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Microtensiometer for Confocal Microscopy Visualization of Dynamic Interfaces

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Molecular rotation at negatively charged surfactant/aqueous interfaces.

Kim T Nguyen¹, Xiaoming Shang, Kenneth B Eisenthal

¹Department of Chemistry, Columbia University, New York, New York 10027, USA.

The Journal of Physical Chemistry. B

|October 6, 2006

Summary

Investigating coumarin 314 (C314) rotational dynamics at charged air/water interfaces revealed slower motion with sodium dodecyl sulfate (SDS) surfactant. The charge effect was less pronounced than expected, despite influencing C314 orientation and spectra.

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Area of Science:

Physical Chemistry
Interface Science
Spectroscopy

Background:

Molecular probes like coumarin 314 (C314) are used to study interfacial dynamics.
Surfactants significantly alter interfacial properties, including molecular probe behavior.
Understanding rotational dynamics at interfaces is crucial for various chemical and physical processes.

Purpose of the Study:

To investigate the influence of charge on the rotational dynamics of coumarin 314 (C314) at air/water interfaces.
To determine the effect of sodium dodecyl sulfate (SDS) surfactant coverage on C314 rotational dynamics.
To compare interfacial rotational dynamics with bulk orientational diffusion.

Main Methods:

Femtosecond time-resolved second harmonic spectroscopy was employed.
The study focused on coumarin 314 (C314) as a molecular probe.
Experiments were conducted at air/water interfaces with varying sodium dodecyl sulfate (SDS) concentrations.

Main Results:

The out-of-plane orientational time constant for C314 at high SDS coverage (100 A2/molecule) was 383 +/- 9 ps.
Rotational dynamics at the SDS-covered interface were slower (383 ps) compared to the clean air/water interface (336 ps).
Interfacial rotational dynamics were over three times slower than the bulk orientational diffusion time (100 ps).

Conclusions:

The charge of sodium dodecyl sulfate (SDS) had a surprisingly small effect on the coumarin 314 (C314) rotation time constant.
Despite the limited impact on rotational time, SDS significantly affects C314 orientation, spectra, and the surfactant phase diagram.
Further research is needed to fully elucidate the interplay between surfactant charge, interfacial structure, and molecular probe dynamics.