Thermodynamic Factors Impacting the Peptide-Driven Self-Assembly of Perylene Diimide Nanofibers

Abstract

Synthetic peptides offer enormous potential to encode the assembly of molecular electronic components, provided that the complex range of interactions is distilled into simple design rules. Here, we report a spectroscopic investigation of aggregation in an extensive series of peptide-perylene diiimide conjugates designed to interrogate the effect of structural variations. By fitting different contributions to temperature dependent optical absorption spectra, we quantify both the thermodynamics and the nature of aggregation for peptides by incrementally varying hydrophobicity, charge density, length, as well as asymmetric substitution with a hexyl chain, and stereocenter inversion. We find that coarse effects like hydrophobicity and hexyl substitution have the greatest impact on aggregation thermodynamics, which are separated into enthalpic and entropic contributions. Moreover, significant peptide packing effects are resolved via stereocenter inversion studies, particularly when examining the nature of aggregates formed and the coupling between π electronic orbitals. Our results develop a quantitative framework for establishing structure-function relationships that will underpin the design of self-assembling peptide electronic materials.

Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides

“…Supramolecular assemblies of perylene bisimides (PBI) have been extensively studied for a wide range of functions, such as industrial pigments, 1 as mimics of biological systems [2][3][4] and as n-type semiconductors for organic electronics including solar cells. 5,6 Practical applications of these systems are hampered by many issues, including poor solubility, high melting temperatures, air sensitivity, difficult processability, low charge carrier mobilities and short charge carrier lifetimes.…”

“…Our laboratory has previously reported a series of non-halogenated PBI derivatives functionalized at the imide positions with two first generation self-assembling minidendrons, (3,4,5)nG1-m-PBI (where n is the number of carbons in the alkyl groups and m is the number of methylenic units between the dendron and the imide group of PBI). [9][10][11] The PBI derivatives self-organized to form a range of 2D and 3D phases, of which the least encountered 3D thermodynamic products are the most desirable for technological applications.…”

Einfluss der Plattendicke auf die Kontaktzeit beim elastischen Stoßvorgang

“…Herein, we show how changes in peptide primary sequence and in the N‐ to ‐C presentation of the peptide chains can influence the nature of the electronically excited states. The infancy of supramolecular electronics in biomaterial contexts demands the explication of predictive structurefunction rules for biopeptide‐driven optoelectronic outcomes, and this work adds to the emerging contemporary interest in understanding how peptide sequence variation impacts electronic interactions within nanoscale materials 14,15. Implications for the construction of more exotic electronic structures using these molecular variations as a foundation will be addressed.…”

Redox‐Active Peptide‐Functionalized Quinquethiophene‐Based Electrochromic π‐Gel

“…Av ariety of biomolecules such as peptides, [1,2] carbohydrates, [3][4][5] nucleobases [6,7] and nucleotides [8] haveb eenf unctionalized with semiconducting organic p-conjugated systemf or the synthesis of self-assembledn anostructuresw hichh ave beenu sedi nt he developmento fs upramolecular electronics. [9][10][11][12][13] Oligothiophene, [14][15][16][17][18] oligo(p-phenylenevinylene)( OPV), [19,20] diacetylene (DA), [21] benzo[ghi]perylenem onoimide (BPI), [22] naphthalened iimide (NDI) [23] andp erylened iimide (PDI) [24][25][26] have been conjugatedw ithv arious peptidem otifs. Ubiquitously, the main objectivei st oa ssemble p-conjugated units into ah ighly-ordered superstructure fore ffective charge-carrier mobility.…”