Monosaccharide phosphorylation

Phosphate esters of glucose, fructose, and other monosaccharides are important metabolic intermediates, and the ribose moiety of nucleotides such as ATP and GTP is phosphorylated at the 5 -position (Figure 7.13). 

Some yeasts are able to add other monosaccharides, like galactose (S. pombe), but with unusual bonds [70], and they also tend to phosphorylate their glycans everywhere to obtain an additional charge on proteins [71]. 

Hexokinase (yeast) 2 800 102 000 Enzyme capable of phosphorylating selected monosaccharides... 

The structural components encountered in E. coli are also present in lipid A of other bacterial sources. Thus, a survey of the structures analyzed shows that lipid A, in general, contain two g/wcoconfigured and pyranosidic D-hexosamine residues (2-amino-2-deoxy-D-glucose, GlcpN, or 2,3-diamino-2,3-dideoxy-D-glucose, GlcpN3N, also termed DAG (49,50)], which are present as a ) -(l — 6)-linked disaccharide (monosaccharide backbones have also been identified, but the respective lipid A lack endotoxic activity). The disaccharide is phosphorylated by one or, in most cases, two phosphate... 

The PPP has two chemical phases an initial irreversible oxidative phase when G6P is decarboxylated and oxidized to form ribulose-5-phosphate (Ru-5-P) followed by a more complicated but reversible non-oxidative phase involving interconversions of phosphorylated monosaccharides with four, five, six or seven carbon atoms. The... 

Fructose is found in honey and fruit and as part of the disaccharide sucrose (common table sugar). Sucrose is hydrolyzed by intestinal brush border sucrase, and the resulting monosaccharides, glucose and fructose, are absorbed into the portal blood. The liver phosphorylates frurtose and cleaves it into glyceraldehyde and DHAP. Smaller amounts are metabolized in renal proximal tubules. The pathway is shown in Figure 1-12-7 important enzymes to remember are ... 

Rare or unnatural monosaccharides have many useful applications as nonnutritive sweeteners, glycosidase inhibitors and so on. For example, L-glucose and L-fructose are known to be low-calorie sweeteners. In addition, rare or unnatural monosaccharides are potentially useful as chiral building blocks for the synthesis of biologically active compounds. Therefore, these compounds have been important targets for the development of enzymatic synthesis based in the use of DHAP-dependent aldolases alone or in combination with isomerases. Fessner et al. showed that rare ketose-1-phosphates could be reached not only by aldol addition catalyzed by DHAP-dependent aldolases, but by enzymatic isomerization/ phosphorylation of aldoses [35]. Thus, for example, L-fructose can be prepared... 

The monosaccharides so formed are actively transported into the epithelial cells (see Fig. 11-44), then passed into the blood to be carried to various tissues, where they are phosphorylated and funneled into the glycolytic sequence. 

Most sugars are rapidly phosphorylated following their entry into cells. They are thereby trapped within the cells, because organic phosphates cannot freely cross membranes without specific transporters. An alternate mechanism for metabolizing a monosaccharide is to convert it to a polyol by the reduction of an aldehyde group, thereby producing an additional hydroxyl group. 

In the mammal, complex polysaccharides which are susceptible to such treatment, are hydrolyzed by successive exposure to the amylase of the saliva, the acid of the stomach, and the disaccharidases (e.g., maltase, invertase, amylase, etc.) by exposure to juices of the small intestine. The last mechanism is very important. Absorption of the resulting monosaccharides occurs primarily in the upper part of the small intestine, from which the sugars are earned to the liver by the portal system. The absorption across die intestinal mucosa occurs by a combination of active transport and diffusion. For glucose, the aclive transport mechanism appears to involve phosphorylation The details are not yet fully understood. Agents which inhibit respiration (e.g., azide, fluoracetic acid, etc.) and phosphorylation (e.g., phlorizin), and those which uncouple oxidation from phosphorylation (e.g., dinitrophenol) interfere with the absorption of glucose. See also Phosphorylation (Oxidative). Once the various monosaccharides pass dirough the mucosa, interconversion of the other... 

On the other hand, the enzymatic synthesis of glycoconjugates and oligosaccharides leads to high product yields in a short time by stereo- and regioselective one-step reactions. All enzymatic reactions are easy to scale up and are carried out in aqueous media under mild conditions. A whole set of enzymes is now available to build up OAT bonds in monosaccharides, COP bonds in activated monosaccharides e.g. phosphorylated sugars or nucleotide sugars, and C-O-C bonds in di- and oligosaccharides (Fig. 1). However, all these enzymatic reactions are limited by the substrate spectrum of the individual enzyme. 

Ribulose (— a-D-Ribulose) (pentose monosaccharide) Universal photosynthetic Calvin Cycle intermediate (phosphorylated) Melvin Calvin (USA, Nobel Prize, 1961, Chemistry, photosynthesis Calvin cycle) Sweet... 

In the cytosol, these monosaccharides can be phosphorylated and subsequently coupled with nucleotides such as uridine diphosphate (e.g., UDP-GlcNAc), guanosine diphosphate (e.g., GDP-mannose), or cytosine monophosphate in the case of sialic acids (Fig. 2b) to create a set of high energy building blocks for glycan assembly. In some cases, such as for the initial steps... 

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