Concentration-Driven Assembly and Sol–Gel Transition of π-Conjugated Oligopeptides

Zhou, Yuecheng; Li, Bo; Li, Songsong; Ardoña, Herdeline Ann M.; Wilson, William L.; Tovar, John D.; Schroeder, Charles M.

doi:10.1021/acscentsci.7b00260

Title: Concentration-Driven Assembly and Sol–Gel Transition of π-Conjugated Oligopeptides

Journal Article · 17 August 2017 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.7b00260 · OSTI ID:1375504

Zhou, Yuecheng ^[1]; Li, Bo ^[2]; Li, Songsong ^[1];

^[3]; Wilson, William L. ^[4];

^[5];

^[6]

Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Materials Science and Engineering
Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Chemical and Biomolecular Engineering
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
Univ. of Illinois, Urbana-Champaign, IL (United States). Frederick Seitz Materials Research Lab.; Harvard Univ., Cambridge, MA (United States). Center for Nanoscale Systems
Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry; Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Materials Science and Engineering
Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Chemical and Biomolecular Engineering; Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Materials Science and Engineering

Advances in supramolecular assembly have enabled the design and synthesis of functional materials with well-defined structures across multiple length scales. Biopolymer-synthetic hybrid materials can assemble into supramolecular structures with a broad range of structural and functional diversity through precisely controlled noncovalent interactions between subunits. Despite recent progress, there is a need to understand the mechanisms underlying the assembly of biohybrid/synthetic molecular building blocks, which ultimately control the emergent properties of hierarchical assemblies. Here in this work, we study the concentration-driven self-assembly and gelation of π-conjugated synthetic oligopeptides containing different π-conjugated cores (quaterthiophene and perylene diimide) using a combination of particle tracking microrheology, confocal fluorescence microscopy, optical spectroscopy, and electron microscopy. Our results show that π-conjugated oligopeptides self-assemble into β-sheet-rich fiber-like structures at neutral pH, even in the absence of electrostatic screening of charged residues. A critical fiber formation concentration c_fiber and a critical gel concentration c_gel are determined for fiber-forming π-conjugated oligopeptides, and the linear viscoelastic moduli (storage modulus G' and loss modulus G") are determined across a wide range of peptide concentrations. These results suggest that the underlying chemical structure of the synthetic π-conjugated cores greatly influences the self-assembly process, such that oligopeptides appended to π-conjugated cores with greater torsional flexibility tend to form more robust fibers upon increasing peptide concentration compared to oligopeptides with sterically constrained cores. Overall, our work focuses on the molecular assembly of π-conjugated oligopeptides driven by concentration, which is controlled by a combination of enthalpic and entropic interactions between oligopeptide subunits.

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Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0011847

OSTI ID:: 1375504

Alternate ID(s):: OSTI ID: 1421386

Journal Information:: ACS Central Science, Vol. 3, Issue 9; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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Self-Assembled Hexa-peri-hexabenzocoronene Graphitic Nanotube Hill, J. P. Science, Vol. 304, Issue 5676 https://doi.org/10.1126/science.1097789	journal	June 2004
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Supramolecular Materials: Self-Organized Nanostructures Stupp, S. I. Science, Vol. 276, Issue 5311, p. 384-389 https://doi.org/10.1126/science.276.5311.384	journal	April 1997
Self-Organized Discotic Liquid Crystals for High-Efficiency Organic Photovoltaics Schmidt-Mende, L. Science, Vol. 293, Issue 5532 https://doi.org/10.1126/science.293.5532.1119	journal	August 2001
Colloid Surface Chemistry Critically Affects Multiple Particle Tracking Measurements of Biomaterials Valentine, M. T.; Perlman, Z. E.; Gardel, M. L. Biophysical Journal, Vol. 86, Issue 6 https://doi.org/10.1529/biophysj.103.037812	journal	June 2004
Static and Dynamic Errors in Particle Tracking Microrheology Savin, Thierry; Doyle, Patrick S. Biophysical Journal, Vol. 88, Issue 1 https://doi.org/10.1529/biophysj.104.042457	journal	January 2005

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