The State Key Laboratory of Molecular Engineering of Polymers and Department of Macromolecular Science, Fudan University , Shanghai 200433, China.
J Am Chem Soc. 2016 Sep 28;138(38):12387-94. doi: 10.1021/jacs.6b05044. Epub 2016 Aug 3.
Mimicking the diverse glyco-conjugate structures in nature is always the dream of scientists. Right now, hierarchical self-assembled structures of natural conjugates of peptides and sugars could not easily be achieved via linear glycopolypeptide with monosaccharides as attachments. In this work, by using a series of well-designed alternating amphiphilic glycopolypeptide brushes (AAGBs) with pendants of glycodendrons and short peptides, various self-assembled morphologies were achieved, including nanowires, nanoribbon, and compound micelles mainly depending on the number ratio of the sugar units to the amino acids species (S/F). Among these morphologies, nanowire attracted our great attention. TEM studies demonstrated that it is formed via a hierarchical self-assembly, i.e., a series of successive processes, including micellization, micelles alignment forming nanofilament, branching of the nanofilaments by micelles, and finally nanowire formation. As far as we know, such hierarchical self-assembly process with high complexity has not been observed in literature for glycopolypeptides even polypeptides, which will deepen our understanding on self-assembly mechanism of natural glyco-conjugates and expand the library of biomimetic materials.
模拟自然界中多样化的糖缀合物结构一直是科学家们的梦想。目前，通过线性糖肽作为附着的糖基化多肽，很难实现具有层次自组装结构的天然肽和糖的共轭物。在这项工作中，通过使用一系列设计良好的交替两亲性糖基化多肽刷（AAGB），其侧链带有糖树突和短肽，实现了各种自组装形态，包括纳米线、纳米带和主要取决于糖单元与氨基酸种类（S/F）数比的复合胶束。在这些形态中，纳米线引起了我们的极大关注。TEM 研究表明，它是通过级联自组装形成的，即包括胶束化、胶束排列形成纳米纤维、纳米纤维的分支以及最终纳米线的形成等一系列连续过程。据我们所知，即使对于多肽而言，这种具有高复杂性的级联自组装过程在糖基化多肽文献中尚未观察到，这将加深我们对天然糖缀合物自组装机制的理解，并扩展仿生材料库。
