Enzymes molecular sieves

Another feature of this particular exopolysaccharide is that gel strength depends upon the temperature used. It is constant between 60-80°C, increasing in strength from 80-100°C and finally changing structure from a single to a triple stranded helix at temperatures over 120°C. This makes it particularly well suited for use as a molecular sieve, immobilised enzyme support and a binding agent. 

Kokufuta, E Jinbo, E, A Hydrogel Capable of Facilitating Polymer Diffusion through the Gel Porosity and Its Application in Enzyme Immobilization, Macromolecules 25, 3549, 1992. Kresge, CT Leonowicz, ME Roth, WJ Vartuli, JC Beck, JS, Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Template Mechanism, Nature 359, 710, 1992. 

This is the first example of a reaction for which the presence of a chelating ligand was observed to facilitate rather than retard metal-catalysed epoxidation (Gao et al., 1987). It was found that the use of molecular sieves greatly improves this process by removing minute amounts of water present in the reaction medium. Water was found to deactivate the catalyst. All these developments led to an improved catalytic version that allows a five-fold increased substrate concentration relative to the stoichiometric method. Sensitive water-soluble, optically active glycidols can be prepared in an efficient manner by an in situ derivatisation. This epoxidation method appears to be competitive with enzyme-catalysed processes and was applied in 1981 for the commercial production of the gypsy moth pheromone, (-1-) disparlure, used for insect control (Eqn. (25)). 

Conducting reactions in nanospace where the dimensions of the reaction vessel are comparable to those of the reactants provides a new tool that can be used to control the selectivity of chemical transformations.1 This dimensional aspect of nano-vessels has been referred to as shape selectivity.2 The effect of spatial confinement can potentially be exerted at all points on the reaction surface but its influence on three stationary points along the reaction coordinate (reactants, transition states, and products) deserve special attention.3,4 (1) Molecular sieving of the reactants, excluding substrates of the incorrect dimension from the reaction site can occur (reactant selectivity). (2) Enzyme-like size selection or shape stabilization of transition states can dramatically influence reaction pathways (transition state selectivity). (3) Finally, products can be selectively retained that are too large to be removed via the nano-vessel openings/pores (product selectivity). 

To a much smaller extent non-enzymic processes have also been used to catalyse the stereoselective acylation of alcohols. For example, a simple tripeptide has been used, in conjunction with acetic anhydride, to convert rram-2-acctylaminocyclohexanol into the (K),(R)-Qster and recovered (S),(S)-alcohol[17]. In another, related, example a chiral amine, in the presence of molecular sieve and the appropriate acylating agent, has been used as a catalyst in the conversion of cyclohexane-1(S), 2(/ )-diol into 2(S)-benzoyloxy-cyclohexan-1 f / j-ol1 IS]. Such alternative methods have not been extensively explored, though reports by Fu, Miller, Vedejs and co-workers on enantioselective esterifications, for example of 1-phenylethanol and other substrates using /. vo-propyl anhydride and a chiral phosphine catalyst will undoubtedly attract more attention to this area1191. 

Mesophase state, 20 78 Mesophiles, in composting, 25 873 Mesophilic digestion, 3 702 Mesophilic enzymes, 3 669 Mesoporous molecular sieves, 16 847—849 Mesostructured hybrid materials, 13 548-549... 

Imbalance in the stoichiometry of polycondensation reactions of AA-BB-type monomers can be overcome by changing to heterofunctional AB-type monomers. Indeed, IIMU has been subjected to bulk polycondensation using lipases as catalyst in the presence of 4 A molecular sieves. At 70 °C, CALB showed 84% monomer conversion and a low molecular weight polymer (Mn 1.1 kDa, PDI 1.9). No significant polymerization was observed with other lipases (except R cepacia lipase, 47% conversion, oligomers only) and in reference reactions with thermally deactivated CALB or in the absence of enzyme. Further optimization of the reaction conditions (60wt% CALB, II0°C, 3 days, 4 A molecular sieves) gave a polymer with Mn of 14.8 kDa (PDI 2.3) in 86% yield after precipitation [42]. 

Maleimido groups are introduced into AChE by reaction of their primary amino groups with the jV-hydroxy-succinimide moiety of SMCC m neutral medium. This reaction is very similar to that used for incorporation of biotin molecules into proteins Prior to this reaction, the enzyme is treated with / /-ethyl maleimide in order to block any thiol groups. Finally, SMCC-AChE is purified by molecular sieve chromatography on a Biogel A 1.5 m column. 

The maj ority of these new plants are corn dry-grind ethanol plants. Approximately 2.5-2.7 gal of ethanol, 17.5 lb of dried distiller s grain (DDG), and 17 lb of carbon dioxide are produced from each bushel of corn processed through a corn dry mill (2). Since 1980, process improvements in enzymes, thermal-tolerant yeasts, molecular sieves, and cogeneration have achieved a 50% reduction in the energy required to produce ethanol from corn (2). Further improvements in efficiencies and reductions in production costs can be expected in the future. 

Figure 18. Molecular sieve HPLC examination of CrATP-induced Ca2+ occlusion in mutants of the SR Ca2+-ATPase. The Ca2+ occluded enzyme was formed by incubation with 10 pM45Ca2+ and CrATP. The enzyme was solubilized by non-ionic detergent and injected into an HPLC column. Absorbance of the eluate was read continuously at 226 nm ( - ), and fractions were collected for analysis of radioactivity (o) or immunoreactivity specific for the Ca2+-ATPase (o). The right panel shows the absence of occluded 45Ca2+ from the Ca2+-ATPase protein peak corresponding to a mutant with severely reduced apparent Ca2+ affinity in the phosphorylation assay (c.f., Figure 17). The left panel shows as control a peak of 45Ca2+ associated with a mutant that binds Ca2+ normally.

To date, no chiral zeolite or molecular sieve has been obtained. However, Newsam et al. (48) have shown that zeolite beta is an intergrowth of two distinct structures polymorph A and B. Polymorph A forms an enantiomorphic pair. Thus, synthesis of one of the enantiomorphs of polymorph A would yield the first chiral zeolite and initiate the possibility of performing intrazeolitic asymmetric catalysis. Shape selective asymmetric catalysis would be the ultimate achievement in shape selective catalysis, and would certainly be a step closer toward truly mimicking enzyme catalysis. 

Tests for extents of coupling are conveniently carried out by molecular-sieve chromatography of conjugated enzyme preparations on appropriate gel columns, and comparison of the elution... 

As in the case of horseradish peroxidase, several synthetic metalloporphyrins in the presence of H2O2 have been found to be potent catalysts for the chemiluminescent oxidation of luminol or isoluminol. The microperoxidases, mainly MP8 and MPll, have been shown to act as functional peroxidase enzyme models. " However, they are readily inactivated within one min of catalytic turnover, and incorporation into a molecular sieve... 

Lipase-mediated esterification of glycerol and fatty acids is also an equilibrium reaction. The extent of esterification depends on the water content of the medium. The accumulation of water during esterification is a concern because it enhances the hydrolysis of the resultant esters. The water, which is produced during this reaction, may be continuously removed and this is usually accomplished by carrying out the reaction in the presence of molecular sieves (17). A small amount of water, however, is needed in the reaction medium to maintain the activity of the enzyme. The ester concentration at equilibrium is dependent on various medium properties, i.e., the water activity of the reaction system. Usually, a low water activity is necessary to obtain a high ester concentration. Water activity, however, is not the only parameter that determines the equilibrium position. The thermodynamic activities of other reaction variables also are important. 

Catalysis by zeolites is a rapidly expanding field. Beside their use in acid catalyzed conversions, several additional areas can be identified today which give rise to new catalytic applications of zeolites. Pertinent examples are oxidation and base catalysis on zeolites and related molecular sieves, the use of zeolites for the immobilization of catalytically active guests (i.e., ship-in-the-bottle complexes, chiral guests, enzymes), applications in environmental protection and the development of catalytic zeolite membranes. Selected examples to illustrate these interesting developments are presented and discussed in the paper. 

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