Stereolithography printing of bone scaffolds using biofunctional calcium phosphate nanoparticles

doi:10.1016/j.jmst.2021.01.062

Abstract

Abstract:

Calcium phosphate (CaP) has been widely used for bone defect repair due to good biocompatibility and osteoconductivity. Additive manufacture of calcium phosphate bioceramics with tailored architectures and improved mechanical properties has recently attracted great attention. Herein, calcium phosphate nanoparticles with the size of ∼89-164 nm were synthesized by the hydrothermal treatment of amorphous calcium phosphate (ACP) precursors at 180 °C for 24 h. Biofunctional elements including Mg, Sr and Zn have been doped into these calcium phosphate nanoparticles. Our results revealed that Mg ²⁺ ions played critical roles in formation of whitlockite-type calcium phosphate (not hydroxyapatite) from ACP precursors. Moreover, gyroid scaffolds with bionic triply periodic minimal surface structures were fabricated using stereolithography printing of these calcium phosphate nanoparticles, which are likely used as biofunctional scaffolds for bone repair.

Key words: Amorphous calcium phosphate, Whitlockite, Stereolithography printing, Triply periodic minimal surfaces, Biofunctional scaffolds

Ihsan UIIah, Lei Cao, Wei Cui, Qian Xu, Rui Yang, Kang-lai Tang, Xing Zhang. Stereolithography printing of bone scaffolds using biofunctional calcium phosphate nanoparticles[J]. J. Mater. Sci. Technol., 2021, 88: 99-108.

Figures/Tables 9

Table 1 Reactant concentrations for synthesis of different samples.

Sample name	Concentration (mol/L)
Sample name	Calcium nitrate tetrahydrate	Magnesium nitrate hexahydrate	Strontium nitrate tetrahydrate	Zinc nitrate hexahydrate	Diammonium hydrogen phosphate
5Mg-ACP	0.91	0.05	0	0	0.64
7Mg-ACP	0.89	0.07	0	0	0.64
10Mg-ACP	0.87	0.10	0	0	0.64
15Mg-ACP	0.83	0.15	0	0	0.65
Mg,Sr-ACP	0.80	0.10	0.05	0	0.63
Mg,Zn-ACP	0.81	0.10	0	0.05	0.64

Fig. 1. (a) XRD patterns and (b) FTIR spectra of different ACP samples, (c) the XPS spectrum of the 10Mg-ACP sample, (d) P2p peaks of 10Mg-ACP, (e) Ca2p peaks of 10Mg-ACP, (f) Mg1s peak of 10Mg-ACP.

Fig. 2. (a) XRD patterns of different CaP samples, (b) partially enlarged XRD patterns from (a), (c) crystal lattice parameters of CaP samples, (d) FTIR spectra of 10Mg-CaP and 15Mg-CaP samples.

Fig. 3. (a) A bright field transmission electron micrograph of 10Mg-ACP nanoparticles, (b) the corresponding SAED pattern from (a), (c) a bright field transmission electron micrograph of 10Mg-CaP nanoparticles, (d) the corresponding SAED pattern from (c).

Fig. 4. (a) The bright field image, (b) the high-angle annular dark field image, (c-f) the EDS mapping of a 10Mg-CaP nanoparticle.

Fig. 5. The schematic illustration of formation of Mg-ACP phase and transformation to calcium phosphate nanocrystals.

Fig. 6. (a) The schematic process for creation of the gyroid model, (b) the printing pattern of the gyroid model for one layer, (c) the morphology of 10Mg-CaP ceramic scaffold after sintering at 1180 °C for 3 h.

Fig. 7. (a) SEM morphology of the 10Mg-CaP scaffold after sintering at 1180 °C for 3 h, (b) the partial enlarged image of the red box in (a), and (c) the EDS result of 10Mg-CaP scaffold based on the red dot site in (b). (d) SEM morphology of the Mg,Zn-CaP scaffold after sintering at 1180 °C for 3 h, (e) the partial enlarged image of the yellow box in (d), (f) the EDS result of Mg,Zn-CaP scaffold based on the yellow dot site in (e).

Fig. 8. (a) Optical density values from CCK-8 assay for MC3T3-E1 cells cultured with the extraction medium from 10Mg-CaP scaffolds (the 10Mg-CaP group) and normal culture medium (the control group) for 1, 3, and 5 d, (b) the porous structures of a 10Mg-CaP scaffold with MC3T3-E1 cells, and (c) cell morphology on the 10Mg-CaP scaffold after culture for 5 d. (c) and (e) are large magnification of the yellow dash boxes in (b) and (d), respectively. The white arrow in (e) shows filopodia of cells and cellular extension.

References 53

[1]	S.V. Dorozhkin, Biomaterials 31 (2010) 1465-1485. DOI PMID
[2]	S.V. Dorozhkin, Acta Biomater. 6 (2010) 4457-4475. DOI PMID
[3]	H. Dai, X. Wang, Y. Han, X. Jiang, S. Li, J. Mater. Sci. Technol. 27 (2011) 431-436.
[4]	T. Yu, C. Gao, J. Ye, M. Zhang, J. Mater. Sci. Technol. 30 (2014) 686-691. DOI URL
[5]	Z. Liu, H. Liang, T. Shi, D. Xie, R. Chen, X. Han, L. Shen, C. Wang, Z. Tian, Ceram. Int. 45 (2019) 11079-11086. DOI URL
[6]	X. Li, Y. Yuan, L. Liu, Y.S. Leung, Y. Chen, Y. Guo, Y. Chai, Y. Chen, Bio-Des. Manuf. 3 (2020) 15-29. DOI URL
[7]	C. Feng, W. Zhang, C. Deng, G. Li, J. Chang, Z. Zhang, X. Jiang, C. Wu, Adv. Sci. 4 (2017), 1700401. DOI URL
[8]	R. Gmeiner, G. Mitteramskogler, J. Stampfl, A.R. Boccaccini, Int. J. Appl. Ceram. Technol. 12 (2015) 38-45. DOI URL
[9]	T. Chartier, C. Chaput, F. Doreau, M. Loiseau, J. Mater. Sci. 37 (2002) 3141-3147. DOI URL
[10]	A. Badev, Y. Abouliatim, T. Chartier, L. Lecamp, P. Lebaudy, C. Chaput, C. Delage, J. Photochem. Photobiol. A: Chem. 222 (2011) 117-122. DOI URL
[11]	N. Matsumoto, K. Sato, K. Yoshida, K. Hashimoto, Y. Toda, Acta Biomater. 5 (2009) 3157-3164. DOI PMID
[12]	S.C. Liou, S.Y. Chen, Biomaterials 23 (2002) 4541-4547. DOI URL
[13]	W. Habraken, P. Habibovic, M. Epple, M. Bohner, Mater. Today 19 (2016) 69-87. DOI URL
[14]	A. Dey, P.H.H. Bomans, F.A. Müller, J. Will, P.M. Frederik, G. De With, N.A.J.M. Sommerdijk, Nat. Mater. 9 (2010) 1010-1014. DOI URL
[15]	F. Nudelman, K. Pieterse, A. George, P.H.H. Bomans, H. Friedrich, L.J. Brylka, P.A.J. Hilbers, G. De With, N.A.J.M. Sommerdijk, Nat. Mater. 9 (2010) 1004-1009. DOI PMID
[16]	A. La Fontaine, A. Zavgorodniy, H. Liu, R. Zheng, M. Swain, J. Cairney, Sci. Adv. 2 (2016) 1-7.
[17]	H. Ding, H. Pan, X. Xu, R. Tang, Cryst. Growth Des. 14 (2014) 763-769. DOI URL
[18]	M. Jiménez, C. Abradelo, J. San Román, L. Rojo, J. Mater. Chem. B Mater. Biol. Med. 7 (2019) 1974-1985. DOI URL
[19]	W. Yu, T. Sun, C. Qi, Z. Ding, H. Zhao, F. Chen, D. Chen, Y. Zhu, Z. Shi, Y. He, ACS Appl. Mater. Interfaces 9 (2017) 3306-3317. DOI URL
[20]	W.C. Lu, E. Pringa, L. Chou, Magnes. Res. 30 (2017) 42-52. DOI URL
[21]	Y. Lai, Y. Li, H. Cao, J. Long, X. Wang, L. Li, C. Li, Q. Jia, B. Teng, T. Tang, J. Peng, D. Eglin, M. Alini, D.W. Grijpma, G. Richards, L. Qin, Biomaterials 197 (2019) 207-219. DOI URL
[22]	Y. Qiao, W. Zhang, P. Tian, F. Meng, H. Zhu, X. Jiang, X. Liu, P.K. Chu, Biomaterials 35 (2014) 6882-6897. DOI URL
[23]	F. Zhao, B. Lei, X. Li, Y. Mo, R. Wang, D. Chen, X. Chen, Biomaterials 178 (2018) 36-47. DOI URL
[24]	O. Guillaume, M.A. Geven, C.M. Sprecher, V.A. Stadelmann, D.W. Grijpma, T.T. Tang, L. Qin, Y. Lai, M. Alini, J.D. de Bruijn, H. Yuan, R.G. Richards, D. Eglin, Acta Biomater. 54 (2017) 386-398. DOI PMID
[25]	D. Ali, M. Ozalp, S.B.G. Blanquer, S. Onel, Eur. J. Mech. B-Fluids 79 (2020) 376-385. DOI URL
[26]	L. Cao, X. Li, X. Zhou, Y. Li, K.S. Vecchio, L. Yang, W. Cui, R. Yang, Y. Zhu, Z. Guo, X. Zhang, ACS Appl. Mater. Interfaces 9 (2017) 9862-9870. DOI URL
[27]	H.D. Kim, H.L. Jang, H.Y. Ahn, H.K. Lee, J. Park, E. Seo Lee, E.A. Lee, Y.H. Jeong, D.G. Kim, K.T. Nam, N.S. Hwang, Biomaterials 112 (2017) 31-43. DOI PMID
[28]	M. Descostes, F. Mercier, N. Thromat, C. Beaucaire, M. Gautier-Soyer, Appl. Surf. Sci. 165 (2000) 288-302. DOI URL
[29]	D.J. Yoo, Int. J. Precis. Eng. Manuf. Technol. 13 (2012) 527-537.
[30]	X. Shi, W. Zeng, Y. Sun, Y. Han, Y. Zhao, P. Guo, J. Mater. Eng. Perform. 24 (2015) 1754-1762. DOI URL
[31]	J. Zhao, Y. Liu, W. Bin Sun, H. Zhang, Chem. Cent. J. 5 (2011) 1-7. DOI URL
[32]	S.V. Dorozhkin, J. Mater. Sci. 42 (2007) 1061-1095. DOI URL
[33]	S.V. Dorozhkin, Int. J. Energ. Mater. Chem. Propuls. 2 (2012) 19-46.
[34]	C. Shao, B. Jin, Z. Mu, H. Lu, Y. Zhao, Z. Wu, L. Yan, Z. Zhang, Y. Zhang, H. Pan, Z. Liu, R. Tang, Sci. Adv. 5 (2019) 1-10.
[35]	A. Lotsari, A. Rajasekharan, M. Halvarsson, M. Andersson, Nat. Commun. 9 (2018) 4170-4181. DOI URL
[36]	W.J.E.M. Habraken, J. Tao, L.J. Brylka, H. Friedrich, L. Bertinetti, A.S. Schenk, A. Verch, V. Dmitrovic, P.H.H. Bomans, P.M. Frederik, J. Laven, P. Van Der Schoot, B. Aichmayer, G. De With, J.J. DeYoreo, N.A.J.M. Sommerdijk, Nat. Commun. 4 (2013) 1507-1512. DOI PMID
[37]	J.M. Sedlak, R.A. Beebe, J. Colloid Interface Sci. 47 (1974) 483-489. DOI URL
[38]	J.M. Holmes, R.A. Beebe, Calcif. Tissue Res. 7 (1971) 163-174. PMID
[39]	E.D. Eanes, Calcium Phosphates Biol. Ind. Syst. (1998) 21-39.
[40]	W. Cui, Q. Song, H. Su, Z. Yang, R. Yang, N. Li, X. Zhang, J. Mater. Sci. Technol. 36 (2020) 27-36. DOI
[41]	W. Cui, S. Wang, R. Yang, X. Zhang, MRS Commun. 9 (2019) 1-8. DOI URL
[42]	H.L. Jang, K. Jin, J. Lee, Y. Kim, S.H. Nahm, K.S. Hong, K.T. Nam, ACS Nano 8 (2014) 634-641. DOI PMID
[43]	S. Lazić, J. Cryst. Growth 147 (1995) 147-154. DOI URL
[44]	B. Dickens, W.E. Browns, J. Solid State Chem. (1977) 253-262.
[45]	S. Kannan, F. Goetz-Neunhoeffer, J. Neubauer, S. Pina, P.M.C. Torres, J.M.F. Ferreira, Acta Biomater. 6 (2010) 571-576. DOI PMID
[46]	S. Kannan, F. Goetz-Neunhoeffer, J. Neubauer, J.M.F. Ferreira, J. Am. Ceram. Soc. 92 (2009) 1592-1595. DOI URL
[47]	K. Matsunaga, T. Kubota, K. Toyoura, A. Nakamura, Acta Biomater. 23 (2015) 329-337. DOI URL
[48]	J. Wei, J. Jia, F. Wu, S. Wei, H. Zhou, H. Zhang, J.W. Shin, C. Liu, Biomaterials 31 (2010) 1260-1269. DOI URL
[49]	D.J. Yoo, Int. J. Precis. Eng. Manuf. Technol. 12 (2011) 61-71.
[50]	A. Paré, B. Charbonnier, P. Tournier, C. Vignes, J. Veziers, J. Lesoeur, B. Laure, H. Bertin, G. De Pinieux, G. Cherrier, J. Guicheux, O. Gauthier, P. Corre, D. Marchat, P. Weiss, ACS Biomater. Sci. Eng. 6 (2020) 553-563. DOI URL
[51]	R. Felzmann, S. Gruber, G. Mitteramskogler, P. Tesavibul, A.R. Boccaccini, R. Liska, J. Stampfl, Adv. Eng. Mater. 14 (2012) 1052-1058. DOI URL
[52]	G. Mitteramskogler, R. Gmeiner, R. Felzmann, S. Gruber, C. Hofstetter, J. Stampfl, J. Ebert, W. Wachter, J. Laubersheimer, Addit. Manuf. 1 (2014) 110-118.
[53]	G. Marchelli, R. Prabhakar, D. Storti, M. Ganter, Rapid Prototyp. J. 17 (2011) 187-194. DOI URL