Cellulose–TBPH interactions from diffusion NMR, rheology and SAXS studies

Cellulose–TBPH interactions from diffusion NMR, rheology and SAXS studies | 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 Cellulose–TBPH interactions from diffusion NMR, rheology and SAXS studies Soline Quilliard, Djibril Rouzaud, Cassandre Kouvatas, Philippe Bazin, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6993367/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 Self-diffusion coefficients, critical concentrations, characteristic radii and interactions between solute and solvent are rarely explored at high polymer concentrations matching realistic processing conditions. At these concentrations, heterogeneous dissolution takes place and common rheological or diffusion models can fail. In this work, these parameters were measured for dilute and concentrated solutions of two microcrystalline celluloses with two different average polymerization degrees in aqueous solutions of tetrabutylphosphonium hydroxide (TBPH). In order to do so, a systematic study was conducted by rheology, small angle X-ray scattering (SAXS) and pulsed field gradient (PFG) stimulated echo NMR. The critical concentrations c* were estimated from NMR diffusion studies and rheology. SAXS and diffusion NMR yielded the gyration and hydrodynamic radii. Cellulose concentration impacted the diffusivity of the system components, revealing different interactions between solvent and solute. The increased presence of poorly dissolved cellulosic fraction above c* abruptly changes the diffusivity of the mobile moieties. It was also found that the amount of tetrabutylphosphonium cations bound to the dissolved cellulose molecules saturated at 50%, regardless of the other conditions. The solutions clearly exhibited a multi-component composition with coexisting objects as diverse as crystallites or near-ideal polymer coils; their relative amount strongly depended on the polymer concentration. This article demonstrates that one technique alone cannot suffice in describing the complexity of these systems over the whole concentration ranges, but combining information from PFG NMR and SAXS data is promising in explaining a wide range of solution states. Microcrystalline Cellulose Tetrabutylphosphonium hydroxide Ionic Liquids Self-diffusion SAXS Rheology Polymer-solvent interactions Full Text Additional Declarations No competing interests reported. Supplementary Files SupportingInformationfinal.docx 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-6993367","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":481153975,"identity":"e760c3da-197d-4091-aa59-f96340fc5d9b","order_by":0,"name":"Soline Quilliard","email":"","orcid":"","institution":"University of Le Havre","correspondingAuthor":false,"prefix":"","firstName":"Soline","middleName":"","lastName":"Quilliard","suffix":""},{"id":481153976,"identity":"fab58ba1-f4c4-477a-9ad0-f6c8dbb0e750","order_by":1,"name":"Djibril Rouzaud","email":"","orcid":"","institution":"Université de Caen Normandie","correspondingAuthor":false,"prefix":"","firstName":"Djibril","middleName":"","lastName":"Rouzaud","suffix":""},{"id":481153977,"identity":"d1a829b4-6dc8-405c-b2b5-ad8f98e42abd","order_by":2,"name":"Cassandre Kouvatas","email":"","orcid":"","institution":"Université de Caen Normandie","correspondingAuthor":false,"prefix":"","firstName":"Cassandre","middleName":"","lastName":"Kouvatas","suffix":""},{"id":481153978,"identity":"3ee184be-e5f3-412a-addd-9bb64394a949","order_by":3,"name":"Philippe Bazin","email":"","orcid":"","institution":"Université de Caen Normandie","correspondingAuthor":false,"prefix":"","firstName":"Philippe","middleName":"","lastName":"Bazin","suffix":""},{"id":481153979,"identity":"26a29587-290e-4644-ba08-00302fdbb54d","order_by":4,"name":"Arnaud Prigent","email":"","orcid":"","institution":"University of Le Havre","correspondingAuthor":false,"prefix":"","firstName":"Arnaud","middleName":"","lastName":"Prigent","suffix":""},{"id":481153980,"identity":"a06a2b6e-9b8d-48b4-9485-913ff7ae99a8","order_by":5,"name":"Arnaud Travert","email":"","orcid":"","institution":"Université de Caen Normandie","correspondingAuthor":false,"prefix":"","firstName":"Arnaud","middleName":"","lastName":"Travert","suffix":""},{"id":481153981,"identity":"6291b993-7a36-4be9-8879-e6097c53dc78","order_by":6,"name":"Benoit Duchemin","email":"data:image/png;base64,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","orcid":"","institution":"University of Le Havre","correspondingAuthor":true,"prefix":"","firstName":"Benoit","middleName":"","lastName":"Duchemin","suffix":""}],"badges":[],"createdAt":"2025-06-27 16:38:04","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6993367/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6993367/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":99315344,"identity":"e51ce50d-eff2-4c2b-b76f-ae0d23af3193","added_by":"auto","created_at":"2025-12-31 16:26:50","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1496252,"visible":true,"origin":"","legend":"","description":"","filename":"Manuscriptfinal.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6993367/v1_covered_f4bc5c15-6ee3-4da7-a59f-df301c15774d.pdf"},{"id":89107533,"identity":"236224aa-0d75-4aa2-b1e7-c874d36e64df","added_by":"auto","created_at":"2025-08-14 17:56:58","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":4552582,"visible":true,"origin":"","legend":"","description":"","filename":"SupportingInformationfinal.docx","url":"https://assets-eu.researchsquare.com/files/rs-6993367/v1/0e52fc45e128a429cb616f29.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Cellulose–TBPH interactions from diffusion NMR, rheology and SAXS studies","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":"Microcrystalline Cellulose, Tetrabutylphosphonium hydroxide, Ionic Liquids, Self-diffusion, SAXS, Rheology, Polymer-solvent interactions","lastPublishedDoi":"10.21203/rs.3.rs-6993367/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6993367/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSelf-diffusion coefficients, critical concentrations, characteristic radii and interactions between solute and solvent are rarely explored at high polymer concentrations matching realistic processing conditions. At these concentrations, heterogeneous dissolution takes place and common rheological or diffusion models can fail. In this work, these parameters were measured for dilute and concentrated solutions of two microcrystalline celluloses with two different average polymerization degrees in aqueous solutions of tetrabutylphosphonium hydroxide (TBPH). In order to do so, a systematic study was conducted by rheology, small angle X-ray scattering (SAXS) and pulsed field gradient (PFG) stimulated echo NMR. The critical concentrations \u003cem\u003ec*\u003c/em\u003e were estimated from NMR diffusion studies and rheology. SAXS and diffusion NMR yielded the gyration and hydrodynamic radii. Cellulose concentration impacted the diffusivity of the system components, revealing different interactions between solvent and solute. The increased presence of poorly dissolved cellulosic fraction above c* abruptly changes the diffusivity of the mobile moieties. It was also found that the amount of tetrabutylphosphonium cations bound to the dissolved cellulose molecules saturated at 50%, regardless of the other conditions. The solutions clearly exhibited a multi-component composition with coexisting objects as diverse as crystallites or near-ideal polymer coils; their relative amount strongly depended on the polymer concentration. This article demonstrates that one technique alone cannot suffice in describing the complexity of these systems over the whole concentration ranges, but combining information from PFG NMR and SAXS data is promising in explaining a wide range of solution states.\u003c/p\u003e","manuscriptTitle":"Cellulose–TBPH interactions from diffusion NMR, rheology and SAXS studies","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-08-14 17:56:53","doi":"10.21203/rs.3.rs-6993367/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":"eefa7a4d-ead3-43c6-9644-9994e55e63da","owner":[],"postedDate":"August 14th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-12-27T20:53:23+00:00","versionOfRecord":[],"versionCreatedAt":"2025-08-14 17:56:53","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6993367","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6993367","identity":"rs-6993367","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}