Polarity of Hydrated Phosphatidylcholine Headgroups

Abstract

The headgroup (H) stratum (sometimes called the polar region) of membrane bilayers is a relevant yet poorly understood solvation phase for small molecules and macromolecules interacting with the membranes. Solvation of compounds in bilayer strata is characterized experimentally by wideand small angle X-ray scattering, neutron diffraction, and various NMR techniques. The quantification is tedious and only available for a limited set of small molecules. Our recently published model of liposome partitioning of small molecules shows that solvation of compounds in the H-stratum of fluid phosphatidylcholine (PC) bilayers correlates well with their solvation in hydrated diacetyl phosphatidylcholine (DAcPC), and solvation in the core (C) depends in a similar way on that in n-hexadecane. These two correlations became a basis for a model describing the location of compounds in the H-and C-strata, and at the connecting interface, as a nonlinear function of the fragment solvation characteristics of the compounds. In this study, refractivity of hydrated DAcPC phases with varying water content was measured and polarity determined using steady-state fluorescence of indole and Nile Red. The results were compared with the published data obtained by other techniques for PC bilayers in liposomes or on solid supports. The demonstrated qualitative agreement, as well as the polarity and refractivity dependencies on the DAcPC concentration, support the suitability of hydrated DAcPC as the H-stratum surrogate. Interestingly, depending on hydrations typical for H-strata of fluid PC bilayers, the dielectric constant could decrease significantly, from 31.0 to 7.3 for 16 and 8 water molecules per headgroup, respectively. Although additional experiments are needed for a confirmation, this observation could help set proper dielectric constant magnitudes in continuum-based computational models of accumulation and crossing of the PC bilayers with varying hydration levels thanks to the temperature or the structure of fatty acid chains.

Local pH at Nonionic and Zwitterionic Lipid/Water Interfaces Revealed by Heterodyne-Detected Electronic Sum-Frequency Generation: A Unified View to Predict Interfacial pH of Biomembranes

“…By plotting those peak wavelengths onto the λ max –ε curve in Figure 5 b, we estimate that the local ε of the DPG/water interface is 25 –1 +2 and that of the DPPC/water interface is 20 –10 +4 , which are in good agreement with reported values. 47 , 48 Then, by using a relation between p K a and ε reported by Fernández and Fromherz, 49 we can estimate p K a of the pH indicator at the interface. Figure 5 a shows the p K a –ε curve of HHC, where p K a becomes lower with increasing ε because A – is more stabilized in a polar medium than HA.…”