McCullagh C M, Soby L M, Jamieson A M, Blackwell J
Department of Macromolecular Science, Case Western Reserve University, Cleveland, Ohio 44106.
Biopolymers. 1992 Dec;32(12):1665-74. doi: 10.1002/bip.360321208.
Solution properties of fractionated ovine submaxillary mucin (OSM) and asialo OSM (aOSM) in aqueous guanidine hydrochloride have been investigated using light scattering and rheological methods. For the first time we present viscometric evidence in both dilute and concentrated solution that the molecular structure of OSM is that of a wormlike chain. The intrinsic viscosity shows molecular weight dependence consistent with the linear extended chain conformation observed by light scattering measurements. The viscoelastic behavior of the OSM fractions in aqueous guanidine hydrochloride was further examined above the overlap concentration as a function of molecular weight and temperature. Under these solvent conditions in which the role of nonbonding intermolecular interactions is minimized, OSM shows predominantly fluid like behavior. However, high molecular weight OSM shows evidence of the existence of an entanglement network at high concentration. The frequency-dependent shear storage and loss moduli at all concentrations and molecular weights can be scaled to yield a master curve by incorporating typical viscoelastic shift parameters. The entanglement molecular weight and concentration are consistent with literature data for extended, semiflexible wormlike chains. The behavior of aOSM is similar to that of intact OSM at comparable degrees of coil overlap, indicating that the terminal sialic acid residue on the carbohydrate side chain has no effect on the rheology of concentrated OSM solutions beyond that due to an increase in the hydrodynamic volume.
采用光散射和流变学方法研究了分级分离的绵羊颌下粘蛋白(OSM)和去唾液酸OSM(aOSM)在盐酸胍水溶液中的溶液性质。我们首次在稀溶液和浓溶液中提供了粘度测定证据,证明OSM的分子结构为蠕虫状链。特性粘度显示出与光散射测量观察到的线性伸展链构象一致的分子量依赖性。在重叠浓度以上,进一步研究了盐酸胍水溶液中OSM级分的粘弹性行为与分子量和温度的关系。在这些使非键合分子间相互作用的作用最小化的溶剂条件下,OSM主要表现出类似流体的行为。然而,高分子量的OSM显示出在高浓度下存在缠结网络的证据。通过纳入典型的粘弹性位移参数,所有浓度和分子量下的频率依赖性剪切储能模量和损耗模量可以进行标度以得到一条主曲线。缠结分子量和浓度与关于伸展的、半柔性蠕虫状链的文献数据一致。在可比的线团重叠程度下,aOSM的行为与完整的OSM相似,这表明碳水化合物侧链上的末端唾液酸残基对浓OSM溶液的流变学没有影响,超出了由于流体力学体积增加所产生的影响。