Reactive sites active center

When combined with the isolation and reactivity studies of the patterned aminosilica (7), the increased activity of the patterned catalysts provide further evidence that the patterning technique developed allows for the synthesis of aminosilicas which behave like isolated, single-site materials (although a true single site nature has not been proven). As the olefin polymerization catalysts supported by the patterned materials show a marked improvement over those materials supported on traditional aminosilicas, these patterned materials should be able to improve supported small molecular catalysis as well. Future improvements in catalysis with immobilized molecular active sites could be realized if this methodology is adopted to prepare new catalysts with isolated, well-defined, single-site active centers. 

Polar monomers such as 2-vinylpyridine and methyl methacrylate are normally polymerized in polar solvents such as tetrahydrofuran and at low temperature (-78 °C). In addition, additives such as LiCl are often added to help lower the rates of termination reactions to levels insignificant in the time frame of the reaction. Block copolymers made with nonpolar and polar monomers start with the nonpolar monomer because of its greater reactivity. These active centers are then typically capped with 1,1-diphenylethylene to lower then-reactivity before the addition of the polar monomer. This helps eliminate side reactions resulting from addition of the active center to electrophilic sites in the polar monomers. The two polar polymers, polystyrene-2-vinylpyridine (PS-P2VP) and polystyrene-poly methyl methacrylate (PS-PMMA) have been extensively studied in thin films. 

Inhibitors must possess chemical and physical properties that will ensure absorption by root tips or penetration by foliar surfaces, and translocation to the active site. Once there they must assume the precise spatial configuration required to complement the molecular architecture of the active center if they are to block the key reaction. A comprehension of comparative biochemistry and information on how plants differ in the architecture of the reactive sites should assist in developing truly selective herbicides. 

Carbohydrates and other biological molecules that contain polysaccharides, such as glycoproteins, can be specifically modified at their sugar residues to produce reactive formyl functionalities. With proteins, this method often allows modification to occur only at specific locals, usually away from critical active centers or binding sites. 

The following sections discuss some of the more common biotinylation reagents available for modification of proteins and other biomolecules. Each biotin derivative contains a reactive portion (or can be made to contain a reactive group) that is specific for coupling to a particular functional group on another molecule. Careful choice of the correct biotinylation reagent can result in directed modification away from active centers or binding sites, and thus preserve the activity of the modified molecule. 

Pore-confinement of the catalytically active center may have favorable effects as demonstrated for (i) protection of the reactive sites from deactivation processes... 

The nature of the titanium-containing active site has been investigated with different techniques, including theoretical calculations. The formation of a hydroperoxidic species or of a bidentate side-on titanium peroxo structure was suggested by many authors . Alternatively, some DFT calculations indicated an undissociated molecule of H2O2 weakly interacting with Ti centers or an active Ti-O-O-Si peroxo moiety as a reactive site . Recently, Lin and Frei reported the first direct detection, obtained using in situ FT-infrared spectroscopy, of a Ti-OOH moiety as active species in the oxidation of small olefins like ethylene or propylene . 

Reactions whose rate is not greatly affected by coordination. Here the reactive site of the ligand is usually quite distant from the coordination center, though a very active attacking reagent can lead to much the same result if it is sufficiently unselective. 

When finely divided silica is treated with methanol and then pyrolyzed, it becomes activated toward chemisorption of various gases341-343. Recent careful spectroscopic studies by Radzig and coworkers344-347 and by Razskazovskii et aZ.348,349 establish beyond reasonable doubt that the principal reactive sites are divalent silicons, (=Si—0)2 Si , silylene centers 350, which participate in a rich chemistry. 

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