechanical and physical performances of the PI/MSNs nanocomposite films, and definitely induced better integration between organic matrix and inorganic nanofillers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41173.
Identifying factors that promote consumer behaviours causing expired domestic food waste
Authors: Farr‐Wharton Geremy , Foth Marcus , Choi Jaz Hee‐Jeong 
Published: July 2014

ABSTRACTMany commentators argue that domestic food waste is strongly influenced by consumer behaviours. This article reports on a study using mixed‐methods to identify key factors responsible for promoting consumer behaviours that lead to domestic food waste through the lens of the value–belief–norm theory. On the basis of the study's findings, three factors are proposed that cause behaviours that lead to food waste: supply knowledge – does a consumer know what food they have available; location knowledge – does a consumer know where to locate food items; and food literacy – to what degree do past experience and acquired knowledge impact on a consumer's food consumption and wastage practices. We analyse the study's findings in light of a review of literature about consumer food wastage behaviours and in turn, present new insights into consumer behaviour, food waste and the use of technology to reduce food waste. Copyright © 2014 John Wiley & Sons, Ltd.
Dissolution of Noble Metals during Oxygen Evolution in Acidic Media
Authors: Cherevko Serhiy , Zeradjanin Aleksandar R. , Topalov Angel A. , Kulyk Nadiia , Katsounaros Ioannis , Mayrhofer Karl J. J. 
Published: July 2014

AbstractThe electrochemical production of hydrogen and hydrocarbons is considered to play a decisive role in the conversion and storage of excess amounts of renewable energy. The electrocatalysis of the oxygen evolution reaction (OER), however, faces significant challenges for practical implementation of electrolyzers. In this work, a comparative study on the activity and stability of oxidized polycrystalline noble metals during the OER is presented. All studied metals exhibit transient and steady‐state dissolution. Transient dissolution takes place during oxide formation and reduction. Steady‐state dissolution depends on the OER mechanism on each surface: On metals such as Ru and Au, for which oxygen from the oxide participates in the OER, the Tafel slope is low and the dissolution rate is high. In contrast, on metals for which oxygen evolves directly from adsorbed water, such as Pt and presumably Pd, the Tafel slopes are high and the dissolution rates are low. This should be considered in the design of optimal OER catalysts.
Fullerene as a Platform for Recyclable TEMPO Organocatalysts for the Oxidation of Alcohols
Authors: Beejapur Hazi Ahmad , Campisciano Vincenzo , Franchi Paola , Lucarini Marco , Giacalone Francesco , Gruttadauria Michelangelo 
Published: July 2014

Abstract[60]Fullerene has been employed successfully as a molecular platform to anchor 12 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) moieties. Such an octahedrally substituted C60‐derivative has been employed as an organocatalyst for the oxidation of primary and secondary alcohols using the Anelli protocol. The reaction showed a general applicability to various alcohols, and the catalyst was recovered easily and could be recycled for at least seven cycles with no loss in catalytic activity. EPR spectroscopy studies revealed that the amount of radicals decreases during the catalytic cycles, even if the recovered material still displays unchanged catalytic activity. This new approach paves the way to use fullerene as a molecular platform to support other kinds of organometallic and organocatalysts as well as for their use as model compounds to understand the behavior of other nanocarbon‐supported catalysts.
Highly Selective Epoxidation of Cycloaliphatic Alkenes with Aqueous Hydrogen Peroxide Catalyzed by [PO4{WO(O2)2}4]3−/Imidazole
Authors: Kamata Keigo , Sugahara Kosei , Ishimoto Ryo , Nojima Susumu , Okazaki Motoya , Matsumoto Takaya , Mizuno Noritaka 
Published: July 2014

AbstractIn the presence of imidazole as an additive, a phosphorus‐containing tetranuclear peroxotungstate, THA3[PO4{WO(O2)2}4] (I, THA=tetra‐n‐hexylammonium), could act as an efficient catalyst for epoxidation of cycloaliphatic alkenes with 30 % aqueous hydrogen peroxide (H2O2). Compound I showed higher catalytic activity and selectivity to epoxide than other tungstates. By using the I/imidazole system, various kinds of cycloaliphatic alkenes could be highly selectively converted into the acid‐sensitive epoxides including industrially important diepoxides in high to excellent yields under the almost stoichiometric conditions. The 1H NMR spectroscopy showed that imidazole would work not only as a proton acceptor but also as a Lewis base to remarkably suppress the acid‐catalyzed ring opening of epoxides.
Photoreversible Assembly–Disassembly of a Polymeric Structure by Using an Azobenzene Photoswitch and Al3+ Ions
Authors: Hatai Joydev , Bandyopadhyay Subhajit 
Published: July 2014

AbstractA nonmacrocyclic azobenzene‐based photochromic receptor in its E isomer forms an extended polymeric assembly with Al3+ ions. Exposure of the E form to UV light at λ=366 nm causes a disassembly of the polymeric structure due to the change in the molecular geometry of the ligand. The linear polymeric structure was regenerated on exposure to visible light.
Atomic Force Microscopy of Novel Zeolitic Materials Prepared by Top‐Down Synthesis and ADOR Mechanism
Authors: Smith Rachel L. , Eliášová Pavla , Mazur Michal , Attfield Martin P. , Čejka Jiří , Anderson Michael W. 
Published: July 2014

AbstractTop‐down synthesis of 2D materials from a parent 3D zeolite with subsequent post‐synthetic modification is an interesting method for synthesis of new materials. Assembly, disassembly, organisation, reassembly (ADOR) processes towards novel materials based on the zeolite UTL are now established. Herein, we present the first study of these materials by atomic force microscopy (AFM). AFM was used to monitor the ADOR process through observation of the changes in crystal surface and step height of the products. UTL surfaces were generally complex and contained grain boundaries and low‐angle intergrowths, in addition to regular terraces. Hydrolysis of UTL to IPC‐1P did not have adverse effects on the surfaces as compared to UTL. The layers remained intact after intercalation and calcination forming novel materials IPC‐2 and IPC‐4. Measured step heights gave good correlation with the X‐ray diffraction determined d200‐spacing in these materials. However, swelling gave rise to significant changes to the surface topography, with significantly less regular terrace shapes. The pillared material yielded the roughest surface with ill‐defined surface features. The results support a mechanism for the majority of these materials in which the UTL layers remain intact during the ADOR process as opposed to dissolving and recrystallising during each step.
Heterobimetallic s‐Block Hydrides by σ‐Bond Metathesis
Authors: Liptrot David J. , Hill Michael S. , Mahon Mary F. 
Published: July 2014

AbstractReactions between PhSiH3 and alkali‐metal diamidoalkylmagnesiates ([M{N(SiMe3)2}2MgBu], M=Li, Na, K) provide either selective alkyl metathesis or the formation of polyhydride aggregates contingent upon the identity of the Group 1 metal. In the case of [M{N(SiMe3)2}2MgBu], this reactivity results in a structurally unprecedented dodecametallic decahydride cluster species.
Copper‐Mediated ortho‐Nitration of (Hetero)Arenecarboxylates
Authors: Katayev Dmitry , Pfister Kai F. , Wendling Timo , Gooßen Lukas J. 
Published: July 2014

AbstractVarious (hetero)arenecarboxylic acids were converted to the corresponding Daugulis amides and nitrated selectively in the ortho‐position in the presence of [CuNO3(PPh3)2] and AgNO2 at 50 °C. A microwave‐assisted saponification allows regenerating the carboxylate group within minutes, which may then be removed tracelessly by protodecarboxylation, or substituted by aryl‐ or alkoxy‐groups via decarboxylative cross‐coupling.
A randomized, double blind, dose escalation, first time in human study to assess the safety, tolerability, pharmacokinetics, and antiviral activity of single doses of GSK2485852 in chronically infected hepatitis C subjects
Authors: Wilfret David A. , Walker Jill , Voitenleitner Christian , Baptiste‐Brown Sharon , Lovern Mark , Kim Joseph , Adkison Kimberly , Shotwell Brad , Mathis Amanda , Moss Lee , Lee Daniel , Yu Lou , Gan Jianjun , Spaltenstein Andrew 
Published: July 2014

AbstractThis first‐time‐in‐human, randomized, double‐blind, placebo‐controlled, dose‐escalation study assessed the safety, tolerability, pharmacokinetics, and antiviral activity of GSK2485852, a hepatitis C virus (HCV) NS5B inhibitor, in 27 chronically infected HCV genotype‐1 subjects. Subjects received GSK2485852 70, 420, and 70 mg with a moderate fat/caloric meal. Safety, pharmacokinetics, antiviral activity, HCV genotype/phenotype, and interleukin 28B genotype were evaluated. A statistically significant reduction in HCV ribonucleic acid (RNA) was observed after a single dose of 420 mg GSK2485852 (−1.33 log10 IU/mL) compared with placebo (−0.09 log10 IU/mL) at 24 hours post‐dose. Subjects receiving 70 mg GSK2485852 were exposed to concentrations above the protein‐adjusted 90% effective concentration for a short time; none experienced a significant decline in HCV RNA (−0.47 log10 copies/mL). GSK2485852 was readily absorbed; however, the observed geometric mean maximum plasma concentration (Cmax) and area under the curve (AUC) values were significantly lower than expected due to a higher‐than‐predicted‐oral clearance. Co‐administration with food reduced the AUC and Cmax of GSK2485852 by 40% and 70%, respectively. Two metabolites were detected in human blood with one having approximately 50% higher concentrations than those of the parent. GSK2485852 was well‐tolerated and exhibited antiviral activity after a single 420 mg dose in HCV subjects.
The effect of mild and moderate hepatic impairment on the pharmacokinetics of tofacitinib, an orally active Janus kinase inhibitor
Authors: Lawendy Nervin , Lamba Manisha , Chan Gary , Wang Rong , Alvey Christine W. , Krishnaswami Sriram 
Published: July 2014

AbstractTofacitinib is an oral Janus kinase inhibitor for the treatment of rheumatoid arthritis. We report here an evaluation of the pharmacokinetics of a single 10 mg dose of tofacitinib in healthy volunteers (n = 6) and subjects with mild (n = 6) or moderate (n = 6) hepatic impairment. Compared to healthy volunteers, tofacitinib area under the plasma concentration–time profile from time 0 to infinity (AUCinf) and maximum observed concentration (Cmax) in subjects with mild hepatic impairment were not altered. In subjects with moderate hepatic impairment, the geometric mean AUCinf and Cmax of tofacitinib were increased (90% confidence intervals of percentage increase) by approximately 65% (25%, 117%) and 49% (12%, 97%), respectively. A single dose of tofacitinib 10 mg resulted in two treatment‐emergent adverse events (AE) in the mild hepatic impairment group, and one in the moderate hepatic impairment group; they were not considered related to study treatment. There were no deaths, serious AEs, discontinuations due to AEs, or dose reductions due to AEs. Data from this study were critical to deriving dose adjustments for subjects with hepatic impairment.
Psychological Well‐Being and Anticipated Positive Personal Events: Their Relationship to Depression
Authors: Edmondson Olivia. J. H. , MacLeod Andrew K. 
Published: July 2014

Well‐being is now defined in a number of multicomponent ways. One approach to defining well‐being—psychological well‐being (PWB; Ryff, )—encompasses six dimensions of positive functioning. This study's first aim was to compare PWB self‐report scores from a group of depressed participants (N = 26) with a non‐depressed group (N = 26). The second aim was to examine anticipated well‐being, specifically, how the positive events people anticipate in the future are seen as being related to various aspects of their well‐being. Participants completed the self‐report scales of PWB and a task which elicited events participants were looking forward to in the future and their thoughts about what was good about those events. Responses about the value of the events were independently coded for the presence of the six PWB dimensions. The depressed group scored significantly lower on all dimensions of self‐reported PWB than the control group, with particularly marked deficits on environmental mastery and self‐acceptance. For anticipated events, positive relations with others was the most commonly present aspect of PWB in participants' responses about what was good about the events. The frequency of PWB dimensions present in participants' responses was similar between the two groups with the exception of the depressed group having more self‐acceptance related responses and fewer positive relationship responses. The well‐established lack of positive anticipation found in depressed individuals is likely to mean a diminished resource for a wide range of aspects of well‐being but especially positive relationships with others. Copyright © 2014 John Wiley & Sons, Ltd.Key Practitioner Message

The treatment of depression is thought to be more effective when it enhances psychological well‐being as well as reducing dysfunction.
In the present study, all dimensions of psychological well‐being were lower in depressed participants with particularly marked deficits in environmental mastery and self‐acceptance, suggesting that these may be particularly important treatment targets.
People with depression show specific deficits in being able to anticipate future positive events.
The present study suggests that anticipated well‐being linked to positive relationships with other people may be particularly impacted by the lack of anticipated future events found in depression.
Impact and penetration resistance of network models of coated lightweight fabric shielding
Authors: Zohdi T. I. 
Published: July 2014

AbstractThere exist a wide range of applications for lightweight ballistic fabric shields, such as the protection of critical structural components in transport systems and the human body. However, some deficiencies are (1) the susceptibility to being abruptly severed by sharp objects, which completely eliminates the fabric's ability to stretch and absorb incoming kinetic energy and (2) environmental degradation of the fabric due to moisture, heat and sunlight, which is of growing concern, since many new fabrics have multiple purposes, such as electrical and chemical sensing, in addition to being part of a protective system. Because of these issues, the coating of fabric can be advantageous, however, it adds weight to the shielding system. Experiments on this type of coated fabric system are extremely time‐consuming. Accord‐ingly, this paper seeks to develop a computational framework using a coated network model in order to capture the basic characteristics of such systems. One aspect of the model's usefulness is that it can provide qualitative information to guide and reduce costly, time‐consuming experiments. Three‐dimensional numerical examples are given to illustrate the computational model. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
3.1: Invited Paper: Oxide Versus LTPS TFTs for Active‐Matrix Displays
Authors: Mativenga Mallory , Geng Di , Jang Jin 
Published: July 2014

AbstractWe have reviewed the comparison of LTPS and Oxide TFTs for AMOLED backplane application. The device performance and stability of ELA based LTPS TFTs are excellent even though the process cost is much higher than that of oxide TFTs. Oxide TFTs, on the other hand, can be manufactured with lost cost and the device performance is good enough for large‐area AMOLED backplane. However, run‐to‐run reproducibility and bias stability of oxide TFTs are much inferior to those of their LTPS counterparts. We propose the bulk accumulation mode oxide TFTs for AMOLED backplane. The advantages of this technology are excellent uniformity and high driving ability as compared with conventional oxide TFTs.