Methacryloyloxydecyl dihydrogen phosphate (MDP) has been speculated to induce mineralization, but there has been no convincing evidence of its ability to induce intrafibrillar mineralization. Polymers play a critical role in biomimetic mineralization as stabilizers/inducers of amorphous precursors. Hence, MDP-induced biomimetic mineralization without polymer additives has not been fully verified or elucidated. By combining 3-dimensional stochastic optical reconstruction microscopy, surface zeta potentials, contact angle measurements, inductively coupled plasma–optical emission spectroscopy, transmission electron microscopy, atomic force microscopy, and Fourier transform infrared spectroscopy with circular dichroism, we show that amphiphilic MDP can not only demineralize dentin by releasing protons as an acidic functional monomer but also infiltrate collagen fibrils (including dentin collagen), unwind the triple helical structure by breaking hydrogen bonds, and finally immobilize within collagen. MDP-bound collagen functions as a huge collagenous phosphoprotein (HCPP), in contrast to chemical phosphorylation modifications. HCPP can induce biomimetic mineralization itself without polymer additives by alternatively attracting calcium and phosphate through electrostatic attraction. Therefore, we herein propose the dual functions of amphiphilic MDP monomer with de- and remineralizing ability. MDP in the free state can demineralize dentin substrates by releasing protons, whereas MDP in the collagen-bound state as HCPP can induce intrafibrillar mineralization. The dual functions of MDP monomer with de- and remineralization properties might create a new epoch in adhesive dentistry and preventive dentistry.

已推测甲基丙烯酰氧基癸基磷酸二氢盐 (MDP) 可诱导矿化，但没有令人信服的证据表明其能够诱导原纤维内矿化。聚合物作为无定形前体的稳定剂/诱导剂在仿生矿化中起着关键作用。因此，没有聚合物添加剂的 MDP 诱导的仿生矿化尚未得到充分验证或阐明。通过将 3 维随机光学重建显微镜、表面 zeta 电位、接触角测量、电感耦合等离子体发射光谱、透射电子显微镜、原子力显微镜和傅里叶变换红外光谱与圆二色性相结合，我们表明，两亲性 MDP 不仅可以通过释放质子作为酸性功能单体使牙本质脱矿质，而且还可以浸润胶原纤维（包括牙本质胶原），通过破坏氢键解开三螺旋结构，并最终固定在胶原蛋白中。与化学磷酸化修饰相反，MDP 结合的胶原蛋白作为一种巨大的胶原蛋白磷蛋白 (HCPP) 发挥作用。HCPP可以通过静电吸引交替吸引钙和磷酸盐，在没有聚合物添加剂的情况下自行诱导仿生矿化。因此，我们在此提出了具有去矿化和再矿化能力的两亲 MDP 单体的双重功能。游离状态的 MDP 可以通过释放质子使牙本质底物脱矿质，而作为 HCPP 的胶原结合状态的 MDP 可以诱导原纤维内矿化。