Table of Contents
Acknowledgements i
中文摘要 ii
Abstract iii
Table of Contents iv
List of Figures vii
List of Tables x
List of Abbreviations xi
Chapter 1 Introduction 1
1.1 Bioprinting 1
1.2 Bone tissue engineering and Bioprinting 3
1.3 Polymer Selection 4
1.3.1 Ideal material properties for bioprinting 4
1.3.2 Gelatin 5
1.3.3 Gelatin Methacrylate 5
1.3.4 Gelatin Methacrylate for Bone tissue engineering 6
1.3.5 Mineralization by Adding Inorganic Phases 7
1.4 Bioactive Glass 9
1.4.1 The 45S5 Bioglass® 9
1.4.2 The fabrication of 45S5 Bioactive Glass 9
1.4.3 Citric acid as catalyst for sol-gel synthesis of Bioactive glass 10
1.5 Photocrossliked Bioink: 12
1.5.1 Cell Source 12
1.5.2 Silanization of the Bioactive glass 12
1.5.3 Photoinitiator 13
1.6 Research objective 14
Chapter 2 Materials and Methods 17
2.1 Preparing of the Bioactive glass 17
2.1.1 Synthesis of the gel-derived Bioactive glass 17
2.1.2 The melt-derived Bioactive glass 17
2.1.3 The Characterization of Bioactive glass 18
2.1.4 In vitro bioactivity tests 19
2.2 The inorganic/organic hydrogel composite 20
2.2.1 Synthesis of gelatin methacryloyl hydrogel 20
2.2.2 Silanization of the gel-derived 45S5 Bioactive Glass 20
2.2.3 Preparation of GelMA/BG composite hydrogels 21
2.2.4 Mechanical properties of the composites 21
2.2.5 Bioactivity of the composites 21
2.3 The in vitro biocompatibility and osteogenic property of cell-laden GelMA/Si-BG hydrogel composites 23
2.3.1 Cell culture 23
2.3.2 Cell-laden GelMA/Si-BG Hydrogel composites 23
2.3.3 Cell viability 23
2.3.4 In vitro osteogenic study 24
2.4 Statistical analysis 25
Chapter 3 Results 27
3.1 Preparing of the Bioactive glass 27
3.1.1 The Characterization of bioactive glass 27
3.1.2 The in vitro bioactivity of Bioactive glasses 28
3.1.3 The selection of gel-derived bioactive glasses from citric acid route 31
3.2 The GelMA-BG/Si-BG hydrogel composites 32
3.2.1 The silanization of the CA3dBG 32
3.2.2 The mechanical properties of GelMA/silanized BG hydrogel composites 33
3.2.3 The in vitro bioactivity of GelMA/silanized BG hydrogel composites 34
3.3 The MSCs-laden GelMA-BG/Si-BG hydrogel composites 35
3.3.1 Cell encapsulation in the GelMA/Si-HAp hydrogel 35
3.3.2 In vitro Osteogenesis evaluation of the cell-laden GelMA/Si-BG hydrogel 35
Chapter 4 Discussion 55
4.1 The gel-derived bioactive glass from citric acid route 55
4.1.2 Characterization of the 45S5 bioactive glasses derived from different aging time and catalyst 55
4.1.3 The mineralization behavior and in vitro bioactivity 57
4.2 The GelMA-BG/Si-BG hydrogel composites 59
4.2.1 The silanization of the BG 59
4.2.2 The GelMA/Si-BG hydrogel 59
4.2.3 The Cell-laden GelMA/Si-BG hydrogel 60
Chapter 5 Conclusion 63
Reference: 64
Appendix 71

List of Figures
Figure 1 The mechanism of the silanization on the silica [79] 16
Figure 2 High magnification (30000X) Scanning electron microscopy (SEM) micrograph of the 45S5 Bioactive glasses. (A) The gel-derived 45S5BG catalyzed by 2M nitric acid after aging for12 h. (B) The commercial melt-derived Activioss™ bioactive glass. (C) The gel-derived 45S5BG catalyzed by 5mM citric acid after aging for12 h. (D) The gel-derived 45S5BG catalyzed by 5mM citric acid after aging for 3d. 38
Figure 3 XRD patterns of the 45S5 Bioactive Glass. From the top to the bottom, the patterns are of the melt-derive Activioss™ bioactive glass, the gel-derived 45S5BG catalyzed by 5mM citric acid after aging for12 h, the gel-derived 45S5BG catalyzed by 5mM citric acid after aging for 3d and the gel-derived 45S5BG catalyzed by 2M nitric acid after aging for12 h, respectively. 39
Figure 4 SEM micrograph of the CA12h after soak in SBF in high magnification (scale bar = 100 nm). 40
Figure 5 SEM micrograph of the CA12h after soak in SBF in high magnification (scale bar = 100 nm). 41
Figure 6 The SEM picture and EDS analysis of the CA12h after immersion in SBF for 28 d. (A) The SEM microscope of the surface of the CA12h after immersion in SBF for 28 d. (B) EDS spectrum of the chosen region on the surface of immersed CA12h. The spectrum 1 table is the elements mapping of the chosen region. 42
Figure 7 The SEM picture and EDS analysis of the CA3d after immersion in SBF for 28 d. (A) The SEM microscope of the surface of the CA3d after immersion in SBF for 28 d. (B) EDS spectrum of the chosen region on the surface of immersed CA3d. The spectrum 1 table is the elements mapping of the chosen region. 43
Figure 8 The XRD of the CA3d after immersion in SBG for 28 days. 44
Figure 9 The XRD of the CA12h after immersion in SBG for 28 days. 44
Figure 10 The other possible crystal phases inside the immersion CA12h in SBF for 28 d. The XRD patterns was analyzed by EVA software. 45
Figure 11 FTIR spectrum of the CA12h after immersion in SBF from 0 to 28 day. 46
Figure 12 FTIR spectrum of the CA3D after immersion in SBF from 0 to 28 day. 46
Figure 13 The SEM microscopes (A,B) and XRD patterns comparing (C) of the silanized BG and original BG. 47
Figure 14 Si2p spectrum of X-ray photoelectron spectra of BG (red) and Si-BG (blue). Si 2p (Si-O) peak at 103.5 eV. The peak shifted to ~102.3 eV. 48
Figure 15 C1s spectrum of the X-ray photoelectron spectra of BG (red) and Si-BG (blue). Charge referenced to adventitious C1s, C-C peak at 284.8eV. C1s spectrum for contamination typically has C-C, C-O-C and O-C=O components. C-O peak at 286eV. C=O peak at 289eV. 48
Figure 16 The SEM/EDS of the GelMA-BG hydrogel composites. (A1)SEM picture of the 15% (w/v) GelMA without BG. (A2) The element mapping of the EDS on A1 region. (B1)SEM picture of the 15% (w/v) GelMA with 5% (w/v) BG. (B2) The element mapping of the EDS on B1 region. (B3) Illustration of the physical incorporation of the BG/GelMA. (C1) SEM picture of the 15% (w/v) GelMA with 5% (w/v) Si-BG. (C2) The element mapping of the EDS on C1 region. (C3) Illustration of the covalent incorporation of the Si-BG/GelMA. 49
Figure 18 The XRD patterns of the GelMA/Si-BG composite after immersion in SBF for 28 day (red) and GelMA/Si-BG composite after immersion in SBF (black). 50
Figure 17 The compressive modulus of the GelMA-BG/Si-BG, the * means significantly different by T-test result (p<0.05). The 15% (w/v) GelMA was used for all composite. 50
Figure 19 Live/dead cell viability assay of the MSC-laden GelMA-BG/Si-BG hydrogels on day 1. The concentration of MSCs in medium in medium was 106 cells/ml (A) 15% GelMA-0% BG. (B) 15% GelMA-1% BG (C) 15% GelMA-3% BG (D) 15% GelMA-5% BG (E) 15% GelMA-1% Si-BG (F) 15% GelMA-3% Si-BG (G) 15% GelMA-5% Si-BG 51
Figure 20 Live/dead cell viability assay of the MSC-laden GelMA-BG/Si-BG hydrogels on day 14. The concentration of MSCs in medium in medium was 106 cells/ml. (A) 15% GelMA-0% BG. (B) 15% GelMA-1% BG (C) 15% GelMA-3% BG (D) 15% GelMA-5% BG (E) 15% GelMA-1% Si-BG (F) 15% GelMA-3% Si-BG (G) 15% GelMA-5% Si-BG 52
Figure 21 Alizarin red staining at the 14th day. The concentration of MSCs in medium in medium was 106 cells/ml without osteogenic supplemental medium. (A) 15% GelMA-0% BG. (B) 15% GelMA-1% BG (C) 15% GelMA-3% BG (D) 15% GelMA-5% BG (E) 15% GelMA-1% Si-BG (F) 15% GelMA-3% Si-BG (G) 15% GelMA-5% Si-BG 53
Figure 22 Alizarin red staining at the 14th day. The concentration of MSCs in medium in medium was 106 cells/ml with osteogenic supplemental medium. (A) 15% GelMA-0% BG. (B) 15% GelMA-1% BG (C) 15% GelMA-3% BG (D) 15% GelMA-5% BG (E) 15% GelMA-1% Si-BG (F) 15% GelMA-3% Si-BG (G) 15% GelMA-5% Si-BG 54
Figure 23 ARS staining on 21st day. 71
 
List of Tables
Table 1 The comparison between the SBF and human blood plasma. 26
Table 2 The flowchart of the synthesis of the gel-derived 45S5 Bioactive glasses. 26
Table 3 Sample BET surface area and Pore size 37

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