STMP and PVPA as Templating Analogs of Noncollagenous Proteins Induce Intrafibrillar Mineralization of Type I Collagen via PCCP Process

Yiru Wang; Yizhou Zhang; Zhe Shen; Yuan Qiu; Chaoyang Wang; Zhifang Wu; Minjuan Shen; Changyu Shao; Ruikang Tang; Matthias Hannig; Baiping Fu; Zihuai Zhou

doi:10.1002/adhm.202400102

STMP and PVPA as Templating Analogs of Noncollagenous Proteins Induce Intrafibrillar Mineralization of Type I Collagen via PCCP Process

Adv Healthc Mater. 2024 Apr 24:e2400102. doi: 10.1002/adhm.202400102. Online ahead of print.

Authors

Affiliations

¹ Stomatology Hospital, School of Stomatology, Zhejiang University School of Medicine, Zhejiang Provincial Clinical Research Center for Oral Diseases, Key Laboratory of Oral Biomedical Research of Zhejiang Province, Cancer Center of Zhejiang University, Engineering Research Center of Oral Biomaterials and Devices of Zhejiang Province, Hangzhou, Zhejiang, 310000, China.
² School of Stomatology, Hangzhou Normal University, Hangzhou, Zhejiang Province, 310000, China.
³ Center for Biomaterials and Biopathways, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang Province, 310000, China.
⁴ Clinic of Operative Dentistry, Periodontology and Preventive Dentistry, Saarland University, 66424, Homburg Saar, Germany.

PMID: 38657167
DOI: 10.1002/adhm.202400102

Abstract

The phosphorylated noncollagenous proteins (NCPs) play a vital role in manipulating biomineralization, while the mechanism of phosphorylation of NCPs in intrafibrillar mineralization of collagen fibril has not been completely deciphered. Poly(vinylphosphonic acid) (PVPA) and sodium trimetaphosphate (STMP) as templating analogs of NCPs induce hierarchical mineralization in cooperation with indispensable sequestration analogs such as polyacrylic acid (PAA) via polymer-induced liquid-like precursor (PILP) process. Herein, STMP-Ca and PVPA-Ca complexes are proposed to achieve rapid intrafibrillar mineralization through polyelectrolyte-Ca complexes pre-precursor (PCCP) process. This strategy is further verified effectively for remineralization of demineralized dentin matrix both in vitro and in vivo. Although STMP micromolecule fails to stabilize amorphous calcium phosphate (ACP) precursor, STMP-Ca complexes facilely permeate into intrafibrillar interstices and trigger phase transition of ACP to hydroxyapatite within collagen. In contrast, PVPA-stabilized ACP precursors lack liquid-like characteristic and crystallize outside collagen due to rigid conformation of PVPA macromolecule, while PVPA-Ca complexes infiltrate into partial intrafibrillar intervals under electrostatic attraction and osmotic pressure as evidenced by intuitionistic 3D stochastic optical reconstruction microscopy (3D-STORM). The study not only extends the variety and size range of polyelectrolyte for PCCP process but also sheds light on the role of phosphorylation for NCPs in biomineralization.

Keywords: PCCP process; intrafibrillar mineralization; phosphorylation; poly(vinylphosphonic acid); sodium trimetaphosphate.

Abstract

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