Title Page
Contents
ABSTRACT 18
Chapter Ⅰ. General Introduction 22
1. Molecule separation in classical mechanics 22
2. Molecule separation in Quantum sieving 24
3. Kinetic control within Metal-organic frameworks 27
4. Research objectives 31
5. REFERENCE 32
Chapter Ⅱ. Single metal-organic framework-embedded nanopit arrays: A new way to control neural stem cell differentiation 35
ATTRIBUTION 35
CONTRIBUTION FROM 35
1. INTRODUCTION 37
2. MATERIALS AND METHODS 41
2.1. Synthesis of nUiO-67 41
2.2. Fabrication of nanopit arrays 41
2.3. Fabrication of RA-SMENA 42
2.4. Characterisation of nanocrystalline UiO-67 (nUiO-67) and SMENA 43
2.5. Cultivation and differentiation of NSCs 44
2.6. Analysis of cell functions 45
2.7. Monitoring the neural differentiation of NSCs 46
3. RESULTSAND DISCUSSION 48
3.1. Design, synthesis, and characterisation of RA⸦nUiO-67 for RA storage and long-term release 48
3.2. Fabrication of single nMOF (RA⸦nUiO-67)-embedded nanopit arrays (SMENA) 53
3.3. Biocompatibility and long-term stability of SMENA 60
3.4. Neurogenesis of NSCs on RA-SMENA with growth medium 66
4. CONCLUSION 97
5. REFERENCE 98
Chapter Ⅲ. Exploiting Dynamic Opening of Apertures in Partially Fluorinated MOF for Enhancing H₂ Desorption Temperature and Isotope Separation 104
ATTRIBUTION 104
CONTRIBUTION FROM 104
1. INTRODUCTION 106
2. MATERIALS AND METHODS 108
2.1. Synthesis of nUiO-67 108
2.2. Characterization 108
2.3. Gas Adsorption Experiment. 108
2.4. TDS Studies of Hydrogen Isotope Separation. 109
2.5. Single-Crystal X-ray Structure Analysis. 109
2.6. In Situ Gas Adsorption Neutron Powder Diffraction. 110
3. RESULTS AND DISCUSSION 112
4. CONCLUSIONS 139
5. REFERENCES 140
Chapter Ⅳ. Hydrogen Isotope Separation by Exploiting the Isotope-Selectivity of MOF 146
ATTRIBUTION 146
CONTRIBUTION FROM 146
1. INTRODUCTION 147
2. MATERIALS AND METHODS 150
2.1. MATERIALS 150
2.2. Synthesis of Cobalt Formate, Co₃(HCOO)₆ 150
2.3. Structural Characterizations 150
2.4. Textural Characterizations and Gas Sorption Analysis 151
2.5. Thermal Desorption Spectroscopic (TDS) studies for H₂ and D₂ 151
3. RESULTS AND DISCUSSION 153
4. CONCLUSION 175
5. REFERENCES 176
ABSTRACT IN KOREAN 179
ACHEIVEMENT 183
Table 2.1. Fold change of neurogenesis-associated genes used in the heat map clustering of the nanopit array, SMENA, and RA-SMENA. All listed genes were significantly... 88
Table 2.2. Gene ontology (GO) terms used for the upregulation of genes involved in multipotency maintenance in each group. GO terms for genes involved in the... 93
Table 2.3. Gene ontology (GO) terms used for the upregulation of genes involved in neurogenesis in each group. GO terms for genes involved in neurogenesis were used... 96
Table 4.1. Separation performance comparison with reported literature using 1:1 isotope mixture 174
Figure 1.1. Control the different adsorption enthalpies (△H) by design the pore space 23
Figure 1.2. (a) The difference in de Broglie wavelength with the molecular weight differences, and (b) the quantum effect with the difference in size of pore and the de... 26
Figure 1.3. (a) Adsorption potential depth as a function of pore diameter (b) Behavior of the well depth (ε) and zero-point energy (E₀) as a function of channel diameter. 26
Figure 1.4. The structure image of Metal-Organic Frameworks. 29
Figure 1.5. Control the pore space within MOFs. 30
Figure 2.1. Schematic illustration of SMENA. (A) Most critical difference between real in vivo and in vitro environments. The in vivo environment is based on three-... 39
Figure 2.2. RA⸦nUiO-67 synthesis and characterisation. (A) Schematic illustration showing massive absorption of RA to nUiO-67 and the continuous release of RA... 50
Figure 2.3. HPLC spectra of all-trans RA and 13-cis RA. 13-cis-retinoic acid peak is represented between 11 and 12 min (black). All-trans-retinoic acid is represented... 52
Figure 2.4. Characterisation of SMENA. (A) Schematic illustration showing the structure of SMENA. (B) Real picture of the large-area nanopit arrays (12 mm x 12... 55
Figure 2.5. Optimisation for nUiO-67s coating onto nanopit arrays with concentrations of nUiO-67s. (A) SEM images of nUiO-67-coated nanopit arrays... 57
Figure 2.6. Optimisation for UiO-67 coating onto nanopit arrays with the speed (in rpm) of spin coating. (A) SEM images of UiO-67-coated nanopit arrays with several... 58
Figure 2.7. Rate of RA release from the SMENA. Amount of RA released nUiO-67 on SMENA for 0 to 24 hours. 59
Figure 2.8. Monitoring the multipotency of the NSCs cultured onto each group at several passages. (A) A schematic illustration showing multipotency of the NSCs at... 62
Figure 2.9. Cell viability test. (A) Cultivation images of cells proliferated onto each group for 6 days. (B) Cell viability of each group, including control, nanopit array,... 64
Figure 2.10. Cellular uptake of nUiO-67 released from the SMENA. (A) TEM analysis of lysate of the NSCs cultured onto the control or SMENA with inorganic... 65
Figure 2.11. Cultivation of the NSCs differentiated in each group for 14 days. Cultivation images of the NSCs cultured onto the control groups with normal... 70
Figure 2.12. Analysis of genes and proteins related to neurogenesis. (A) A schematic illustration showing different differentiation mechanisms between the control group... 71
Figure 2.13. Immunocytochemistry analysis for monitoring the multipotency of the NSCs at day 7 of neural differentiation. Immunocytochemical staining images of the... 73
Figure 2.14. Immunocytochemistry analysis for monitoring of the multipotency of the NSCs day 14 of neural differentiation. Immunocytochemical staining images of... 75
Figure 2.15. Cultivation of NSCs in normal growth medium. Cultivation images of the NSCs cultured onto each group including control, nanopit array, RA-SMENA... 76
Figure 2.16. Tuj1-stained immunocytochemistry images of the NSCs cultured in normal growth medium. (A-C) Tuj1-stained immunofluorescence images of the... 77
Figure 2.17. Cultivation of the NSCs differentiated in the control, nanopit array, and SMENA groups using the early differentiation induction method. (A) Schematic... 78
Figure 2.18. Cultivation of the NSCs differentiated on a normal TCP with the early and normal differentiation induction methods. Cellular morphological comparison... 79
Figure 2.19. RT-qPCR analysis for investigating neural differentiation induced with the normal and early differentiation induction methods. RT-qPCR analysis of neural... 80
Figure 2.20. Effect of excess RA treatment in the early stage of differentiation on neurogenesis. (A) Schematic illustration of four differentiation protocols designed to... 81
Figure 2.21. RT-qPCR analysis for monitoring of the multipotency of the NSCs during neurogenesis. Monitoring of the multipotency of the NSCs for 14 days as neural... 83
Figure 2.22. Qualitative analysis of monitoring of neurogenesis on each group. RT-qPCR analysis for monitoring the multipotency of NSCs during neurogenesis. Ratio... 84
Figure 2.23. FACS analysis for neurogenesis of the NSCs differentiated in each group. FACS analysis of neuronal differentiation of the NSC markers (Nestin, Tuj1,... 85
Figure 2.24. Analysis of total mRNA expressions of differentiated cells from NSCs. (A) Heat-map clustering with a dendrogram of significantly upregulated genes... 86
Figure 2.25. Scatter plot of Nanopit array and SMENA. Scatter plot of expressed genes analysed by RNA sequencing. In total, 1,774 genes associated with... 87
Figure 3.1. Unit cell (a-c) and crystal structure (e-g) of FMOFCu. The yellow, green, and brown spheres represent the volume of pores A, B, and C, respectively. (a) ac... 120
Figure 3.2. Crystal structure of FMOFCu, and pore network analysis with grid space of 0.1 Å for the probe sphere. Three cavities (A, B, C) can be identified and are... 121
Figure 3.3. 2-D view of tri-modal structured FMOFCu, showing the ac plane cut at the height of the aperture between cavity B and C. The colors indicate each Cavity... 122
Figure 3.4. SEM image of FMOFCu framework. 123
Figure 3.5. Thermogravimetric analysis (TGA) for as synthesized FMOFCu. 124
Figure 3.6. PXRD patterns of FMOFCu as (a)synthesized, (b) Simulated. 125
Figure 3.7. FT-IR spectra of FMOFCu (red) and CPHFP (black). 126
Figure 3.8. BET isotherm of sample FMOFCu at 1 bar and 77K using N₂ (top) and 20 K using H₂ (bottom). Closed and open symbols represent the absorption and... 127
Figure 3.9. Isotherms for H₂ adsorption (closed) and desorption (open) on FMOFCu at various temperatures (25-120 K) in the pressure range 0-1 bar. For isotherms... 128
Figure 3.10. Hydrogen adsorption and desorption isotherms of FMOFCu at various temperatures: (a) 19.5 K, (b) 25 K, (c) 40 K, (d) 60 K, (e) 77 K, (f) 100 K, and (g)... 129
Figure 3.11. Deuterium adsorption and desorption isotherms of FMOFCu at various temperatures: (a) 23 K, (b) 25 K, (c) 40 K, (d) 60 K, (e) 77 K, (f) 100 K, and (g) 120... 130
Figure 3.12. Neutron Powder Diffraction (NPD) measured at 24K under vacuum and fulling loading of D₂, showing no structural change by gas sorption. 131
Figure 3.13. H₂ (black) and D₂ (red) pure gas thermal desorption spectra of FMOFCu. 132
Figure 3.14. H₂ (black) and D₂ (red) thermal desorption spectra of a 10 mbar 1/1 H₂/D₂ isotope mixture on FMOFCu for 10 min at various exposure temperatures... 133
Figure 3.15. The comparison H₂ and D₂ desorption spectra of 10 mbar 1:1 isotope mixture loading for a different exposure temperature: 60K, 77K, and 87K, of... 134
Figure 3.16. Isosteric heat of adsorption of hydrogen for FMOFCu as function of the adsorption amount. 135
Figure 3.17. H₂ and D₂ thermal desorption spectra of a 50 mbar 1/1 H₂/D₂ isotope mixture on FMOFCu for 10 and 300 min at various exposure temperatures (Texp): 25...[이미지참조] 136
Figure 3.18. Kinetic effect of FMOFCu at 25 K. H₂ and D₂ desorption spectra of 50 mbar 1:1 isotope mixture loading for a different exposure time: (a) 10 min, (b) 60... 137
Figure 3.19. Schematic View of the Trimodal Structure of FMOFCu. 138
Figure 4.1. Top view of crystal structure of CoFA with zig-zag channel running along the b axis, and the plausible binding sites for H₂ and D₂ inside the channel. 157
Figure 4.2. FT-IR spectrum of Co₃(HCOO)₆. 158
Figure 4.3. PXRD patterns of Co₃(HCOO)₆ with the simulated PXRD patterns of desolvated Co₃(HCOO)₆. 159
Figure 4.4. TGA of Co₃(HCOO)₆. 160
Figure 4.5. N₂ sorption isotherm of Co₃(HCOO)₆ measured at 77 K. 161
Figure 4.6. Isotherms of (a) H₂ and (b) D₂ sorption on CoFA measured at 20 K and 23 K (black), 40 K (red), 77 K (blue), and 87 K (pink) with the pressure shown in... 162
Figure 4.7. Pure gas (H₂ and D₂) thermal desorption spectra of CoFA measured with heating rate of 3 K min⁻¹. 163
Figure 4.8. Equimolar D₂/H₂ mixture TDS spectra of CoFA measured at 30 K and 10 min exposure time with varying pressure loading. 164
Figure 4.9. TDS spectra of H₂/D₂ mixture measured at exposure temperature of 25 K with varying (a) pressure loading @ 10 min holding and (b) exposure time @ 1... 165
Figure 4.10. Equimolar D₂/H₂ mixture TDS spectra of CoFA measured at 40 K and 10 min exposure time with varying (a) pressure loading and (b) exposure time. 166
Figure 4.11. Equimolar D₂/H₂ mixture TDS spectra of CoFA measured at 60 K and 10 min exposure time with varying pressure loading. 167
Figure 4.12. Equimolar D₂/H₂ mixture, SD₂/H₂ as a function of (a) pressure loading and (b) exposure temperature. 168
Figure 4.13. H₂ uptake (dotted line) and D₂ uptake (solid line) at strong binding site with increase in pressure loading at various temperatures. 169
Figure 4.14. Equimolar D₂/H₂ mixture, SD₂/H₂ as a function of exposure time at 25 K/1 bar and 40 K/111 mbar. 170
Figure 4.15. (a) TDS spectra measured at 25 K and 10 min exposure time with exposure of 30 mbar D₂ and 1 bar of equimolar H₂/D₂ mixture. (b) The comparison... 171
Figure 4.16. TDS spectra measured at 30 K and 10 min exposure time with exposure of D₂ (1 mbar to 30 mbar) and equimolar D₂/H₂ mixture (22 mbar to 1 bar). 172
Figure 4.17. TDS spectra measured at 40 K and 10 min exposure time with exposure of D₂ (20 mbar) and equimolar D₂/H₂ mixture (100 and 500 mbar). 173