Defect modification of calcium silicate and its application in oral bacteriostasis and tooth remineralization

doi:10.7518/hxkq.2025.2025004

Abstract

Abstract:

Objective Calcium silicate (CSO) is modified to give it photothermal antibacterial properties. Its application potential in tooth mineralization and oral antibacterial is evaluated. Methods Based on defect-engineering modification strategy, a series of CSO-T samples (CSO-300, CSO-400, CSO-500, CSO-600) was obtained by introducing oxygen vacancy into CSO through thermal reduction using sodium borohydride. The samples were tested using scanning electron microscopy (SEM), X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet near-infrared absorption spectroscopy, and infrared thermography. The powder samples with the best photothermal performance and the most suitable material concentration (CSO-500, 500 μg/mL) were selected for subsequent experiments. High resolution transmission electron microscopy was used to analyze the microstructure and morphology of the sample, and MTT assay and Calcein AM/PI live/dead cell staining were used to evaluate the toxicity and compatibility of the sample to human oral keratinocytes. Escherichia coli and Staphylococcus aureus were selected for photothermal antibacterial experiments to evaluate their in vitro antibacterial performance. SEM, energy dispersive spectrometer, and micro Vickers hardness tester were used to evaluate the ability of materials to induce in vitro remineralization of detached teeth. Results Oxygen vacancies changed the crystal type and lattice spacing of CaSiO₃, broadened the light-absorption range, and gave it a good photothermal conversion ability in response to near infrared. Invitro experiments showed that the modified CaSiO₃ could promote the formation of hydroxyapatite on the tooth surface, thereby promoting the remineralization of teeth and improving the teeth hardness. Moreover, it had photothermal antibacterial properties and no cytotoxicity. Conclusion Defect-modified black calcium silicate has multiple functions, such as promoting tooth remineralization and photothermal bacteriostatic. When combined with the infrared luminescent toothbrush, it can simply and effectively treat tooth enamel erosion and oral bacteriostatic diseases caused by the excessive consumption of carbonated beverages and other daily bad living habits. This combination is expected to achieve the synergic treatment effect of tooth remineralization and oral bacteriostatic through daily cleaning is expected.

Key words: tooth remineralization, calcium silicate, photothermal effect, bacteriostasis, oxygen vacancy

CLC Number:

R783.1

Hu Yuanyuan, Zhang Shuyan, Zhang Jianhua, Luo Hongrong, Li Yunfeng, Zhang Jing, Chen Xianchun. Defect modification of calcium silicate and its application in oral bacteriostasis and tooth remineralization[J]. West China Journal of Stomatology, 2025, 43(5): 648-659.

Figures/Tables 11

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

Fig 9

Fig 10

Tab 1

References 56

[1]	Zhai QM, Dong ZW, Wang W, et al. Dental stem cell and dental tissue regeneration[J]. Front Med, 2019, 13(2): 152-159.
[2]	Sato T, Fukuzawa Y, Kawakami S, et al. The onset of dental erosion caused by food and drinks and the preventive effect of alkaline ionized water[J]. Nutrients, 2021, 13(10): 3440.
[3]	Carvalho TS, Lussi A. Age-related morphological, histological and functional changes in teeth[J]. J Oral Rehabilitation, 2017, 44(4): 291-298.
[4]	Zhang LY, Fang ZH, Li QL, et al. A tooth-binding antimicrobial peptide to prevent the formation of dental biofilm[J]. J Mater Sci Mater Med, 2019, 30(4): 45.
[5]	de Paula Zago LH, de Annunzio SR, de Oliveira KT, et al. Antimicrobial photodynamic therapy against metronidazole-resistant dental plaque bactéria[J]. J Photochem Photobiol B, 2020, 209: 111903.
[6]	West NX, Joiner A. Enamel mineral loss[J]. J Dent, 2014, 42: S2-S11.
[7]	Amaya Arbeláez MI, de Paula e Silva ACA, Navegante G, et al. Proto-oncogenes and cell cycle gene expression in normal and neoplastic oral epithelial cells stimulated with soluble factors from single and dual biofilms of Candida albicans and Staphylococcus aureus [J]. Front Cell Infect Microbiol, 2021, 11: 627043.
[8]	Altalhi AM, AlNajdi LN, Al-Harbi SG, et al. Laser therapy versus traditional scaling and root planing: a comparative review[J]. Cureus, 2024, 16(6): e61997.
[9]	Vinel A, Al Halabi A, Roumi S, et al. Non-surgical pe-riodontal treatment: SRP and innovative therapeutic approaches[M]//Advances in Experimental Medicine and Biology. Cham: Springer International Publishing, 2022: 303-327.
[10]	Haridy MF, Ahmed HS, Kataia MM, et al. Fracture resistance of root canal-treated molars restored with ceramic overlays with/without different resin composite base materials: an in vitro study[J]. Odontology, 2022, 110(3): 497-507.
[11]	Primus C, Gutmann JL, Tay FR, et al. Calcium silicate and calcium aluminate cements for dentistry reviewed[J]. J Am Ceram Soc, 2022, 105(3): 1841-1863.
[12]	Janini ACP, Bombarda GF, Pelepenko LE, et al. Antimicrobial activity of calcium silicate-based dental mate-rials: a literature review[J]. Antibiotics, 2021, 10(7): 865.
[13]	刘学申. 人牙釉质酸蚀损伤的相关影响因素研究[D]. 成都: 西南交通大学, 2012.
	Liu XS. Study on the erosion behavior and factors of human tooth enamel[D]. Chengdu: Southwest Jiaotong University, 2012.
[14]	Diba MN, Goudouri OM, Tapia F, et al. Magnesium-containing bioactive polycrystalline silicate-based ceramics and glass-ceramics for biomedical applications[J]. Curr Opin Solid State Mater Sci, 2014, 18(3): 147-167.
[15]	Zadehnajar P, Mirmusavi MH, Eil Bakhtiari SS, et al. Recent advances on akermanite calcium-silicate ceramic for biomedical applications[J]. Int J Appl Ceram Technol, 2021, 18(6): 1901-1920.
[16]	Li XK, Wang JF, Joiner A, et al. The remineralisation of enamel: a review of the literature[J]. J Dent, 2014, 42: S12-S20.
[17]	Hornby K, Ricketts SR, Philpotts CJ, et al. Enhanced enamel benefits from a novel toothpaste and dual phase gel containing calcium silicate and sodium phosphate salts[J]. J Dent, 2014, 42: S39-S45.
[18]	孙岳魁, 冯希平, 王进防, 等. 一种新型牙膏的形成牙釉矿物质机理研究[J]. 口腔护理用品工业, 2017, 27(3): 17-23.
	Sun YK, Feng XP, Wang JF, et al. Research on the formation mechanism of mineral glaze of a new type of toothpaste[J]. Toothpaste Indust, 2017, 27(3): 17-23.
[19]	Liu H, Xing F, Zhou YX, et al. Nanomaterials-based photothermal therapies for antibacterial applications[J]. Mater Des, 2023, 233: 112231.
[20]	Li CW, Cheng Y, Li DW, et al. Antitumor applications of photothermal agents and photothermal synergistic therapies[J]. Int J Mol Sci, 2022, 23(14): 7909.
[21]	Dash SR, Kundu CN. Photothermal therapy: a new approach to eradicate cancer[J]. Curr Nanosci, 2022, 18(1): 31-47.
[22]	Ren X, Hao RX, Yang YQ, et al. A facile and green stra-tegy to achieve metallized woven carbon fiber through the triple roles of dopamine in in situ thermal reduction of Ag[J]. Compos Commun, 2023, 40: 101585.
[23]	Shi X, Zheng H, Kannan AM, et al. Effect of thermally induced oxygen vacancy of α-MnO₂ nanorods toward oxygen reduction reaction[J]. Inorg Chem, 2019, 58(8): 5335-5344.
[24]	唐洁吟, 王刚, 刘聪, 等. 微纳米生物活性玻璃诱导牙本质再矿化研究[J]. 无机材料学报, 2022, 37(4): 436-444.
	Tang JY, Wang G, Liu C, et al. Dentin remineralization induced by micro-nano bioactive glass spheres[J]. J Inorgan Mater, 2022, 37(4): 436-444.
[25]	Memarpour M, Shafiei F, Rafiee A, et al. Effect of hydroxyapatite nanoparticles on enamel remineralization and estimation of fissure sealant bond strength to remineralized tooth surfaces: an in vitro study[J]. BMC Oral Heal, 2019, 19: 92.
[26]	Wu J, Qin N, Bao DH. Effective enhancement of piezocatalytic activity of BaTiO₃ nanowires under ultrasonic vibration[J]. Nano Energy, 2018, 45: 44-51.
[27]	Ernst B, Setayesh T, Nersesyan A, et al. Investigations concerning the impact of consumption of hot beverages on acute cytotoxic and genotoxic effects in oral mucosa cells[J]. Sci Rep, 2021, 11: 23014.
[28]	Liang KN, Gao Y, Li JS, et al. Effective dentinal tubule occlusion induced by polyhydroxy-terminated PAMAM dendrimer in vitro [J]. RSC Adv, 2014, 4(82): 43496-43503.
[29]	Xu Z, Neoh KG, Kishen A. A biomimetic strategy to form calcium phosphate crystals on type I collagen substrate[J]. Mater Sci Eng C, 2010, 30(6): 822-826.
[30]	Kim C, Lim YJ, Kim YE, et al. An efficient method for the selective syntheses of sodium telluride and symmetrical diorganyl tellurides and the investigation of reaction pathways[J]. Molecules, 2024, 29(22): 5398.
[31]	Pang XL, Feng QG, Qiu TY, et al. Defective TiO₂ prepared via synchronous crystallization and constraint reduction strategy with enhanced photocatalytic activity[J]. Mater Electron, 2021, 32: 20327-20341.
[32]	Li YX, Zhou GL, Yin JZ, et al. Aboundent oxygen defects in CoFe-LDH derivatives for enhanced photo-thermal synergistic catalytic hydrogen production from Na-BH4[J]. Int J Hydrog Energ, 2023, 22: 16745-16755.
[33]	Zhang YQ, Han WJ, Ding LL, et al. Insight into the re-gulation between crystallinity and oxygen vacancies of BiVO₄ affecting the photocatalytic oxygen evolution activity[J]. Catal Sci Technol, 2022, 12: 4040-4049.
[34]	Kang ZH, Lin EZ, Qin N, et al. Effect of oxygen vacancies and crystal symmetry on piezocatalytic properties of Bi₂WO₆ ferroelectric nanosheets for wastewater decontamination[J]. Environ Sci Nano, 2021, 8(5): 1376-1388.
[35]	Kumari rajendran R, Aggarwal D, Bonvalet Rolland M, et al. Design and development of large-diameter Mg-Zn-Ca bulk metallic glass for biomedical applications: a mechanical and corrosion perspective[J]. Intermetallics, 2024, 175: 108520.
[36]	Gupta SK, Modak B, Das D, et al. Light harvesting from oxygen vacancies and A- and B-site dopants in CaSnO₃ perovskite through efficient photon utilization and local site engineering[J]. ACS Appl Electron Mater, 2021, 3(7): 3256-3270.
[37]	Bi X, Du GH, Kalam A, et al. Tuning oxygen vacancy content in TiO₂ nanoparticles to enhance the photocatalytic performance[J]. Chem Eng Sci, 2021, 234: 116440.
[38]	Zhang GQ, Jiang WS, Hua SX, et al. Constructing bulk defective perovskite SrTiO₃ nanocubes for high performance photocatalysts[J]. Nanoscale, 2016, 8(38): 16963-16968.
[39]	Lin YK, Chen RS, Chou TC, et al. Thickness-dependent binding energy shift in few-layer MoS₂ grown by che-mical vapor deposition[J]. ACS Appl Mater Interfaces, 2016, 8(34): 22637-22646.
[40]	Kumar A, Kumar M, Navakoteswara Rao V, et al. Unra-veling the structural and morphological stability of oxygen vacancy engineered leaf-templated CaTiO₃ towards photocatalytic H₂ evolution and N₂ fixation reactions[J]. J Mater Chem A, 2021, 9(31): 17006-17018.
[41]	Xu H, Yan CL, Li RZ, et al. Synergetic modulation of surface alkali and oxygen vacancy over SrTiO₃ for the CO₂ photodissociation[J]. Nanotechnology, 2022, 33(8): 085401.
[42]	Feng S, Wang T, Liu B, et al. Enriched surface oxygen vacancies of photoanodes by photoetching with enhan-ced charge separation[J]. Angew Chem, 2020, 132(5): 2060-2064.
[43]	Yang JS, Li BX. First-principles study of Ga₇As₇ ionic cluster and influence of multi-charge on its structure[J]. Chin Phys B, 2010, 19(9): 097103.
[44]	Cai JM, Cao A, Huang JJ, et al. Understanding oxygen vacancies in disorder-engineered surface and subsurface of CaTiO₃ nanosheets on photocatalytic hydrogen evolution[J]. Appl Catal B Environ, 2020, 267: 118378.
[45]	Mesoudy AE, MacHon D, Ruediger A, et al. Band gap narrowing induced by oxygen vacancies in reactively sputtered TiO₂ thin films[J]. Thin Solid Films, 2023, 769: 139737.
[46]	Li JJ, Cai SC, Yu EQ, et al. Efficient infrared light promoted degradation of volatile organic compounds over photo-thermal responsive Pt-rGO-TiO₂ composites[J]. Appl Catal B Environ, 2018, 233: 260-271.
[47]	Wang YF, Barhoumi A, Tong R, et al. BaTiO₃-core Au-shell nanoparticles for photothermal therapy and bimodal imaging[J]. Acta Biomater, 2018, 72: 287-294.
[48]	Dai L, Fu P, Chen JM, et al. Nitrogen doping mediated oxygen vacancy and Ti valence regulation to enhance photocatalytic H₂ generation[J]. Int J Hydrog Energy, 2023, 48(67): 26187-26199.
[49]	Tan HQ, Zhao Z, Zhu WB, et al. Oxygen vacancy enhanced photocatalytic activity of pervoskite SrTiO₃ [J]. ACS Appl Mater Interfaces, 2014, 6(21): 19184-19190.
[50]	Yang J, Wu PF, Weng YL, et al. Rational design and antimicrobial potency assessment of abaecin analogues[J]. ACS Biomater Sci Eng, 2023, 9(12): 6698-6714.
[51]	Wang XQ, Wang YF, Wang K, et al. Bifunctional antica-ries peptides with antibacterial and remineralizing effects[J]. Oral Dis, 2019, 25(2): 488-496.
[52]	Li JF, Ma LL, Li ZY, et al. Oxygen vacancies-rich heterojunction of Ti₃C₂/BiOBr for photo-excited antibacterial textiles[J]. Small, 2022, 18(5): 202104448.
[53]	Hu T, Lan D, Wang J, et al. Construction of NiCo₂O₄/NiCoO₂ co-embedded porous bio-carbon with rich heterogeneous interfaces for excellent bacteriostatic microwave radiation protection[J]. Carbon, 2025, 232: 119798.
[54]	Jiang Y, Li J, Zeng Z, et al. Organic photodynamic nanoinhibitor for synergistic cancer therapy[J]. Angew Chem Int Ed Engl, 2019, 58(24): 8161-8165.
[55]	Sarna-Boś K, Skic K, Boguta P, et al. Elemental mapping of human teeth enamel, dentine and cementum in view of their microstructure[J]. Micron, 2023, 172: 103485.
[56]	Davidson CL, Hoekstra IS, Arends J. Microhardness of sound, decalcified and etched tooth enamel related to the calcium content[J]. Caries Res, 1974, 8(2): 135-144.

项目	酸蚀前牙齿	酸蚀后牙齿	CSO-500处理后酸蚀牙	CSO处理后酸蚀牙
O/%	78.47	90.43	66.24	80.52
P/%	9.64	4.95	13.34	8.99
Ca/%	11.89	4.62	20.42	10.49
Ca/P	1.23	0.93	1.53	1.17