The sequential arrangement of PS chains on hydrophobic and hydrophilic surfaces can be described by adsorption reactions and their associated thermodynamic factors. On goethite, initial PS adsorption results from strong electrostatic interactions (CIP, contact ion pair) between the carboxylate groups of PS and goethite's protonated (≡FeOH2 + ) surface, with concomitant surface dehydration. This type of interactions are energetically favorable, with an increase in system entropy and decrease in enthalpy. Importantly, this initial approach of PS towards the goethite surface results in the more hydrophobic groups of the PS (e.g., methyl ester) to be exposed to the aqueous phase producing a more hydrophobic surface (Figures and). It is not surprising then that subsequent PS molecules would approach and react with the initially adsorbed PS via their more hydrophobic groups (methylester and alkylamide). On the hydrophobic diamond surface, the adsorption behavior of the polysaccharide chains shifts. Here, initial PS adsorption results from weak van der Waals interactions between primarily methylester groups of the PS and the diamond's surface; surface dehydration also occurs but to a lessen extent. A consequence of this initial PS adsorption is that carboxylate groups are exposed to the aqueous phase producing a more hydrophilic surface (Figures and). In contrast to PSgoethite, initial PS-diamond interactions decrease the entropy of the system because of the order imposed to water molecules by the ionic carboxylate group.