Freddi G, Pessina G, Tsukada M
Stazione Sperimentale per la Seta, Milano, Italy.
Int J Biol Macromol. 1999 Mar-Apr;24(2-3):251-63. doi: 10.1016/s0141-8130(98)00087-7.
Bombyx mori silk fibers were dissolved in N-methyl morpholine N-oxide (MMNO), an organic cyclic amine oxide used for the solvent spinning of regenerated cellulosic fibers. The commercial MMNO monohydrate used in this study as a solvent for silk is a hygroscopic compound crystalline at room temperature, which becomes an active solvent after melting at 76 degrees C. The degree of hydration of MMNO was checked by DSC measurements. The solvation power of MMNO towards silk fibroin drastically decreased at a water content > or = 20-21% w/w. Dissolution of silk required both thermal and mechanical energy. The optimum temperature was 100 degrees C. At lower temperatures dissolution proceeded very slowly. At higher temperatures, rapid depolymerization of silk fibroin occurred. The value of the Flory-Huggins interaction parameter chi for the MMNO-H2O-silk fibroin system was -8.5, suggesting that dissolution is a thermodynamically favored process. The extent of degradation of silk fibroin was assessed by measuring the intrinsic viscosity and determining the amino acid composition of silk after regeneration with an aqueous methanol solution, which was effective in removing the solvent and coagulating silk. Regenerated silk fibroin membranes were characterized by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. The prevailing molecular conformation of silk fibroin chains was the beta-sheet structure, as shown by the intense amide I-III bands at 1704, 1627, 1515, 1260, and 1230 cm(-1). The value of the I1260/I1230 intensity ratio (crystallinity index) was 0.68, comparable to that of the fibers. The DSC thermogram was characteristic of a silk fibroin material with unoriented beta-sheet crystalline structure, with an intense decomposition endotherm at 294 degrees C. The SEM examination of fractured surfaces showed the presence of a dense microstructure with a very fine texture formed by densely packed roundish particles of about 100-200 nm diameter.
家蚕丝纤维溶解于N-甲基吗啉-N-氧化物(MMNO)中,MMNO是一种用于再生纤维素纤维溶剂纺丝的有机环状氧化胺。本研究中用作丝绸溶剂的市售一水合MMNO是一种在室温下结晶的吸湿性化合物,在76℃熔化后成为活性溶剂。通过差示扫描量热法(DSC)测量来检查MMNO的水合程度。当水含量≥20 - 21%(w/w)时,MMNO对丝素蛋白的溶剂化能力急剧下降。丝绸的溶解需要热能和机械能。最佳温度为100℃。在较低温度下,溶解过程非常缓慢。在较高温度下,丝素蛋白会迅速解聚。MMNO - H₂O - 丝素蛋白体系的弗洛里 - 哈金斯相互作用参数χ值为 - 8.5,这表明溶解是一个热力学上有利的过程。通过测量特性粘度并在用甲醇水溶液再生后测定丝绸的氨基酸组成来评估丝素蛋白的降解程度,甲醇水溶液可有效去除溶剂并使丝绸凝固。通过红外光谱、差示扫描量热法和扫描电子显微镜对再生丝素蛋白膜进行表征。丝素蛋白链的主要分子构象为β - 折叠结构,如在1704、1627、1515、1260和1230 cm⁻¹处的强酰胺I - III带所示。I1260/I1230强度比(结晶度指数)的值为0.68,与纤维的相当。DSC热谱图是具有未取向β - 折叠晶体结构的丝素蛋白材料的特征,在294℃有强烈的分解吸热峰。对断裂表面的扫描电子显微镜检查显示存在致密的微观结构,其纹理非常精细,由直径约100 - 200 nm的紧密堆积的圆形颗粒形成。