Sugar-Based Polyamides: Self-Organization in Strong Polar Organic Solvents.
Sugar-Based Polyamides: Self-Organization in Strong Polar Organic Solvents.
复制标题
糖基聚酰胺：在强极性有机溶剂中自组织。
DOI：
10.1021/acs.biomac.5b00977
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发表时间：
2015
影响因子：
6.2
通讯作者：
I. Negulescu
中科院分区：
文献类型：
--
作者：
Cornelia Rosu;P. Russo;W. Daly;R. Cueto;J. Pople;R. Laine;I. Negulescu
观察到类似于螺旋的周期性图案自发地形成后，无辅助冷却的d-葡糖二酸和d-半乳糖二酸为基础的聚酰胺溶液中的N-甲基-N-吗啉氧化物（NMMO）一水合物。在基于d-半乳糖醛酸的聚酰胺/离子液体（IL）溶液中进行了类似的观察。通过光学、偏振光和共聚焦显微镜测定来研究形态以揭示图案细节。差示扫描量热法用于监测溶液的热行为。小角和广角X射线散射数据反映了自组织模式的复杂性和异质性。发现浓度和温度等因素会影响螺旋尺寸和几何形状。环之间的距离遵循一阶指数衰减作为聚合物浓度的函数。傅立叶变换红外显微光谱分析的螺旋指出，从聚合物主链的葡萄糖单元的溶剂和侧羟基之间的氢键。在NMMO一水合物中的缩酮保护的d-半乳糖醛酸聚酰胺的自组织成螺旋的测试证实了单糖的侧链游离羟基对这些图案的形成的重要性。在NMMO一水合物溶液中以高浓度对基于d-半乳糖苷的聚酰胺进行的流变学揭示了通过纺丝将这些材料加工成纤维所需的最佳条件。这些糖基聚酰胺的自组织模拟了某些生物材料。
Periodic patterns resembling spirals were observed to form spontaneously upon unassisted cooling of d-glucaric acid- and d-galactaric acid-based polyamide solutions in N-methyl-N-morpholine oxide (NMMO) monohydrate. Similar observations were made in d-galactaric acid-based polyamide/ionic liquid (IL) solutions. The morphologies were investigated by optical, polarized light and confocal microscopy assays to reveal pattern details. Differential scanning calorimetry was used to monitor solution thermal behavior. Small- and wide-angle X-ray scattering data reflected the complex and heterogeneous nature of the self-organized patterns. Factors such as concentration and temperature were found to influence spiral dimensions and geometry. The distance between rings followed a first-order exponential decay as a function of polymer concentration. Fourier-Transform Infrared Microspectroscopy analysis of spirals pointed to H-bonding between the solvent and the pendant hydroxyl groups of the glucose units from the polymer backbone. Tests on self-organization into spirals of ketal-protected d-galactaric acid polyamides in NMMO monohydrate confirmed the importance of the monosaccharide's pendant free hydroxyl groups on the formation of these patterns. Rheology performed on d-galactaric-based polyamides at high concentration in NMMO monohydrate solution revealed the optimum conditions necessary to process these materials as fibers by spinning. The self-organization of these sugar-based polyamides mimics certain biological materials.