Molecular ordering effects in bulk and at lipid/water nanoscopic interfaces: A story of water, light, and order

Water is ubiquitous on Earth, playing a critical role for a plethora of structures, processes and chemical reactions in nature. Its unique physicochemical properties originate mainly from its hydrogen bond network. Despite its recognized importance, many aspects of the structure of water as a liquid remain elusive. It is especially difficult to understand the complex nature of fluctuations and ordering in pure water, or to get a complete picture of aqueous interfaces at the molecular level. In this thesis, our aim is to improve our understanding of the underlying interactions between water and ions, macromolecules, and interfaces, especially the long range interactions. To this aim, we use two nonlinear optical techniques, second harmonic scattering (SHS) and vibrational sum frequency scattering (SFS), on liquid water as well as on model lipid membranes mimicking the cell membranes. We investigate with SHS how the orientational ordering of water molecules is affected by temperature changes and nuclear quantum effects. Scattering measurements of pure water reveal that the intermolecular correlations undergo a symmetry transformation with increasing temperature. On the other hand, with increasing temperature, aqueous electrolyte solutions exhibit a diminished influence of the combined electrostatic field on the water- water correlations. This trend is predicted qualitatively by a Debye-Hückel model, but not quantitatively due to its non-inclusion of hydrogen bonding and nuclear quantum effects. These insights facilitate the elaboration of future nuclear quantum mechanical models of water. The same interactions are further studied by a comparison of pure liquid water and pure liquid carbon tetrachloride. SHS measurements and simulations reveal that transient nanoscale voids exist in water and carbon tetrachloride. The coherent SHS emissions observed in water are generated by charge density fluctuations around the cavities. These measurements strongly hint towards non-uniformity in the structure of water, on femtosecond timescale and nanometric range. Next, we turn towards the structure of water around model lipid membranes. We explore first the three-dimensional confinement of liquid water inside liposomes of various size. By analyzing SHS patterns of zwitterionic and anionic liposomes, we observe that the effect of confinement is visible on a range of a hundred nanometers, larger compared to the previously reported ranges on the order of a nanometer or about ten nanometers. The water orientational ordering at the interface as well as the surface potential of the liposomes are retrieved with a nonlinear light scattering modeling, showing that the confinement effect is mainly attributable to the hydrogen bond network. The effect is in particular 8 times larger for light water than for heavy water. Finally, we investigate how the water structure is modified around lipid monolayers and bilayers. The hydration of lipid membranes is asymmetric with respect to charge. SHS and vibrational SFS reveal that the charge hydration asymmetry is drastically different depending on the nature of the lipid layer. It depends on a delicate balance between electrostatic and hydrogen bonding interactions. The charge hydration asymmetry is further modified by the presence of charges on the lipid headgroups on both sides of the bilayers