SDS triggered transformation of highly hydrophobic Pluronics® nanoaggregate into polymer-rich and surfactant-rich mixed micelles

Patel, Divya; Ray, Debes; Tiwari, Sanjay; Kuperkar, Ketan; Aswal, Vinod K.; Bahadur, Pratap

doi:10.1016/j.molliq.2021.117812

Cited by 13 publications

(20 citation statements)

References 46 publications

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“…Previous investigations have revealed the thickness of the ULVs to be significantly smaller due to the interdigitating of the hydrophobic tails. ,, The scattering from the head group region is small and can be neglected. It is generally accepted that for the aggregates formed from surfactants, some solvent (D 2 O) molecules penetrate the head group region to some extent and thus decrease the contrast, thereby reducing the apparent bilayer thickness measured by SANS.…”

Section: Resultsmentioning

confidence: 99%

“…Here, the CP has been determined by observing an abrupt turbidity appearance in the solution with a progressive temperature increase. The CP measurements were repeated a minimum of three times within a temperature range of ±0.1 °C. ,,, …”

Section: Methodsmentioning

confidence: 99%

“…The He–Ne, 4 mW laser (wavelength λ o = ∼635 nm) was used as the incident beam with the scattering angle 90°. The D h was recorded considering three consecutive measurements for each sample. ,− …”

Section: Methodsmentioning

confidence: 99%

“…The CP (which is often related to the dehydration of the PEO moiety with the progressive increase in temperature) of 1% w/v L81, i.e., ∼20 °C along with their CMT (<20 °C) is in accordance with the literature data. 16,30 The degree of hydrophobicity exhibited by the three cationic surfactants followed the order: DTAB < 12-2-12 < DDAB. 5,6,63,64 Studies have also inferred that the clouding phenomenon in these conventional Pluronics can be impacted by the presence of additives, where both a deferral and an improvement were noticed.…”

Section: ■ Introductionmentioning

confidence: 99%

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Rationalizing the Design of Pluronics–Surfactant Mixed Micelles through Molecular Simulations and Experiments

et al. 2023

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Aqueous systems comprising polymers and surfactants are technologically important complex fluids with tunable features dependent on the chemical nature of each constituent, overall composition in mixed systems, and solution conditions. The phase behavior and self-assembly of amphiphilic polymers can be changed drastically in the presence of conventional ionic surfactants and need to be clearly understood. Here, the self-aggregation dynamics of a triblock copolymer (Pluronics L81, EO3PO43EO3) in the presence of three cationic surfactants (with a 12C long alkyl chain but with different structural features), viz., dodecyltrimethylammonium bromide (DTAB), didodecyldimethylammonium bromide (DDAB), and ethanediyl-1,2-bis(dimethyldodecylammonium bromide) (12-2-12), were investigated in an aqueous solution environment. The nanoscale micellar size expressed as hydrodynamic diameter (D h) of copolymer–surfactant mixed aggregates was evaluated using dynamic light scattering, while the presence of a varied micellar geometry of L81–cationic surfactant mixed micelles were probed using small-angle neutron scattering. The obtained findings were further validated from molecular dynamics (MD) simulations, employing a simple and transferable coarse-grained molecular model based on the MARTINI force field. L81 remained molecularly dissolved up to ∼20 °C but phase separated, forming turbid/translucent dispersion, close to its cloud point (CP) and existed as unstable vesicles. However, it exhibited interesting solution behavior expressed in terms of the blue point (BP) and the double CP in the presence of different surfactants, leading to mixed micellar systems with a triggered morphology transition from unstable vesicles to polymer-rich micelles and cationic surfactant-rich micelles. Such an amendment in the morphology of copolymer nanoaggregates in the presence of cationic surfactants has been well observed from scattering data. This is further rationalized employing the MD approach, which validated the effective interactions between Pluronics–cationic surfactant mixed micelles. Thus, our experimental results integrated with MD yield a deep insight into the nanoscale interactions controlling the micellar aggregation (Pluronics-rich micelles and surfactant-rich micelles) in the investigated mixed system.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Rationalizing the Design of Pluronics–Surfactant Mixed Micelles through Molecular Simulations and Experiments

et al. 2023

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“…Surfactant and polymer interactions and the various structures formed in aqueous solution have received much attention owing to their extensive applications in many industrial formulations. − Anionic surfactants such as sodium dodecylsulfate (SDS) interact with nonionic polymers such as poly(ethylene oxide) (PEO) in aqueous solutions above a certain concentration called the critical association (or aggregation) concentration (CAC), which is typically much lower than the critical micellization concentration (CMC) of the surfactant in the absence of a polymer. ,,, With an increase in the surfactant concentration comes a certain polymer saturation point (PSP) where the polymer chains become saturated with bound surfactant and, above the PSP, surfactant micelles that are free, i.e., not associated with polymer, begin to form. ,, The generally accepted picture for the association between PEO and surfactants is that of surfactant micelles bound along the PEO chain in a pearl-necklace configuration. ,− The interactions between polymers and surfactants depend highly on their relative charge and the hydrophobicity. ,− …”

Section: Introductionmentioning

confidence: 99%

Binding of Perfluorooctanoate to Poly(ethylene oxide)

et al. 2022

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To inform the design of polymer-based adsorbent materials for sequestration of per- and polyfluoroalkyl substances (PFAS) from aqueous solution, we report here on the critical aggregation concentration (CAC), shape, size, composition, and interactions of assemblies formed in water between perfluorooctanoic acid ammonium salt (PFOA) and the nonionic polymer poly(ethylene oxide) (PEO), obtained from complementary experiments (conductivity, surface tension, pyrene fluorescence, viscosity, and small-angle neutron scattering (SANS)) and atomistic molecular dynamics (MD) simulations. PEO–PFAS binding commences at concentrations lower than the PFOA critical micelle concentration (CMC) and is driven by PEO localizing on the micelle surface and shielding the fluorocarbon parts of PFOA from contact with water. PFOA + PEO mixed micelles have a 10% higher association number and are 40% more elongated compared to polymer-free PFOA micelles. This is the first investigation on the structure of polymer + fluorocarbon surfactant mixed micelles and contributes fundamental insights into the association of water-soluble polymers with PFAS surfactants.

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Exploring the potential of surface-active copolymers on P123 micelles for drug solubility enhancement and in vitro cytotoxicity assay

Tripathi,

Vaswani,

Bhatia

et al. 2024

Colloid Polym Sci

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SDS triggered transformation of highly hydrophobic Pluronics® nanoaggregate into polymer-rich and surfactant-rich mixed micelles

Cited by 13 publications

References 46 publications

Rationalizing the Design of Pluronics–Surfactant Mixed Micelles through Molecular Simulations and Experiments

Rationalizing the Design of Pluronics–Surfactant Mixed Micelles through Molecular Simulations and Experiments

Binding of Perfluorooctanoate to Poly(ethylene oxide)

Exploring the potential of surface-active copolymers on P123 micelles for drug solubility enhancement and in vitro cytotoxicity assay

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