Fluorinated surfactants are used in a wide range of applications that involve aqueous solvents incorporating various additives. The presence of organic compounds such as urea is expected to affect the self-assembly of fluorinated surfactants, however, very little is known about this. We investigated the effect of urea on the micellization in water of the common fluorinated surfactant ammonium perfluorooctanoate (APFO), and on the structure and microenvironment of the micelles that APFO forms. Addition of urea to aqueous APFO solution decreased the critical micellization concentration (CMC) and increased the counterion dissociation. The observed increase in surface area per APFO headgroup and decrease in packing density at the micelle surface suggest the localization of urea at the micelle surface in a manner that reduces headgroup repulsions. Micropolarity data further support this picture. The results presented here indicate that significant differences exist between urea effects on fluorinated surfactant and on hydrocarbon surfactant micellization in aqueous solution. For example, the CMC of sodium dodecyl sulfate (SDS) increased with urea addition, while the increase in surface area per headgroup and packing density of SDS with urea addition are much lower than those observed for APFO. This study informs fluorinated surfactant fate and transport in the environment, and also applications involving aqueous media in which urea or similar additives are present.
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Effects of solvent and micellar encapsulation on the photostability of avobenzone
The photodegradation of avobenzone ( AV ), the only ultraviolet filter molecule approved by the Food and Drug Administration to absorb UVA radiation, is an important problem in sunscreen formulations. In this paper, the photophysics and photostability of AV in various solvent systems and in aqueous micelles are studied. AV in its keto–enol tautomer functions as an effective UVA protection agent. AV is highly susceptible to photoinduced diketonization in both nonpolar solvents and in aqueous aggregates but is considerably more stable in polar, protic solvents like methanol. By studying its stability in different surfactant solutions, we show that incorporation of AV into sodium dodecylsulfate (SDS) micelles can achieve stability levels comparable to neat methanol. Steady-state spectral shifts, fluorescence anisotropy, and time-resolved fluorescence decay measurements are all consistent with AV experiencing a polar environment after micellar encapsulation. It is proposed that AV is encapsulated in the palisade layer of the SDS micelles, which allows access to water molecules that facilitate the re-formation of the enol form after photon absorption and relaxation. Although the detailed mechanism of AV tautomerization remains unclear, this work suggests that tuning the chemical microenvironment of AV may be a useful strategy for improving sunscreen efficacy.
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- Award ID(s):
- 1810514
- NSF-PAR ID:
- 10177107
- Date Published:
- Journal Name:
- Photochemical & Photobiological Sciences
- Volume:
- 19
- Issue:
- 3
- ISSN:
- 1474-905X
- Page Range / eLocation ID:
- 390 to 398
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Ideal multifunctional ultraviolet radiation (UVR) absorbents with excellent photostability, high molar absorptivity, broadband UVR screening, and desired skin sensorial properties remain a significant challenge for the sunscreen industry. The potential of the nanocomplex (NCx) formed by microwave synthesis of ZnO quantum dots (QDs) in the presence of Avobenzone (Av) for achieving these goals is reported. The NCx exhibits unique synergy between ZnO QD and Av components, which enhances the photostability and molar absorptivity, extends UVA filtering range, and provides a visible emission that matches the typical human in vivo skin emission color. Density functional theory (DFT) and time‐dependent DFT calculations of ZnO‐Av hybrid structures and comparison of their spectroscopic features with experiments suggest that ZnO QDs catalyze the formation of highly photostable surface enolate species via aldol condensation reaction. The combination of experiments and computations used in this study can advance the science and technology of photoprotection.
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The interaction in aqueous solutions of surfactants with amphiphilic polymers can be more complex than the surfactant interactions with homopolymers. Interactions between the common ionic surfactant sodium dodecyl sulfate (SDS) and nonionic amphiphilic polymers of the poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO-PPO-PEO) type have been probed utilizing a variety of experimental techniques. The polymer amphiphiles studied here are Pluronic F127 (EO100PO65EO100) and Pluronic P123 (EO19PO69EO19), having the same length PPO block but different length PEO blocks and, accordingly, very different critical micellization concentrations (CMC). With increasing surfactant concentration in aqueous solutions of fixed polymer content, SDS interacts with unassociated PEO-PPO-PEO molecules to first form SDS-rich SDS/Pluronic assemblies and then free SDS micelles. SDS interacts with micellized PEO-PPO-PEO to form Pluronic-rich SDS/Pluronic assemblies, which upon further increase in surfactant concentration, break down and transition into SDS-rich SDS/Pluronic assemblies, followed by free SDS micelle formation. The SDS-rich SDS/Pluronic assemblies exhibit polyelectrolyte characteristics. The interactions and mode of association between nonionic macromolecular amphiphiles and short-chain ionic amphiphiles are affected by the polymer hydrophobicity and its concentration in the aqueous solution. For example, SDS binds to Pluronic F127 micelles at much lower concentrations (~0.01 mM) when compared to Pluronic P123 micelles (~1 mM). The critical association concentration (CAC) values of SDS in aqueous PEO-PPO-PEO solutions are much lower than CAC in aqueous PEO homopolymer solutions.more » « less
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Abstract The prevalence of anion‐cation contacts in biomolecular recognition under aqueous conditions suggests that ionic interactions should dominate the binding of anions in solvents across both high and low polarities. Investigations of this idea using titrations in low polarity solvents are impaired by interferences from ion pairing that prevent a clear picture of binding. To address this limitation and test the impact of ion‐ion interactions across multiple solvents, we quantified chloride binding to a cationic receptor after accounting for ion pairing. In these studies, we created a chelate receptor using aryl‐triazole CH donors and a quinolinium unit that directs its cationic methyl inside the binding pocket. In low‐polarity dichloromethane, the 1 : 1 complex (log
K 1 : 1~ 7.3) is more stable than neutral chelates, but fortuitously comparable to a preorganized macrocycle (logK 1 : 1~ 6.9). Polar acetonitrile and DMSO diminish stabilities of the charged receptor (logK 1 : 1~ 3.7 and 1.9) but surprisingly 100‐fold more than the macrocycle. While both receptors lose stability by dielectric screening of electrostatic stability, the cationic receptor also pays additional costs of organization. Thus even though the charged receptor has stronger binding in apolar solvents, the uncharged receptor has more anion affinity in polar solvents. -
Sodium naphthenates (NaNs), found in crude oils and oil sands process-affected water (OSPW), can act as surfactants and stabilize undesirable foams and emulsions. Despite the critical impact of soap-like NaNs on the formation, properties, and stability of petroleum and OSPW foams, there is a significant lack of studies that characterize foam film drainage, motivating this study. Here, we contrast the drainage of aqueous foam films formulated with NaN with foams containing sodium dodecyl sulfate (SDS), a well-studied surfactant system, in the relatively low concentration regime ( c /CMC < 12.5). The foam films exhibit drainage via stratification, displaying step-wise thinning and coexisting thick–thin regions manifested as distinct shades of gray in reflected light microscopy due to thickness-dependent interference intensity. Using IDIOM (interferometry digital imaging optical microscopy) protocols that we developed, we analyze pixel-wise intensity to obtain thickness maps with high spatiotemporal resolution (thickness <1 nm, lateral ∼500 nm, time ∼10 ms). The analysis of interference intensity variations over time reveals that the aqueous foam films of both SDS and NaN possess an evolving, dynamic, and rich nanoscopic topography. The nanoscopic thickness transitions for stratifying SDS foam films are attributed to the role played by damped supramolecular oscillatory structural disjoining pressure contributed by the confinement-induced layering of spherical micelles. In comparison with SDS, we find smaller concentration-dependent step size and terminal film thickness values for NaN, implying weaker intermicellar interactions and oscillatory structural disjoining pressure with shorter decay length and periodicity.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9pp00483a
