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. 2021 Apr 5:35:13-24.
doi: 10.1016/j.jare.2021.03.009. eCollection 2022 Jan.

In situ synthesis of hydroxyapatite nanorods on graphene oxide nanosheets and their reinforcement in biopolymer scaffold

Cijun Shuai  1   2   3 , Bo Peng  1 , Pei Feng  1 , Li Yu  1 , Ruilin Lai  4 , Anjie Min  5
Affiliations

In situ synthesis of hydroxyapatite nanorods on graphene oxide nanosheets and their reinforcement in biopolymer scaffold

Cijun Shuai et al. J Adv Res. .

Abstract

Introduction: It is urgently needed to develop composite bone scaffold with excellent mechanical properties and bioactivity in bone tissue engineering. Combining graphene oxide (GO) and hydroxyapatite (HAP) for the reinforcement of biopolymer bone scaffold has emerged as a promising strategy. However, the dispersion of GO and HAP remains to be a big challenge.

Objectives: In this present work, the mechanical properties of GO and the bioactivity of and HAP were combined respectively via in situ synthesis for reinforcing biopolymer bone scaffold.

Methods: GO nanosheets were employed to in situ synthesize GO-HAP nanocomposite via hydrothermal reaction, in which their abundant oxygen-containing groups served as anchor sites for the chelation of Ca2+ and then Ca2+ absorbed HPO42- via electrovalent bonding to form homogeneously dispersed HAP nanorods. Thereby, the GO-HAP nanocomposite was blended with biopolymer poly-L-lactic acid (PLLA) for fabricating biopolymer scaffold by selective laser sintering (SLS).

Results: GO nanosheets were uniformly decorated with HAP nanorods, which were about 60 nm in length and 5 nm in diameter. The compressive strength and modulus of PLLA/12%GO-HAP were significantly increased by 53.71% and 98.80% compared to the pure PLLA scaffold, respectively, explained on the base of pull out, crack bridging, deflection and pinning mechanisms. Meanwhile, the mineralization experiments indicated the PLLA/GO-HAP scaffold displayed good bioactivity by inducing the formation of apatite layer. Besides, cell culturing experiments demonstrated the favorable cytocompatibility of scaffold by promoting cell adhesion and proliferation.

Conclusions: The present findings show the potential of PLLA/GO-HAP composite scaffold via in situ synthesis in bone tissue engineering.

Keywords: Bioactivity; GO; HAP; In situ synthesis; Mechanical properties.

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Conflict of interest statement

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Figures

None
Graphical abstract
Fig. 1
Fig. 1
Schematic diagram of the preparation of GO-HAP composite powders via in situ synthesis (a), the preparation of PLLA/GO-HAP composite powders (b), the three orthographic views of the PLLA/GO-HAP (c) and PLLA (d) scaffolds.
Fig. 2
Fig. 2
Raman spectra (a), FTIR spectra (b) and XRD spectra (c) of GO and GO-HAP.
Fig. 3
Fig. 3
SEM morphologies (a, d) and the corresponding EDS mapping images (b, e), TEM images (c, f) of GO (a-c) and GO-HAP (d-f) powders.
Fig. 4
Fig. 4
In situ grown mechanism of HAP nanorods on GO nanosheets: pure GO nanosheets (a), chelation of Ca2+ with GO nanosheets (b), growth and crystallization of HAP nanorods (c), nucleation of HAP (d).
Fig. 5
Fig. 5
Morphologies of the pure PLLA scaffold (a), and the PLLA/GO-HAP scaffolds with 4% (b), 8% (c), 12% (d) and 16% (e) mass fractions of GO-HAP.
Fig. 6
Fig. 6
Compressive properties of the pure PLLA and PLLA/GO-HAP scaffolds: compression testing image (a), stress-strain curves (b), variation of compressive strength (c), variation of compressive modules (d).
Fig. 7
Fig. 7
SEM images of crack propagation in the PLLA/GO-HAP scaffolds including pull out (a), crack bridging (b), crack deflection (c), crack pinning (d), and the corresponding crack extension model (e).
Fig. 8
Fig. 8
The morphologies of the PLLA/GO-HAP scaffolds with 4% (a, e), 8% (b, f), 12% (c, g) and 16% (d, h) mass fractions of GO-HAP after SBF immersion for 28 d, and the corresponding EDS spectra (i-l).
Fig. 9
Fig. 9
The TGA spectra (a), DTG spectra (b), DSC spectra (c), XRD pattern (d) and contact angle (e) of the pure PLLA and PLLA/GO-HAP scaffolds.
Fig. 10
Fig. 10
The fluorescence staining of cells after culturing on the PLLA/12%GO-HAP scaffolds for 1 (a), 3 (b) and 5 (c) d, and morphology of cells after culturing on the PLLA/12%GO-HAP scaffolds for 1 (d), 3 (e) and 5 (f) d. The corresponding statistical analysis of cell densities (g) and cell area (h).
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