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排序方式: 共有290条查询结果,搜索用时 906 毫秒
281.
de Clippel F Dusselier M Van Rompaey R Vanelderen P Dijkmans J Makshina E Giebeler L Oswald S Baron GV Denayer JF Pescarmona PP Jacobs PA Sels BF 《Journal of the American Chemical Society》2012,134(24):10089-10101
A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Br?nsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Br?nsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Br?nsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Br?nsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Br?nsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in methanol at slightly elevated reaction temperature. The hybrid catalyst proved to be recyclable in various successive runs when used in alcohol solvent. 相似文献
282.
We investigate quantum fluctuations of a vortex lattice in a one-dimensional optical lattice for realistic numbers of particles and vortices. Our method gives full access to all the modes of the vortex lattice and we discuss in particular the Bloch bands of the Tkachenko modes. Because of the small number of particles in the pancake Bose-Einstein condensates at every site of the optical lattice, finite-size effects become very important. Therefore, the fluctuations in the vortex positions are inhomogeneous and the melting of the lattice occurs from the outside inwards. By looking into correlations between neighboring vortices, we identify new solid and liquid phases. Tunneling between neighboring pancakes substantially reduces the inhomogeneity as well as the size of the fluctuations. 相似文献
283.
Verdoes M Florea BI Menendez-Benito V Maynard CJ Witte MD van der Linden WA van den Nieuwendijk AM Hofmann T Berkers CR van Leeuwen FW Groothuis TA Leeuwenburgh MA Ovaa H Neefjes JJ Filippov DV van der Marel GA Dantuma NP Overkleeft HS 《Chemistry & biology》2006,13(11):1217-1226
The proteasome is an essential evolutionary conserved protease involved in many regulatory systems. Here, we describe the synthesis and characterization of the activity-based, fluorescent, and cell-permeable inhibitor Bodipy TMR-Ahx(3)L(3)VS (MV151), which specifically targets all active subunits of the proteasome and immunoproteasome in living cells, allowing for rapid and sensitive in-gel detection. The inhibition profile of a panel of commonly used proteasome inhibitors could be readily determined by MV151 labeling. Administration of MV151 to mice allowed for in vivo labeling of proteasomes, which correlated with inhibition of proteasomal degradation in the affected tissues. This probe can be used for many applications ranging from clinical profiling of proteasome activity, to biochemical analysis of subunit specificity of inhibitors, and to cell biological analysis of the proteasome function and dynamics in living cells. 相似文献
284.
Baffreau J Leroy-Lhez S Hudhomme P Groeneveld MM van Stokkum IH Williams RM 《The journal of physical chemistry. A》2006,110(49):13123-13125
Two n-type molecular materials are covalently combined into a new photovoltaic component for polymer solar cells. Light harvesting by the perylenediimide results in very fast energy transfer to the fullerene unit, as shown with femtosecond transient absorption spectroscopy in toluene solution. Two energy transfer rates are observed of 2.5 x 10(12) s-1 (53%) and 2 x 10(11) s-1 (47%), attributed to two conformations. The final excited state that is populated is a perylenediimide-based triplet state that is formed on the nanosecond time scale with a high yield. 相似文献
285.
Lai WC McLean N Gansmüller A Verhoeven MA Antonioli GC Carravetta M Duma L Bovee-Geurts PH Johannessen OG de Groot HJ Lugtenburg J Emsley L Brown SP Brown RC DeGrip WJ Levitt MH 《Journal of the American Chemical Society》2006,128(12):3878-3879
A new double-quantum solid-state NMR pulse sequence is presented and used to measure one-bond 13C-13C J-couplings in a set of 13C2-labeled rhodopsin isotopomers. The measured J-couplings reveal a perturbation of the electronic structure at the terminus of the conjugated chain but show no evidence for protein-induced electronic perturbation near the C11-C12 isomerization site. This work establishes NMR methodology for measuring accurate 1JCC values in noncrystalline macromolecules and shows that the measured J-couplings may reveal local electronic perturbations of mechanistic significance. 相似文献
286.
Biased Born-Oppenheimer molecular dynamics simulations are performed to compute redox potential and free energy curves for the redox half reaction Ag(+)-->Ag(2+)+e(-) in aqueous solution. The potential energy surfaces of reactant and product state are linearly coupled and the system transferred from the reduced state to the oxidized state by variation of the coupling parameter from 0 to 1. The redox potential is obtained by thermodynamic integration of the average ionization energy of Ag(+). Diabatic free energy curves of reduced (R) and oxidized (O) states are obtained to good statistical accuracy by reweighting and combining the set of biased distributions of the ionization energy. The diabatic free energy curves of Ag(+) and Ag(2+) are parabolic over a wide range of the reaction coordinate in agreement with the linear response assumption that underlies Marcus theory. However, we observe deviations from parabolic behavior in the equilibrium region of Ag(+) and find different values for the reorganization free energy of R (1.4 eV) and O (0.9 eV). The computed reorganization free energy of Ag(2+) is in good agreement with the experimental estimate of 0.9-1.2 eV obtained from photoelectron spectroscopy. As suggested by our calculations, the moderate deviation from linear response behavior found for Ag(+) is likely related to the highly fluxional solvation shell of this ion, which exhibits water exchange reactions on the picosecond time scale of the present molecular dynamics simulation. 相似文献
287.
288.
The paper deals with a mathematical model which describes how the collection of key phrases (and key words) evolves as a field of science develops. The experimental material is based on statistical observations on the sets of key phrases which have been assigned to papers in representative major journals in the field in question. Asymptotic properties of the model are considered, as well as estimators for the parameters of the model with particular emphasis on estimators that can indicate at what stage a collection of key phrases can be assumed as complete for the field in question at a given moment in time. 相似文献
289.
A fast and potentially economic method for creating a composite material of polypropylene (PP) with liquid crystalline polymers (LCPs) was explored. The LCPs were dispersed in the PP matrix in a conventional extrusion process and subsequently drawn in order to obtain a highly uniaxially molecular orientation of the LCP fibres. The strongest mechanical properties were found after rapid cooling of the blend, which was optimally exploited in thin filaments where cooling was fast enough to prevent fibre break-up and/or orientation relaxation. To enable the production of extrudates which are thick enough to be cut into self-reinforced pellets, a fused multi-filament technology was developed. In this technology several thin filaments were extruded/drawn and rapidly cooled to a temperature between the crystallisation temperatures of the LCP and the PP. After solidification of the LCP, the single filaments were fused to a multifilament strand and further cooled to room temperature. The thick multifilament LCP reinforced PP strands were cut into pellets and used in injection-and compression-moulding processes. This processing took place between the melting temperature of the PP and the LCP, with retention of the aspect ratio and the molecular orientation of the LCP fibres. 相似文献
290.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献