Hasegawa Teruaki, Haraguchi Shuichi, Numata Munenori, Li Chun, Bae Ah-Hyun, Fujisawa Tomohisa, Kaneko Kenji, Sakurai Kazuo, Shinkai Seiji
Graduate School of Engineering, Kyushu University, Hakozaki 6-10-1, Fukuoka 812-8581, Japan.
Org Biomol Chem. 2005 Dec 21;3(24):4321-8. doi: 10.1039/b510646j. Epub 2005 Nov 8.
Schizophyllan interacts with various 1,4-diphenylbutadiyne derivatives to induce their chirally-twisted packing. A series of referential experiments using other polysaccharides (amylose, pullulan, dextran, etc.) and a carbohydrate-appended detergent (dodecyl-beta-d-glucopyranoside) indicates that these 1,4-diphenylbutadiyne derivatives are accommodated within a tubular cavity constructed by a helical superstructure of schizophyllan. In these 1,4-diphenylbutadiyne derivatives, 1,4-bis(p-propionamidophenyl)butadiyne can be easily polymerized through UV-irradiation, in which schizophyllan acts as a one-dimensional mold to produce the corresponding poly(diacetylene)s with fibrous morphologies. Detailed investigations on this unique approach to prepare the nanofibers revealed that it includes two individual processes, that is, 1) UV-mediated polymerization of encapsulated 1,4-bis(p-propionamidophenyl)butadiyne to produce immature nanofibers and 2) their reorganization through hydrophobic interfiber interactions into ordered nanofibers. The other 1,4-diphenylbutadiyne derivatives could not be polymerized through UV-irradiation, indicating that the p-propionamido-functionalities play substantial roles for a suitable packing of the monomer for the polymerization. The other 1,4-diphenylbutadiyne derivatives, however, can be also polymerized through gamma-ray irradiation in the presence of schizophyllan to give the corresponding poly(diacetylene)-nanofibers, emphasizing the wide applicability of the schizophyllan-based strategy for polymerization of various 1,4-diphenylbutadiyne derivatives.
裂褶多糖与各种1,4 - 二苯基丁二炔衍生物相互作用,诱导它们形成手性扭曲堆积。一系列使用其他多糖(直链淀粉、支链淀粉、葡聚糖等)和一种碳水化合物连接的洗涤剂(十二烷基 - β - D - 吡喃葡萄糖苷)的对照实验表明,这些1,4 - 二苯基丁二炔衍生物被容纳在由裂褶多糖的螺旋超结构构建的管状腔内。在这些1,4 - 二苯基丁二炔衍生物中,1,4 - 双(对 - 丙酰胺基苯基)丁二炔可通过紫外线照射轻松聚合,其中裂褶多糖作为一维模板,生成具有纤维形态的相应聚二乙炔。对这种制备纳米纤维的独特方法的详细研究表明,它包括两个独立过程,即:1)紫外线介导的封装1,4 - 双(对 - 丙酰胺基苯基)丁二炔聚合以产生未成熟的纳米纤维,以及2)它们通过疏水纤维间相互作用重组为有序的纳米纤维。其他1,4 - 二苯基丁二炔衍生物不能通过紫外线照射聚合,这表明对 - 丙酰胺基官能团对于单体聚合的合适堆积起着重要作用。然而,其他1,4 - 二苯基丁二炔衍生物也可以在裂褶多糖存在下通过γ射线照射聚合,得到相应的聚二乙炔纳米纤维,这强调了基于裂褶多糖的策略对各种1,4 - 二苯基丁二炔衍生物聚合的广泛适用性。