In order to understand the relationship between chemical structure and physical properties of cereal beta-glucans, the beta-glucans with identical M-w (98.4-99.2 kDa) and R-g (21.1-22.0 nm) were isolated from chal and gwangan barley, and ohl oat, and their linkage structure, flow behavior, and thermal properties were investigated. Previously, we established a purification method of 3-O-cellobiosyl-glucose (DP3) and 3-O-cellotriosyl-glucose (DP4) (Yoo, Lee, Chang, Lee, & Yoo, 2007) and applied these authentic standards to quantify the ratio of beta-(1,4)/(1,3) linkages in cereal beta-glucans. beta-Glucans isolated from two barley cultivars had greater proportion of DP3 than did the oat, and within barley cultivars chal barley beta-glucan had significantly larger amount of DP3 over gwangan cultivar. Thus, chal barley beta-glucan had the greatest molar ratio (2.53) of DP3 to DP4, and ohl oat had the lowest (1.51). While all the beta-glucan solutions showed strong shear thinning behavior, ohl oat P-glucan with higher proportion of DP4 exhibited the highest viscosity among the beta-glucan samples. After 3 freeze-thaw cycles of 3% (w/v) beta-glucan samples, chal barley beta-glucan had lower onset (T-o) and peak (T-p) temperatures (28.3 and 36.7 degrees C, respectively) than those of gwangan barley (33.6 and 39.9 degrees C) and ohl oat (37.9 and 46.9 degrees C) did, and the heat scan profiles were thermoreversible. The T-o and T-p of inter-chain associations decreased as the DP3:DP4 ratio of the beta-glucan increased. From this study, it was suggested that cellotetraosyl units and longer beta-(1,4)linked segments would be a major contributor for improving solution viscosity and gel formation of cereal beta-glucans. (C) 2012 Elsevier Ltd. All rights reserved.