The role of headgroup structural modifications in aggregation behavior of imidazolium surfactants: Combining experiments and computational modeling.
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| Title: | The role of headgroup structural modifications in aggregation behavior of imidazolium surfactants: Combining experiments and computational modeling. |
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| Authors: | Katsyuba, Sergey A.1 (AUTHOR), Kuznetsova, Darya A.1 (AUTHOR), Kuznetsov, Denis M.1 (AUTHOR), Gerasimova, Tatiana P.1 (AUTHOR), Gaynanova, Gulnara A.1 (AUTHOR), Zakharova, Lucia Ya.1 (AUTHOR) luciaz@mail.ru, Sinyashin, Oleg G.1 (AUTHOR) |
| Source: | Journal of Molecular Liquids. Oct2025, Vol. 435, pN.PAG-N.PAG. 1p. |
| Subjects: | Critical micelle concentration, Computer simulation, Empirical research, Imidazoles, Molecular dynamics, Molecular self-assembly |
| Abstract: | Previous studies of imidazolium surfactants with diverse headgroup modifications revealed that while alkyl chain length systematically influences critical micelle concentration (CMC) values, the impact of headgroup structure remains unclear. To address this issue, the effects of structural variations in the headgroup on aggregation behavior of these amphiphiles were analyzed using data obtained from both experimental and computational methods. CMC, zeta potential, size characteristics of micelles and pre-micelle of 1-decyl-3-methylimidazolium bromide ([C 10 mim]Br), their morphology and the solubilizing ability were analyzed experimentally by the methods of tensiometry, conductometry, spectrophotometry, fluorimetry, dynamic and electrophoretic light scattering. These results are supplemented by comparative analysis of experimental and computational data on longer-chain homologues and carbamate-functionalized analogs. Computational modeling included optimization of surfactant monomers in aqueous solutions using the semi-empirical quantum mechanical (QM) method GFN2-xTB with combined implicit and explicit treatment of surrounding water. Micelles with the lowest aggregation numbers and pre-micelle of [C 10 mim]Br were modeled by clusters of the corresponding sizes grown from the abovementioned optimized aqueous surfactants. Molecular dynamics simulations of these aqueous solution droplets using the general force field GFN-FF and QM evaluation of the atomic charges of the modeled species at the GFN2-xTB level allowed us to obtain structures with dimensions, surface charge and degree of counterions' binding qualitatively matching their experimental counterparts. Stronger hydration of head group of carbamate-substituted species relative to their parent 1-alkyl-3-methylimidazolium surfactants, revealed by the computations, suggests this factor as one of the reasons of the smaller CMC values found experimentally for the former amphiphiles relative to the latter. [Display omitted] • Imidazolium surfactants with methyl- and carbamate moieties were studied. • Two series of surfactants were compared in terms of their self-assembling behavior. • Experimental and computational methods were used for the study. • The GFN2-xTB semi-empirical quantum mechanical method was used in the work. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Molecular Liquids is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 187791537 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: The role of headgroup structural modifications in aggregation behavior of imidazolium surfactants: Combining experiments and computational modeling. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Katsyuba%2C+Sergey+A%2E%22">Katsyuba, Sergey A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Kuznetsova%2C+Darya+A%2E%22">Kuznetsova, Darya A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Kuznetsov%2C+Denis+M%2E%22">Kuznetsov, Denis M.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Gerasimova%2C+Tatiana+P%2E%22">Gerasimova, Tatiana P.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Gaynanova%2C+Gulnara+A%2E%22">Gaynanova, Gulnara A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zakharova%2C+Lucia+Ya%2E%22">Zakharova, Lucia Ya.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> luciaz@mail.ru</i><br /><searchLink fieldCode="AR" term="%22Sinyashin%2C+Oleg+G%2E%22">Sinyashin, Oleg G.</searchLink><relatesTo>1</relatesTo> (AUTHOR) – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Molecular+Liquids%22">Journal of Molecular Liquids</searchLink>. Oct2025, Vol. 435, pN.PAG-N.PAG. 1p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Critical+micelle+concentration%22">Critical micelle concentration</searchLink><br /><searchLink fieldCode="DE" term="%22Computer+simulation%22">Computer simulation</searchLink><br /><searchLink fieldCode="DE" term="%22Empirical+research%22">Empirical research</searchLink><br /><searchLink fieldCode="DE" term="%22Imidazoles%22">Imidazoles</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+dynamics%22">Molecular dynamics</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+self-assembly%22">Molecular self-assembly</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Previous studies of imidazolium surfactants with diverse headgroup modifications revealed that while alkyl chain length systematically influences critical micelle concentration (CMC) values, the impact of headgroup structure remains unclear. To address this issue, the effects of structural variations in the headgroup on aggregation behavior of these amphiphiles were analyzed using data obtained from both experimental and computational methods. CMC, zeta potential, size characteristics of micelles and pre-micelle of 1-decyl-3-methylimidazolium bromide ([C 10 mim]Br), their morphology and the solubilizing ability were analyzed experimentally by the methods of tensiometry, conductometry, spectrophotometry, fluorimetry, dynamic and electrophoretic light scattering. These results are supplemented by comparative analysis of experimental and computational data on longer-chain homologues and carbamate-functionalized analogs. Computational modeling included optimization of surfactant monomers in aqueous solutions using the semi-empirical quantum mechanical (QM) method GFN2-xTB with combined implicit and explicit treatment of surrounding water. Micelles with the lowest aggregation numbers and pre-micelle of [C 10 mim]Br were modeled by clusters of the corresponding sizes grown from the abovementioned optimized aqueous surfactants. Molecular dynamics simulations of these aqueous solution droplets using the general force field GFN-FF and QM evaluation of the atomic charges of the modeled species at the GFN2-xTB level allowed us to obtain structures with dimensions, surface charge and degree of counterions' binding qualitatively matching their experimental counterparts. Stronger hydration of head group of carbamate-substituted species relative to their parent 1-alkyl-3-methylimidazolium surfactants, revealed by the computations, suggests this factor as one of the reasons of the smaller CMC values found experimentally for the former amphiphiles relative to the latter. [Display omitted] • Imidazolium surfactants with methyl- and carbamate moieties were studied. • Two series of surfactants were compared in terms of their self-assembling behavior. • Experimental and computational methods were used for the study. • The GFN2-xTB semi-empirical quantum mechanical method was used in the work. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Molecular Liquids is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1016/j.molliq.2025.128131 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 1 StartPage: N.PAG Subjects: – SubjectFull: Critical micelle concentration Type: general – SubjectFull: Computer simulation Type: general – SubjectFull: Empirical research Type: general – SubjectFull: Imidazoles Type: general – SubjectFull: Molecular dynamics Type: general – SubjectFull: Molecular self-assembly Type: general Titles: – TitleFull: The role of headgroup structural modifications in aggregation behavior of imidazolium surfactants: Combining experiments and computational modeling. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Katsyuba, Sergey A. – PersonEntity: Name: NameFull: Kuznetsova, Darya A. – PersonEntity: Name: NameFull: Kuznetsov, Denis M. – PersonEntity: Name: NameFull: Gerasimova, Tatiana P. – PersonEntity: Name: NameFull: Gaynanova, Gulnara A. – PersonEntity: Name: NameFull: Zakharova, Lucia Ya. – PersonEntity: Name: NameFull: Sinyashin, Oleg G. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 10 Text: Oct2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 01677322 Numbering: – Type: volume Value: 435 Titles: – TitleFull: Journal of Molecular Liquids Type: main |
| ResultId | 1 |
