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SCIENCE CHINA Materials, Volume 60, Issue 6: 516-528(2017) https://doi.org/10.1007/s40843-017-9038-5

Symmetry-breaking assembled porous calcite microspheres and their multiple dental applications

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  • ReceivedMar 10, 2017
  • AcceptedApr 19, 2017
  • PublishedMay 16, 2017

Abstract

Biomedical applications of porous calcium carbonate (CaCO3) microspheres have been mainly restricted by their aqueous instability and low remineralization rate. To overcome these obstacles, a novel symmetry-breaking assembled porous calcite microsphere (PCMS) was constructed in an ethanol/water mixed system using a two-step vapor-diffusion/aging crystallization strategy. In contrast to the conventional additive-induced crystallization method, the present strategy was performed under mild conditions and was free from any foreign additives, thus avoiding the potential contamination of the final product. Meanwhile, the prepared PCMSs were characterized by their highly uniform spherical morphology and large open pores, which are favorable for large protein delivery. An antimicrobial study of immunoglobulin Y (IgY)-loaded PCMSs revealed excellent antimicrobial activity against Streptococcus mutans. More importantly, they showed surprisingly rapid transformation to bone minerals in physiological medium. Evaluation of the in vitro efficacy of PCMSs in dentinal tubule occlusion demonstrated their powerful potential to serve as a catalyst in the repair of dental hard tissue. Therefore, the developed PCMSs show great promise as multifunctional biomaterials for dental treatment applications.


Funded by

National Natural Science Foundation of China(51402329,81500806)

Science Foundation for Youth Scholar of State Key Laboratory of High Performance Ceramics and Superfine Microstructures(SKL201404)

Shanghai Excellent Academic Leaders Program(14XD1403800)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (51402329 and 81500806), the Science Foundation for Youth Scholar of State Key Laboratory of High Performance Ceramics and Superfine Microstructures (SKL201404) and Shanghai Excellent Academic Leaders Program (14XD1403800).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Ma M and Yan Y contributed to this work equally. Ma M designed and synthesized the samples; Ma M, Yan Y, Chern S, Qi S and Shang G performed the experiments; Ma M wrote the paper with support from Qi C, Chen H and Wang R. All authors contributed to the general discussion.


Author information

Ming Ma received his PhD degree from Shanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS) in 2013. He is now an associate professor of SICCAS. His research focuses on the design of mesoporous materials for biomedical applications including anticancer drug delivery, medical imaging and dental restoration.


Yanhong Yan obtained her PhD degree from Wuhan University under the supervision of Prof. Mingwen Fan. She is now a dentist at the Department of Pediatric Dentistry, School of Stomatology, Tongji University. Her research focuses on the structure and properties of anti-dental caries biomaterials.


Raorao Wang obtained his PhD degree from Matsumoto Dental University in Japan under the supervision of Prof. Hiroo Miyazawa. He is now the director of Stomatological Department, Shanghai Tenth People’s Hospital of Tongji University. His research interest focuses on the stem cell-based biological tooth repair and regeneration.


Hangrong Chen received her PhD degree from SICCAS in 2001. She is now a professor of SICCAS, and deputy director of the State Key Laboratory of High Performance Ceramics and Superfine Microstructure. Her research areas include the synthesis of mesoporous materials, multifunctional inorganic biomedical nanomaterials and environmental catalytic materials.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


References

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  • Figure 1

    (a) Schematic illustration of the two-step synthetic procedure for PCMSs. Step I: vapor-diffusion process. Step 2: aging crystallization process via soaking PCMS in a mixed water/ethanol solution (R=1/50) at 30°C for 7 days. (b–e) Morphological and XRD characterizations of PCMSs: (b) TEM image of PCMSs. (c, d) SEM images of PCMSs. Fig. 1d shows the enlargement of the selected square region in (c). The arrows indicate the large-pore on the MPs surface. (e) TEM size distribution of PCMSs. Over 200 particles in different fields of views were analyzed for the size distribution. (f) The XRD pattern of PCMSs. The inset high-resolution TEM image shows the lattice fringe of PCMSs.

  • Figure 2

    SEM images of samples obtained by two-step vapor-diffusion/aging crystallization strategy. (a, c, e) SEM images of the intermediate products synthesized in the first step: (a) R=0; (c) R=1/160; (e) R=1/40. (b, d, f) SEM images of the final products after two-step synthetic process: (b) R=0; (d) R=1/160; (f) R=1/40.

  • Figure 3

    Characterizations of IgY protein loading capacity for PCMSs. (a) FTIR spectra of free IgY, empty PCMSs and PCMSs-IgY. The arrow indicates the specific absorption peak at 1648 cm−1. (b) UV-vis spectra of supernatant solution after loading PCMSs and CMCs with the same initial concentration of IgY (1 mg mL−1), separately. The inside table shows the calculated encapsulation efficiency and loading capacity of each sample.

  • Figure 4

    (a) Schematic demonstration of the in vitro antibacterial activity evaluation of the PCMSs-IgY against S. mutans. (b, c) The S. mutans colonies (b) and the corresponding surviving S. mutans counts (c) after different treatments for 12 h.

  • Figure 5

    SEM images and Raman spectra showing the conversion of samples to hydroxyapatite in PBS solution. (a, c) SEM images of PCMSs after soaking in PBS for (a) 2 and (c) 24 h. Lath-like surface morphology formed after soaking for 2h. (b) Raman spectra of PCMSs after soaking in PBS for 2 h. H indicate the characteristic peaks of hydroxyapatite. (d, f) SEM images of counterpart samples CMCs after soaking in PBS for (a) 2 and (c) 24 h. Nanometer sized lath-like agglomerates are shown on the surface of rhombohedral calcite after soaking CMCs in PBS for 2 h. The arrow in Fig. 5f indicates the unreacted rhombohedral calcite. (e) Raman spectrum of CMCs after soaking in PBS for 2 h. C indicates the characteristic peaks of calcite. Only a minority of calcite converts to hydroxyapatite structure for CMCs within 2 h.

  • Figure 6

    SEM images of dentinal tubules before (a) and after treatment with the PCMSs (b–e) and MCCPs group (f). (b, c) The PCMSs-treated dentin surface was incubated in PBS solution for 15 min. The arrows in Fig. 6c indicate the broken porous particles within tubules. (d–f) SEM images of the groups containing PCMSs (d, e) and MCCPs (f) after tooth-brushing for 7 days: (d, f) magnified ×1000, (e) magnified ×3000. (g) Schematic illustration of the hydroxyapatite formation mechanism of PCMSs within dentin tubules.

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