Metallic Nanoparticles in Heterogeneous Catalysis

Catalysis Letters - Heterogeneous catalysis is a chemical process achieved at solid–gas or solid–liquid interfaces. Many factors including the particle size, shape and metal-support...     

Enzymatic degradation of thermoresponsive poly(N‐isopropylacrylamide) grafted to carboxymethylcellulose copolymers

The enzymatic degradation of poly(N‐isopropyl acrylamide) (PNIPAM) grafted to carboxymethylcellulose (CMC) copolymers with a cellulasic preparation (Trichoderma viride) was studied. The enzymatic activity of the cellulasic preparation against CMC and the grafted copolymers was determined by the Petterson–Porath method, while their reduced viscosity variation in the presence of the same preparation was also followed. It has been shown that the enzymatic degradation behavior depends on the copolymer composition and the reaction temperature. Reducing sugars analysis showed that the experimental values for the grafted copolymers were higher than the calculated ones. At 50°C, the enzymatic reaction is completed in about 20 min for the copolymers, whereas for CMC it takes more than 40 min. It can be concluded that their enzymatic degradation is facilitated by the presence of the PNIPAM grafts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1383–1386, 2003     

The first measurement of an absolute surface concentration of reaction intermediates in ethylene hydrogenation

The first measurement of a turnover rate with respect to surface intermediate concentration in a high pressure heterogeneous catalytic reaction is reported. By using infrared-visible sum frequency generation to study the hydrogenation of ethylene on Pt(111), it was found that the surface concentration of -bonded ethylene, the key reaction intermediate, represented approximately 4% of a monolayer. Thus the absolute turnover rate per surface adsorbed ethylene molecule is 25 times faster than the rate measured per platinum atom. To explain these results, we propose a model of weakly adsorbed ethylene intermediates reacting on atop sites.     

Jordan surfaces in simply connected digital spaces

Certain tasks in multidimensional digital image analysis, in particular surface detection and volume estimation, lead us to the study of surfaces in the digital environment. It is desirable that these surfaces should have a Jordan property analogous to that of simple closed curves in two dimensions-namely, that they should partition the underlying space into an inside and an outside which are disconnected from each other. A version of this property, called near-Jordanness, has been previously defined and has been shown to be useful within a general theory of surfaces in digital spaces. The definition of a near-Jordan surface is global: it demands that all paths from the interior to the exterior cross the surface. This makes it difficult in many practical applications to check whether surfaces are near-Jordan. The work reported in this paper is motivated by the desire for a local condition, such that if a surface satisfies this condition at each of its elements, then it is guaranteed to be near-Jordan. In the search for such a condition, we were led to a concept of simple connectedness of a digital space, which resembles simple connectedness in ordinary topological spaces. We were then able to formulate the desired local condition for simply connected digital spaces. Many digital spaces, in particular those based on the commonly-studied tessellations of n-dimensional Euclidean space, are shown to be simply connected and thus our theory yields general sufficient conditions for boundaries in binary pictures to be near-Jordan.     

Common coupling and pointer variables,with application to a Linux case study

Both common coupling and pointer variables can exert a deleterious effect on the quality of software. The situation is exacerbated when global variables are assigned to pointer variables, that is, when an alias to a global variable is created. When this occurs, the number of global variables increases, and it becomes considerably harder to compute quality metrics correctly. However, unless aliasing is taken into account, variables may incorrectly appear to be unreferenced (neither defined nor used), or to be used without being defined. These ideas are illustrated by means of a case study of common coupling in the Linux kernel.

Relationship between Creativity, Imitation, and Cultural Diversity

There are both benefits and drawbacks to cultural diversity. It can lead to friction and exacerbate differences. However, as with biological diversity, cultural diversity is valuable in times of upheaval; if a previously effective solution no longer works, it is good to have alternatives available. What factors give rise to cultural diversity? This paper describes a preliminary investigation of this question using a computational model of cultural evolution. The model is composed of neural network based agents that evolve fitter ideas for actions by (1) inventing new ideas through modification of existing ones, and (2) imitating neighbors'' ideas. Numerical simulations indicate that the diversity of ideas in a population is positively correlated with both the proportion of creators to imitators in the population, and the rate at which creators create. This is the case for both minimum and peak diversity of actions over the duration of a run.     

Adjusting Some Properties of Poly(methacrylic acid) (Nano)Composite Hydrogels by Means of Silicon-Containing Inorganic Fillers

The present work aims to show how the main properties of poly(methacrylic acid) (PMAA) hydrogels can be engineered by means of several silicon-based fillers (Laponite XLS/XLG, montmorillonite (Mt), pyrogenic silica (PS)) employed at 10 wt% concentration based on MAA. Various techniques (FT-IR, XRD, TGA, SEM, TEM, DLS, rheological measurements, UV-VIS) were used to comparatively study the effect of these fillers, in correlation with their characteristics, upon the structure and swelling, viscoelastic, and water decontamination properties of (nano)composite hydrogels. The experiments demonstrated that the nanocomposite hydrogel morphology was dictated by the way the filler particles dispersed in water. The equilibrium swelling degree (SDe) depended on both the pH of the environment and the filler nature. At pH 1.2, a slight crosslinking effect of the fillers was evidenced, increasing in the order Mt < Laponite < PS. At pH > pKa_MAA (pH 5.4; 7.4; 9.5), the Laponite/Mt-containing hydrogels displayed a higher SDe as compared to the neat one, while at pH 7.4/9.5 the PS-filled hydrogels surprisingly displayed the highest SDe. Rheological measurements on as-prepared hydrogels showed that the filler addition improved the mechanical properties. After equilibrium swelling at pH 5.4, G’ and G” depended on the filler, the Laponite-reinforced hydrogels proving to be the strongest. The (nano)composite hydrogels synthesized displayed filler-dependent absorption properties of two cationic dyes used as model water pollutants, Laponite XLS-reinforced hydrogel demonstrating both the highest absorption rate and absorption capacity. Besides wastewater purification, the (nano)composite hydrogels described here may also find applications in the pharmaceutical field as devices for the controlled release of drugs.     

The role of adsorbate overlayers in thiophene hydrodesulfurization over molybdenum and rhenium single crystals

Thiophene hydrodesulfurization (HDS) has been investigated over model single crystal catalysts of molybdenum and rhenium. Thiophene HDS is a structure sensitive reaction over rhenium and a structure insensitive reaction over molybdenum. Adsorbed sulfur decreases the activity of both Re(0001) and Mo(100) surfaces while adsorbed carbon has distinctly different effects on the catalytic properties of the two metals. Carbon overlayers deactivate the Re(0001) surface but have no effect on the HDS activity of the Mo(100) surface. Radiotracer³⁵S and¹⁴C studies indicate that HDS occurs on an adsorbate overlayer on molybdenum comprised primarily of carbon. HDS over rhenium, on the other hand, occurs on the bare metal surface. This appears to be responsible for the observed differences in the influence of surface structure on HDS activity.