Structural studies on the core and lipid A region of a 4‐amino‐L‐arabinose‐lacking Rc‐type mutant of Proteus mirabilis

Abstract
The structure of the 4-amino-L-arabinose-lacking lipopolysaccharide of the Proteus mirabilis Rc-type mutant R4, derived from wild-type O28, was elucidated. The lipopolysaccharide core structure has previously been partially characterized. The linkage between heptose and deoxyoctulosinic acid(dOclA) is now reported, as well as the structure of the lipid A moiety of this mutant strain. Besides the tentative identification of an .alpha.-linked glucosamine disaccharide in the lipid A backbone accompanying the usual .beta.1 .fwdarw. 6-linked glucosamine-disaccharide, the only significant structural variation to previous studies was the lack of substitution of the C-4'' phosphate by 4-amino-L-arabinose. In addition, the substitution at C-8 of one dOclA unit by 4-amino-L-arabinose, previously reported for the R45 mutant of P. mirabilis 1959, is lacking in this R mutant. Also in addition to previous findings, the terminal unit of heptose was found to be substituted at C-7 with phosphorylethanolamine (PEtN) and not only with phosphate, although this substitution is not complete as demonstrated by the relevant signals in 31P-NMR. Additional studies with the wild-type strain P. mirabilis O28 revealed the presence of 4-amino-L-arabinose in both the core and the lipid A regions suggesting that the R4 mutant is defective in the biosynthesis of this amino sugar rather than in its transfer. Otherwise the lipid A regions of the mutant and the wild-type strain show no structural differences. The following formula is proposed for the lipopolysaccharide of 4-amino-L-arabinose-lacking mutant R4/O28 P. mirabilis is presented.