Sequence-dependent mechanical, photophysical and electrical properties of pi-conjugated peptide hydrogelators

Ardoña, Herdeline Ann M.; Besar, Kalpana; Togninalli, Matteo; Katz, Howard E.; Tovar, John D.

doi:10.1039/c5tc00100e

Cited by 50 publications

(111 citation statements)

References 67 publications

(93 reference statements)

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“…For example, the investigation of bulk electrical properties of conductive films comprised of peptide-oligothiophene nanostructures and its dependence on the amino acid sequence showed how the inherent aggregation into films could vary simply through peptide substitutions, and hence affect the surface roughness of the films that are correlated to the sheet resistance of the material. 103 This coincides with the findings for pure peptide conductance wherein the morphology and peptide content (i.e., more aromatic residues for electron transport) are crucial in improving the conductance of peptide nanostructures. 109 Peptide-oligothiophene hydrogelators have been incorporated as active layers of FET, resulting in hole mobilities ranging from 10 -5 to 0.03 cm 2 V -1 s -1 .…”

Section: From the Molecular To The Macroscalesupporting

confidence: 82%

Peptide π-Electron Conjugates: Organic Electronics for Biology?

2015

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Highly ordered arrays of π-conjugated molecules are often viewed as a prerequisite for effective charge-transporting materials. Studies involving these materials have traditionally focused on organic electronic devices, with more recent emphasis on biological systems. In order to facilitate the transition to biological environments, biomolecules that can promote hierarchical ordering and water solubility are often covalently appended to the π-electron unit. This review highlights recent work on π-conjugated systems bound to peptide moieties that exhibit self-assembly and aims to provide an overview on the development and emerging applications of peptide-based supramolecular π-electron systems.

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Section: From the Molecular To The Macroscalesupporting

confidence: 82%

Peptide π-Electron Conjugates: Organic Electronics for Biology?

2015

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“…Peptide composition has a direct influence on both the structure of the assembled nanomaterials, such as the extent of fibrillisation, as well as their functionality, such as the energy transport characteristics. [13,20] For example, different peptide chemistries have been observed to produce nanomaterials with excited state exciton outcomes spanning from the formation of 'charge-trapped' excimer states that might be useful for light emission applications, to the formation of strong electronic coupling relevant for charge carrier transport. [20] Future computational studies can help to unravel the molecular-level morphologies underpinning this structure and function, and help guide the rational design of new biocompatible optoelectronic nanomaterials for energy transport and storage applications.…”

Section: Discussionmentioning

confidence: 99%

“…[19] Conjugated peptides in particular offer a water soluble and biofunctional medium to fabricate self-assembled aggregates with tunable biological and electronic properties. [10,13,17,18,20] CONTACT Andrew L. Ferguson alf@illinois.edu Supplemental data for this article can be accessed 10.1080/08927022.2015.1125997.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics, morphology, and kinetics of early-stage self-assembly of π-conjugated oligopeptides

Thurston

Tovar

Ferguson

2016

Molecular Simulation

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Synthetic oligopeptides containing π -conjugated cores self-assemble novel materials with attractive electronic and photophysical properties. All-atom, explicit solvent molecular dynamics simulations of Asp-Phe-Ala-Gly-OPV3-Gly-Ala-Phe-Asp peptides were used to parameterise an implicit solvent model to simulate early-stage self-assembly. Under low-pH conditions, peptides assemble into β-sheet-like stacks with strongly favorable monomer association free energies of F ≈ −25k B T . Aggregation at high-pH produces disordered aggregates destabilised by Coulombic repulsion between negatively charged Asp termini ( F ≈ −5k B T ). In simulations of hundreds of monomers over 70 ns we observe the spontaneous formation of up to undecameric aggregates under low-pH conditions. Modeling assembly as a continuoustime Markov process, we infer transition rates between different aggregate sizes and microsecond relaxation times for early-stage assembly. Our data suggests a hierarchical model of assembly in which peptides coalesce into small clusters over tens of nanoseconds followed by structural ripening and diffusion limited aggregation on longer time scales. This work provides new molecular-level understanding of early-stage assembly, and a means to study the impact of peptide sequence and aromatic core chemistry upon the thermodynamics, assembly kinetics, and morphology of the supramolecular aggregates. ARTICLE HISTORY

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“…39 Specifically, we reduced our search space to the 11 3 = 1331 candidates in the set defined by X ∈ {Ala, Gly, Glu, Ile, Leu, Met, Phe, Trp, Tyr, Val, Asp} to avoid charged and/or polar amino acids expected to interfere with low-pH triggered assembly 31 and focus on those residues that have expressed good assembly behavior in previous experimental work. 22,[99][100][101] We perform active learning over DXXX-OPV3-XXXD sequences following the four-part protocol -molecular simulation, VAE latent space embedding, GPR surrogate model construction, optimal selection of next candidates -described in Section 2.2 and illustrated in Fig. 2.…”

Section: Active Learning Identification Of Optimal Candidatesmentioning

confidence: 99%

Discovery of Self-Assembling π-Conjugated Peptides by Active Learning-Directed Coarse-Grained Molecular Simulation

et al. 2020

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Electronically-active organic molecules have demonstrated great promise as novel soft materials for energy harvesting and transport. Self-assembled nanoaggregates formed from π-conjugated oligopeptides composed of an aromatic core flanked by oligopeptide wings offer emergent optoelectronic properties within a water soluble and biocompatible substrate. Nanoaggregate properties can be controlled by tuning core chemistry and peptide composition, but the sequence-structure-function relations remain poorly characterized. In this work, we employ coarse-grained molecular dynamics simulations within an active learning protocol employing deep representational learning and Bayesian optimization to efficiently identify molecules capable of assembling pseudo-1D nanoaggregates with good stacking of the electronically-active π-cores. We consider the DXXX-OPV3-XXXD oligopeptide family, where D is an Asp residue and OPV3 is an oligophenylene vinylene oligomer (1,4-distyrylbenzene), to identify the top performing XXX tripeptides within all 20 3 = 8,000 possible sequences. By direct simulation of only 2.3% of this space, we identify molecules predicted to exhibit superior assembly relative to those reported in prior work. Spectral clustering of the top candidates reveals new design rules governing assembly. This work establishes new understanding of DXXX-OPV3-XXXD assembly, identifies promising new candidates for experimental testing, and presents a computational design platform that can be generically extended to other peptide-based and peptide-like systems.

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Sequence-dependent mechanical, photophysical and electrical properties of pi-conjugated peptide hydrogelators

Abstract: An investigation of how systematic variation of peptide sequence influences the nanoscale and bulk properties of 1D-nanostructure forming peptide–π–peptide hydrogelators is reported herein.

Cited by 50 publications

References 67 publications

Peptide π-Electron Conjugates: Organic Electronics for Biology?

Peptide π-Electron Conjugates: Organic Electronics for Biology?

Thermodynamics, morphology, and kinetics of early-stage self-assembly of π-conjugated oligopeptides

Discovery of Self-Assembling π-Conjugated Peptides by Active Learning-Directed Coarse-Grained Molecular Simulation

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