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Unraveling Hydrophobic Interactions at the Molecular Scale Using Force Spectroscopy and Molecular Dynamics Simulations

Title: Unraveling Hydrophobic Interactions at the Molecular Scale Using Force Spectroscopy and Molecular Dynamics Simulations
Authors: Stock, Philipp; Monroe, Jacob; Utzig, Thomas; Shell, Scott; Smith, David; Valtiner, Markus
Contributors: Max-Planck-Institut für Eisenforschung GmbH, Germany; University of California Santa Barbara, United States; #PLACEHOLDER_PARENT_METADATA_VALUE#
Publisher Information: American Chemical Society (ACS)
Publication Year: 2020
Collection: TU Wien: reposiTUm
Subject Terms: AFM; hydrophobic interaction; Jarzynski’s equality; molecular dynamics; peptide; self-assembled monolayer; single-molecule force spectroscopy; steered molecular dynamics
Description: This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes ; Interactions between hydrophobic moieties steer ubiquitous processes in aqueous media, including the self-organization of biologic matter. Recent decades have seen tremendous progress in understanding these for macroscopic hydrophobic interfaces. Yet, it is still a challenge to experimentally measure hydrophobic interactions (HIs) at the single-molecule scale and thus to compare with theory. Here, we present a combined experimental–simulation approach to directly measure and quantify the sequence dependence and additivity of HIs in peptide systems at the single-molecule scale. We combine dynamic single-molecule force spectroscopy on model peptides with fully atomistic, both equilibrium and nonequilibrium, molecular dynamics (MD) simulations of the same systems. Specifically, we mutate a flexible (GS)5 peptide scaffold with increasing numbers of hydrophobic leucine monomers and measure the peptides’ desorption from hydrophobic self-assembled monolayer surfaces. Based on the analysis of nonequilibrium work-trajectories, we measure an interaction free energy that scales linearly with 3.0–3.4 kBT per leucine. In good agreement, simulations indicate a similar trend with 2.1 kBT per leucine, while also providing a detailed molecular view into HIs. This approach potentially provides a roadmap for directly extracting qualitative and quantitative single-molecule interactions at solid/liquid interfaces in a wide range of fields, including interactions at biointerfaces and adhesive interactions in industrial applications. ; NSF ; German Research Foundation (DFG) ; Center for Scientific Computing at UCSB (NSF) ; National Science Foundation Graduate Research Fellowship Program ; European Research Council (ERC) ; 2586 ; 2597 ; 12
Document Type: article in journal/newspaper
Language: English
ISSN: 1936-086X
Relation: ACS Nano; DMR-1312548; VA 689/3-1; CNS-0960316; DGE 1144085; 677663; https://resolver.obvsg.at/urn:nbn:at:at-ubtuw:3-4666; http://hdl.handle.net/20.500.12708/75; AC15307977; urn:nbn:at:at-ubtuw:3-4666
Availability: https://resolver.obvsg.at/urn:nbn:at:at-ubtuw:3-4666; https://hdl.handle.net/20.500.12708/75
Rights: open
Accession Number: edsbas.AC2E5F5B
Database: BASE