Influence of the glycosidic linkage on the solution conformation of glucans

In order to gain a better understanding of the influence of β-glycosidic linkages on the solution conformation of glucans, a comparison was made between the carboxymethyl derivatives of cellulose (CMC, 100% 1,4-), barley glucan (CMGG, 30 : 70 1,3 : 1,4-) and curdlan (CMCd, 100% 1,3-glycosidic), each with an average degree of substitution of DS = 1.0–1.5 and molar masses of 144 000–720 000 g mol^–1. For this purpose curdlan and barley glucan were chemically modified, whereas carboxymethylcellulose was available as a commercial sample. Via congo red analysis it was proved for the microbial β-1,3-glucans curdlan (unsubstituted) and scleroglucan (one β-1,6-linked glucose side group on every third monomer unit) that substituents in glucan derivatives weaken an existing helical structure but that reduction of the molar mass with ultrasound has no influence on the helices. The molecular parameters M_w, M_n, R_G, L_P and η] were determined by means of SEC/MALLS measurements and viscometry and the chain mobility was quantified using the ¹³C NMR relaxation times, T₁, of the different polymers. From this it was possible to derive η]-M_w relationships. For all samples, the exponent ν of the R_G-M_W relationship lay in the range 0.54–0.59, from which it is possible to deduce a coiled solution structure. However, β-1,3-glucans occupy 25% less volume than β-1,4-glucans and exhibit less chain mobility. Hence β-1,4-glucans should be considerably more viscous than β-1,3-glucans, as was indeed demonstrated by rheological flow curves of 6% solutions of the carboxymethylglucan derivatives. The zero-shear viscosity, η₀, decreases by 3 decades in the order of CMC > CMGG > CMCd.