Carbohydrate carrying molecules

Several are the consequences which can be expected from the cluster organization of carbohydrate carrying molecules in the... 

Primary metabolic processes are those which evolve primary metabolites such as fats, carbohydrates, proteins and nucleic acids which are common to all living species. Metabolism involves very many reaction sequences, which are frequently cyclic and interacting. These reactions are almost all enzyme-catalysed and they often employ special energy-carrying molecules. 

Both photosynthesis occurring in plants, and the oxidation of carbohydrate during food metabolism are complex multistage enzyme-catalysed processes which utilise phosphate energy-carrying molecules. 

This chapter deals with three important classes of biotransformations. Firstly, those enzymes that catalyse the stereoselective formation of carbon-carbon bonds will be examined. These enzymes, whose natural functions often are to degrade carbohydrate-like molecules, have proved to be versatile catalysts for C—C bond synthesis. Secondly, we shall look at those enzymes that mediate the formation of C—X bonds, where X = O, N, S, Hal (halogen). These enzymes are termed lyases (see Table 2.1) and often carry out very simple reactions (e.g. the addition of water to a double bond) with very high stereoselectivity and regioselectivity. Finally, the application of a range of enzymes (including C—C bond formation) to carbohydrate synthesis will be examined. This chapter will conclude with some examples of the ways in which multienzyme reactions can be constructed to enable highly complex molecules to be assembled in an efficient manner. 

Biopolymers such as proteins, nucleic acids and carbohydrates carry a number of charged groups in their monomers. Therefore, they can also be referred to as either polyampholytes or polyelectrolytes. Polyelectrolyte molecules carry only one type of charge regardless of the solution pH. Thus, these can be polyanionic or polycationic. In contrast, polyampholyte molecules can bear positive or negative charge depending on solution pH. For example, proteins contain both acidic and basic residues that selectively dissociate as per solution pH. 

Experimental procedures have been described in which the desired reactions have been carried out either by whole microbial cells or by enzymes (1—3). These involve carbohydrates (qv) (4,5) steroids (qv), sterols, and bile acids (6—11) nonsteroid cycHc compounds (12) ahcycHc and alkane hydroxylations (13—16) alkaloids (7,17,18) various pharmaceuticals (qv) (19—21), including antibiotics (19—24) and miscellaneous natural products (25—27). Reviews of the microbial oxidation of aUphatic and aromatic hydrocarbons (qv) (28), monoterpenes (29,30), pesticides (qv) (31,32), lignin (qv) (33,34), flavors and fragrances (35), and other organic molecules (8,12,36,37) have been pubflshed (see Enzyp applications, industrial Enzyt s in organic synthesis Elavors AND spices). 

Long-chain polyisoprenoid. molecules with a terminal alcohol moiety are called, polyprenols. The dolichols, one class of polyprenols (Figure 8.18), consist of 16 to 22 isoprene units and, in the form of dolichyl phosphates, function to carry carbohydrate units in the biosynthesis of glycoproteins in animals. Polyprenyl groups serve to anchor certain proteins to biological membranes (discussed in Chapter 9). 

The remainder of this chapter will deal with natural polymers. These are large molecules, produced by plants and animals, that carry out the many life-sustaining processes in a living cell. The cell membranes of plants and the woody structure of trees are composed in large part of cellulose, a polymeric carbohydrate. We will look at the structures of a variety of different carbohydrates in Section 23.3. Another class of natural polymers are the proteins. Section 23.4 deals with these polymeric materials that make up our tissues, bone, blood, and even hair. ... 

Discussion. Hydroxyl groups present in carbohydrates can be readily acetylated by acetic (ethanoic) anhydride in ethyl acetate containing some perchloric acid. This reaction can be used as a basis for determining the number of hydroxyl groups in the carbohydrate molecule by carrying out the reaction with excess acetic anhydride followed by titration of the excess using sodium hydroxide in methyl cellosolve. 

The above classification and the following description of some of the properties of the carbohydrate constituents of these substances are not exhaustive but are intended primarily to focus attention on them and to illustrate the nature of the problems awaiting study. It is rather remarkable that comparatively few investigations have yet been carried out on their protein constituents, but on attempting structural studies it must be realized that one encounters all the difficulties inherent in protein chemistry with the added complication of the presence of complex carbohydrate molecules. 

The detachment of the glycopeptide from the resin and deprotection of the amino acid side chains as well as the removal of the acid-labile carbohydrate protecting groups were simultaneously carried out using TFA/H20/thioanisole/ethanedithiol (87.5 5 5 2.5). This treatment proceeded without affecting the glycosidic bonds and furnished the target molecule 38. 

HIV is a typical member of the retrovirus family, in that it is an enveloped virus that carries RNA as its genetic information. The structure of HIV (Fig. 2) has been determined by electron microscopy. The viral membrane is acquired from the infected cell as the virus buds through the cell membrane. Inserted into the viral membrane are protein molecules coupled to carbohydrates (glycoproteins) which are essential for viral infectivity and probably also play a role in the... 

The pathway from simple molecules to the peptidoglycan of the bacterial cell wall is lengthy and complex. Many of the details are well known but need not concern us here. Suffice it to say that long carbohydrate chains are synthesized, subsequently decorated with shorter amino acid chains, and these are finally cross-linked to provide a strong strnctnre. It is this final cross-linking step that is inhibited by the p-lactam antibiotics. The consequence is that cell wall biosynthesis cannot be completed and cell death ensnes. Again, the mammalian host carries out no similar reactions so that similar consequences do not ensne for the host orgaiusm. 

Macromolecules of biological origin perform various functions in the body. For example, proteins which perform the role of biological catalysts in the body are called enzymes, those which are crucial to communication system in the body are called receptors. Carrier proteins carry polar molecules across the cell membrane. Nucleic acids have coded genetic information for the cell. Lipids and carbohydrates are structural parts of the cell membrane. We shall explain the drug-target interaction with the examples of enzymes and receptors. 

Nucleic acids, proteins, some carbohydrates, and hormones are informational molecules. They carry directions for the control of biological processes. With the exception of hormones, these are macromolecules. In all these interactions, secondary forces such as hydrogen bonding and van der Waals forces, ionic bonds, and hydrophobic or hydrophilic characteristics play critical roles. Molecular recognition is the term used to describe the ability of molecules to recognize and interact bond—specifically with other molecules. This molecular recognition is based on a combination of the interactions just cited and on structure. 

Molecular mechanics calculations have been carried out on a wide range of chemical compounds including hydrocarbons, heteroatomic molecules, steroids, carbohydrates and proteins. Furthermore, a variety of information has been obtained such as heats of formation, rotational barriers, and rates of reaction (18,2,19). The major advantage of this method over other computational methods is that it is reasonably fast to perform in comparison to formal molecular orbital calculations. 

---