The roles of 10-methacryloyloxydecyl dihydrogen phosphate and its calcium salt in preserving the adhesive–dentin hybrid layer

10-Methacryloyloxydecyl dihydrogen phosphate (MDP) has been regarded as the most effective dentin-bonding monomer for more than 20 years. Although the dentin-bonding promoting effect of MDP has been well demonstrated, the mechanisms by which it benefits the stably of collagen within the adhesive-dentin hybrid layer are not currently fully understood. The objective of this study was to investigate the roles of MDP and its calcium salt in preserving the adhesive-dentin hybrid layer.MDP-conditioned collagen was investigated by Fourier-transform infrared spectroscopy, Ultraviolet-visible spectroscopy, and molecular docking. The structural changes to the dentin surface upon acid-etching and MDP-conditioning were observed by SEM. X-ray diffraction and nuclear magnetic resonance were used to investigate the chemical interactions between MDP and HAp. The collagen-protecting effects of MDP and its Ca salt were investigated using in-situ zymography, rhMMP-9 colorimetric assay, hydroxyproline assay, and molecular docking.MDP forms a stable collagen-phosphate complex through hydrogen bonding with the collagen in dentin. Furthermore, it generates MDP-Ca salts that are deposited on the dentin collagen scaffold, protecting it from degradation. Moreover, both free MDP and the MDP-Ca salt inhibit matrix metallopeptidase and exogenous proteases, with the inhibitory effect of the calcium salt being significantly stronger than that of the free form.MDP-based adhesives preserve the collagen within the hybrid layer by simultaneously improving collagen's resistance to exogenous enzymes and inhibiting MMP activity, both of which contribute to the longevity of dentin-resin bonding.