DOI: 10.1111/j.1432-1033.1982.tb05924.x. The Chemical Structure of Lipid A

10.1111/j.1432-1033.1982.tb05924.x

Crossref journal-article

Wiley

European Journal of Biochemistry (311)

Abstract

In Salmonella minnesota lipopolysaccharide the lipid A backbone, a substituted diphosphorylated β1,6‐linked D‐glucosamine disaccharide molecule, carries approximately seven residues of fatty acids: one each of dodecanoic, hexadecanoic, D‐3‐hydroxytetradecanoic and D‐3‐O‐(tetradecanoyl)‐tetradecanoic acid in ester linkage and two of D‐3‐hydroxytetradecanoic acid in amide linkage. In the present study it is shown that treatment of the lipopoly‐ saccharide with alkali at elevated temperature leads, through a β‐elimination reaction, to the generation of amice‐ bound δ2‐tetradecenoic acid. This suggested that the 3‐hydroxyl group of amide‐bound hydroxy fatty acids carried a substituent. To elucidate the nature of the substituent, free Salmonella lipid A was methylated with methyl iodine in the presence of silver salts followed by mild acid hydrolysis, a procedure which is known to cleave amide (and not ester) bonds selectively. In the hydrolysate, by means of combined gas‐liquid chromatography/mass spectrometry the methyl esters of 3‐O‐(dodecanoyl)‐tetradecanoic and 3‐O‐(hexadecanoyl)‐tetradecanoic acid were identified. This shows that in lipid A amide‐linked 3‐hydroxytetradecanoic acid residues are 3–0‐acylated by dodecanoic and hexadecanoic acid, respectively.Quantitative analyses suggest that the Salmonella lipid A backbone is substituted by four D‐3‐hydroxytetra‐ decanoyl residues, two being present as esters and two as amides. The nonhydroxylated fatty acids are not bound directly to the backbone. Rather, they are attached to hydroxyl groups of 3‐hydroxytet radecanoyl residues: specifically, tetradecanoic acid substitutes ester‐bound and dodecanoic and hexadecanoic acid amide‐bound 3‐hydroxytetradecanoic acid.

Bibliography

WOLLENWEBER, H., BROADY, K. W., LUDERITZ, O., & RIETSCHEL, E. T. (1982). The Chemical Structure of Lipid A. European Journal of Biochemistry, 124(1), 191â198. Portico.

Authors 4

Horst‐Werner WOLLENWEBER (first)
Kevin W. BROADY (additional)
Otto LUDERITZ (additional)
Ernst Th RIETSCHEL (additional)

References 31 Referenced 93

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Dates

Type	When
Created	20 years, 5 months ago (March 3, 2005, 4:57 p.m.)
Deposited	1 year, 9 months ago (Nov. 23, 2023, 12:20 p.m.)
Indexed	1 year, 9 months ago (Nov. 23, 2023, 5:22 p.m.)
Issued	43 years, 4 months ago (May 1, 1982)
Published	43 years, 4 months ago (May 1, 1982)
Published Online	20 years, 5 months ago (March 3, 2005)
Published Print	43 years, 4 months ago (May 1, 1982)

Funders 0

None

BibTeX

@article{WOLLENWEBER_1982, title={The Chemical Structure of Lipid A: Demonstration of Amide‐Linked 3‐Acyloxyacyl Residues in Salmonella minnesota Re Lipopolysaccharide}, volume={124}, ISSN={1432-1033}, url={http://dx.doi.org/10.1111/j.1432-1033.1982.tb05924.x}, DOI={10.1111/j.1432-1033.1982.tb05924.x}, number={1}, journal={European Journal of Biochemistry}, publisher={Wiley}, author={WOLLENWEBER, Horst‐Werner and BROADY, Kevin W. and LUDERITZ, Otto and RIETSCHEL, Ernst Th}, year={1982}, month=may, pages={191–198} }

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