Glycolipids sequences

In this chapter we will examine how cells and enzymes are used in the transformation of lipids. The lipids are, of course, a very diverse and complex series of molecular entities including fatty acids, triglycerides, phospholipids, glycolipids, aliphatic alcohols, waxes, terpenes and steroids. It is usual to teach about these molecules, in a biochemical context, in more or less the order given above, since this represents a logical sequence leading from simple molecules to the more complex. Here, however, we have adopted a different strategy. 

Oligosaccharide and polysaccharide structures occur not only in free form but often as parts of glycopeptides or glycoproteins [11] or of glycolipids [21]. It can be cumbersome to designate their structures by using the recommendations of 2-Carb-37. The use of three-letter symbols for monosaccharide residues is therefore recommended. With appropriate locants and anomeric descriptors, long sequences can thus be adequately described in abbreviated form. 

Fig. 15.—Sequence of One of the Oligosaccharides Obtained from the Trehalose-containing Glycolipids of Mycobacteria kansasii. [Cleavage positions in the positive-ion mode (Pathway C, Section IV,2) are shown above the sequence. Cleavage positions in the negative-ion mode (Pathway B, Section IV,2) are shown below the sequence.

Specific degradation of the carbohydrate chain has been extensively discussed in a few articles (for reviews, see Refs. 5, 7, 8,35, and 58). In the following discussion, we shall briefly present some applications that have been valuable in the sequence study of glycoprotein and glycolipid saccharides. 

Lipid transfer peptides and proteins occur in eukaryotic and prokaryotic cells. In vitro they possess the ability to transfer phospholipids between lipid membranes. Plant lipid transfer peptides are unspecific in their substrate selectivity. They bind phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol, and glycolipids. Some of these peptides have shown antifungal activity in vitro The sequences of lipid transfer proteins and peptides contain 91-95 amino acids, are basic, and have eight cysteine residues forming four disulfide bonds. They do not contain tryptophan residues. About 40% of the sequence adopts a helical structure with helices linked via disulfide bonds. The tertiary structure comprises four a-helices. The three-dimensional structure of a lipid transfer peptide from H. vulgare in complex with palmitate has been solved by NMR. In this structure the fatty acid is caged in a hydrophobic cavity formed by the helices. 

Most sialylations so far reported have been achieved with soluble transferases, and seldom on a more than 20-/imol scale (see Table IX), with the intention to prepare and describe sequences present in glycoproteins and glycolipids. Trisaccharide < -D-Neu5Ac-(2— 3)-/J-D-Galp-(l — 3)-/J-d-... 

Figure 1. A typical sequence of sample preparation manipulations for a procedure of Soxhlet extraction followed by preparative column chromatography for a solid sample - e.g., glycolipids out of wheat flour. Note that equivalently complex processes are encountered with "simple liquid-solid or liquid-liquid extractions followed by a series of back extractions - e.g., pesticides from fish tissue. (Reproduced with permission by Hewlett-Packard, HP Publication (43)5091-2102E, (1991), in preparation.)...

Therefore, the evidence obtained from the two derivatives is conclusive concerning the sequence of the 12-sugar glycolipid. 

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