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[Display omitted] • Zinc, released from bioactive materials, was incorporated into dentin with in approximately 50 µm. • Zinc-doped dentin demonstrated 30% less acid solubility, helping to improve its anti-carcinogenicity. • Zinc was incorporated into dentin in a four-fold coordination , indicating a newly generated covalent bond. • Quantum beam and synchrotron radiation technologies help in analyzing the bonding states of dentinal elements. Dental caries, the world's most prevalent infectious disease, is caused by the diffusion of hydroxyl ions into tooth structures. To prevent dental caries, the application of fluoride (F) and zinc (Zn) ions to teeth surfaces are potential effective measures. In this study, The ionic influence, especially the chemical bond of F and Zn, on the acid resistance of dentin were investigated by particle induced X-ray / gamma-ray emission, X-ray diffraction, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The results showed Zn was distributed in the limited surface layer of dentin without altering its crystal structure. From the Zn K edge extended X-ray absorption fine structure, Zn incorporated into dentin was surrounded by oxygen and demonstrated four-fold coordination. The bond length and chemical state of Zn–O in Zn doped dentin suggested newly generated Zn–O covalent bond, which may improve acid resistance of dentin. This study showed that the atomic and molecular structures, such as the molecular distances and chemical state, influenced acid resistance of teeth, emphasizing the validity of chemical state analysis for understanding properties in biomaterials. [ABSTRACT FROM AUTHOR]