Catalytically active sites

FIGURE 5.46 Interaction of the serine hydroxyl residue in the catalytically active site of acetylcholinesterase enzyme with esters of organophosphates or carbamates. The interaction leads to binding of the chemical with the enzyme, inhibition of the enzyme, inhibition of acetylcholine hydrolysis, and thus accumulation of acetylcholine in the synapses. 

The final step of the whole reaction process is the desorption of the products. This step is essential not only for the practical purpose of collecting and storing the desired output, but also for the regeneration of the catalytic active sites of the surface. Most reactions have at least one rate-hmiting step, which frequently makes the reaction prohibitively slow for practical purposes when, e.g., it is intended for homogeneous (gas or fluid) media. The role of a good solid-state catalyst is to obtain an acceptable... 

Probably all adenylyl cyclases are inhibited competitively by substrate analogs, which bind at the site and to the enzyme configuration with which cation-ATP binds (cf Fig. 4). One of the best competitive inhibitors is (3-L-2, 3 -dideoxy adenosine-5 -triphosphate ( 3-L-2, 3 -dd-5 -ATP Table 4) [4], which allowed the identification of the two metal sites within the catalytic active site (cf Fig. 4) [3]. This ligand has also been labeled with 32P in the (3-phosphate and is a useful ligand for reversible, binding displacement assays of adenylyl cyclases [4]. The two inhibitors, 2, 5 -dd-3 -ATP and 3-L-2, 3 -dd-5 -ATP, are comparably potent... 

Lipases have also been used as initiators for the polymerization of lactones such as /3-bu tyro lac tone, <5-valerolactone, e-caprolactone, and macrolides.341,352-357 In this case, the key step is the reaction of lactone with die serine residue at the catalytically active site to form an acyl-enzyme hydroxy-terminated activated intermediate. This intermediate then reacts with the terminal hydroxyl group of a n-mer chain to produce an (n + i)-mer.325,355,358,359 Enzymatic lactone polymerization follows a conventional Michaelis-Menten enzymatic kinetics353 and presents a controlled character, without termination and chain transfer,355 although more or less controlled factors, such as water content of the enzyme, may affect polymerization rate and the nature of endgroups.360... 

Figure 4.7. Schematic representation of the location of electrocatalytically and catalytically active sites in a section perpendicular to the catalyst film-solid electrolyte interface.

This kinetic relationship provides the necessary link between the gas-phase concentration ai and the concentration of A in its adsorbed form, which is denoted as [AS]. The units for surface concentration are moles per unit area of catalyst surface. S denotes a catalytically active site on the surface, also with units of moles per area of catalyst surface. 

The advantages of microreactors, for example, well-defined control of the gas-liquid distributions, also hold for photocatalytic conversions. Furthermore, the distance between the light source and the catalyst is small, with the catalyst immobilized on the walls of the microchannels. It was demonstrated for the photodegradation of 4-chlorophenol in a microreactor that the reaction was truly kinetically controlled, and performed with high efficiency [32]. The latter was explained by the illuminated area, which exceeds conventional reactor types by a factor of 4-400, depending on the reactor type. Even further reduction of the distance between the light source and the catalytically active site might be possible by the use of electroluminescent materials [19]. The benefits of this concept have still to be proven. 

Assuming that substituted Sb at the surface may work as catalytic active site as well as W, First-principles density functional theory (DFT) calculations were performed with Becke-Perdew [7, 9] functional to evaluate the binding energy between p-xylene and catalyst. Scalar relativistic effects were treated with the energy-consistent pseudo-potentials for W and Sb. However, the binding strength with p-xylene is much weaker for Sb (0.6 eV) than for W (2.4 eV), as shown in Fig. 4. 

AXB) shows time courees of amounts of evolved hydrogen and decalin conversions with caibon-supported platinum-based catalysts unda" supeiheated liquid-film conditions. Enhancement of dehydrogenation activities for decalin was realized by using fiiese composite catalysts. The Pt-W / C composite catalyst exhibited the hipest reaction rate at the initial stage, whereas the Pt-Re / C composite catalyst showed the second highest reaction rate in addition to low in sensitivity to retardation due to naphthaloie adsorbed on catalytic active sites [1-5], as indicated in Fig. 2(A) ). 

Zeolites are used in various applications such as household detergents, desiccants and as catalysts. In the mid-1960s, Rabo and coworkers at Union Carbide and Plank and coworkers at Mobil demonstrated that faujasitic zeolites were very interesting solid acid catalysts. Since then, a wealth of zeolite-catalyzed reactions of hydrocarbons has been discovered. Eor fundamental catalysis they offer the advantage that the crystal structure is known, and that the catalytically active sites are thus well defined. The fact that zeolites posses well-defined pore systems in which the catalytically active sites are embedded in a defined way gives them some similarity to enzymes. 

What is the most important property to consider when designing a catalyst for an industrial process (a) the rate per catalytically active site (b) the rate per unit weight of catalyst or (c) the rate per unit volume of catalyst Explain your answer. 

The Fe(l1l) surface is composed of four-fold coordinated atoms and exposed second layer atoms that are seven-fold coordinated while the Fe(l10) and Fe(lOO) planes have only six-fold and four-fold coordinated atoms respectively. Here we have defined the coordination number as the number of nearest neighbor atoms. Dumesic s proposal that the seven-fold coordinated atom is an important component of the catalytically active site is not contradicted by our results ( ). It is also worth noting that the relative roughness or openess of the each plane follows the same progression as their catalytic activities. Table II also shows that the activity of each of the two less active surfaces was markedly enhanced by sputtering with Ar. It is possible that sputtering has exposed seven-fold coordinate atoms at the surface or that it is the roughness of the surface that is responsible for the structure senstivity of the reaction rate. 

Hydrodenitrogenation (HDN) is an important process in petroleum refining. It removes nitrogen from oil distillates, so that less NOx pollutes the air when oil is burned and poisoning of the subsequent refining catalysts is reduced when the oil is processed further. Although HDN has been studied intensively and different reaction mechanisms, catalytic active sites, and functions of the catalytic components have been proposed, there are stiU many questions to be answered in order to better mderstand the reaction and the catalyst (1-4). 

It has been revealed that the formation of protonic acid sites from molecular hydrogen is observable for the catalysts other than Pt/S042--Zr02, and the protonic acid sites thus formed act as catalytically active sites for acid-catalyzed reaction. We propose the concept "molecular hydrogen-originated protonic acid site" as a widely applicable active sites for solid acid catalysts. 

The idea of using organic metal complexes as catalysts for electrochemical reactions (Jasinski, 1964) can be traced back to the biocatalysts in which such complexes often are the catalytically active sites and which are distinguished by a high catalytic activity. This area has seen a strong development starting in the 1960s. 

As we demonstrate in this chapter, enzymes can be extremely active electrocatalysts at ambient temperatures and mild pH, and have significantly higher reaction selectivity than precious metals. The main disadvantage in applying redox enzymes for electrocatalysis arises from their large size, which means that the catalytic active site density is low. Enzymes also have a relatively short hfetime (usually not more than a few months), making them more suited to disposable applications. 

Carbon-supported Ru-Sn catalyst Ru and Sn Mossbauer measurements were performed to investigate catalysts of ruthenium and tin supported on activated carbon (Ru-Sn/C). The samples were subjected to different reducing and oxidizing treatments. The presence of tin leads to a substantial increase of the Lamb-Mossbauer factor of the metallic Ru-particles showing that tin strengthens the attachment of the particles to the support. The close contact between the two metals appears to be decisive for the formation of catalytically active sites (Ru-Sn and Ru-SnOj,-)... 

Next, we investigated the experimental parameters for hydrogenolysis of Cbz-protected amino acids. It is important to carefully select the experimental parameters so that the reactions are not limited by diffusion of hydrogen to the catalytically active sites. The diffusion of hydrogen can be affected by temperature, agitation speed, as well as the number of catalytically active sites... 

A catalytic reaction is one in which more than one turnover or event occurs per reaction center or catalytically active site (that is, the turnover number [TON] is greater than 1). Thus a reaction is not catalytic if it is stoichiometric or if its TON is less than 1. A reaction might indeed involve a true catalyst and under some circumstances be catalytic, but if one or fewer turnovers occur per active site, it is not a catalytic reaction. 

To catalyze asymmetric transformations, catalytically active sites can be incorporated in different areas of a dendrimer a) chiral sites at the periphery, b) chiral sites in cavities or at the core, c) achiral sites which are surrounded by chiral branches in the interior of the dendrimer. 

The rate of a catalytic reaction depends on the rate of diffusion of both substrates and products to and from the catalytic sites. Therefore it is of outmost importance that the catalytically active sites are freely accessible for reactions. Only dendrimers of low generation number can possibly be expected to be suitable carriers for catalytically active sites, especially when these are located in the interior. In high-generation dendrimers with crowded surfaces catalytic activity of an internal site would be prevented. On the other hand, a crowded surface will not only hinder access to an interior ligand site but will also cause steric hindrance between groups attached to it and thus prevent high reactivity of sites at the periphery. 

Brunner et al. attached chiral branches to non-chiral catalytically active sites. With the aim to influence the enantioselectivity of transition metal catalyzed reactions they synthesized several dendritically enlarged diphosphines such as 81 [101] (Fig. 29). In situ prepared catalysts from [Rh(cod)Cl]2and81 have been tested in the hydrogenation of (a)-N-acetamidocinnamic acid. After 20 hours at 20 bar H2-pressure (Rh/substrate ratio 1 50) the desired product was obtained with an enantiomer ratio of 51 49. 

Fig. 30. Dendritic TADDOL derivatives carrying the catalytically active site either at the periphery (84) or in the center (85) [105,106]...

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