On mild acid degradation of Pseudomonas aeruginosa 0 : 3(a),c, 0 : 3a,d,e and 0 : 3(a),d,f lipopolysaccharides 0-specific polysaccharides were isolated. The trisaccharide repeating units of 0 : 3(a),c and 0 : 3a,d,e polysaccharides contained 2-acetamido-2,6-dideoxy-~-galactose and 2,3-(1-acetyl-2-methyl-2-imidazolino-5,4)-2,3-dideoxy-D-mannuronic acid, which were identified previously as the constituents of P. aeruginosa 0 : 3 a,b and 0 : 3a,d 0-specific polysaccharides, as well as 2,3-diacetamido-2,3-dideoxy-~-guluronic acid, which has never before been found in nature. The last monosaccharide was identified without being isolated in the free state, by means of 13C nuclear magnetic resonance spectroscopy.The structures of 0 : 3(a),c and 0 : 3a,d,e polysaccharides were established by selective hydrogen fluoride solvolysis followed by modification of the trisaccharides obtained and analysis of the I3C nuclear magnetic resonance spectra at each modification stage. The polysaccharides possessed similar structures of repeating units differing from each other in the anomeric configuration of the N-acetylfucosamine residue only : +4)~ManImU-(81 -+ 4)~Gul(NAc),U(al -P 3)~FucNAc(@l-and +4)oManImU(fll + 4)~Gul(NAc),U(al4 3)~FucNAc(al-,whereThe same components were detected in the 0: 3(a),d,f polysaccharide but not in the same stoichiometric ratio; this polysaccharide possessed no regular structure.The immunochemical study of lipopolysaccharides of all five P. aeruginosa 0 : 3 serotypes showed a definite interrelation between their serological properties and structures of the corresponding 0-specific polysaccharides.In the course of systematic chemical and immunochemical studies of Pseudomonas aeruginosa lipopolysaccharides we focused our attention on the most heterogeneous serogroup 0 : 3, which includes, according to Lanyi's classification Recently we have shown that four of the five 0 : 3 serotypes possessed similar polysaccharide chains of lipopolysaccharides [4]. The chains are composed of repeating trisaccharide units containing 2-acetamido-2,6-dideoxy-~-galactose and two acidic aminosugars, namely, 2,3-( 1 -acetyl-2-methyl-2-imidazolino-5,4)-2,3-dideoxy-~-mannuronic acid and 2,3-diacetamido-2,3-dideoxyuronic acid. The complete structures were established for the repeating units of 0 : 3a,b and 0 : 3a,d polysaccharides containing 2,3-diacetamido-2,3-dideoxy-~-mannuronic acid as the third component [5].Abbreviations. DFUCNAC, 2-acetamido-2,6-dideoxy-~-galactose; DMan(NAc)ZU, 2,3-diacetamido-2,3-dideoxy-~-mannuronic acid ; ~G u l -(NAc)2U, 2,3-diacetamido-2,3-dideoxy-~-guluronic acid; DManImU, 2,3-(l-acetyl-2-methyl-2-~midazolino-5,4)-2,3-dideoxy-~-mannuron~c acid.The present article gives an account of the evidence on the chemical structures of the repeating units of 0-specific polysaccharides P. aeruginosa 0 : 3(a),c and 0 : 3a,d,e containing 2,3-diacetamido-2,3-dideoxy-~-guluronic acid, and characterization of the irregular polysaccharide 0 : 3(a),d,f. In addition, the results of serological studies covering all th...