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Synthesis and characterization of nanoparticulate niobium- and zinc-doped bioglass-ceramic/chitosan hybrids for dental applications

  • Original Paper: Characterization methods of sol-gel and hybrid materials
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Abstract

Dental caries and periodontal disease are responsible for the most frequent set of chronic diseases in humans, for which no perfectly regenerative solutions are available yet. As a result, materials combining an intrinsic antibacterial activity with tissue regeneration properties for minimally invasive dental therapies are in high demand. Here we report on the fabrication and characterization of a novel nanocomposite material for such dental applications. The material is composed of narrowly disperse Na2O–CaO–P2O5–SiO2 bioglass-ceramic nanoparticles, 30–70 nm in diameter, doped with antibacterial and osteogenic zinc and niobium ions, and hybridized with chitosan. These systems were characterized for their particle size, morphology, atomic and phase composition, and glass-ceramic/polymer interface with the use of transmission electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction and Fourier transform infrared spectroscopy. After annealing at 680 °C, amorphous silica in the bioglass-ceramic coexisted with silicalite-1 and combeite, the average crystallite size of which was 20–40 nm. In spite of the significantly better incorporation of zinc than of niobium inside the glass-ceramic network, zinc did not affect the particle size and shape distribution, while niobium lowered the average particle size. Chitosan increased the hydration capacity of the bioglass-ceramic and it formed a continuous interface around the bioglass-ceramic nanoparticles, devoid of micropores. This intimacy of the interface was confirmed by the downshift of the critical Si–O(–Si) vibration modes in the bioglass-ceramic upon hybridization with chitosan. The addition of zinc ions hampered the partial recrystallization during annealing by interfering with the Si–O network restructuring, in direct proportion with its concentration. Niobium ions produced a similar structure-breaking effect, which was evidenced, as in the case of zinc, by upshifting the antisymmetric Si–O–Si stretch of the bridging oxygen and increasing the full-width at half maxima for all the major Si–O(–Si) vibration modes. The effective electrostatic attraction between the aminated hydrocarbon chains of chitosan and the negatively charged silanol groups of silica may extend to the interaction with dentin collagen fibrils decalcified due to caries, making the material of potential interest for adhesive fillers of cariogenic lesions in teeth. Both the undoped and the doped bioactive glass-ceramics interacted favorably with odontoblast-like cells, accentuating their potential for further research for applications in minimally invasive reparative dentistry.

Highlights

  • Chitosan-coated Zn- or Nb-doped Na2O–CaO–P2O5–SiO2 bioglass ceramic was synthesized and characterized.

  • Chitosan increased the hydration capacity and formed a continuous interface around the nanoparticles.

  • Zn hampered the recovery during annealing and Nb promoted it.

  • Both Zn and Nb exhibited structure-breaking effects on the Si–O–Si glassy network.

  • Zn-doped material was less viable to odontoblasts than the control and the Nb-doped one at low dosages.

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Acknowledgements

This work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infrastructure (NNCI). Part of this research was supported by an East Carolina University faculty startup award to SG.

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Authors and Affiliations

  1. TardigradeNano, Irvine, CA, 92604, USA

    Vuk Uskoković

  2. School of Dental Medicine, East Carolina University, Greenville, NC, 27834, USA

    Gabriel Abuna, Ramiro Mendonca Murata & Saulo Geraldeli

  3. Department of Restorative Dentistry, Piracicaba Dental School, Campinas State University, Piracicaba, SP, 13414-903, Brazil

    Paulo Ferreira & Mario Alexandre Coelho Sinhoreti

  4. MP Biomedicals, Irvine, CA, 92618, USA

    Victoria M. Wu

  5. Department of Materials Science & Engineering, University of Florida, Gainesville, FL, 32611, USA

    Laurie Gower

  6. Department of Dental Materials and Prosthodontics, Ribeirao Preto School of Dentistry, University of Sao Paulo, Ribeirão Preto, SP, 14040-904, Brazil

    Fernanda Carvalho Panzeri Pires-de-Souza

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  1. Vuk Uskoković
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  2. Gabriel Abuna
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  3. Paulo Ferreira
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  4. Victoria M. Wu
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  7. Ramiro Mendonca Murata
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  8. Mario Alexandre Coelho Sinhoreti
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  9. Saulo Geraldeli
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Contributions

VU, LG and SG conceptualized the study. PRBdC, FCPP-d-S and MACS synthesized the bioglass ceramic. VU and VMW synthesized the bioglass ceramic/chitosan hybrid. VU performed the diffractometric and spectroscopic characterizations and analyses. SG performed the TEM analysis. GA performed the biological characterization under the supervision of VU, VMW, RMM and SG. VU interpreted the data and wrote the paper with the input from LG and SG. SG supervised the project.

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Correspondence to Vuk Uskoković.

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Uskoković, V., Abuna, G., Ferreira, P. et al. Synthesis and characterization of nanoparticulate niobium- and zinc-doped bioglass-ceramic/chitosan hybrids for dental applications. J Sol-Gel Sci Technol 97, 245–258 (2021). https://doi.org/10.1007/s10971-020-05442-5

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  • DOI: https://doi.org/10.1007/s10971-020-05442-5

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