Thermodynamic Surface Characterization of Sustainable Polymers by Advanced Inverse Gas Chromatography Revealing Nonlinear Lewis Acid–Base Interactions for Environmental and Biomedical Applications

Thermodynamic Surface Characterization of Sustainable Polymers by Advanced Inverse Gas Chromatography Revealing Nonlinear Lewis Acid–Base Interactions for Environmental and Biomedical Applications | 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 Research Article Thermodynamic Surface Characterization of Sustainable Polymers by Advanced Inverse Gas Chromatography Revealing Nonlinear Lewis Acid–Base Interactions for Environmental and Biomedical Applications Tayssir Hamieh This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9456072/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 7 You are reading this latest preprint version Abstract The development of sustainable polymer systems for environmental and biomedical applications requires a rigorous understanding of the surface thermodynamics governing intermolecular interactions. In this work, an advanced inverse gas chromatography (IGC) methodology is employed to investigate the temperature-dependent surface energetics and molecular interaction properties of representative sustainable polymers, namely polylactic acid (PLA) and cellulose acrylate (CA). A unified thermodynamic framework is developed, enabling the quantitative determination of London dispersive surface energy, Lewis acid–base parameters, and adsorption free energies as explicit functions of temperature. The approach integrates key molecular descriptors, including deformation polarizability, ionization energy, and intermolecular separation distance, providing a consistent description of both dispersive and specific interactions at polymer interfaces. The results demonstrate that adsorption is governed by a coupled and temperature-dependent interplay between dispersive forces and polar interactions. The London dispersive surface energy exhibits a strictly linear decrease with temperature, while the intermolecular separation distance and the effective molecular surface area are shown to vary linearly, confirming that structural descriptors of adsorption are thermodynamic quantities rather than fixed geometric parameters. A central contribution of this work is the validation of the five-parameter Hamieh model for Lewis acid–base interactions. Statistical analysis (R², RMSE, AIC, and BIC) demonstrates its clear superiority over classical models, highlighting the essential role of amphoteric coupling and nonlinear donor–acceptor effects. The analysis reveals two distinct interfacial regimes: PLA exhibits a predominantly dispersive and basic character with weak nonlinearity, whereas CA displays a strongly amphoteric, heterogeneous, and nonlinear behavior. Importantly, the proposed framework establishes direct relationships between surface thermodynamic parameters and functional performance, providing predictive insight into adsorption, wettability, and interfacial compatibility. These findings offer a robust basis for the rational design of sustainable polymer materials for environmental remediation and biomedical applications, including pollutant removal, drug delivery, and tissue engineering. This work establishes a general thermodynamic methodology for the characterization of polymer interfaces, bridging molecular-scale interactions and macroscopic behavior, and highlighting the potential of advanced IGC for the development of next-generation sustainable materials. Sustainable polymers Surface thermodynamics Dispersive surface energy Lewis acid–base interactions Nonlinear adsorption Polymer–interface interactions Environmental remediation Biomedical materials Full Text Additional Declarations No competing interests reported. Supplementary Files Supplementarymaterials.pdf Cite Share Download PDF Status: Under Review Version 1 posted Reviewers agreed at journal 16 May, 2026 Reviews received at journal 10 May, 2026 Reviewers agreed at journal 30 Apr, 2026 Reviewers invited by journal 30 Apr, 2026 Editor assigned by journal 30 Apr, 2026 Submission checks completed at journal 28 Apr, 2026 First submitted to journal 28 Apr, 2026 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-9456072","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":632438239,"identity":"8ecc7788-e06d-4515-bc42-c974cc683a7c","order_by":0,"name":"Tayssir Hamieh","email":"data:image/png;base64,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","orcid":"","institution":"Maastricht University","correspondingAuthor":true,"prefix":"","firstName":"Tayssir","middleName":"","lastName":"Hamieh","suffix":""}],"badges":[],"createdAt":"2026-04-18 11:23:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9456072/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9456072/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":108807723,"identity":"39952ad7-b969-48ab-bf1e-b9ed9af572ee","added_by":"auto","created_at":"2026-05-08 15:31:20","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":770234,"visible":true,"origin":"","legend":"","description":"","filename":"NewpaperHamiehforDiscoverMaterials.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9456072/v1_covered_9ac325c2-cff5-497e-a05e-198bc39c6d88.pdf"},{"id":108799875,"identity":"18be1597-f3c7-4541-963d-b7767996c168","added_by":"auto","created_at":"2026-05-08 14:02:07","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":419616,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementarymaterials.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9456072/v1/a5023546524b206a9694974d.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Thermodynamic Surface Characterization of Sustainable Polymers by Advanced Inverse Gas Chromatography Revealing Nonlinear Lewis Acid–Base Interactions for Environmental and Biomedical Applications","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"discover-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"dime","sideBox":"Learn more about [Discover Materials](https://www.springer.com/journal/43939)","snPcode":"","submissionUrl":"","title":"Discover Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Sustainable polymers, Surface thermodynamics, Dispersive surface energy, Lewis acid–base interactions, Nonlinear adsorption, Polymer–interface interactions, Environmental remediation, Biomedical materials","lastPublishedDoi":"10.21203/rs.3.rs-9456072/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9456072/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe development of sustainable polymer systems for environmental and biomedical applications requires a rigorous understanding of the surface thermodynamics governing intermolecular interactions. In this work, an advanced inverse gas chromatography (IGC) methodology is employed to investigate the temperature-dependent surface energetics and molecular interaction properties of representative sustainable polymers, namely polylactic acid (PLA) and cellulose acrylate (CA).\u003c/p\u003e \u003cp\u003eA unified thermodynamic framework is developed, enabling the quantitative determination of London dispersive surface energy, Lewis acid\u0026ndash;base parameters, and adsorption free energies as explicit functions of temperature. The approach integrates key molecular descriptors, including deformation polarizability, ionization energy, and intermolecular separation distance, providing a consistent description of both dispersive and specific interactions at polymer interfaces.\u003c/p\u003e \u003cp\u003eThe results demonstrate that adsorption is governed by a coupled and temperature-dependent interplay between dispersive forces and polar interactions. The London dispersive surface energy exhibits a strictly linear decrease with temperature, while the intermolecular separation distance and the effective molecular surface area are shown to vary linearly, confirming that structural descriptors of adsorption are thermodynamic quantities rather than fixed geometric parameters.\u003c/p\u003e \u003cp\u003eA central contribution of this work is the validation of the five-parameter Hamieh model for Lewis acid\u0026ndash;base interactions. Statistical analysis (R\u0026sup2;, RMSE, AIC, and BIC) demonstrates its clear superiority over classical models, highlighting the essential role of amphoteric coupling and nonlinear donor\u0026ndash;acceptor effects. The analysis reveals two distinct interfacial regimes: PLA exhibits a predominantly dispersive and basic character with weak nonlinearity, whereas CA displays a strongly amphoteric, heterogeneous, and nonlinear behavior.\u003c/p\u003e \u003cp\u003eImportantly, the proposed framework establishes direct relationships between surface thermodynamic parameters and functional performance, providing predictive insight into adsorption, wettability, and interfacial compatibility. These findings offer a robust basis for the rational design of sustainable polymer materials for environmental remediation and biomedical applications, including pollutant removal, drug delivery, and tissue engineering.\u003c/p\u003e \u003cp\u003eThis work establishes a general thermodynamic methodology for the characterization of polymer interfaces, bridging molecular-scale interactions and macroscopic behavior, and highlighting the potential of advanced IGC for the development of next-generation sustainable materials.\u003c/p\u003e","manuscriptTitle":"Thermodynamic Surface Characterization of Sustainable Polymers by Advanced Inverse Gas Chromatography Revealing Nonlinear Lewis Acid–Base Interactions for Environmental and Biomedical Applications","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-05-08 14:02:03","doi":"10.21203/rs.3.rs-9456072/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"278603138962592213953351857346914744292","date":"2026-05-16T09:07:31+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-10T08:30:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"59814783385621372673678621530164129715","date":"2026-04-30T12:12:26+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-04-30T09:29:08+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-04-30T04:52:25+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-04-28T15:17:00+00:00","index":"","fulltext":""},{"type":"submitted","content":"Discover Materials","date":"2026-04-28T13:11:04+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"discover-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"dime","sideBox":"Learn more about [Discover Materials](https://www.springer.com/journal/43939)","snPcode":"","submissionUrl":"","title":"Discover Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"ddf5b960-233d-4f56-8321-45e0d7c4f211","owner":[],"postedDate":"May 8th, 2026","published":true,"recentEditorialEvents":[{"type":"reviewerAgreed","content":"278603138962592213953351857346914744292","date":"2026-05-16T09:07:31+00:00","index":27,"fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-10T08:30:33+00:00","index":18,"fulltext":""},{"type":"reviewerAgreed","content":"59814783385621372673678621530164129715","date":"2026-04-30T12:12:26+00:00","index":17,"fulltext":""},{"type":"reviewersInvited","content":"12","date":"2026-04-30T09:29:08+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-04-30T04:52:25+00:00","index":"","fulltext":""}],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-05-08T14:02:03+00:00","versionOfRecord":[],"versionCreatedAt":"2026-05-08 14:02:03","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9456072","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9456072","identity":"rs-9456072","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}