Lipopolysaccharide structure Salmonella

Using PTLC six major fractions of lipids (phospholipids, free sterols, free fatty acids, triacylglycerols, methyl esters, and sterol esters) were separated from the skin lipids of chicken to smdy the penetration responses of Schistosoma cercaria and Austrobilharzia variglandis [79a]. To determine the structure of nontoxic lipids in lipopolysaccharides of Salmonella typhimurium, monophosphoryl lipids were separated from these lipids using PTLC. The separated fractions were used in FAB-MS to determine [3-hydroxymyristic acid, lauric acid, and 3-hydroxymyristic acids [79b]. 

FIGURE 7-32 Bacterial lipopolysaccharides. (a) Schematic diagram of the lipopolysaccharide of the outer membrane of Salmonella ty-phimurium. Kdo is 3-deoxy-o-manno-octulosonic acid, previously called ketodeoxyoctonic acid Hep is L-glycero-D-mannoheptose AbeOAc is abequose (a 3,6-dideoxyhexose) acetylated on one of its hydroxyls. There are six fatty acids in the lipid A portion of the molecule. Different bacterial species have subtly different lipopolysaccharide structures, but they have in common a lipid region (lipid A), a core oligosaccharide, and an "O-specific" chain, which is the prin-... 

Qureshi, N., Mascagni, P., Ribi, E., Takayama, K. Monophosphoryl lipid A obtained from lipopolysaccharides of Salmonella minnesota R595. Purification of the dimethyl derivative by high performance liquid chromatography and complete structural determination. J Biol Chem 260 (1985) 5271-5278. 

Brandenburg, K. Fourier transform infrared spectroscopy characterization of the lamellar and non-lamellar structures of free lipid A and Re lipopolysaccharides from Salmonella Minnesota and Escherichia coli. Biophys J 64 (1993) 1215-1231. 

Garidel, P., Rappolt, M., Schromm, A.B., Howe, J., Lohner, K., Andra, J., Koch, M.H., Brandenburg, K. Divalent cations affect chain mobility and aggregate structure of lipopolysaccharide from Salmonella minnesota reflected in a decrease of its biological activity, Biochim Biophys Acta 1715 (2005) 122-131. 

Olsthoom, M.M., Petersen, B.O., Duus, J., Haverkamp, J., Thomas-Oates, J.E., Bock, K., Holst, O. The structure of the linkage between the O-specific polysaccharide and the core region of the lipopolysaccharide from Salmonella enterica serovar Typhimurium revisited. Eur J Biochem 267 (2000) 2014-2027. 

Unger, F.M., Christian, R., Schulz, G., Waldstten F., Brade, H., Zhringer, U., Rietschel, E.T. Structure of the 3-Deoxyoctulosonate (Kdo-) Region of Lipopolysaccharide from Salmonella minnesota Re 595, Xllth International Carbohydrate Symposium, July 1-7, 1984, Utrecht, The Netherlands Abstract Book (1984) 348. 

Table 13.1 Structures of inner and outer cores of lipopolysaccharides from Salmonella RC, Escherichia coil R3, and E. coli J5 rough mutants8... 

Osborn, M.J. Biosynthesis and structure of the core region of lipopolysaccharide in Salmonella typhimurium. Ann N Y Acad Sci 133 (1966) 375-383. 

Qureshi, N., Takayama, K., Ribi, E. Purification and structural determination of non-toxic lipid-A from lipopolysaccharide of Salmonella typhimurium. J Biol Chem 257 (1982) 11808-11815. Raetz, C.R., Whitfield, C. Lipopolysaccharide endotoxins. Annu Rev Biochem 71 (2002) 635-700. Reed, S.G., Bertholet, S., Coler, R.N., Friede, M. New horizons in adjuvants for vaccine development. Trends Immunol 30 (2009) 23-32. 

An example is the structural elucidation of the lipopolysaccharide from Salmonella typhi. It contains n-glucose, n-galactose, o-mannose, l-... 

Figure 1 Structure of lipopolysaccharide (LPS) from gram-negative Salmonella species.

One of the most impressive findings has been the discovery of lipid intermediates in the biosynthesis of polysaccharides (see Refs. 2 and 465.) At least two structurally different types of these compounds exist the intermediate may be an isoprenoid alcohol ester of the glycosyl pyrophosphate or the analogous derivative of the glycosyl phosphate. Derivatives of the first type are formed by reaction between the sugar nucleotide and the alcohol phosphate, for example, undecaprenyl phosphate (120), which participates in the biosynthesis of Salmonella lipopolysaccharide.466... 

Figure 1 represents the general structure of Salmonella lipopolysaccharides. They contain an external polysaccharide, the O-antigenic chain, and an innermost component, termed lipid A. O-chain and lipid A are linked to each other by an oligosaccharide referred to as the core. O-Specific Chains. As indicated in Figure 1, O chains are in general made up of repeating units of di-, tri-, or higher oligosaccharides. In rare cases the O-chain is a homopolysaccharide. The structure of the O-chain is unique to each bacterial serotype great diversity is encountered in the structures of O-chains.

Galactosamine-induced sensitization to the lethal effects of endotoxin. Proc. Natl. Acad. Sci. USA, 76, 5939-59 13 Inage, M., Chaki, H., Kusumoto, S., and Shiba, T. (1980). Synthesis of Lipopolysaccharide corresponding to fundamental structure of Salmonella-type lipid A. Tetrahedron Lett. 21, 3889-3892 Jans son, P.-E., Lindberg, A. A., Lindberg, B., and Wollin, R. (1981). 

The structure of the lipopolysaccharide region from Salmonella typhimurium provides a good model system and is shown in Figure 1. The LPS is composed of four major components ... 

Of the lipid portions of bacterial macromolecular amphiphi-les, that of lipopolysaccharides is the structurally most complex. For its designation the term lipid A has been coined. More specifically, it was suggested that the lipid, as it is present in intact lipopolysaccharide, should be called lipid A, while the lipid in a separated form should be termed free lipid A (10,11). This nomenclature will be used throughout this paper. In the following, ways and methods will be described which have been used to elucidate the chemical structure of lipid A. The present discussion will deal in more detail with the elucidation of the structure of Salmonella lipid A. Relative to this structure, chemical features of other lipid A s will then be discussed. 

In contrast to the backbone structure which represents a constant portion of lipid A the phosphate groups with their various substituents comprise a variable region of lipid A. This natural, obviously restricted interbacterial diversity of phosphate substituents demonstrates that lipid A s of different origin are distinct in their fine structure. In some cases (like Salmonella and Escherichia) the substitution of the backbone phosphate group is not quantitative. This implies a certain heterogeneity of a given lipopolysaccharide preparation expressed on the level of its lipid A component. 

Seydel, U., Koch, M.H.J., Brandenburg, K. Structural polymorphisms of rough mutant lipopolysaccharides Rd to Ra from Salmonella mirmesota. J Struct Biol 110 (1993) 232-243. 

Heinrichs, D.E., Yethon, J.A., Whitfield, C. Molecular basis for structural diversity in the core regions of the lipopolysaccharides of Escherichia coli and Salmonella enterica. Mol Microbiol 30(2) (1998) 221-232. 

Kaniuk, N.A., Vinogradov, E., Whitfield, C. Investigation of the structural requirements in the lipopolysaccharide core acceptor for ligation of O antigens in the genus Salmonella WaaL ligase is not the sole determinant of acceptor specificity. J Biol Chem 279 (2004) 36470-36480. 

---