Self-Assembling Nanofibers from Thiophene–Peptide Diblock Oligomers: A Combined Experimental and Computer Simulations Study

Abstract

We report herein the synthesis of a novel type of hybrid compound that consists of a poly(ethylene oxide) (PEO) functionalized β-sheet peptide sequence covalently linked to an alkylated quaterthiophene moiety. Compounds of this class are highly promising for technological applications because their self-assembly and stimuli-responsive behavior, which is mainly caused by the peptide moieties, combined with the potential semiconducting properties of oligothiophenes provides unprecedented opportunities for the design of advanced materials at the nanoscale in such areas as, for example, organic electronics and sensor design for chemical and biomedical applications. The compound presented herein is experimentally shown to form stable fibrillar aggregates that are visualized by both transmission electron and atomic force microscopy. We developed a theoretical methodology to study the possible intermolecular arrangements and their characteristic features with the help of all-atom MD simulations, while simultaneously incorporating available experimental data into the model. Large-scale atomistic simulations of several fibrillar aggregates with different molecular arrangements were performed. The results of the simulations are compared with experimental data, which leads to the proposition of a likely model for the arrangement of the individual molecules within the observed aggregates.

Self-organizing bioinspired oligothiophene–oligopeptide hybrids

“…Peptide moieties are depicted with arrows, thiophene moiety using van der Waals spheres; images c2, c3, d2, d3 use van der Waals representation also for the peptide part for clarity [23]. …”

Combined atom-transfer radical polymerization and ring-opening polymerization to design polymer-polypeptide copolymer conjugates toward self-aggregated hybrid micro/nanospheres for dye encapsulation

“…Such conjugate materials have potential wide‐ranging biomedical, tissue engineering, biomaterial, and drug‐delivery applications . Furthermore, peptide–polymer conjugates may enable them to self‐assemble into functional well‐defined micro/nanostructured biomolecular materials with great implications in both biological and nonbiological applications …”

Oligopeptide‐Assisted Self‐Assembly of Oligothiophenes: Co‐Assembly and Chirality Transfer

“…[39,40] It should be noted that QTDA showed a much larger redshift compared with that of QT, which indicates that the assembly of QT and QTDA should be quite different. [9][10][11][12][13][14][15][16][17][18][19][20][21] It would be interesting to investigate whether such chirality transfer could be realized by weak interactions between a chiral oligopeptide and the achiral oligothiophenes. [9] It is known that when chiral peptide segments are covalently attached to achiral p-conjugated systems, the chirality will be transferred to the conjugated oligomers.…”

“…[1][2][3][4][5] Oligopeptides are one of the most attractive biomolecules to adjust the stacking mode of p-conjugated oligomers because of their structural variation and their ability to form various secondary structures, such as a-helices and b-sheets. [6][7][8] Extended p-conjugated oligomers, such as oligothiophenes [9][10][11][12][13][14][15][16][17][18][19][20][21] and oligo(p-phenylenevinylene)s, [22][23][24] have good electro-optical properties and show many potential applications. [9][10][11][12][13][14] These moieties have been covalently linked to oligopeptides and their assembly behavior and the corresponding properties were investigated.…”