Synthesis and characterization of non-stoichiometric hydroxyapatite nanoparticles using unmodified and modified starches

Authors

DOI:

https://doi.org/10.33448/rsd-v9i12.10996

Keywords:

Nanopowder; Chemical precipitation; Calcium-rich hydroxyapatite; Calcium oxide.

Abstract

Non-stoichiometric hydroxyapatite (HAp) presents an additional phase in its structure due to calcium or phosphorus excess, which can influence the material’s mechanical properties, as well as its bioactivity and biodegradability. While stoichiometric HAp, with calcium to phosphorus ratio (Ca/P) of 1.67, has been widely investigated, only a few studies have reported the synthesis of HAp with higher Ca/P ratio. In this work, non-stoichiometric HAp nanoparticles were synthesized using chemical precipitation method followed by a calcination protocol. In order to achieve better process control with chemical precipitation, starch, a natural additive, was applied. Three types of starch were selected for comparison: nonionic starch (NS), soluble starch (SS), and cationic starch (CS). Infrared spectroscopy and chemical analysis results confirmed the non-stoichiometric profile of the synthesized HAp, with a 1.98 Ca/P ratio. X-ray diffraction (XRD) results showed that HAp and calcium oxide (CaO) crystalline phases were obtained and no residual starch was detected. Rietveld refinements confirmed that, for all three types of starch, the content of crystalline HAp was greater than 96.5% and the unit cell volume was not affected. Scanning electron microscopy (SEM) showed agglomeration of particles. Nanoparticle tracking analysis (NTA) results demonstrated that the use of SS produced the smallest particles (approximately 60nm).

References

Araújo, M. N. P., Vieira, W. E. da S., Carvalho, L. P. de, Melo, H. D. F. de, Souza, T. C. de, & Berenguer, R. A. (2020). Obtenção e caracterização de hidroxiapatita obtida por síntese hidrotermal e caracterização. Research, Society and Development, 9(11), e535911100247–e535911100247.

Bengtsson, Å., Shchukarev, A., Persson, P., & Sjöberg, S. (2009). A solubility and surface complexation study of a non-stoichiometric hydroxyapatite. Geochimica et Cosmochimica Acta, 73(2), 257–267.

Bonel, G., Heughebaert, J.-C., Heughebaert, M., Lacout, J. L., & Lebugle, A. (1988). Apatitic Calcium Orthophosphates and Related Compounds for Biomaterials Preparation. Annals of the New York Academy of Sciences, 523(1 Bioceramics), 115–130.

Brown, P. W., Hocker, N., & Hoyle, S. (1991). Variations in Solution Chemistry During the Low-Temperature Formation of Hydroxyapatite. Journal of the American Ceramic Society, 74(8), 1848–1854.

Fowler, B. O. (1974). Infrared studies of apatites. I. Vibrational assignments for calcium, strontium, and barium hydroxyapatites utilizing isotopic substitution. Inorganic Chemistry, 13(1), 194–207.

Gomes, F. D. C., Amorim, J. D. P. de, Silva, G. S. da, Souza, K. C. de, Pinto, A. F., Santos, B. S., & Costa, A. F. de S. (2020). Preparation and Characterization of Hydroxyapatite by the precipitation method and heat treatment. Research, Society and Development, 9(6), e172963549–e172963549.

Greish, Y. E. (2011). Phase evolution during the low temperature formation of stoichiometric hydroxyapatite-gypsum composites. Ceramics International, 37(3), 715–723.

Ishikawa, K., Ducheyne, P., & Radin, S. (1993). Determination of the Ca/P ratio in calcium-deficient hydroxyapatite using X-ray diffraction analysis. Journal of Materials Science: Materials in Medicine, 4(2), 165–168.

Jane, J. (2015). Starch Properties, Modifications, and Applications. Journal of Macromolecular Science, Part A, 52(12), ebi-ebi.

Kakiage, M., Iwase, K., & Kobayashi, H. (2015). Effect of citric acid addition on disaggregation of crystalline hydroxyapatite nanoparticles under calcium-rich conditions. Materials Letters, 156, 39–41.

Kaur, L., & Singh, J. (2016). Starch: Modified Starches. In Encyclopedia of Food and Health (pp. 152–159). Elsevier.

Kim, S., Ryu, H.-S., Shin, H., Jung, H. S., & Hong, K. S. (2005). In situ observation of hydroxyapatite nanocrystal formation from amorphous calcium phosphate in calcium-rich solutions. Materials Chemistry and Physics, 91(2–3), 500–506.

Lima, T. A. R. M., Ilavsky, J., Hammons, J., Sarmento, V. H. V., Rey, J. F. Q., & Valerio, M. E. G. (2017). Synthesis and synchrotron characterisation of novel dual-template of hydroxyapatite scaffolds with controlled size porous distribution. Materials Letters, 190, 107–110.

Liu, H., Guan, Y., Wei, D., Gao, C., Yang, H., & Yang, L. (2016). Reinforcement of injectable calcium phosphate cement by gelatinized starches. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 104(3), 615–625.

Masina, N., Choonara, Y. E., Kumar, P., Toit, L. C. du, Govender, M., Indermun, S., & Pillay, V. (2017). A review of the chemical modification techniques of starch. Carbohydrate Polymers, 157, 1226–1236.

Mastalska-Poplawska, J., Sikora, M., Izak, P., & Goral, Z. (2019). Applications of starch and its derivatives in bioceramics. JOURNAL OF BIOMATERIALS APPLICATIONS, 34(1), 12–24.

Meskinfam, M., M. A. S|Jazdarreh,H|Zare,K. (2011). Biocompatibility evaluation of nano hydroxyapatite-starch biocomposites. Journal of Biomedical Nanotechnology, 7(3), 455–459.

Miculescu, F., Maidaniuc, A., Voicu, S. I., Thakur, V. K., Stan, G. E., & Ciocan, L. T. (2017). Progress in Hydroxyapatite–Starch Based Sustainable Biomaterials for Biomedical Bone Substitution Applications. ACS Sustainable Chemistry & Engineering, 5(10), 8491–8512.

Motta, J. F. G., de Souza, A. R., Gonçalves, S. M., Madella, D. K. S. F., de Carvalho, C. W. P., Vitorazi, L., & de Melo, N. R. (2020). Development of active films based on modified starches incorporating the antimicrobial agent lauroyl arginate (LAE) for the food industry. Food and Bioprocess Technology.

Nawaz, H., Waheed, R., Nawaz, M., & Shahwar, D. (2020). Physical and Chemical Modifications in Starch Structure and Reactivity. In M. Emeje (Ed.), Chemical Properties of Starch. IntechOpen.

Okada, M., & Furuzono, T. (2007). Nano-Sized Ceramic Particles of Hydroxyapatite Calcined with an Anti-Sintering Agent. Journal of Nanoscience and Nanotechnology, 7(3), 848–851.

Omori, Y., Okada, M., Takeda, S., & Matsumoto, N. (2014). Fabrication of dispersible calcium phosphate nanocrystals via a modified Pechini method under non-stoichiometric conditions. Materials Science and Engineering: C, 42, 562–568.

Ramesh, S., Tan, C. Y., Hamdi, M., Sopyan, I., & Teng, W. D. (2007). The influence of Ca/P ratio on the properties of hydroxyapatite bioceramics. 64233A.

Ravaglioli, A., & Krajewski, A. (1992). Bioceramics. Springer Netherlands.

Raynaud, S., Champion, E., Bernache-Assollant, D., & Thomas, P. (2002). Calcium phosphate apatites with variable Ca/P atomic ratio I. Synthesis, characterisation and thermal stability of powders. Biomaterials, 23(4), 1065–1072.

Rey, C., Combes, C., Drouet, C., Grossin, D., Bertrand, G., & Soulié, J. (2017). 1.11 Bioactive Calcium Phosphate Compounds: Physical Chemistry ☆. In Comprehensive Biomaterials II (pp. 244–290).

Rodríguez-Carvajal, J. (1993). Recent advances in magnetic structure determination by neutron powder diffraction. Physica B: Condensed Matter, 192(1–2), 55–69.

Royer, A., Viguie, J. C., Heughebaert, M., & Heughebaert, J. C. (1993). Stoichiometry of hydroxyapatite: Influence on the flexural strength. Journal of Materials Science: Materials in Medicine, 4(1), 76–82.

Sadat-Shojai, M., Khorasani, M.-T., Dinpanah-Khoshdargi, E., & Jamshidi, A. (2013). Synthesis methods for nanosized hydroxyapatite with diverse structures. Acta Biomaterialia, 9(8), 7591–7621.

Sadjadi, M. S., Meskinfam, M., Sadeghi, B., Jazdarreh, H., & Zare, K. (2010). In situ biomimetic synthesis, characterization and in vitro investigation of bone-like nanohydroxyapatite in starch matrix. Materials Chemistry and Physics, 124(1), 217–222.

Small, J. C. (1919). A method for the preparation of soluble starch. Journal of the American Chemical Society, 41(1), 113–120.

Wang, H., Lee, J.-K., Moursi, A., & Lannutti, J. J. (2003). Ca/P ratio effects on the degradation of hydroxyapatitein vitro. Journal of Biomedical Materials Research, 67A(2), 599–608.

Yang, L., Ning, X., Bai, Y., & Jia, W. (2013). A scalable synthesis of non-agglomerated and low-aspect ratio hydroxyapatite nanocrystals using gelatinized starch matrix. Materials Letters, 113, 142–145.

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Published

25/12/2020

How to Cite

PEREA, G. N. R. .; SILVA, M. B. .; FREITAS, B. X.; SANTOS, Ésoly M. B. dos .; LOPES, L. C. R. .; VITORAZI, L.; SANTOS, C. dos . Synthesis and characterization of non-stoichiometric hydroxyapatite nanoparticles using unmodified and modified starches. Research, Society and Development, [S. l.], v. 9, n. 12, p. e30791210996, 2020. DOI: 10.33448/rsd-v9i12.10996. Disponível em: https://www.rsdjournal.org/index.php/rsd/article/view/10996. Acesso em: 25 apr. 2024.

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Engineerings