Biomimetic selectivity

In one of our earliest approaches to such biomimetic selectivity, directed by the geometry of the catalyst-substrate complex, we examined the directed substitution of an aromatic ring bound into the cydodextrin cavity [142,143]. Anisole was chlorinated by HOC1 entirely in the para position when it was bound into a-cydodextrin, while in... 

The development of highly selective chemical sensors for complex matrixes of medical, environmental, and industrial interest has been the object of greate research efforts in the last years. Recently, the use of artificial materials - molecularly imprinted polymers (MIPs) - with high recognition properties has been proposed for designing biomimetic sensors, but only a few sensor applications of MIPs based on electrosynythesized conductive polymers (MIEPs) have been reported [1-3]. 

In summary, these recently obtained results demonstrate that certain amphi-pathic peptoid sequences designed to mimic both the helical structure and approximate length of magainin helices are also capable of selective and biomimetic antibacterial activity. These antibacterial peptoids are helical in both aqueous buffer and in the presence of lipid vesicles. Ineffective (non-antibacterial) peptoids exhibit weak, random coil-like CD, with no spectral intensification in the presence of lipid vesicles. Selective peptoids exhibit stronger CD signals in bacterial-mimetic vesicles than in mammalian-mimetic vesicles. Non-selective peptoids exhibit intensely helical CD in both types of vesicles. 

Results discussed above show in several lines a distinct biomimetic-type activity of iron complexes stabilized in the ZSM-S matrix. The most important feature is their unique ability to coordinate a very reactive a-oxygen form which is similar to the active oxygen species of MMO. At room temperature a-oxygen provides various oxidation reactions including selective hydroxylation of methane to methanol. Like in biological oxidation, the rate determining step of this reaction involves the cleavage of C-H bond. 

Bakke et al. (1982) have shown how montmorillonite catalyses chlorination and nitration of toluene nitration leads to 56 % para and 41 % ortho derivative compared to approximately 40 % para and 60 % ortho derivatives in the absence of the catalyst. Montmorillonite clays have an acidity comparable to nitric acid / sulphuric acid mixtures and the use of iron-exchanged material (Clayfen) gives a remarkable improvement in the para, ortho ratio in the nitration of phenols. The nitration of estrones, which is relevant in making various estrogenic drugs, can be improved in a remarkable way by using molecular engineered layer structures (MELS), while a reduction in the cost by a factor of six has been indicated. With a Clayfen type catalyst, it seems possible to manipulate the para, ortho ratio drastically for a variety of substrates and this should be useful in the manufacture of fine chemicals. In principle, such catalysts may approach biomimetic chemistry our ability to predict selectivity is very limited. 

Metalloporphyrinosilicas as a new class of hybrid organic-inorganic materials were prepared by polymerization of 3- er -butyl-5-vinylsalicylaldehyde with styrene and divinylbenzene and used as selective biomimetic oxidation catalyst.27 Synthesis and structural characterization of rare-earth bisfdimethyl-silyl)amides and their surface organometallic chemistry on mesoporous silicate MCM-41 have been reported.28... 

The intercalated catalysts can often be regarded as biomimetic oxidation catalysts. The intercalation of cationic metal complexes in the interlamellar space of clays often leads to increased catalytic activity and selectivity, due to the limited orientations by which the molecules are forced to accommodate themselves between sheets. The clays have electrostatic fields in their interlayer therefore, the intercalated metal complexes are more positively charged. Such complexes may show different behavior. For example, cationic Rh complexes catalyze the regioselective hydrogenation of carbonyl groups, whereas neutral complexes are not active.149 Cis-Alkenes are hydrogenated preferentially on bipyridyl-Pd(II) acetate intercalated in montmorillonite.150 The same catalyst was also used for the reduction of nitrobenzene.151... 

The aim of this overview is first to present the general principles of electrocatalysis by metal complexes, followed by a series of selected examples published over the last 20 years illustrating the major electrochemical reactions catalyzed by metal complexes and their potential applications in synthetic and biomimetic processes, and also in the development of sensory devices. The area of metal complex catalysts in electrochemical reactions was reviewed in 1990.1... 

Microporous material20 will demonstrate will show some sieve effects, polymers including some functional groups will also exhibit some selectivity, the best selectivity is exhibited by molecular imprinted polymers21. In some cases, the functionality is used to provide biomimetic compounds with certain recognition sites. These will be discussed later in connection with biopolymers. 

As we increasingly understand the chemistry performed by living systems, in particular that catalyzed by enzymes, we will continue to develop biomimetic methods to achieve some of the special selectivities that enzymes show. Enzymes can selectively bind a particular molecule out of the mixture of substances in the cell, then hold it in such a way that the geometry of the enzyme-substrate com-... 

The cucurbit [n]uril family (CB[n]) of molecular containers possess remarkable binding affinities and selectivities (Ka values up to 1012M-1, Krei values up to 106) which renders them useful as a component of molecular machines, sensors, and biomimetic systems (123-125). Recently, Wagner and coworkers have reported (126) that CB[10] - with its spacious 870A3 cavity - is capable of acting as a host for free base and metalated tetra (Af-methylpyridinium)porphyrins 19a-d (Fig. 17). Despite the large ellipsoidal deformation of CB[10] upon complexation, the complexed porphyrins retain their fundamental UV/VIS, fluorescence, and electrochemical properties. The CB[ 10] porphyrin... 

Diversity-Based Approaches to Selective Biomimetic Oxidation Catalysis Albrecht Berkessel... 

Selective Conversion of Hydrocarbons with H202 Using Biomimetic Non-heme Iron and Manganese Oxidation Catalysts... 

Panacene (61) is a metabolite of the sea hare Aplysia brasiliana and acts as a fish antifeedent [61]. The synthesis of the racemic natural product, published by Feldman et al. [77] in 1982, takes advantage of the anti-selective SN2 -substitution of the propargylic mesylate 67 with LiCuBr2 (Scheme 18.21). In contrast, the later attempted biomimetic synthesis by treatment of the enyne 68 with NBS or 2,4,4,6-tetrabromocyclohexadienone did not proceed stereoselectively and led to a 1 1 mixture of the target molecule 61 together with its allenic epimer [78]. 

Biorefineries New catalytic pretreatment of plant materials Valorization, pretreatment or disposal of co-products and wastes from biorefinery by catalytic treatments New and/or improved catalytic processes for chemicals production through the integration of the biorefinery concept and products into the existing chemical production chain New advanced catalytic solutions to reduce waste emissions (solid, air and, especially, water) New catalysts to selectively de-oxygenate products from biomass transformation Catalysts to selectively convert chemicals in complex multicomponent feedstocks New biomimetic catalysts able to operate under mild conditions Small catalytic pyrolysis process to produce stabilized oil for further processing in larger plants... 

Enzymes are known to show high enantio-selectivity, which is a parameter one wishes to install in the MIP as well. That this is possible was demonstrated in a recent paper on enantio-selective ester hydrolysis catalyzed by MIP. The MIP imprinted with the D-enantiomer preferentially hydrolyzed the D-ester with rate enhancements of up to three comp ared to the CP [117]. Although these findings may be far from outstanding, they represent remarkable results on the route towards the generation of competitive biomimetic catalysts. 

Rather than using the protein molecule as a whole, the imprinting of selected protein epitopes may present a more practical approach. Imprints of such patches may then act as receptors for these parts of the protein. It could be shown that an MIP imprinted with a tetrapeptide was able to recognize not only the template but also a protein bearing the same 3-amino acid terminus as the peptide template [129]. If this approach proves to be successful in other cases as well, MI-based recognition will no longer be limited to small molecules. The result will be even more antibody like biomimetic polymers. 

The evidence examined here pertains to hydrolysis of the peptide bond and of proteins in water under various conditions of pH and temperature. Selective hydrolysis by artificial or biomimetic catalysts is not discussed (e.g., [65] [66]). 

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