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Vierros, Sampsa, and Maria Sammalkorpi. Physical Chemistry Chemical Physics 20.9 (2018): 6287-6298.
1-Hexanol is demonstrated as a potent additive for tuning the structural and interactional behavior of nonionic surfactant micelles, specifically C12E10 (decyl-hexa(ethylene oxide)) in aqueous systems. Dynamic light scattering and cloud point measurements reveal that low to moderate 1-hexanol concentrations mimic thermal effects, enhancing micelle-micelle attraction. Molecular dynamics simulations elucidate that at hexanol-to-surfactant ratios ≤ 0.5, hexanol predominantly solubilizes into the palisade layer, decreasing headgroup chain density and thereby increasing intermicellar attraction.
At higher ratios (≥ 1.5), 1-hexanol induces micelle swelling and partial core formation via reverse-hexanol structures-mimicking bulk-octanol behavior-within micelle interiors. These larger, more loosely packed micelles exhibit rougher surfaces and altered curvature, which can significantly impact colloidal stability and encapsulation capacity.
This fine-tuning effect of 1-hexanol on micelle architecture and inter-aggregate interactions is of great interest in the formulation of advanced micellar systems, where controlled size, polarity distribution, and phase behavior are critical. Applications include drug delivery vehicles, emulsion design, catalysis enhancement platforms, and green chemistry microenvironments.
Overall, 1-hexanol serves as a valuable co-solvent and structuring agent for nonionic surfactant systems, enabling precise modulation of micellar characteristics to meet the physicochemical demands of diverse industrial and research-based applications.
Zhang, Kaili, et al. Journal of Dispersion Science and Technology (2019).
1-Hexanol plays a critical role in modulating the complex phase behavior of mixed anionic-cationic surfactant systems, specifically in the sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB)/NaBr/H₂O quaternary system. When incorporated at a molar ratio greater than 1 relative to total surfactant concentration, 1-hexanol eliminates surfactant-induced precipitation and promotes the formation of thermally stable aqueous two-phase systems (ATPS) and lamellar liquid crystals (LCs).
This behavior is attributed to 1-hexanol's ability to insert itself between SDS and CTAB molecules, disrupting strong electrostatic interactions and preventing charge-neutralized aggregation. As a result, stable and macroscopically homogeneous LC phases emerge, identified by the characteristic "Maltese cross" textures under polarized optical microscopy. Notably, these mesophases exhibit remarkable thermal stability, with phase boundaries remaining nearly unchanged across a temperature range of 40-70 °C.
The ability of 1-hexanol to expand LC and ATPS domains while suppressing surfactant precipitation highlights its value in tailoring the self-assembly behavior of oppositely charged surfactant systems. This has promising implications for controlled release formulations, membrane templating, and formulation of structured fluids in personal care, pharmaceutical, and materials chemistry.
Thus, 1-hexanol is an effective co-solvent for stabilizing and expanding functional mesophases in ionic surfactant mixtures, offering a versatile tool for phase engineering in complex fluid systems.
Patel, Vijay, et al. Rsc Advances 5.107 (2015): 87758-87768.
1-Hexanol plays a critical role in modulating the morphology and rheological behavior of cetyltrimethylammonium tosylate (CTAT) micellar systems, widely used in personal and home care formulations. At moderate CTAT concentrations (e.g., 20 mM), the incorporation of low concentrations of 1-hexanol (\~0.25%) significantly increases solution viscosity, indicative of micelle elongation and entanglement. Cryo-TEM and small-angle neutron scattering (SANS) reveal that 1-hexanol induces a transition from short cylindrical micelles to wormlike structures and, at higher loading, to closed bilayer vesicles.
NMR studies further indicate that 1-hexanol locates primarily within the palisade region of the micelles, disturbing headgroup packing and promoting micelle growth. However, at higher CTAT concentrations (e.g., 30 mM), densely packed micelles hinder hexanol penetration, leading to a monotonic decrease in viscosity upon hexanol addition.
These results demonstrate that 1-hexanol enables fine control over micelle morphology and solution viscoelasticity by tuning the balance between hydrophobic insertion and steric packing. Such tunability is vital for tailoring the performance of surfactant-based systems in applications like controlled release, foaming agents, and rheology modifiers.
In summary, 1-hexanol is an effective structural modulator for CTAT micelles, facilitating targeted micelle-to-vesicle transitions and enabling the rational design of micellar fluids with customized flow and functional properties.
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