In this work, we examine the electronic and morphological consequences of constitutional isomerism in tri- and tetrablock biohybrid self-assembling molecules that display three regimes of “hydrophobic” composition. A solubilizing hydrophilic peptide head group is attached covalently to a π-conjugated oligothiophene unit that undergoes π–π stacking interactions and introduces a unique quadrupolar character, a hydrophobic peptide segment that encourages hydrogen bonding, and in some cases, a terminal n-alkyl tail that further triggers hydrophobic collapse. We examine constitutional isomerism by swapping the presentation of these disparate hydrophobic blocks in these complex π-conjugated peptides. We found that constitutional isomerism in molecules containing two peptide segments and the π-conjugated oligomer greatly impacts solubility, nanostructure lateral bundling, and the mode of molecular packing that ultimately dictates electronic communication among the π-conjugated units. Furthermore, we found that this effect is not diluted by the addition of an n-alkyl tail that also provides access to a range of nanoarchitectures from spheres to elongated micellar structures, rods, and ribbons.

中文翻译：

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三种疏水性的故事：体构异构对π共轭肽纳米结构演变和电子通信的影响

在这项工作中，我们研究了三嵌段和四嵌段生物杂化自组装分子中构成异构现象的电子学和形态学后果，这些分子表现出三种“疏水”组成。可溶的亲水性肽头基团共价连接至π-共轭的低聚噻吩单元，该单元经历π-π堆积相互作用并引入独特的四极特性，即疏水性肽段，可促进氢键，在某些情况下，其末端为n-烷基尾部进一步引发疏水性塌陷。我们通过交换这些复杂的π-共轭肽中这些不同的疏水性嵌段的存在来研究结构异构现象。我们发现，包含两个肽段和π共轭低聚物的分子中的结构异构现象极大地影响了溶解度，纳米结构横向束缚以及最终决定π共轭单元之间电子通信的分子堆积方式。此外，我们发现通过添加正烷基尾部并不能减轻这种影响，该正烷基尾部还提供了从球形到细长的胶束结构，杆和带的一系列纳米结构的访问。