From spectral fluctuations to acoustic response of a soft interface using the second law

Membrane-protein systems constitute an important avenue for a variety of targeted therapies. The ability to alter these systems remotely via physical fields is highly desirable for the advance of noninvasive therapies. Biophysical action of acoustic fields in particular holds immense potential for applications in drug delivery and neuro-modulation. Here we investigate the optical response of solvato-chromic fluorescent probe Laurdan, embedded in multilamellar lipid vesicles, subjected to broadband pressure impulses of the order of 1Mpa peak amplitude and pulse width of less than 10μs. The response is quantified in terms of the shift in fluorescence spectra using a ratiometric technique. Based on the fluctuation dissipation theorem applied to a coupled membrane-fluorophore system, it is shown that the perturbation of the fluorescence spectra of embedded molecules to the pressure impulses is determined by the thermodynamic state of the interface, or in other words, the thermodynamic susceptibilities such as the compressibility or heat capacity of the system. However, given that the thermodynamic susceptibilities of such systems, especially in native biological environment, are not easy to obtain experimentally, a necessary corollary to the thermodynamic approach is derived. This establishes a direct relation between the width of the emission spectra and the thermodynamic susceptibilities of the system. The result has practical importance as it gives access to the thermodynamic properties of the membrane from steady state fluorescence measurement without the need to perturb the system. Simply stated, the experiments show that the magnitude of the perturbation response of a membrane system to an acoustic insult is proportional to the width of the emission spectrum of the embedded membrane probe. Finally, there exists a direct correlation between the solvation (miscibility) and permeation of a molecule through a membrane and the implications of this study for acoustically induced enhanced permeability of the membrane are discussed.