Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates

Abstract Biomolecular condensates formed by intrinsically disordered proteins (IDPs) are semidilute solutions. These can be approximated as solutions of blob-sized segments, which are peptide-sized motifs. We leveraged the blob picture and molecular dynamics simulations to quantify differences betwe...

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Main Authors: Xiangze Zeng, Rohit V. Pappu
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Communications Chemistry
Online Access:https://doi.org/10.1038/s42004-025-01502-5
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author Xiangze Zeng
Rohit V. Pappu
author_facet Xiangze Zeng
Rohit V. Pappu
author_sort Xiangze Zeng
collection DOAJ
description Abstract Biomolecular condensates formed by intrinsically disordered proteins (IDPs) are semidilute solutions. These can be approximated as solutions of blob-sized segments, which are peptide-sized motifs. We leveraged the blob picture and molecular dynamics simulations to quantify differences between inter-residue interactions in model compound and peptide-based mimics of dense versus dilute phases. The all-atom molecular dynamics simulations use a polarizable forcefield. In model compound solutions, the interactions between aromatic residues are stronger than interactions between cationic and aromatic residues. This holds in dilute and dense phases. Cooperativity within dense phases enhances pairwise interactions leading to finite-sized nanoscale clusters. The results for peptide-based condensates paint a different picture. Backbone amides add valence to the associating molecules. While this enhances pairwise inter-residue interactions in dilute phases, it weakens pair interactions in dense phases, doing so in a concentration-dependent manner. Weakening of pair interactions enables fluidization characterized by short-range order and long-range disorder. The higher valence afforded by the peptide backbone generates system-spanning networks. As a result, dense phases of peptides are best described as percolated network fluids. Overall, our results show how peptide backbones enhance pairwise interactions in dilute phases while weakening these interactions to enable percolation within dense phases.
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spelling doaj-art-d5fd141f5f844eaf92febdafde7332672025-08-20T03:08:05ZengNature PortfolioCommunications Chemistry2399-36692025-04-018111410.1038/s42004-025-01502-5Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensatesXiangze Zeng0Rohit V. Pappu1Department of Biomedical Engineering and Center for Biomolecular Condensates, The James McKelvey School of Engineering, Washington University in St. LouisDepartment of Biomedical Engineering and Center for Biomolecular Condensates, The James McKelvey School of Engineering, Washington University in St. LouisAbstract Biomolecular condensates formed by intrinsically disordered proteins (IDPs) are semidilute solutions. These can be approximated as solutions of blob-sized segments, which are peptide-sized motifs. We leveraged the blob picture and molecular dynamics simulations to quantify differences between inter-residue interactions in model compound and peptide-based mimics of dense versus dilute phases. The all-atom molecular dynamics simulations use a polarizable forcefield. In model compound solutions, the interactions between aromatic residues are stronger than interactions between cationic and aromatic residues. This holds in dilute and dense phases. Cooperativity within dense phases enhances pairwise interactions leading to finite-sized nanoscale clusters. The results for peptide-based condensates paint a different picture. Backbone amides add valence to the associating molecules. While this enhances pairwise inter-residue interactions in dilute phases, it weakens pair interactions in dense phases, doing so in a concentration-dependent manner. Weakening of pair interactions enables fluidization characterized by short-range order and long-range disorder. The higher valence afforded by the peptide backbone generates system-spanning networks. As a result, dense phases of peptides are best described as percolated network fluids. Overall, our results show how peptide backbones enhance pairwise interactions in dilute phases while weakening these interactions to enable percolation within dense phases.https://doi.org/10.1038/s42004-025-01502-5
spellingShingle Xiangze Zeng
Rohit V. Pappu
Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates
Communications Chemistry
title Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates
title_full Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates
title_fullStr Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates
title_full_unstemmed Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates
title_short Backbone-mediated weakening of pairwise interactions enables percolation in peptide-based mimics of protein condensates
title_sort backbone mediated weakening of pairwise interactions enables percolation in peptide based mimics of protein condensates
url https://doi.org/10.1038/s42004-025-01502-5
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AT rohitvpappu backbonemediatedweakeningofpairwiseinteractionsenablespercolationinpeptidebasedmimicsofproteincondensates