The Porod‐Kratky persistence lengths, monomer and polymer radii, and Flory coefficients of a number of β0–1,4 linked hexosans have been compared to each other and to the β‐1,4 linked xylan pentosans of wood by applying the Eizner‐Ptitsyn viscosity equations to intrinsic viscosity and molecular weight analyses from a number of sources. The analyses were made on fractions of cellulose acetate, cellulose nitrate, cellulose caproate, the diethylacetamide derivative of cellulose xanthate, cellulose in cadoxene and in the alkaline ferric tartrate solvent, FeTNa, the galactomannan triacetate of guar, and the glucomannan triacetate of orchid salep tuber. Xylans from spruce and birch, polystyrene, and a branched dextran were also investigated. The persistence lengths of the hexosan derivatives, except the cellulose trinitrate, were remarkably similar and were found to vary from 48 A. for the cellulose caproate determined under theta conditions to 58 A. for the galactomannan triacetate. The persistence lengths of cellulose in the two complexing solvents (72 A.) were nearly identical, confirming that these solvents do not increase the solution dimensions of cellulose greatly. The configuration of the polymers were ranked on a common graph by plotting the log of the polymer radii to contour length ratios vs. the log of the contour length. The investigation shows that the 0–1,4 linked hexosans have a common configuration which is independent of the length of the derivative side group or of single α‐1,6 linked side groups, as in the galactomannan. The configuration of the hexosans is also independent of whether the main chain is composed of glucose or mannose, or a mixture of these sugars. The greater rigidity of the hexosans, in comparison to the pentosans, is explained in the former by hindrance between the C2 group of the one sugar with the C6 group of the next, which is absent in the pentosan that has no C6. Analogy is made to the hindered racemization in substituted biphenyls to explain the great rigidity of cellulose trinitrate, whose persistence length is 132 A.
synopsisPrevious results on the hydrodynamic and configurational properties of fully acetylated guaran in acetonitrile have been reexamined in light of the recent Eizner-Ptitsyn theory for the intrinsic viscosity of the semirigid macromolecule. Numerical values for the hydrodynamic function arising in the theory were calculated by numerical summation on an electronic computer and are tabulated. The theory is found to remove some of the inconsistencies inherent in earlier hydrodynamic theories and leads to reasonable values of the persistence length and monomeric friction coefficient of guaran acetate. The persistence length calculated from viscosity data was 57.8 A., only slightly lower than the limiting value of 64 A. obtained from light scattering. The ratio of monomeric friction coefficient to solvent viscosity was S/qo = 6rr0 = 57.3 A., from which a value of ro = 3.04 A. was obtained for the hydrodynamic radius of the monomer unit.
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