Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, USA.
J Am Chem Soc. 2010 Nov 17;132(45):16112-9. doi: 10.1021/ja106340f. Epub 2010 Oct 22.
The aqueous self-assembly of a sequence-specific bioinspired peptoid diblock copolymer into monodisperse superhelices is demonstrated to be the result of a hierarchical process, strongly dependent on the charging level of the molecule. The partially charged amphiphilic diblock copolypeptoid 30-mer, N-(2-phenethyl)glycine-N-(2-carboxyethyl)glycine, forms superhelices in high yields, with diameters of 624 ± 69 nm and lengths ranging from 2 to 20 μm. Chemical analogs coupled with X-ray scattering and crystallography of a model compound have been used to develop a hierarchical model of self-assembly. Lamellar stacks roll up to form a supramolecular double helical structure with the internal ordering of the stacks being mediated by crystalline aromatic side chain-side chain interactions within the hydrophobic block. The role of electrostatic and hydrogen bonding interactions in the hydrophilic block is also investigated and found to be important in the self-assembly process.
序列特异性仿生肽两亲嵌段共聚物在水溶液中自组装为单分散超螺旋结构,证明是一个分层次过程的结果,强烈依赖于分子的荷电水平。部分带电的两亲性肽两亲嵌段共聚物 30 -mer,N-(2-苯乙基)甘氨酸-N-(2-羧乙基)甘氨酸,以高产率形成超螺旋,直径为 624±69nm,长度从 2 到 20μm 不等。化学模拟物与模型化合物的 X 射线散射和晶体学的结合被用来开发自组装的层次模型。层状堆积物卷起形成超分子双链结构,内部堆积的有序性由疏水嵌段中结晶芳香侧链-侧链相互作用介导。亲水嵌段中静电和氢键相互作用的作用也被研究,并发现它们在自组装过程中很重要。