{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T12:24:53Z","timestamp":1787228693178,"version":"build-2736575974"},"reference-count":37,"publisher":"American Chemical Society (ACS)","issue":"33","license":[{"start":{"date-parts":[[2026,8,10]],"date-time":"2026-08-10T00:00:00Z","timestamp":1786320000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100006369","name":"George Mason University","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100006369","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation (NSF)","doi-asserted-by":"crossref","award":["BMAT 2041751"],"award-info":[{"award-number":["BMAT 2041751"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,20]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Replicating the protective dielectric environment of natural cytochromes within synthetic assemblies is essential for the development of air-stable bioelectronics. We report a redox-triggered \u201csupramolecular gate\u201d in self-assembled peptide amphiphile (PA) nanofibers that provide significant kinetic protection to ferrous heme B under aerobic conditions. By systematically varying side-chain steric bulk and hydrophobicity in a series of c16HHX4K3 PAs, we identified a phenylalanine variant (c16HHFL3K3) that extends the ferrous lifetime to over five seconds. Using a comprehensive multicomponent kinetic model, we resolve an initial protection phase in the c16HHFL3K3 variant that is absent in smaller side-chain controls like alanine. Potentiometric titrations revealed massive redox hysteresis (\u0394Em up to 305 mV), representing the mechanistic barrier required for the transition to a \u201clocked\u201d state. Circular dichroism spectra support this transition as a cooperative increase in superhelical twisting upon reduction. These findings establish sequence-specific design rules for stimulus-responsive \u201cinsulation\u201d in peptide-based materials, enabling the protection of reactive redox centers in atmospheric environments.<\/jats:p>","DOI":"10.1021\/acs.jpcb.6c02307","type":"journal-article","created":{"date-parts":[[2026,8,10]],"date-time":"2026-08-10T07:02:54Z","timestamp":1786345374000},"page":"8423-8433","source":"Crossref","is-referenced-by-count":0,"title":["Quantifying the Sequence-Dependent Kinetic Protection\nof Reduced Heme in Peptide Amphiphile Nanofibers"],"prefix":"10.1021","volume":"130","author":[{"given":"Blake","family":"Campbell","sequence":"first","affiliation":[{"name":"George Mason University , , , ,","place":["Fairfax, Virginia, United States, 22030"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Abigail","family":"Rogers","sequence":"additional","affiliation":[{"name":"George Mason University , , , ,","place":["Fairfax, Virginia, United States, 22030"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nathan A.","family":"Hernandez-Martinez","sequence":"additional","affiliation":[{"name":"George Mason University , , , ,","place":["Fairfax, Virginia, United States, 22030"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4161-2834","authenticated-orcid":true,"given":"Subas","family":"Dangi","sequence":"additional","affiliation":[{"name":"George Mason University , , , ,","place":["Fairfax, Virginia, United States, 22030"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1471-9510","authenticated-orcid":true,"given":"Lee A.","family":"Solomon","sequence":"additional","affiliation":[{"name":"George Mason University , , , ,","place":["Fairfax, Virginia, United States, 22030"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,10]]},"reference":[{"issue":"2","key":"2026082007201418800_cit1","doi-asserted-by":"publisher","first-page":"361","DOI":"10.1016\/j.cell.2019.03.029","article-title":"Structure of Microbial\nNanowires Reveals Stacked\nHemes That Transport Electrons over Micrometers","volume":"177","author":"Wang","year":"2019","journal-title":"Cell"},{"issue":"3","key":"2026082007201418800_cit2","doi-asserted-by":"publisher","first-page":"2002797","DOI":"10.1002\/advs.202002797","article-title":"Reactive Oxygen\nSpecies-Regulating Strategies Based on Nanomaterials for Disease Treatment","volume":"8","author":"Zhang","year":"2021","journal-title":"Adv. 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Chem."},{"issue":"1","key":"2026082007201418800_cit30","doi-asserted-by":"publisher","first-page":"77","DOI":"10.1096\/fj.01-0442hyp","article-title":"A Possible\nRole for \u03a0-stacking in the Self-assembly of Amyloid Fibrils","volume":"16","author":"Gazit","year":"2002","journal-title":"FASEB J."},{"issue":"5","key":"2026082007201418800_cit31","doi-asserted-by":"publisher","first-page":"225","DOI":"10.1016\/j.trechm.2025.03.002","article-title":"Advances\nin the Design of \u03c0-Conjugated Peptide Assemblies","volume":"7","author":"Nguyen","year":"2025","journal-title":"Trends Chem."},{"issue":"2","key":"2026082007201418800_cit32","doi-asserted-by":"publisher","first-page":"2100066","DOI":"10.1002\/mats.202100066","article-title":"Investigation of Self-Assembly of\nSymmetric and Asymmetric\nPeptide Bolaamphiphiles by COSMO-RS and Atomistic Simulations and\nTheir Interactions with POPC Bilayers","volume":"31","author":"Lebedenko","year":"2022","journal-title":"Macromol.\nTheory Simul."},{"key":"2026082007201418800_cit33","doi-asserted-by":"publisher","first-page":"411","DOI":"10.1016\/S0076-6879(78)54026-3","article-title":"Redox Potentiometry:\nDetermination of Midpoint Potentials of Oxidation-Reduction Components\nof Biological Electron-Transfer Systems","volume":"54","author":"Dutton","year":"1978","journal-title":"Methods\nEnzymol."},{"issue":"25","key":"2026082007201418800_cit34","doi-asserted-by":"publisher","first-page":"4686","DOI":"10.1039\/D3SM00363A","article-title":"Self-Assembled Aggregates\nBased on\nCationic Amphiphilic Peptides: Structural Insight","volume":"19","author":"Rosa","year":"2023","journal-title":"Soft Matter."},{"issue":"4","key":"2026082007201418800_cit35","doi-asserted-by":"publisher","first-page":"411","DOI":"10.1017\/S0033583515000062","article-title":"Electron Flow through\nBiological Molecules: Does Hole\nHopping Protect Proteins from Oxidative Damage?","volume":"48","author":"Winkler","year":"2015","journal-title":"Q. Rev. Biophys."},{"issue":"17","key":"2026082007201418800_cit36","doi-asserted-by":"publisher","first-page":"5133","DOI":"10.1021\/bi027067e","article-title":"Characterization of\nthe Heme Environmental Structure of Cytoglobin,\na Fourth Globin in Humans","volume":"42","author":"Sawai","year":"2003","journal-title":"Biochemistry"},{"issue":"24","key":"2026082007201418800_cit37","doi-asserted-by":"publisher","first-page":"8483","DOI":"10.1073\/pnas.0408766102","article-title":"Neuroglobin, Nitric Oxide, and Oxygen: Functional Pathways\nand Conformational Changes","volume":"102","author":"Brunori","year":"2005","journal-title":"Proc. Natl. Acad.\nSci. U. S. A."}],"container-title":["The Journal of Physical Chemistry B"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcb.6c02307","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/33\/8423\/66468953\/acs.jpcb.6c02307.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/33\/8423\/66468953\/acs.jpcb.6c02307.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T11:35:37Z","timestamp":1787225737000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article\/130\/33\/8423\/5250959\/Quantifying-the-Sequence-Dependent-Kinetic"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,10]]},"references-count":37,"journal-issue":{"issue":"33","published-online":{"date-parts":[[2026,8,10]]},"published-print":{"date-parts":[[2026,8,20]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcb.6c02307","relation":{},"ISSN":["1520-6106","1520-5207"],"issn-type":[{"value":"1520-6106","type":"print"},{"value":"1520-5207","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,10]]}}}