Ribose-5-phosphate isomerase, sugar

Ribulose-5-phosphate (3.13) can be converted to ribose-5-phosphate (3.14) and xylulose 5-phosphate (3.15), by the enzymes ribose-5-phosphate isomerase and ribulose 5-phosphate 3-epimerase, respectively. The two pentose-phosphate molecules, 3.14 and 3.15, are converted to a C3 and a C7 sugar-phosphate, glyceraldehyde 3-phosphate (3.4) and sedoheptulose-7-phosphate (3.16), respectively, via the action of atransketolase. 

Ribose-5-phosphate isomerase, which catalyses the interconversion of ribose-5-phosphate and ribulose-5-phosphate, activates the carbonyl differently. The aldose substrate can form a furanose (but not a pyranose) ring, but the furanose forms are so disfavoured (see Table 1.1) that there are likely to be appreciable amounts of open-chain sugar present at equilibrium. Moreover, this equilibrium, involving only furanose forms whose opening is possibly assisted by general acid catalysis from the 5-phosphate, is likely to be achieved rapidly. Although the enzyme from other sources crystallise with ring forms of the substrate bound, that from Thermus thermophilus crystallises with both ribose-... 

Measurements of the crude specific activity (mmoles of product synthesized per minute per mg of protein in the supernatant after a 50,000 x g centrifugation) of the two isomerases in E. coli indicated that the conversion of D-ribulose-5-phosphate to D-ri-bose-5-phosphate was approximately 20- to 30-fold greater than the conversion of D-ribulose-5-phosphate to D-arabinose-5-phosphate. This rate of reaction strongly pulls the reaction substrate to D-ribose-5-phosphate, since the isomerase reaction at equilibrium strongly favors the formation of the aldo-sugar over the key intermediate D-ribulose-5-phosphate. 

The pentose phosphate pathway also catalyzes the interconversion of three-, four-, five-, six-, and seven-carbon sugars in a series of non-oxidative reactions. All these reactions occur in the cytosol, and in plants part of the pentose phosphate pathway also participates in the formation of hexoses from CO2 in photosynthesis. Thus, D-ribulose 5-phosphate can be directly converted into D-ribose 5-phosphate by phosphopentose isomerase, or to D-xylulose 5-phosphate by phosphopentose epimerase. D-Xylulose 5-phosphate can then be combined with D-ribose 5-phosphate to give rise to sedoheptulose 7-phosphate and glyceraldehyde-3-phosphate. This reaction is a transfer of a two-carbon unit catalyzed by transketolase. Both products of this reaction can be further converted into erythrose 4-phosphate and fructose 6-phosphate. The four-carbon sugar phosphate erythrose 4-phosphate can then enter into another transketolase-catalyzed reaction with the D-xylulose 5-phosphate to form glyceraldehyde 3-phosphate and fructose 6-phosphate, both of which can finally enter glycolysis. 

Interconversion of a keto sugar (ribulose 5-phosphate or fructose-6-phosphate) and an aldo sugar (ribose 5-phosphate or glucose-6-phosphate) by an isomerase. 

The answer is e. (Murray, pp 219-229. Scrivei pp 1521-1552. Sack, pp 121-138. Wilson, pp 287-317.) The pentose phosphate pathway generates reducing power in the form of NADPH in the oxidative branch of the pathway and synthesizes five-carbon sugars in the nonoxidative branch of the pathway. The pentose phosphate pathway also carries out the interconversion of three-, four-, five-, six-, and seven-carbon sugars in the nonoxidative reactions. The final sugar product of the oxidative branch of the pathway is ribulose-5-phosphate. The first step of the nonoxidative branch of the pathway is the conversion of ribulose-5-phosphate to ribose-5-phosphate or xylulose-5-phosphate in the presence of the enzymes phosphopentose isomerase and phosphopentose epimerase, respectively. Thus ribulose-5-phosphate is a key intermediate that is common to both the oxidative and nonoxidative branches of the pentose phosphate pathway. 

In contrast to phosphohydrolases, the phosphatase activity of enzymes which non-hydrolytically catalyse the transfer of phosphate groups can be stimulated by vanadate. Vanadate can spontaneously form esters with unphosphorylated substrates such as sugars. These vanadate esters act as alternative substrates for mutases and isomerases, stimulating their phosphatase activity. Examples are phosphoglucomutase, which catalyses the mutation (phosphate shift) between glucose-1-phosphate and glucose-6-phosphate, and phosphoribose isomerase, which catalyses the isomerisation between ribose-5-phosphate and ribulose-5-phosphate.P ]... 

The epimerase and isomerase convert ribulose 5-phosphate to two other 5-carbon sugars (Fig. 29.7). The isomerase converts ribulose 5-phosphate to ribose 5-phos-phate. The epimerase changes the stereochemical position of one hydroxyl group (at carbon 3), converting ribulose 5-phosphate to xylulose 5-phosphate. 

The remainder of the pathway consists of a series of isomerase and group tranx/er reactions (Fig. 11-26). These produce sugar phosphates ranging in size from the 3-carbon glyceraldehyde 3-phosphate to the 7-carbon sedoheptulose 7-phosphate. Also derived from ribulose 5-phosphate is ribose 5-phosphate, an essential component of ribonucleosides and ribonucleotides. The group exchange reactions are catalyzed by transaldolase... 

The arabinose isomerase has been separated from the transphosphoryl-ase specific for ribulose from extracts of E. coli. It had been observed earlier that the product of n-arabinose metabolism in these extracts was an acid-stable pentose phosphate. Thus the product of ribulose phosphorylation was either itself a 5-phosphate or was converted to a moiety of this type such as ribose-5-phosphate. It may be noted that straight-chain sugar phosphates such as ribulose-5-phosphate or 2-desoxy deriva-tives are not as stable to acid as a compound like the furanose ribose-6-phosphate, which may have been the final product analyzed in the study of n-arabinose metabolism. 

---