The density functional theory (DFT/B3LYP) calculations were applied to investigate the interaction of a Pt6 particle with the ZSM-5 zeolite framework. The electronic structure of the metal particle is strongly affected by the interaction with basic framework oxygens and acid sites of the zeolite support. Adsorption on basic sites (Eads = 6 kcal/mol) favors the formation of the electron enriched metal cluster. Interaction of the platinum cluster with the acid site characterized by stabilization energy of 47 kcal/mol results in oxidation of the metal particle and suppression of Brønsted acidity of the support. The hypothesis is put forward that the oxidized platinum particle can function as an active site for the alkane isomerisation on platinum supported high silica zeolites. 相似文献
Several aspects of heterogeneous catalytic kinetics over induced nonuniform surfaces are considered. The reaction mechanism is thought to occur through a surface collision of species, adsorbed on two distinct surface sites, which display nonuniform behavior. The expressions for rates of elementary reactions have been deduced within the framework of the surface electronic gas model, which accounts for the case of inhomogeneous surface. Equations for catalyst activity in the range of medium coverage have been derived and compared with the power-law model. 相似文献
Potential for large-scale physical transport processes to affect recruitment of Lake Michigan yellow perch (Perca flavescens) was studied by examining the variation in larval distribution, growth rate, and settlement during June–August 1998–2003 using a 3D particle transport model linked with an individual-based bioenergetics growth model. In all years, virtual larvae were released nearshore in southwestern Lake Michigan, a known and important spawning region for yellow perch. For any given year, the same circulation pattern and water temperature either promoted or reduced yellow perch settlement depending on the consumption rates and settlement size chosen in the growth model. Increased consumption increased the number of settled larvae and expanded the total area where larvae settled, whereas increased settlement size reduced the number of settled larvae and reduced the overall settlement area. Interannual variability in circulation patterns and water temperature also resulted in contrasting larval settlement rates, settlement locations, and size of settlement areas between years. Model predictions were most consistent with field observations of age-0 yellow perch from Illinois and Michigan waters when settlement was assumed to occur at 50 mm. Moreover, our model suggests that larvae originating from southwestern Lake Michigan can recruit anywhere within the southern basin and even in the northern basin. Future model improvement will require information on the relative contribution of various sectors to the larval pool, their distribution with reference to the hydrodynamic landscape, the feeding and growth of yellow perch during their pelagic phase, and the size at transition to demersal stage. 相似文献
This work presents an extension of grid generation techniques for finite-volume discretizations of density-driven flow in fractured porous media, in which fractures are considered as low-dimensional manifolds and are resolved by sides of grid elements. The proposed technique introduces additional degrees of freedom for the unknowns assigned to the fractures and thus allows to reconstruct jumps of the solution over a fracture. Through the concept of degenerated elements, the proposed technique can be used for arbitrary junctions of fractures but is sufficiently simple regarding the implementation and allows for the application of conventional numerical solvers. Numerical experiments presented at the end of the paper demonstrate the applicability of this technique in two and three dimensions for complicated fracture networks. 相似文献
The methylation of adenosine in the N6 position (m6A) is a widely used modification of eukaryotic mRNAs. Its importance for the regulation of mRNA translation was put forward recently, essentially due to the ability of methylated mRNA to be translated in conditions of inhibited cap-dependent translation initiation, e.g., under stress. However, the peculiarities of translation initiation on m6A-modified mRNAs are not fully known. In this study, we used toeprinting and translation in a cell-free system to confirm that m6A-modified mRNAs can be translated in conditions of suppressed cap-dependent translation. We show for the first time that m6A-modified mRNAs display not only decreased elongation, but also a lower efficiency of translation initiation. Additionally, we report relative resistance of m6A-mRNA translation initiation in the absence of ATP and inhibited eIF4A activity. Our novel findings indicate that the scanning of m6A-modified leader sequences is performed by a noncanonical mechanism. 相似文献
It is expensive to obtain labeled real-world visual data for use in training of supervised algorithms. Therefore, it is valuable to leverage existing databases of labeled data. However, the data in the source databases is often obtained under conditions that differ from those in the new task. Transfer learning provides techniques for transferring learned knowledge from a source domain to a target domain by finding a mapping between them. In this paper, we discuss a method for projecting both source and target data to a generalized subspace where each target sample can be represented by some combination of source samples. By employing a low-rank constraint during this transfer, the structure of source and target domains are preserved. This approach has three benefits. First, good alignment between the domains is ensured through the use of only relevant data in some subspace of the source domain in reconstructing the data in the target domain. Second, the discriminative power of the source domain is naturally passed on to the target domain. Third, noisy information will be filtered out during knowledge transfer. Extensive experiments on synthetic data, and important computer vision problems such as face recognition application and visual domain adaptation for object recognition demonstrate the superiority of the proposed approach over the existing, well-established methods. 相似文献
Summary: Compacted fiber composites offer unique properties due to their lack of an extraneous matrix. The conditions of processing ultra‐high molecular weight polyethylene (UHMWPE) fibers were simulated in a heated pressure cell. In situ X‐ray diffraction measurements were used to follow the relevant transitions and the changes in the degree of crystallinity during melting and crystallization. The results strongly support the suggestion that the hexagonal crystal phase, in which the chain conformation is extremely mobile on the segmental level, constitutes the physical basis of compaction technologies for processing UHMWPE fibers into a single‐polymer composite. This report suggests that using a pseudo‐phase diagram outlining the occurrence of different phases during slow heating and the degree of crystallinity can provide valuable insight into the technological parameters relevant for optimal processing conditions.
A polymer-supported Pd catalyst was investigated in hydrogenation of citral (3,7-dimethyl-2,6-octadienal), which is a stereoisomer with an isolated and a conjugated double bond as well as a carbonyl group. The catalyst was a fibrous polymer-supported catalyst modified with functional groups and immobilized metals. A comparison of the polymer-supported catalyst with conventional catalysts was made. 相似文献
Micro-mesoporous aluminosilicates based on ZSM-5 zeolite, obtained by a dual template method, as well as in the presence of a dual-functional template (i.e. a Gemini-type surfactant), were tested in the oxidation of furfural with hydrogen peroxide. Even substantial changes in acidity and porosity of the catalysts result in minor variations of selectivity towards the desired products. Application of the synthesized zeolite-based materials in the oxidation of furfural with hydrogen peroxide leads to formation of 2(5H)-furanone (yield up to 28.5%) and succinic acid (up to 19.5%) as the main C4 reaction products. The kinetic model developed previously to treat the results for oxidation of furfural over sulfated zirconia was able to describe the data also for micro-mesoporous aluminosilicates.