Effects of Phosphoric Acid Pre-Etching on Chemisorption between Enamel and MDP-Containing Universal Adhesives: Chemical and Morphological Characterization, and Evaluation of Its Potential

This study aimed to provide evidence that phosphoric acid pre-etching is necessary for the chemisorption between enamel and 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-containing universal adhesives. Three MDP-containing universal adhesives: Single Bond Universal (SBU), All Bond Universal (ABU), and Clearfil Universal Bond Quick (CBQ), as well as an experimental MDP-containing adhesive (EX) were investigated. Clearfil SE Bond (CSE) was a control and untreated enamel (UE) was another control. Self-etch (SE) and etch-and-rinse (ER) bonding modes were employed for universal adhesives. The enamel surfaces with different treatments were observed with a scanning electron microscope (SEM). The chemical bonds in the enamel reactants were determined using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and nuclear magnetic resonance (NMR). The charge changes with phosphoric acid pre-etching or without were characterized by ζ-potential. FTIR confirmed the chemisorption between enamel and MDP-containing adhesives. XPS and 31P NMR studies detected improved chemical affinity to the phosphoric acid etching + MDP-containing universal adhesives applied with enamel. The ζ-potential of MDP-containing universal adhesives absorbed with enamel, with or without etching became more negative compared with that of UE (P < 0.05). Furthermore, single etching created a negative ζ-potential with a higher absolute value (P = 0.009). Phosphoric acid pre-etching can increase the negative charge on the enamel surface and facilitate the chemical reactions of MDP and hydroxyapatite (HAp) to produce more calcium salts, thus improving the chemisorption between enamel and MDP-containing universal adhesives.