Looking for potential quality indicators, which could be used in early selection of breeding materials, the structural features of cell wall arabinoxylans (AX) from outer layers of the grain (pooled shorts and bran fractions) were studied in two ryes with diverse breadmaking quality. The successive alkaline extraction of water-unextractable material with saturated Ba(OH)(2), followed by water and 1 and 4 M NaOH, resulted in four purified fractions, Ba, BaH, 1Na, and 4Na, respectively, that became water soluble after their isolation. The AX present in these fractions constituted similar to 43, 12, 14, and 4% of their total amount recovered. Moreover, two xylan-enriched fractions, 1Na.P and 4Na.P (arabinose-to-xylose ratios, Ara/Xyl, of 0.07 and 0.19, respectively), were self-precipitated from both NaOH-extractable fractions. Polysaccharides of these fractions, containing mainly xylose, represented similar to 16 and 1% of AX recovered. In the BaH and 1Na, AX coexisted with bet! a-glucans, which predominated in the former protein-free fraction. On the contrary, hemicelluloses in the 1Na fraction were associated with protein as well. Further fractionation of the water-soluble materials by ammonium sulfate revealed that the parent AX populations in the Ba, BaH, and 1Na were composed of 3-4 subfractions with different degrees of substitution (Ara/Xyl of similar to 0.4, 0.8, and 1.1), whereas 4Na was almost totally built of highly substituted AX (Ara/Xyl of 1.1). Despite a comparable proportion of un-, mono-, and disubstituted xylopyranosyl residues in the chain of Ba(OH)(2)-extractable AX isolated from both ryes, the H-1 NMR and Fourier transform infrared demonstrated the marked differences in their spectral profiles, suggesting different substitution patterns of these dominating polysaccharides. The high molecular weight population present in the Ba fraction also differentiated well two ryes with opposite breadmaking quality.