Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition
Mixtures of cationic and anionic surfactants often originate bilayer structures, such as vesicles and lamellar liquid crystals, that can be explored as model membranes for fundamental studies or as drug and gene nanocarriers. Here, we investigated the aggregation properties of two catanionic mixture...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-02-01
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| Series: | Membranes |
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| Online Access: | https://www.mdpi.com/2077-0375/13/2/178 |
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| author | Isabel S. Oliveira Sandra G. Silva Maria Luísa do Vale Eduardo F. Marques |
| author_facet | Isabel S. Oliveira Sandra G. Silva Maria Luísa do Vale Eduardo F. Marques |
| author_sort | Isabel S. Oliveira |
| collection | DOAJ |
| description | Mixtures of cationic and anionic surfactants often originate bilayer structures, such as vesicles and lamellar liquid crystals, that can be explored as model membranes for fundamental studies or as drug and gene nanocarriers. Here, we investigated the aggregation properties of two catanionic mixtures containing biomimetic surfactants derived from serine. The mixtures are designated as 12Ser/8-8Ser and 14Ser/10-10Ser, where mSer is a cationic, single-chained surfactant and n-nSer is an anionic, double-chained one (m and n being the C atoms in the alkyl chains). Our goal was to investigate the effects of total chain length and chain length asymmetry of the catanionic pair on the formation of catanionic vesicles, the vesicle properties and the vesicle/micelle transitions. Ocular observations, surface tension measurements, video-enhanced light microscopy, cryogenic scanning electron microscopy, dynamic and electrophoretic light scattering were used to monitor the self-assembly process and the aggregate properties. Catanionic vesicles were indeed found in both systems for molar fractions of cationic surfactant ≥0.40, always possessing positive zeta potentials (<i>ζ</i> = +35–50 mV), even for equimolar sample compositions. Furthermore, the 14Ser/10-10Ser vesicles were only found as single aggregates (i.e., without coexisting micelles) in a very narrow compositional range and as a bimodal population (average diameters of 80 and 300 nm). In contrast, the 12Ser/8-8Ser vesicles were found for a wider sample compositional range and as unimodal or bimodal populations, depending on the mixing ratio. The aggregate size, pH and zeta potential of the mixtures were further investigated. The unimodal 12Ser/8-8Ser vesicles (<<i>D</i><sub>H</sub>> ≈ 250 nm, pH ≈ 7–8, <i>ζ</i> ≈ +32 mV and a cationic/anionic molar ratio of ≈2:1) are particularly promising for application as drug/gene nanocarriers. Both chain length asymmetry and total length play a key role in the aggregation features of the two systems. Molecular insights are provided by the main findings. |
| first_indexed | 2024-03-11T08:26:29Z |
| format | Article |
| id | doaj.art-9df8771341404b22becf127074855398 |
| institution | Directory Open Access Journal |
| issn | 2077-0375 |
| language | English |
| last_indexed | 2024-03-11T08:26:29Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Membranes |
| spelling | doaj.art-9df8771341404b22becf1270748553982023-11-16T22:02:24ZengMDPI AGMembranes2077-03752023-02-0113217810.3390/membranes13020178Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle TransitionIsabel S. Oliveira0Sandra G. Silva1Maria Luísa do Vale2Eduardo F. Marques3CIQUP, IMS (Institute of Molecular Sciences), Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto, PortugalLAQV-REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto, PortugalLAQV-REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto, PortugalCIQUP, IMS (Institute of Molecular Sciences), Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto, PortugalMixtures of cationic and anionic surfactants often originate bilayer structures, such as vesicles and lamellar liquid crystals, that can be explored as model membranes for fundamental studies or as drug and gene nanocarriers. Here, we investigated the aggregation properties of two catanionic mixtures containing biomimetic surfactants derived from serine. The mixtures are designated as 12Ser/8-8Ser and 14Ser/10-10Ser, where mSer is a cationic, single-chained surfactant and n-nSer is an anionic, double-chained one (m and n being the C atoms in the alkyl chains). Our goal was to investigate the effects of total chain length and chain length asymmetry of the catanionic pair on the formation of catanionic vesicles, the vesicle properties and the vesicle/micelle transitions. Ocular observations, surface tension measurements, video-enhanced light microscopy, cryogenic scanning electron microscopy, dynamic and electrophoretic light scattering were used to monitor the self-assembly process and the aggregate properties. Catanionic vesicles were indeed found in both systems for molar fractions of cationic surfactant ≥0.40, always possessing positive zeta potentials (<i>ζ</i> = +35–50 mV), even for equimolar sample compositions. Furthermore, the 14Ser/10-10Ser vesicles were only found as single aggregates (i.e., without coexisting micelles) in a very narrow compositional range and as a bimodal population (average diameters of 80 and 300 nm). In contrast, the 12Ser/8-8Ser vesicles were found for a wider sample compositional range and as unimodal or bimodal populations, depending on the mixing ratio. The aggregate size, pH and zeta potential of the mixtures were further investigated. The unimodal 12Ser/8-8Ser vesicles (<<i>D</i><sub>H</sub>> ≈ 250 nm, pH ≈ 7–8, <i>ζ</i> ≈ +32 mV and a cationic/anionic molar ratio of ≈2:1) are particularly promising for application as drug/gene nanocarriers. Both chain length asymmetry and total length play a key role in the aggregation features of the two systems. Molecular insights are provided by the main findings.https://www.mdpi.com/2077-0375/13/2/178amino acid-based surfactantscatanionic vesiclesself-assemblyasymmetric chain lengthsdrug/gene delivery |
| spellingShingle | Isabel S. Oliveira Sandra G. Silva Maria Luísa do Vale Eduardo F. Marques Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition Membranes amino acid-based surfactants catanionic vesicles self-assembly asymmetric chain lengths drug/gene delivery |
| title | Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition |
| title_full | Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition |
| title_fullStr | Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition |
| title_full_unstemmed | Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition |
| title_short | Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition |
| title_sort | model catanionic vesicles from biomimetic serine based surfactants effect of the combination of chain lengths on vesicle properties and vesicle to micelle transition |
| topic | amino acid-based surfactants catanionic vesicles self-assembly asymmetric chain lengths drug/gene delivery |
| url | https://www.mdpi.com/2077-0375/13/2/178 |
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