Saiki Erika, Yoshida Misato, Kurahashi Kei, Iwase Hiroki, Shikata Toshiyuki
Cellulose Research Unit, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509, Japan.
Division of Natural Resources and Eco-materials, Graduate School of Agriculture, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo 183-8509, Japan.
ACS Omega. 2022 Aug 9;7(33):28849-28859. doi: 10.1021/acsomega.2c01859. eCollection 2022 Aug 23.
The conformation and structure of methyl cellulose (MC) ether samples dissolved in pure water under dilute conditions were carefully reconsidered based on the results obtained using small-to-wide-angle neutron scattering (S-WANS), static light scattering (SLS), dynamic light scattering (DLS), and viscometric techniques. The examined MC samples possessed an average degree of substitution by methyl groups per glucose unit of ca 1.8 and weight average molar masses ( ), ranging from 23 to 790 kg mol. S-WANS experiments clearly demonstrated that the samples possess highly elongated rigid rodlike local structures in deuterium oxide solutions with weak periodicities of ca 0.4 and 1.0 nm on a length scale, which correspond to the average intermolecular distance between molecular chain portions facing each other in the formed rodlike structure and the repeating length of the monomeric cellobiose unit of molecular chains, respectively. Ratios of the particle length () to the radius of gyration ( ) determined by SLS techniques approximately showed the relationship = holding in rigid rods over the entire range examined in this study. However, the folding number, defined as the ratio of the average molecular contour length () to , remained at the value of ∼ 2, representing an elongated one-folded hairpin structure, until ∼ 300 kg mol and increased substantially up to ca 4.9 at the highest of 790 kg mol. The observed increase in the value corresponded well with an increase in the diameter of the formed rod with increasing observed in the S-WANS data. The dependencies of the translational diffusion coefficient determined via DLS measurements and that of the intrinsic viscosity detected via viscometric techniques also distinctly demonstrated that particles formed by the MC samples dissolved in aqueous solution behave as elongated rigid rods irrespective of .
基于小角到广角中子散射(S-WANS)、静态光散射(SLS)、动态光散射(DLS)和粘度测定技术所获得的结果,对在稀溶液条件下溶解于纯水中的甲基纤维素(MC)醚样品的构象和结构进行了仔细的重新考量。所研究的MC样品每个葡萄糖单元的甲基平均取代度约为1.8,重均摩尔质量( )范围为23至790 kg/mol。S-WANS实验清楚地表明,这些样品在氧化氘溶液中具有高度拉长的刚性棒状局部结构,在长度尺度上具有约0.4和1.0 nm的弱周期性,这分别对应于在形成的棒状结构中相互面对的分子链部分之间的平均分子间距离以及分子链的单糖纤维二糖单元的重复长度。通过SLS技术测定的粒子长度( )与回转半径( )的比值在本研究考察的整个 范围内大致呈现出刚性棒中 = 的关系。然而,定义为平均分子轮廓长度( )与 的比值的折叠数在 约为300 kg/mol之前保持在约2的值,代表一种拉长的单折叠发夹结构,而在最高 为790 kg/mol时大幅增加至约4.9。观察到的 值的增加与S-WANS数据中随着 增加所观察到的形成的棒的直径增加很好地对应。通过DLS测量确定的平移扩散系数以及通过粘度测定技术检测到的特性粘度的 依赖性也清楚地表明,溶解在水溶液中的MC样品形成的粒子表现为拉长的刚性棒,与 无关。