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951.
Isothermal Cyclic Conversion of Methane into Methanol over Copper‐Exchanged Zeolite at Low Temperature
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Patrick Tomkins Ali Mansouri Dr. Selmi E. Bozbag Dr. Frank Krumeich Dr. Min Bum Park Dr. Evalyn Mae C. Alayon Dr. Marco Ranocchiari Prof. Dr. Jeroen A. van Bokhoven 《Angewandte Chemie (International ed. in English)》2016,55(18):5467-5471
Direct partial oxidation of methane into methanol is a cornerstone of catalysis. The stepped conversion of methane into methanol currently involves activation at high temperature and reaction with methane at decreased temperature, which limits applicability of the technique. The first implementation of copper‐containing zeolites in the production of methanol directly from methane is reported, using molecular oxygen under isothermal conditions at 200 °C. Copper‐exchanged zeolite is activated with oxygen, reacts with methane, and is subsequently extracted with steam in a repeated cyclic process. Methanol yield increases with methane pressure, enabling reactivity with less reactive oxidized copper species. It is possible to produce methanol over catalysts that were inactive in prior state of the art systems. Characterization of the activated catalyst at low temperature revealed that the active sites are small clusters of copper, and not necessarily di‐ or tricopper sites, indicating that catalysts can be designed with greater flexibility than formerly proposed. 相似文献
952.
Basic Physicochemical Properties of Polyethylene Glycol Coated Gold Nanoparticles that Determine Their Interaction with Cells
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Dr. Pablo del Pino Fang Yang Dr. Beatriz Pelaz Dr. Qian Zhang Karsten Kantner Raimo Hartmann Dr. Natalia Martinez de Baroja Marta Gallego Marco Möller Dr. Bella B. Manshian Dr. Stefaan J. Soenen René Riedel Prof. Dr. Norbert Hampp Prof. Dr. Wolfgang J. Parak 《Angewandte Chemie (International ed. in English)》2016,55(18):5483-5487
A homologous nanoparticle library was synthesized in which gold nanoparticles were coated with polyethylene glycol, whereby the diameter of the gold cores, as well as the thickness of the shell of polyethylene glycol, was varied. Basic physicochemical parameters of this two‐dimensional nanoparticle library, such as size, ζ‐potential, hydrophilicity, elasticity, and catalytic activity ,were determined. Cell uptake of selected nanoparticles with equal size yet varying thickness of the polymer shell and their effect on basic structural and functional cell parameters was determined. Data indicates that thinner, more hydrophilic coatings, combined with the partial functionalization with quaternary ammonium cations, result in a more efficient uptake, which relates to significant effects on structural and functional cell parameters. 相似文献
953.
Dr. Artur Ciesielski Jürgen Weippert Dr. Artur Böttcher Yuyoung Shin Georgian Melinte Prof. Dr. Ovidiu Ersen Dr. Cinzia Casiraghi Prof. Dr. Xinliang Feng Prof. Dr. Klaus Müllen Prof. Dr. Manfred M. Kappes Prof. Dr. Paolo Samorì Dr. Marco Cecchini 《Chemphyschem》2016,17(3):352-357
Providing a quantitative understanding of the thermodynamics involved in molecular adsorption and self‐assembly at a nanostructured carbon material is of fundamental importance and finds outstanding applications in the graphene era. Here, we study the effect of edge perchlorination of coronene, which is a prototypical polyaromatic hydrocarbon, on the binding affinity for the basal planes of graphite. First, by comparing the desorption barrier of hydrogenated versus perchlorinated coronene measured by temperature‐programmed desorption, we quantify the enhancement of the strength of physisorption at the single‐molecule level though chlorine substitution. Then, by a thermodynamic analysis of the corresponding monolayers based on force‐field calculations and statistical mechanics, we show that perchlorination decreases the free energy of self‐assembly, not only enthalpically (by enhancing the strength of surface binding), but also entropically (by decreasing the surface concentration). The functional advantage of a chemically modulated 2D self‐assembly is demonstrated in the context of the molecule‐assisted liquid‐phase exfoliation of graphite into graphene. 相似文献
954.
We introduce a global wave front set suitable for the analysis of tempered ultradistributions of quasi-analytic Gelfand–Shilov type. We study the transformation properties of the wave front set and use them to give microlocal existence results for pullbacks and products. We further study quasi-analytic microlocality for classes of localization and ultradifferential operators, and prove microellipticity for differential operators with polynomial coefficients. 相似文献
955.
Pauline Fournier Iwan Cornelius Mattia Donzelli Herwig Requardt Christian Nemoz Marco Petasecca Elke Bräuer-Krisch Anatoly Rosenfeld Michael Lerch 《Journal of synchrotron radiation》2016,23(5):1180-1190
Microbeam radiation therapy (MRT) is a novel irradiation technique for brain tumours treatment currently under development at the European Synchrotron Radiation Facility in Grenoble, France. The technique is based on the spatial fractionation of a highly brilliant synchrotron X‐ray beam into an array of microbeams using a multi‐slit collimator (MSC). After promising pre‐clinical results, veterinary trials have recently commenced requiring the need for dedicated quality assurance (QA) procedures. The quality of MRT treatment demands reproducible and precise spatial fractionation of the incoming synchrotron beam. The intensity profile of the microbeams must also be quickly and quantitatively characterized prior to each treatment for comparison with that used for input to the dose‐planning calculations. The Centre for Medical Radiation Physics (University of Wollongong, Australia) has developed an X‐ray treatment monitoring system (X‐Tream) which incorporates a high‐spatial‐resolution silicon strip detector (SSD) specifically designed for MRT. In‐air measurements of the horizontal profile of the intrinsic microbeam X‐ray field in order to determine the relative intensity of each microbeam are presented, and the alignment of the MSC is also assessed. The results show that the SSD is able to resolve individual microbeams which therefore provides invaluable QA of the horizontal field size and microbeam number and shape. They also demonstrate that the SSD used in the X‐Tream system is very sensitive to any small misalignment of the MSC. In order to allow as rapid QA as possible, a fast alignment procedure of the SSD based on X‐ray imaging with a low‐intensity low‐energy beam has been developed and is presented in this publication. 相似文献
956.
Marco P. Monopoli Cláudia Sá e Cunha Miguel Prudêncio Eulália Pereira Iseult Lynch Kenneth A. Dawson Ricardo Franco 《Particle & Particle Systems Characterization》2016,33(12):906-915
Conjugates formed by antibody adsorption to gold nanoparticles (AuNP) have found extensive utilization in immunoassays due to the high surface area and interesting optical and electronic properties of the nanomaterials. Nevertheless, the mechanism of formation of antibody‐AuNP conjugates and their antigen binding characteristics have not been sufficiently explored in terms of specificity and consequent clinical applicability. Dynamic light scattering and related techniques have been successfully employed to detect antigen binding to antibody‐AuNP complexes. Here, a range of different techniques from the bionanotechnology realm have been applied to obtain a detailed picture of a competitive immunoassay for malaria antigen detection, based on fluorescence‐quenching by AuNPs. Both agarose gel electrophoresis and differential centrifugal sedimentation (DCS) analyses provide binding constants in the same order of magnitude, for antibody binding to AuNP and for antigen binding to antibody‐AuNP conjugates. Both techniques are also able to reveal inhibition of antigen binding in the presence of a major blood plasma protein, transferrin (via competitive binding). DCS is further used to show inhibition of the binding of the antigen in the presence of human plasma, a realistic testing condition, of high relevance to the implementation of immunoassays at the clinical level. 相似文献
957.
Gabriella Cavallo Giancarlo Terraneo Alessandro Monfredini Marco Saccone Arri Priimagi Tullio Pilati Giuseppe Resnati Pierangelo Metrangolo Duncan W. Bruce 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(21):6408-6412
Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen‐bonded supramolecular anions [CnF2 n+1‐I⋅⋅⋅I⋅⋅⋅I‐CnF2 n+1]− are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen‐bonded liquid crystals, and 2) imidazolium‐based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation. 相似文献
958.
Marco Bortoluzzi Eleonora Ferretti Guido Pampaloni Stefano Zacchini 《Journal of Coordination Chemistry》2016,69(18):2766-2774
The complex [NbOF3(Ipr)]2, 1, was afforded in crystalline form by reaction of NbF5 with the bulky NHC ligand 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) in toluene by slow contact with moisture air. The molecular structure of 1 was ascertained by X-ray diffraction, providing the first example of a dinuclear NbOF3 derivative and also a rare case of niobium compound with a monodentate NHC. A DFT investigation has shown that the Nb–C bond consists of a weak NHC to Nb σ donation, reinforced by an electrostatic contribution presumably favored by the presence of the ancillary fluoride ligands. The computed enthalpy for the dissociation of one Ipr from 1 is ca. 36 kcal mol?1. The presence of bulky 2,6-diisopropylphenyl substituents on the carbene ligand has negligible influence on the Nb–C bond, as highlighted by DFT analyses on simplified models. 相似文献
959.
960.
Marco Cirant 《偏微分方程通讯》2016,41(8):1324-1346
We consider stationary viscous mean-field games (MFG) systems in the case of local, decreasing and unbounded coupling. These systems arise in ergodic MFG theory and describe Nash equilibria of games with a large number of agents aiming at aggregation. We show how the dimension of the state space, the behavior of the coupling, and the Hamiltonian at infinity affect the existence and nonexistence of regular solutions. Our approach relies on the study of Sobolev regularity of the invariant measure and a blow-up procedure that is calibrated on the scaling properties of the system. In very special cases, we observe uniqueness of solutions. Finally, we apply our methods to obtain new existence results for MFG systems with competition, namely, when the coupling is local and increasing. 相似文献