Stimulus-Induced Relief of Intentionally Incorporated Frustration Drives Refolding of a Water-Soluble Biomimetic Foldamer

Henriksen, Hanne C.; Sowers, Adam J.; Travis, Christopher R.; Vulpis, Troy D.; Cope, Thomas A.; Ouslander, Sarah K.; Russell, Alexander F.; Gagné, Michel R.; Pophristic, Vojislava; Liu, Zhiwei; Waters, Marcey L.

doi:10.1021/jacs.3c09883

Cited by 1 publication

(1 citation statement)

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“…Supramolecular assembly, which utilizes randomly oriented molecules to form ordered functional structures based on a bottom-up approach, is a ubiquitous process in nature. − As a representative class of biomimetic smart molecules, foldamers can spontaneously assemble into elaborate three-dimensional structures, which could be crucial to realize specific functions. − A variety of organic foldamers, such as peptidomimetics and aromatic amide oligomers, have been reported with a propensity to assemble into folded structures via cooperative hydrogen bond and π–π interactions. − These foldamers have wide applications in stimuli-responsive luminescent materials, − ion channels, , catalysis, , and so on. , …”

Section: Introductionmentioning

confidence: 99%

Markov State Models Reveal How Folding Kinetics Influence Absorption Spectra of Foldamers

Wang,

Li,

Zheng

2024

J. Chem. Theory Comput.

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Self-assembly of platinum(II) complex foldamers is an essential approach to fabricate advanced luminescent materials. However, a comprehensive understanding of folding kinetics and their absorption spectra remains elusive. By constructing Markov state models (MSMs) from large-scale molecular dynamics simulations, we reveal that two largely similar dinuclear alknylplatinum(II) terpyridine foldamers, Pt-PEG and Pt-PE with slightly different bridges, exhibit distinctive folding kinetics. Particularly, Pt-PEG bears bridge-dominant, plane-dominant, and cooperative pathways, while Pt-PE only prefers the plane-dominant pathway. Such preference originates from their difference in intrabridge electrostatic interactions, leading to contrastive distributions of metastable states. We also found that the bridge-dominant pathway for Pt-PEG becomes more favorable when lowering the temperature. Interestingly, based on the comprehensive conformation ensembles from our MSMs, we reveal the conformation-dependent absorption spectra of Pt-PEG and Pt-PE. Our theoretical spectra not only align with experimental results but also reveal the contributions of diverse conformations to the overall absorption bands explicitly, facilitating the rational design of stimuli-responsive smart luminescent molecules.

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