Enzyme exclusion

Contrary to the Fuji process, BASF described the characterization and cloning of an L-specific pantolactone hydrolase from Agrobacterium tumefa-ciens [103,104]. This enzyme exclusively opens up the undesired lactone l-1 12, providing a more direct route to d-1 12 (Scheme 35, right side). In addition, this new process is expected to be much more robust toward the competing spontaneous chemical hydrolysis, which could theoretically cause a diminished optical yield in the Fuji process. The enzymatic resolution of d/l-112 in repeated batches with membrane filtration techniques provided d-1 12 in 50% yield and with 90-95% ee. By immobilization onto Eupergit C it was possible to obtain a stable biocatalyst which was easy to use in repeated batch reactions. 

A process for the production of D-a-amino acids has been developed by Roche Diagnostics based on the enzyme D-hydantoinase [115]. The recombinant protein was covalently fixed onto a carrier and used for the synthesis of a broad range of natural and artificial D-amino acids (132, Scheme 41). Starting from racemic hydantoins d/l-130, the enzyme exclusively hydrolyzed d-130 to 131, and new d-130 was internally produced by continuous in situ racemization of l-130. The process worked especially well with 5-(p-hydroxyphenyl)- and 6-phenylhydantoin, affording the corresponding amino acids 132 in high yield and optical purity. The number of reuse cycles until 50% of the initial enzyme activity was reached was calculated to be as high as - 200. Unfortunately, this process has never been used in the production of D-amino acids, as diazotation was found to be too noxious and complicated. 

Optically inactive starting materials can give optically active products only if they are treated with an optically active reagent or if the reaction is catalyzed by an optically active substance The best examples are found m biochemical processes Most bio chemical reactions are catalyzed by enzymes Enzymes are chiral and enantiomerically homogeneous they provide an asymmetric environment m which chemical reaction can take place Ordinarily enzyme catalyzed reactions occur with such a high level of stereo selectivity that one enantiomer of a substance is formed exclusively even when the sub strate is achiral The enzyme fumarase for example catalyzes hydration of the double bond of fumaric acid to malic acid m apples and other fruits Only the S enantiomer of malic acid is formed m this reaction... 

Enzyme catalyzed reductions of carbonyl groups are more often than not com pletely stereoselective Pyruvic acid for example is converted exclusively to (5) (+) lactic acid by the lactate dehydrogenase NADH system (Section 15 11) The enantiomer... 

The enzyme is a single enantiomer of a chiral molecule and binds the coenzyme and substrate m such a way that hydride is transferred exclusively to the face of the carbonyl group that leads to (5) (+) lactic acid Reduction of pyruvic acid m the absence of an enzyme however say with sodium borohydride also gives lactic acid but as a racemic mixture containing equal quantities of the R and S enantiomers... 

Ultimately a plasmid is defined by its mode of DNA repHcation. DNA repHcation is initiated at a single, characteristic sequence, termed the origin. The origin sequence determines the copy number of the plasmid relative to the host chromosome and the host enzymes that are involved in plasmid repHcation. Two different plasmids that contain the same origin sequence are termed incompatible. This term does not refer to the active exclusion of one plasmid by another from the ceU but rather to a stochastic process by which the two plasmids are partitioned differentially into progeny ceUs. A ceU which contains two plasmids of the same incompatibiHty group segregates two clonal populations, each of which has one of the two plasmids in it. 

Approximately 95% of the malt produced is used to make beet while small amounts are used as distillers and food malts. Distillers malt, which is used to convert starch-containing grains into fermentable sugars, is prepared almost exclusively for its enzymes, especially a-amylase (see Beverage SPIRITS, distilled). Food malts are sold for their davor and/or enzyme contribution to food products. 

The primary disadvantage of the conjugate addition approach is the necessity of performing two chiral operations (resolution or asymmetric synthesis) ia order to obtain exclusively the stereochemicaHy desired end product. However, the advent of enzymatic resolutions and stereoselective reduciag agents has resulted ia new methods to efficiently produce chiral enones and CO-chain synthons, respectively (see Enzymes, industrial Enzymes in ORGANIC synthesis). Eor example, treatment of the racemic hydroxy enone (70) with commercially available porciae pancreatic Hpase (PPL) ia vinyl acetate gave a separable mixture of (5)-hydroxyenone (71) and (R)-acetate (72) with enantiomeric excess (ee) of 90% or better (204). 

Pesticides are susceptible to a variety of transformations in the environment, including both chemical degradation and microbial metaboHsm. Microbial transformations are catalyzed exclusively by enzymes, whereas chemical transformations are mediated by a variety of organic and inorganic compounds. Many pesticide transformations can occur either chemically or biologically. Consequentiy, most pesticide dissipation studies include sterile treatments to... 

Bacitracin. Bacitracin, a cycHc peptide active against gram-positive bacteria, was discovered in 1943. Bacitracin received dmg certification in 1949 (60—62). Whereas human usage of bacitracin is almost exclusively topical, the vast majority of bacitracin manufactured worldwide is used as an animal feed additive. Reviews of work on bacitracin include its chemistry (63—67), comprehensive aspects (62), medical aspects (62,68), biosynthesis on large enzyme complexes and genetics (69—71), and production (71,72). 

Barley may have either two or six rows of fertile kernels, and, because it differs ia so many other quaUties, there are several thousand varieties. European breweries almost exclusively use two-row barleys six-row barleys are predominant ia the United States. The two-row barleys are richer ia extract than the six-row. However, the latter is richer ia enzymes which are important when large amounts of adjuncts are being used. 

Proteins may consist exclusively of a polymeric chain of amino acids these are the simple proteins. Quite often some other chemical component is covalendy bonded to the amino acid chain. Glycoproteins and Hpoproteins contain sugar and Hpid components, respectively. Porphyrins are frequently associated with proteins, eg, in hemoglobin. Proteins bound to other chemical components are called conjugated proteins. Most enzymes are conjugated proteins. 

For the equiUbrium-controUed enzyme-catalyzed peptide synthesis the equiUbrium position Hes far over in the direction of the hydrolysis, and under physiological conditions, the product yield is negligible. The equiUbrium position is deterrnined exclusively by thermodynamic factors and like any other catalysts the enzymes only accelerate the attainment of the equiUbrium. 

The nature of the penicillin derivatives accessible by this "feeding" route was severely limited by the fact that the acylat-ing enzyme of the Penicillium molds would accept only those carboxylic acids which bore at least some resemblance to its natural substrates. A breakthrough in this field was achieved by the finding that rigid exclusion of all possible side-chain substrate from the culture medium afforded 6-APA as the main fermentation... 

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