ABSTRACTThree hull‐less barley genotypes containing starches with variable amylose content (23.8% normal, 4.3% waxy, 41.8% high‐amylose barley) were pearled to 10% and then roller‐milled to produce pearling by‐products (PBP), flour, and fiber‐rich fractions (FRF). PBP were enriched in arabinoxylans, protein, and ash and contained small amounts of starch and β‐glucans. FRF were considerably enriched in β‐glucans and arabinoxylans. The solubility of β‐glucans was higher in PBP than in FRF. The solubility of arabinoxylans was higher in FRF than in PBP. Small amounts of arabinogalactans detected in barley were concentrated in the outer portion of the barley kernel. The content and solubility of nonstarch polysaccharides (NSP) in various milling fractions was also dependent on the type of barley. To obtain more detailed information about the content and molecular structure of NSP, each milling fraction was sequentially extracted with water, alkaline [Ba(OH)2], again with water, and finally with NaOH. These extractions resulted in four sub‐fractions: WE, Ba(OH)2, Ba(OH)2/H2O, and NaOH. β‐Glucans and arabinoxylans exhibited structural heterogeneity derived from differences in their location within the kernel as well as from the genetic origin of barley. The WE arabinoxylans from FRF and flour had a substantially lower degree of branching than those from PBP. The WE arabinoxylans from FRF of high‐amylose and normal barley contained more unsubstituted Xylp residues but fewer doubly‐substituted and singly‐substituted Xylp at O‐2 than their counterparts from PBP. The WE arabinoxylans from FRF of waxy barley had a relatively high content of doubly‐substituted, but very few singly‐substituted Xylp residues. In all three barley genotypes, the ratio of tri‐ to tetrasaccharides in β‐glucans from PBP was higher than from flour and FRF. Substantial differences in the molecular weight of NSP in different milling fractions were also observed.
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