The name carrageenin (1, 2) n7as first applied to the polysaccharide which can be extracted with hot water from certain red seaweeds, where it occurs as an intercellular constituent. The main source ol carrageenin is the alga Chondrzis crispus, but similar material has been isolated from C. ocellat~is (3) and Gigartina stellata (4).In 1953, Smith and Coolc (5) reported the separation of two major discrete polysaccharide components from carrageenin. This was achieved by fractionation with potassiu~n chloride which, when added to a dilute solution of carrageenin, causes one component to gel. This gel fraction, which constitutes approximately forty per cent of unfractionated carrageenin, has been designated K-carrageenin. I t has been shown (6) to be cornposed of residues of 3,6-anhydro-D-galactose and sulphated D-galactose in approximately equimolar amounts. The other major polysaccharide co~nponent is insensitive to potassium ion, and can be recovered fro111 the mother liquor by ethanol precipitation (5,7,8) ; this fraction has been ter~necl A-carrageenin. In addition to K-and A-carrageenin, minor amounts of other polysaccharides occur in carrageenin preparations as indicated by the detection of s~nall amounts of L-galactose, glucose, ancl xylose in hydrolyzates (8).Although the structure of A-carrageenin has not been extensively investigated, results from X-ray analysis (9) and periodate oxiclation (8) of the polysaccharide, together \vith data from methylation of unfractionated carrageenin (4, 10, ll., 12), suggest that it consists essentially of a sulphated galactan in which D-galactose residues are linked glycosidicall~~ through positions 1 and 3, ancl bear sulphate half-ester groups on position 4. The purpose of the present work was to obtain clefinitive evidence for the fundamental structural linkage in A-carrageenin.The polysaccharide was isolatecl from commercial carrageenin by fractionation with potassiu~n chloride (5,7,8). Analytical figures for three separate preparations are show11in Table I. Acid hyclrolyzates of the preparations were shown chromatographically t o contain galactose ancl a trace of xylose only. Since sulphatecl polysaccharides do not lend the~nselves easily to examination by exhaustive methylation, a ~nethoct involving partial degradation was indicated. This was accomplished most satisEactorily by acetolysis, in which degradation of the polymer was accompanied by rapid desulphation to give a good yield of neutral oligosaccharide acetates.A-Carrageenin was treated with a mixture of acetic anhydride and acetic acid containing sulphuric acid (6%) a t 25' C for 71 hours, and the sulphate-free product was deacetylated