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PRISM: a phase-resolved surface equation of state across the full Langmuir isotherm. Reference:
The model employed in SurfFitter, the PRISM model, is derived from basic thermodynamics equations. This was originally meant for lipid monolayers, but it is extrapolable for any insoluble surfactant monolayers. For that reason, fitting parameters are denoted as \(\mathrm{APL}\) (Area Per Lipid) instead of \(\mathrm{MMA}\) (Mean Molecular Area). PRISM identifies the regimes of single-phase and phase coexistence in the isotherm taking as fitting parameters all the \(\mathrm{APL}\),\(\pi\) values that mark the boundaries between phases (white dots in the figure above). The article referenced above provides a more detailed explanation of the model.
- At regions of pure phase \(\beta\), lipids occupy an average molecular area between \(\mathrm{APL}^\beta_{min}\) and \(\mathrm{APL}^\beta_{max}\), and the surface pressure increases with the monolayer compression according to the elasticity modulus \(K^\beta\) of that phase.
- At coexistence regions, for any \(\mathrm{APL}\) value, lipids in the \(\beta,\beta'\) phases occupy a constant average molecular area \(\mathrm{APL}^\beta_{min}\) and \(\mathrm{APL}^\beta_{max}\), respectively. The proportion of lipids at each phase changes across compression. The surface pressure, according strictely to the Gibbs phase rule, is constant and equal to \(\pi^{\beta\beta'}\) (PRISM-I). However, there might be some deviations from ideality (light slopes in the isotherms) due to line tension between phase domains (PRISM-DC).
SurfFitter implementation of the PRISM model considers the introduction of PRISM-DC parameters \(s, a\) only when statistically justified. Additionally, based on the isotherm initial shape SurfFitter discriminates the presence of four phases in the isotherm (S-C-E-G) or only three (C-E-G and S-C-G). In any case, the PRISM model fitted parameters allow to extract additional thermodynamic information of the system:
| Degrees of surface coverage, \(\theta^\beta\) | The ratio of surface area occupied by each phase. |
| Surface concentration, \(\Gamma^\beta\) | The number of molecules in a certain phase per unit area of the total surface. |
| Elasticity modulus, \(K\) | It is the inverse of the compressibility modulus. It is defined as \(ln\frac{d\pi \mu}{dA}\). |
| Chemical potential, \(\Delta \mu\) | The change in chemical potential provoked by a change in surface area. |
| First derivative of the chemical potential with respect to the surface tension, \(\frac{d\Delta \mu}{d\gamma}\) | The rate of change of the chemical potential with respect to the surface tension, which is equal to the surface area. At constant temperature, \(\frac{d\Delta \mu}{d\gamma} = - \frac{d\Delta \mu}{d\pi} = A\) |
S-solid, C-condensed, E-expanded, G-gas, b-bulk water, s-surface water.
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