Theoretical study on the hydrophobic and hydrophilic hydration on large solutes: The case of phthalocyanines in water

A theoretical study on the hydration phenomena of three representative Phthalocyanines (Pcs): the metal-free, H2Pc, and the metal-containing, Cu-phthalocyanine, CuPc, and its soluble sulphonated derivative, [CuPc(SO3)4]4−, is presented. Structural and dynamic properties of molecular dynamics trajectories of these Pcs in solution were evaluated. The hydration shells of the Pcs were defined by means of spheroids adapted to the solute shape. Structural analysis of the axial region compared to the peripheral region indicates that there are no significant changes among the different macrocycles, but that of [CuPc(SO3)4]4−, where the polyoxoanion presence induces a typically hydrophilic hydration structure. The analyzed water dynamic properties cover mean residence times, translational and orientational diffusion coefficients, and hydrogen bond network. These properties allow a thorough discussion about the simultaneous existence of hydrophobic and hydrophilic hydration in these macrocycles, and indicate the trend of water structure to well define shells in the environment of hydrophobic solutes. The comparison between the structural and dynamical analysis of the hydration of the amphipathic [CuPc(SO3)4]4− and the non-soluble Cu–Pc shows a very weak coupling among the hydrophilic and hydrophobic fragments of the macrocycle. Quantitative results are employed to revisit the iceberg model proposed by Frank and Evans, leading to conclude that structure and dy- namics support a non-strict interpretation of the iceberg view, although the qualitative trends pointed out by the model are supported.Junta de Andalucía P11-FQM7607Ministerio de Ciencia e Innovación CTQ2008-0527