Block co-oligomers have gained increasing attention for fine and precise control of self-assembled nanostructures. Recently, we demonstrated that cellodextrin phosphorylase (CDP) catalyzed the propagation of cello-oligosaccharides from monofunctional oligo(ethylene glycol) (OEG) primers, namely, glycosyl acceptors, for the synthesis of diblock co-oligomers and their crystalline assemblies. Therefore, the application of appropriate oligomeric primers to the CDP-catalyzed synthetic system has the potential to further extend the synthesis of unique cellulosic block co-oligomers. In this study, we investigated the CDP-catalyzed propagation of cello-oligosaccharide chains from bifunctional oligomeric primers. Two types of primers (Glc-BiP and Cello-BiP) were synthesized by introducing d-glucose and cellobiose into both ends of OEG with five repeating units via a Huisgen cycloaddition reaction. It was plausible from systematic characterizations that cello-oligosaccharide chains were propagated from one end of Glc-BiP, whereas the chains were propagated from both ends of Cello-BiP. The findings will be significant to gain fundamental knowledge on the CDP-catalyzed synthesis of various cellulosic block co-oligomers and have the potential to produce novel cellulosic nano- to macroscale materials.

嵌段共聚低聚物由于自组装纳米结构的精细和精确控制而受到越来越多的关注。最近，我们证明纤维糊精磷酸化酶 (CDP) 催化纤维寡糖从单功能寡（乙二醇）（OEG）引物（即糖基受体）增殖，用于合成双嵌段共寡聚体及其结晶组装体。因此，将合适的寡聚引物应用于 CDP 催化的合成系统有可能进一步扩展独特的纤维素嵌段共寡聚体的合成。在这项研究中，我们研究了来自双功能寡聚引物的纤维寡糖链的 CDP 催化传播。通过引入d合成了两种类型的引物（Glc-BiP 和 Cello-BiP）-葡萄糖和纤维二糖通过 Huisgen 环加成反应进入具有五个重复单元的 OEG 的两端。从系统表征来看，纤维寡糖链是从 Glc-BiP 的一端传播的，而链是从 Cello-BiP 的两端传播的，这是有道理的。这些发现对于获得 CDP 催化合成各种纤维素嵌段共聚低聚物的基础知识具有重要意义，并有可能生产新型纤维素纳米到宏观材料。