Triplet Exciton Delocalization in Organic-Quantum Dots Hybrid Photo-Systems: A Pathway to Improved Phototherapy and Theragnostics

Triplet Exciton Delocalization in Organic-Quantum Dots Hybrid Photo-Systems: A Pathway to Improved Phototherapy and Theragnostics | 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 Article Triplet Exciton Delocalization in Organic-Quantum Dots Hybrid Photo-Systems: A Pathway to Improved Phototherapy and Theragnostics Anoklase Ayitou, Sarita Rawool, Neal Ramseier, Samjhana Maharjan, and 7 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6839005/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract In this work, we engineered hybrid photo-assemblies consisting of an organic triplet chromophore (QDM) and core-shell CdSe/ZnS, CdZnS/ZnS, core CdZnS, or CdS quantum dots (QD). Photophysical data shows that the presence of the QD in the vicinity of the QDM enhances spin-orbit coupling (SOC), resulting in the depopulation of the singlet excited state to create the corresponding triplet transient species with an accelerated intersystem crossing (ISC) of rate constants in the range kISC = 8.6–18 x1010 s-1 and a three-fold increase of triplet lifetime for the hybrids. Further photophysical, electrochemical, and computational investigations revealed that the triplet state of QDM is delocalized into the QD bands, which explains the increased triplet lifetime of the hybrids. Moreover, triplet photosensitization of molecular oxygen (3O2) using the hybrids produced 1O2 with a Φ(1O2) of 67% (in toluene) and 64% (in water) for the hybrid photo-material(s) compared to that of QDM alone (52% in toluene and 28% in water). This enhanced quantum efficiency was corroborated in dendritic cell viability assays, with cell death rates as high as 97%. The inherent emissive properties of QD component(s) facilitated the use of our new hybrid photo-assemblies as multifunctional platforms for synergistic bio-imaging and phototherapy. Physical sciences/Materials science/Nanoscale materials/Organic–inorganic nanostructures Physical sciences/Energy science and technology/Energy modelling Hybrid photo-materials Exciton delocalization Heavy atom effect Triplet photochemistry Singlet oxygen and photodynamic therapy Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SRAJAQDMQD050724SIFinal060525V2.pdf Supplemental Materials Cite Share Download PDF Status: Posted 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-6839005","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":470941493,"identity":"f23fb0ea-6af8-4a6d-a8d4-4ffd95e5d329","order_by":0,"name":"Anoklase Ayitou","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAtUlEQVRIiWNgGAWjYJCCA0Asx8AMYrIRqwWox5g0LSBrEhsYiNXC337G8PCHisPpG44zP2D4UHaYsBaJMzkGBw6cOZy74TCbAeOMc0RoYTgA1HKwDaSFh4GZt40ILfLn34C1pBuAtPwlRovBDYgtCWAtjMRoMbzxrODAmTPphjOBfjnYcy6dsBa588mbP1RUWMvznT/88MGPMmvCWhgYOAzgzAPEqAcC9gdEKhwFo2AUjIIRCwAaCkIWRd5fkAAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0001-6355-2564","institution":"University of Illinois Chicago","correspondingAuthor":true,"prefix":"","firstName":"Anoklase","middleName":"","lastName":"Ayitou","suffix":""},{"id":470941494,"identity":"e06a0a1d-0226-4e20-8a29-afa7b62f05f0","order_by":1,"name":"Sarita Rawool","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Sarita","middleName":"","lastName":"Rawool","suffix":""},{"id":470941495,"identity":"417fd496-fb2d-42d1-8e8e-ad55bf4bfc56","order_by":2,"name":"Neal Ramseier","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Neal","middleName":"","lastName":"Ramseier","suffix":""},{"id":470941496,"identity":"6e5e75aa-495c-445f-968b-ba406b3505a5","order_by":3,"name":"Samjhana Maharjan","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Samjhana","middleName":"","lastName":"Maharjan","suffix":""},{"id":470941497,"identity":"8d7047fc-9fee-4b56-870d-1b5e68cc17b1","order_by":4,"name":"Steve Lee","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Steve","middleName":"","lastName":"Lee","suffix":""},{"id":470941498,"identity":"13433c88-63ad-4654-bd08-bb557a032a9a","order_by":5,"name":"Krishna Prasad","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Krishna","middleName":"","lastName":"Prasad","suffix":""},{"id":470941499,"identity":"83896aff-7f1c-45e5-af8c-1df905829240","order_by":6,"name":"Parakh Patel","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Parakh","middleName":"","lastName":"Patel","suffix":""},{"id":470941500,"identity":"a20af4aa-4147-4496-b93e-7b358633898a","order_by":7,"name":"Joshua Bruno","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Joshua","middleName":"","lastName":"Bruno","suffix":""},{"id":470941501,"identity":"192cda47-59f7-46b5-a4ab-b14b79396fa1","order_by":8,"name":"Ksenija Glusac","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Ksenija","middleName":"","lastName":"Glusac","suffix":""},{"id":470941502,"identity":"8fb1c8a7-4f26-439b-9f53-8bdecb1b7ea0","order_by":9,"name":"Preston Snee","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Preston","middleName":"","lastName":"Snee","suffix":""},{"id":470941503,"identity":"af6a471d-7013-4e53-936e-3a1c4a545b0f","order_by":10,"name":"Ying Hu","email":"","orcid":"","institution":"University of Illinois Chicago","correspondingAuthor":false,"prefix":"","firstName":"Ying","middleName":"","lastName":"Hu","suffix":""}],"badges":[],"createdAt":"2025-06-06 18:20:44","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6839005/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6839005/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":89062808,"identity":"91edcab5-64fa-4513-886c-6b8dc0330a97","added_by":"auto","created_at":"2025-08-14 09:44:25","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3294422,"visible":true,"origin":"","legend":"Article File","description":"","filename":"SRAJAQDMQDmanuscriptFinal060525V3.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6839005/v1_covered_0f6d0361-b6b3-4333-b519-348286c15802.pdf"},{"id":84828859,"identity":"ef389cce-f58b-41ae-9e47-de16c2a12767","added_by":"auto","created_at":"2025-06-17 18:08:58","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":5301058,"visible":true,"origin":"","legend":"Supplemental Materials","description":"","filename":"SRAJAQDMQD050724SIFinal060525V2.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6839005/v1/77c08c479d527d185d420d3c.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Triplet Exciton Delocalization in Organic-Quantum Dots Hybrid Photo-Systems: A Pathway to Improved Phototherapy and Theragnostics","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"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":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Hybrid photo-materials, Exciton delocalization, Heavy atom effect, Triplet photochemistry, Singlet oxygen and photodynamic therapy","lastPublishedDoi":"10.21203/rs.3.rs-6839005/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6839005/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"In this work, we engineered hybrid photo-assemblies consisting of an organic triplet chromophore (QDM) and core-shell CdSe/ZnS, CdZnS/ZnS, core CdZnS, or CdS quantum dots (QD). Photophysical data shows that the presence of the QD in the vicinity of the QDM enhances spin-orbit coupling (SOC), resulting in the depopulation of the singlet excited state to create the corresponding triplet transient species with an accelerated intersystem crossing (ISC) of rate constants in the range kISC = 8.6–18 x1010 s-1 and a three-fold increase of triplet lifetime for the hybrids. Further photophysical, electrochemical, and computational investigations revealed that the triplet state of QDM is delocalized into the QD bands, which explains the increased triplet lifetime of the hybrids. Moreover, triplet photosensitization of molecular oxygen (3O2) using the hybrids produced 1O2 with a Φ(1O2) of 67% (in toluene) and 64% (in water) for the hybrid photo-material(s) compared to that of QDM alone (52% in toluene and 28% in water). This enhanced quantum efficiency was corroborated in dendritic cell viability assays, with cell death rates as high as 97%. The inherent emissive properties of QD component(s) facilitated the use of our new hybrid photo-assemblies as multifunctional platforms for synergistic bio-imaging and phototherapy.","manuscriptTitle":"Triplet Exciton Delocalization in Organic-Quantum Dots Hybrid Photo-Systems: A Pathway to Improved Phototherapy and Theragnostics","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-17 18:08:53","doi":"10.21203/rs.3.rs-6839005/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"7dc5523b-c30d-4d9c-b327-5191516c415a","owner":[],"postedDate":"June 17th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":50015121,"name":"Physical sciences/Materials science/Nanoscale materials/Organic\u0026#x2013;inorganic nanostructures"},{"id":50015122,"name":"Physical sciences/Energy science and technology/Energy modelling"}],"tags":[],"updatedAt":"2025-08-14T09:36:08+00:00","versionOfRecord":[],"versionCreatedAt":"2025-06-17 18:08:53","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6839005","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6839005","identity":"rs-6839005","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}