This study aimed to evaluate the surface (γs) and interaction (ΔGiwi) free energy and calcium (Ca2+) and phosphate (PO43−) adsorption to dental enamel treated with sodium trimetaphosphate (TMP) or calcium glycerophosphate (CaGP) that had or had not been exposed to CaPO4-containing solutions. Bovine enamel blocks (n = 192; 24 blocks/group) were treated (2 mL/block; 2 min) with TMP (0%, 1%, 3%, and 9%) and CaGP (0, 0.25, 0.5, and 1%) or exposed to a CaPO4-containing solution. The adsorption of these compounds by enamel was assessed before and after treatment. γs and ΔGiwi and their apolar (γsLW and ΔGiwiLW) and polar (γsAB and ΔGiwiAB) components and acid-base interactions (γs+s) were determined by the contact angles. The data were subjected to ANOVA, followed by the Student-Newman-Keuls test (p < 0.05). The adsorption of TMP was dose dependent (p < 0.001), and it reduced γs and γsAB and increased ΔGiwiABGiwi > 0) and γs when compared with the group without TMP (p < 0.001). The immersion in CaPO4-containing solution increased γs and γsAB and reduced ΔGiwiABGiwi > 0) and γs (p < 0.001). There was a correlation between the adsorption of TMP and Ca2+ (r = 0.916; p < 0.001) and PO43− (r = 0.899; p < 0.001). The adsorption of CaGP on the enamel was dose dependent (p < 0.001), reducing γs, ΔGiwiABGiwi < 0), γsLW, and γs when compared to the group without CaGP (p < 0.001). When exposed to the CaPO4-containing solution, there was an increase in ΔGiwiABGiwi > 0), γsLW, and γs and a decrease in γsAB (p < 0.001) without adsorption of Ca2+ by enamel. It may be concluded that TMP and CaGP were adsorbed onto the enamel, producing hydrophilic and hydrophobic surfaces, respectively. TMP produces electron donor sites that induce Ca2+ adsorption, while CaGP releases Ca2+ into the medium.

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