Efficient N-sulfopropylation of chitosan with 1,3-propane sultone in aqueous solutions: neutral pH as the key condition

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dc.authoridHeydari, Abolfazl/0000-0002-7746-7480
dc.authoridLacik, Igor/0000-0001-6037-3747
dc.authoridDarroudi, Mahdieh/0000-0002-9152-2642
dc.contributor.authorHeydari, Abolfazl
dc.contributor.authorDarroudi, Mahdieh
dc.contributor.authorLacik, Igor
dc.date.accessioned2025-02-20T08:42:17Z
dc.date.available2025-02-20T08:42:17Z
dc.date.issued2021
dc.departmentTürk-Alman Üniversitesien_US
dc.description.abstractConjugation of strong anionic sulfonate groups to chitosan (CS) is typically used for converting the weak cationic CS to its polyampholyte derivatives, which are of interest to different areas benefiting from both cationic and anionic groups. The content of anionic charges can be tuned by varying the level of sulfonation, which is a fundamental characteristic expressed as the degree of substitution (DS). The subject of this work is the synthesis of the representative polyampholyte of this class, N-(3-sulfopropyl)chitosan salt (SPCS), by the reaction of CS with 1,3-propane sultone (PrS) in water. According to the literature, this reaction is mostly performed under acidic conditions and should lead to SPCS with high DS values. We found that such DS values are likely overestimated due to the presence of a non-covalently bonded sulfopropyl group, originating from extensive PrS hydrolysis, in the SPCS structure. In this work, the combination of experimental and theoretical approaches resulted in selecting a neutral pH for the SPCS synthesis, which increased the efficiency of the N-sulfopropylation reaction. Quantum chemistry calculations suggest that this finding primarily corresponds with the higher reactivity of PrS to a non-protonated glucosamine unit compared to a protonated one, where the molar fraction of the non-protonated unit at neutral pH is remarkably higher than that at acidic pH. The developed purification conditions make the SPCS free from the non-covalently bonded sulfopropyl groups. We show that true DS values can be obtained by NMR regardless of the level of SPCS purity, and also by elemental analysis for completely pure SPCS. It is noticeable that while the true DS values for SPCS synthesized under acidic conditions are limited to only around 5%, these values range between 25 and 95% for SPCS synthesized under neutral conditions and can be readily controlled by the weight ratio between CS and PrS. Hence, this work provides guidelines for a simple yet feasible and highly effective sulfopropylation reaction with PrS under aqueous conditions.
dc.description.sponsorshipJuvenile Diabetes Research Foundation (JDRF) [2-SRA-2018-521-S-B]; Chicago Diabetes Project; Slovak Research and Development Agency [APVV-18-0480, APVV-14-0858]; Slovak Grant Agency [VEGA 2/0140/20]; Integrated Infrastructure Operational Programme - ERDF [313021T081]
dc.description.sponsorshipThis work was supported by the Juvenile Diabetes Research Foundation (JDRF) Grant No. 2-SRA-2018-521-S-B, the Chicago Diabetes Project, the Slovak Research and Development Agency under the contract numbers APVV-18-0480 and APVV-14-0858, and the Slovak Grant Agency VEGA 2/0140/20. This work was performed during the implementation of the project Building-up Centre for advanced materials application of the Slovak Academy of Sciences, ITMS project code 313021T081 supported by the Integrated Infrastructure Operational Programme funded by the ERDF. The numerical calculations reported in this work were performed at SANCAR, Turkish-German University System and Nodes of Computational Applications and Research.
dc.identifier.doi10.1039/d1re00089f
dc.identifier.endpage2158en_US
dc.identifier.issn2058-9883
dc.identifier.issue11en_US
dc.identifier.scopus2-s2.0-85118305151
dc.identifier.startpage2146en_US
dc.identifier.urihttps://doi.org/10.1039/d1re00089f
dc.identifier.urihttps://hdl.handle.net/20.500.12846/1629
dc.identifier.volume6en_US
dc.identifier.wosWOS:000686304600001
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoen
dc.publisherRoyal Soc Chemistry
dc.relation.ispartofReaction Chemistry & Engineering
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/closedAccess
dc.snmzKA_WOS_20250220
dc.subjectSulfonated Chitosanen_US
dc.subjectChemical Modificationen_US
dc.subjectGraphene Oxideen_US
dc.subjectDerivativesen_US
dc.subjectIonizationen_US
dc.subjectBiopolymeren_US
dc.subjectHydrolysisen_US
dc.subjectReactivityen_US
dc.subjectMechanismen_US
dc.subjectEnergiesen_US
dc.titleEfficient N-sulfopropylation of chitosan with 1,3-propane sultone in aqueous solutions: neutral pH as the key condition
dc.typeArticle

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