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Published on: March 18, 2020
Hydration Shell Changes in Surfactant Aggregate Transitions Revealed by Raman-MCR Spectroscopy
Yutan Shen1,2, Bin Liu1,2, Jie Cui3
1CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Investigating surfactant hydration, this study reveals how changes in aggregate structure, like micelle shape, significantly alter water properties. This dehydration impacts water
Area of Science:
- Physical Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Hydration states are crucial for the structure and function of self-assembled systems.
- Understanding water interactions within aggregates informs their behavior and applications.
Purpose of the Study:
- To investigate the hydration properties of aggregates formed by three cationic ammonium surfactants.
- To correlate changes in surfactant aggregate structure with alterations in water hydration.
Main Methods:
- Raman multivariate curve resolution (Raman-MCR) was the primary technique.
- Differential scanning calorimetry and nuclear magnetic resonance spectroscopy provided complementary data.
- Analysis focused on water tetrahedral order and hydrogen bonding within hydration shells.
Main Results:
- Surfactant aggregate transitions (spherical to rodlike/wormlike micelles) induced significant dehydration (20-60%) in 12-3-12(Br)2.
- Dehydration weakened water tetrahedral order and hydrogen bonds around both headgroups and hydrophobic chains.
- Didodecyldimethylammonium bromide (DDAB) vesicles showed distinct hydration water species, with multicompartment vesicles exhibiting reduced water order.
- Dodecyltrimethylammonium bromide (DTAB) formed spherical micelles with hydration structures similar to 12-3-12(Br)2 spherical micelles.
Conclusions:
- Surfactant self-assembly and structural transitions directly influence the hydration shell's water properties.
- The study provides a foundation for understanding hydration in complex biological self-assemblies.
- Tailoring surfactant structures offers a means to control hydration and potentially function.
