Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation

Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Physical Sciences - Article Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation Keding Lu, Huan Song, Hongyang Cui, Huabin Dong, Ce Chen, Wenyu Wei, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8176734/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Isoprene is the most abundant biogenic volatile organic compounds (BVOCs) and has far-reaching impacts on secondary organic aerosol (SOA) formation globally 1-6. Atmospheric oxidation of isoprene produces a diverse range of isomeric radicals that drive subsequent chain propagation and mechanistic branching 7-10. However, no high-throughput experimental characterization of isomeric-resolved radicals of isoprene is available, leaving critical gaps in our understanding of the underlying molecular mechanisms. Here we establish a radical-omics approach that enables isomer-specific identification and detection of hundreds of radical species generated in the VOCs oxidation system. Applied to the OH-initiated reaction of isoprene, four OH-added allylic radicals were experimentally quantified to derive their branching ratios. In addition, hydrogen-abstraction was found to be an unexpectedly important pathway, contributing up to 8.80 ± 3.21% of the total branching. Incorporating the updated mechanism into a global chemical transport model shows that this pathway contributes up to 13.5% of the total isoprene-derived low-volatility SOA over tropical rainforests. Our findings provide a missing experimental foundation for isoprene chemistry via the combination of radical screening with targeted mechanistic validation, thereby revealing hidden reaction pathways under complex atmospheric conditions. Earth and environmental sciences/Environmental sciences/Environmental chemistry/Atmospheric chemistry Earth and environmental sciences/Environmental sciences/Environmental impact Full Text Additional Declarations There is NO Competing Interest. Supplementary Files NatureSI1118.pdf Supplementary Materials for Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8176734","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Physical Sciences - Article","associatedPublications":[],"authors":[{"id":556692039,"identity":"985a0128-7511-445d-8e7d-439f597a05df","order_by":0,"name":"Keding Lu","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAsklEQVRIiWNgGAWjYBACCQbmBoYPDAkgtgGxWhgbGGeQrIWZhyQtkg2MbdK2O9ISG9ibt0kw1NwhrEWaAagl90xOYgPPsTIJhmPPCGuRA2tpq0hskMgxk2BsOEykFkuQFvk3RGoBO4yxDegwCR4itUg2MzZb9p5JM27jSSu2SDhGhBaJ480Hb/zckSzbz354440PNURoYWAGYsYGBgY2ECeBCA0QANIyCkbBKBgFowAnAADl6zLpj8tbpQAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0001-9425-9520","institution":"Peking University","correspondingAuthor":true,"prefix":"","firstName":"Keding","middleName":"","lastName":"Lu","suffix":""},{"id":556692040,"identity":"9ae57ac2-4ead-41fd-9639-92e5e71b4873","order_by":1,"name":"Huan Song","email":"","orcid":"https://orcid.org/0000-0002-6884-9014","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Huan","middleName":"","lastName":"Song","suffix":""},{"id":556692041,"identity":"9af2f57b-888d-4c58-a60d-160070b0b960","order_by":2,"name":"Hongyang Cui","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Hongyang","middleName":"","lastName":"Cui","suffix":""},{"id":556692042,"identity":"6695a37a-f257-403e-a040-e41b6743bda1","order_by":3,"name":"Huabin Dong","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Huabin","middleName":"","lastName":"Dong","suffix":""},{"id":556692043,"identity":"72d3d5e4-266b-441f-8ffe-56c5dbbff468","order_by":4,"name":"Ce Chen","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Ce","middleName":"","lastName":"Chen","suffix":""},{"id":556692044,"identity":"fbefdf98-3619-45f2-a9a9-d67b5a060ff6","order_by":5,"name":"Wenyu Wei","email":"","orcid":"","institution":"State Key Laboratory of Regional Environment and Sustainability, College of Environmental Sciences and Engineering, Peking University, Beijing, China","correspondingAuthor":false,"prefix":"","firstName":"Wenyu","middleName":"","lastName":"Wei","suffix":""},{"id":556692045,"identity":"8f6a6301-b657-427d-ba58-149b2570ae18","order_by":6,"name":"Yang Li","email":"","orcid":"","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Yang","middleName":"","lastName":"Li","suffix":""},{"id":556692046,"identity":"f8479541-78a6-497d-b7e6-822d25945053","order_by":7,"name":"Qindan Zhu","email":"","orcid":"https://orcid.org/0000-0003-2173-4014","institution":"Massachusetts Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Qindan","middleName":"","lastName":"Zhu","suffix":""},{"id":556692047,"identity":"ebe0d086-58d7-4c18-9ffa-e42581db4e6d","order_by":8,"name":"Bo Tang","email":"","orcid":"","institution":"Beijing Normal University","correspondingAuthor":false,"prefix":"","firstName":"Bo","middleName":"","lastName":"Tang","suffix":""},{"id":556692048,"identity":"8ef42858-ddb7-4d09-b9ba-a4020ae26ef7","order_by":9,"name":"Chongqin Zhu","email":"","orcid":"https://orcid.org/0000-0002-8316-1816","institution":"Beijing Normal University","correspondingAuthor":false,"prefix":"","firstName":"Chongqin","middleName":"","lastName":"Zhu","suffix":""},{"id":556692049,"identity":"47065bc1-5145-4370-af4c-64a7ec2e001e","order_by":10,"name":"Xuefei Ma","email":"","orcid":"https://orcid.org/0000-0002-8200-4675","institution":"State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering, Peking University, Beijing","correspondingAuthor":false,"prefix":"","firstName":"Xuefei","middleName":"","lastName":"Ma","suffix":""},{"id":556692050,"identity":"dfce262f-ad82-4f82-9ab2-5412e60a96e9","order_by":11,"name":"Zhaofeng Tan","email":"","orcid":"https://orcid.org/0000-0002-3808-1964","institution":"Peking University","correspondingAuthor":false,"prefix":"","firstName":"Zhaofeng","middleName":"","lastName":"Tan","suffix":""},{"id":556692051,"identity":"7748bf42-ab65-4d1e-8b92-5866d6fa006a","order_by":12,"name":"Shiyi Chen","email":"","orcid":"","institution":"State Key Joint Laboratory of Environmental Simulation and Pollution Control, College of Environmental Sciences and Engineering","correspondingAuthor":false,"prefix":"","firstName":"Shiyi","middleName":"","lastName":"Chen","suffix":""},{"id":556692052,"identity":"cba45642-9ffa-4140-9922-8f113eda18d7","order_by":13,"name":"Yi Wan","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Yi","middleName":"","lastName":"Wan","suffix":""}],"badges":[],"createdAt":"2025-11-21 22:00:33","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8176734/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8176734/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":97900754,"identity":"8ef9a95e-6304-43d0-896b-4e4c09f49b26","added_by":"auto","created_at":"2025-12-10 15:45:49","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1061758,"visible":true,"origin":"","legend":"Article File","description":"","filename":"NatureMS1118.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8176734/v1_covered_e99c22b8-be11-44bf-9b74-61d28694601e.pdf"},{"id":97880357,"identity":"0727e03f-9807-4f85-bfe8-9d048248ffa5","added_by":"auto","created_at":"2025-12-10 12:20:26","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2865125,"visible":true,"origin":"","legend":"Supplementary Materials for Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation","description":"","filename":"NatureSI1118.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8176734/v1/ae9cbfa05d92e0ac97e97989.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-8176734/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8176734/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Isoprene is the most abundant biogenic volatile organic compounds (BVOCs) and has far-reaching impacts on secondary organic aerosol (SOA) formation globally 1-6. Atmospheric oxidation of isoprene produces a diverse range of isomeric radicals that drive subsequent chain propagation and mechanistic branching 7-10. However, no high-throughput experimental characterization of isomeric-resolved radicals of isoprene is available, leaving critical gaps in our understanding of the underlying molecular mechanisms. Here we establish a radical-omics approach that enables isomer-specific identification and detection of hundreds of radical species generated in the VOCs oxidation system. Applied to the OH-initiated reaction of isoprene, four OH-added allylic radicals were experimentally quantified to derive their branching ratios. In addition, hydrogen-abstraction was found to be an unexpectedly important pathway, contributing up to 8.80 ± 3.21% of the total branching. Incorporating the updated mechanism into a global chemical transport model shows that this pathway contributes up to 13.5% of the total isoprene-derived low-volatility SOA over tropical rainforests. Our findings provide a missing experimental foundation for isoprene chemistry via the combination of radical screening with targeted mechanistic validation, thereby revealing hidden reaction pathways under complex atmospheric conditions.","manuscriptTitle":"Radical-Omics Reveals the Hydrogen-Abstraction Pathway of Isoprene Oxidation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-12-10 12:20:21","doi":"10.21203/rs.3.rs-8176734/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"875daa7e-8dd3-4b4f-9e40-a2e9fa87aa7c","owner":[],"postedDate":"December 10th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":59243856,"name":"Earth and environmental sciences/Environmental sciences/Environmental chemistry/Atmospheric chemistry"},{"id":59243857,"name":"Earth and environmental sciences/Environmental sciences/Environmental impact"}],"tags":[],"updatedAt":"2025-12-10T12:20:21+00:00","versionOfRecord":[],"versionCreatedAt":"2025-12-10 12:20:21","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8176734","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8176734","identity":"rs-8176734","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}