Cryogelation of cereal β-glucans: structure and molecular size effects

The effects of molecular size and fine structure of mixed-linkage cereal (1→3), (1→4) β- -glucans (β-glucans) on their cryogelation behavior were investigated. Values of apparent molecular weight (M_w) for oat β-glucans ranged between 65 and 200×10³, whereas the respective values for both barley and wheat β-glucan preparations were about 200×10³. The fine structure of cereal β-glucans, as assessed by high-performance anion-exchange chromatography of the cellulosic oligomers released by the action of lichenase, revealed differences in the relative amounts of 3-O-β-cellobiosyl- -glucose (DP3) and 3-O-β-cellotriosyl- -glucose (DP4) units only among the different genera of cereals; the weight percent of DP3 units estimated as 67.1, 63.3, and 55.3–55.8% for wheat, barley, and oat β-glucans, respectively. Aqueous β-glucan solutions (1–3% w/v) were subjected to 12 freezing (−18 °C for 24 h) and thawing (5 °C for 24 h) cycles. The phenomenological appearance of the gelled materials obtained after this process as well as the yield of cryostructurates were influenced by the initial solution concentration, the number of freeze–thaw cycles, as well as by the molecular features of the β-glucans. Such effects were unraveled by studying the cryogelation process with differential scanning calorimetry (DSC), small strain dynamic rheometry, and large deformation mechanical measurements. For the cereal β-glucan cryogels the storage modulus, G′, increased and the tan δ decreased with decreasing polysaccharide molecular size and with increasing initial solution concentration, number of freeze–thaw cycles, and trisaccharide segments in the polymeric chains. The apparent melting enthalpy values (ΔH) of β-glucan cryostructurates, as determined from the DSC endothermic peaks, increased with decreasing molecular size and with increasing amount of cellotriose units, but they were independent of the number of freeze–thaw cycles. The DSC melting temperature of the gel network was found to increase with the molecular size and amount of DP3 units of β-glucans. Moreover, large deformation mechanical tests (compression mode) revealed an increase in strength of cereal β-glucan cryogels with increasing molecular size and decreasing trisaccharide units in the polysaccharide preparation.