Title Page
Contents
Abstract 18
Ⅰ. Introduction 24
1. Research Background 24
1.1. Porous polymer films 24
1.2. Pore-Selective functionalization of HCP films 29
1.3. Selective functionalization of pores by self-assembly 30
1.4. Selective functionalization of pores by self-assembly followed by additional treatment 33
1.5. Functionalization of pores using water as a reactant 35
1.6. Functionalization of pores accompanying interfacial reactions with a non-aqueous reactant 38
1.7. Selective functionalization of pores accompanying interfacial reaction 40
2. Purpose of study 43
Ⅱ. Research and results 44
Ⅱ-1 Fabrication and characterization of pore-selective silver-functionalized honeycomb-patterned porous film and its application for antibacterial activity 44
1. Introduction 45
2. Materials and methods 47
3. Results and Discussion 52
Ⅱ-2. Antibacterial Activity of Polyaniline Coated in the Patterned Film Depending on the Surface Morphology and Acidic Dopant 80
1. Introduction 81
2. Materials and methods 83
3. Results and Discussion 90
Ⅱ-3. Analysis of kinetic release of dye from the temperature-sensitive poly (N-isopropylacrylamide) functionalized porous polystyrene film 108
1. Introduction 109
2. Materials and methods 111
3. Results and Discussion 114
Ⅱ-4. Iron oxide nanoparticles embedded in porous films for tannic acid detection 128
1. Introduction 129
2. Materials and methods 131
3. Results and discussion 135
Ⅱ-5. Polypyrrole/metal nanoparticle composite incorporated in the porous honeycomb-patterned film as a novel micro-reactor system: application to the degradation of organic dyes and antibacterial activity 153
1. Introduction 154
2. Material and methods 156
3. Results and discussion 161
Ⅲ. Discussion 178
Ⅳ. Conclusion 183
References 187
Curriculum Vitae 210
List of Research Achievements 213
Conferences 213
Journal Papers 213
Table 1. Summary of reports for the pore-selective functionalization of HCP films with a reactant in the polymer solution and an external agent for completion of the reaction. 35
Table 2. Summary of reports using one reactant in a polymer solution and water from the humid atmosphere as another reactant. 37
Table 3. Summary of reports using two reactants, one in the polymer solution and the other in a humid atmosphere for the functionalization of pores in HCP films. 40
Table 4. Pairwise interaction energies of the H2O–H2O, H2O-Ag+, and Ag+-Ag+ systems. 57
Table 5. The zone of inhibition of the fabricated films against E. coli and S. aureus. 103
Figure 1. A sequence of stages for the preparation of HCP porous film by the BF method. (a) Polymer solution in a volatile solvent under humid conditions; (b)... 26
Figure 2. Possible site-selective functionalization of HCP films by modified BF method. (a) Top, (b) bottom, and (c) pore surface functionalization. 29
Figure 3. A sequence of stages of pore-selective functionalization by self-assembly of amphiphilic polymer. (a) Polymer solution containing amphiphilic polymer in a... 31
Figure 4. Pore-selective functionalization of HCP films by using water as a reactant. The polymer solution containing a reactant reactive to water is cast under humid... 37
Figure 5. A sequence of stages of pore-selective functionalization by self-assembly accompanied by chemical reaction. (a) polymer solution containing... 42
Figure 6. The overall process of the fabrication of pore-selective Ag-coated HCP porous films by the rBF method. In this study, AgNO₃ concentration is fixed but the... 49
Figure 7. Experimental processes employed to study the antibacterial and antibiofilm activities of the pore-selective Ag-embedded films. 52
Figure 8. Typical SEM images of the morphology and cross-section of HCP porous PS and PF films. (a) PS, (b) PF-10, (c) PF-20, (d) PF-30, and (e) PF-40 films. 54
Figure 9. Static water contact angle analysis of the top surfaces of PS, PF-10, PF-20, PF-30, and PF-40 HCP porous films. It shows increased wettability of HCP... 55
Figure 10. Reduction of AgNO₃ by ferrocene via an interfacial reaction at the junction of two liquids. (a) Photograph image showing a time-dependent color... 57
Figure 11. Typical SEM images of the morphology and cross-section of Ag-functionalized films (a) PF-Ag-10, (b) PF-Ag-20, (c) PF-Ag-30, and (d) PF-Ag-40. 59
Figure 12. Optical laser microscopic images of PF-Ag-20 film showing (a) a single pore, (b) the width of one pore, (c) the morphology of the Ag-coated film, and (d)... 60
Figure 13. Images for the PF-Ag-20 showing pore-selective Ag functionalization (a) Typical SEM-EDX spectra and (b) elemental mapping. 62
Figure 14. (a) XPS survey and high-resolution scan spectra of (b) Fe2p and (c) Ag3d of the porous PF-20 film before and after Ag-functionalization. (d) Quantitative... 64
Figure 15. (a) Comparison of the contact angles of the PS, PF-20, PF-Ag-10, PF-Ag-20, and PF-Ag-30 films. Contact angle measurement for each film was... 66
Figure 16. Step-by-step mechanism of the pore-selective Ag functionalization of the HCP porous films. AgNO₃ is reduced by ferrocene in the water droplet/polymer... 67
Figure 17. UV-vis spectrum of the PF-Ag-20 film showing the peak for Ag and ferrocene. 68
Figure 18. The flexibility of the PS, PF-10, PF-Ag-10, PF-Ag-20, and PF-Ag-30 films. The Ag functionalized films showed similar flexibility to PS and PF-10 films... 68
Figure 19. Antibacterial activity of the PF-Ag films. (a) Antibacterial activity of the control, PS, PF-Ag-10, PF-Ag-20, PF-Ag-30, and PF-Ag-40 films against E. coli... 71
Figure 20. Fluorescence images of the PS, PF-Ag-20, and PF-Ag-30 films exposed to EGFP plasmid-transformed E. coli for different time intervals. (a) The PS film... 74
Figure 21. Typical SEM images of the PF-Ag-20 film incubated with E. coli and S. aureus. Magnified images of (i-ii) live E. coli and S. aureus at the interpore surface,... 76
Figure 22. (a) Typical SEM images of biofilm formation on the (i) PS, (ii) PF-Ag-10, (iii) PF-Ag-20, (iv) PF-Ag-30, and (v) PF-Ag-40 films with different... 78
Figure 23. The overall scheme of PANI functionalization. (a) Fabrication of HCP (top) and flat (bottom) PCL films. (b) Interfacial polymerization of PANI at the... 87
Figure 24. SEM images of (a) f-PANI, (b) PCL, (c) HCP-PANI, and (d) HCP-SPANI films. There was no significant difference in the HCP pattern of the HCP... 92
Figure 25. SEM-EDX and qualitative-quantitative elemental mapping analysis of (a) f-PANI, (b) HCP-PANI, and (c) HCP-SPANI films. All three films showed the... 94
Figure 26. Characterization of fabricated films. (a) UV-Vis, (b) FT-IR, (c) TGA, and (d) DTA analysis of f-PANI, HCP-PANI, and HCP-SPANI films. 98
Figure 27. (a) Water contact angle and (b) conductivity of f-PANI, HCP-PANI, and HCP-SPANI films. 100
Figure 28. Chemical structure of (a) PANI ES in HCl, and (b) PANI ES in H₂SO₄. Doping of positive and negative charges on the backbone of the PANI chain for the... 101
Figure 29. Antibacterial activity of the fabricated films. Disk diffusion assay of fabricated films against (a) E. coli and (b) S. aureus and the bacterial growth % of... 104
Figure 30. Antibiofilm activities of the fabricated films against (a) E. coli (b) S. aureus after 24 hours of biofilm growth measured at OD₅₇₀. The data are the average... 107
Figure 31. Schematic diagram showing the fabrication process of PS-PNIPAAm film. (a) The process for the fabrication of PS-COOH film by a modified BF method,... 112
Figure 32. Typical SEM images of (a) PS-CHO HCP film, (b) PS-COOH HCP film, and (c) PS-PNIPAAm at different magnifications, respectively. The right images are... 117
Figure 33. Detailed experimental scheme showing the release of RhG from the PS-PNIPAAm film by temperature-responsive release by a gradual increase in temperature. 118
Figure 34. Temperature responsive RhG release in PS-PNIPAAm film above the LCST of PNIPAAm by (a) RhG release over time at different temperatures as... 121
Figure 35. Typical SEM images of PS-PNIPAAm film depending on the temperature, (a) obtained after loading RhG on the film in 0.5g L¯¹ aqueous solution... 123
Figure 36. (a) Interaction of RhG and PNIPAAm. (b) The schematic diagram for the desorption-adsorption equilibrium in water and thermo-responsive release due to the... 125
Figure 37. (a) FT-IR spectrum of RhG-loaded PS-PNIPAAm film. (b) EDX spectrum of PS-PNIPAAm without (left) and with RhG-loaded (right). 127
Figure 38. Schematic representation of the formation of Fe₂O₃ NPs in the pores of the PS porous film via a single-step process. 133
Figure 39. Schematic representation showing hybrid Fe₂O₃ NPs porous film for naked-eye TA detection platform. 134
Figure 40. Typical SEM images and corresponding pore-diameter distribution curves of the porous PS-Fe films. (a) PS-Fe-5, (b) PS-Fe-10, (c) PS-Fe-15, and (d)... 137
Figure 41. Characterization of the fabricated films. (a) UV-vis of PS-15, PS-Fe-5, PS-Fe-10, PS-Fe-15, and PS-Fe-20, (b) FT-IR spectra, and (c) TGA of PS-Fe films... 140
Figure 42. Properties of the fabricated films. (a) Water contact angle and (b) conductivity of the fabricated films. 141
Figure 43. TA sensing by the Fe₂O₃ NPs embedded hybrid films. (a) photographic image of the TA sensing system showing a change in color of TA solution after a... 143
Figure 44. Optimization of PS-Fe films for TA sensing. (a) Graph showing incubation time of PS-Fe-15 film with 1,000 μM TA. Absorbance spectra (~780 nm)... 145
Figure 45. Interference study with PS-Fe-15 film and (i) Tannic acid, (ii) GA, (iii) 3-aminophenol, (iv) 2,6-Dimethylphenol, (v) 4-(4-Nitrophenylazo)phenol, (vi)... 147
Figure 46. TA sensing mechanism by the coordination of Fe₂O₃ NP and TA. 149
Figure 47. Stability of the PS-Fe-15 film. UV-vis spectra of the solution of TA dissolved (a) in different solvents before and after the addition of the film showing a... 151
Figure 48. Reusability and recyclability of the PS-Fe-15 film for up to 5 cycles. 152
Figure 49. Schematic presentation of the fabrication of (a) PCL-PPy/MNPs, (b) PCL-PPy, and (c) PCL-Cu HCP films using the modified BF method. 159
Figure 50. Morphology and chemical distribution in the HCP film. Typical SEM images of (a) PCL, (b) PCL-PPy, (c) PCL-Cu, and (d) PCL-PPy/Cu. (e) Elemental... 163
Figure 51. Mechanism of polymerization and reduction of metal salt simultaneously for the formation of PCL-PPy/Cu incorporated pores using the... 165
Figure 52. Characterization of the fabricated films. (a) FT-IR spectra of PCL, PCL-PPy, PCL-Cu, and PCL-PPy/Cu films, (b) UV-vis spectrum of PCL-PPy/Cu film,... 168
Figure 53. (a) XPS survey of PCL-PPy and PCL-PPy/Cu films with their corresponding high-resolution scan spectra of Cu2p3/2 and Fe2p1/2, and (b) XRD... 169
Figure 54. Catalytic degradation of MO dye by (a) PCL-PPy, (b) PCL-Cu, and (c) PCL-PPy/Cu, and (d) their Ln(C/C₀) vs time. 171
Figure 55. Catalytic degradation of MB dye by (a) PCL-PPy, (b) PCL-Cu, and (c) PCL-PPy/Cu, and (d) their Ln(C/C₀) vs time. 172
Figure 56. Typical SEM images of (a) PCL-PPy/Ag, and (b) PCL-PPy/Au films with their corresponding elemental mapping images. 173
Figure 57. Reduction mechanism of MO and MB inside the pores of the HCP films used as a microreactor 175
Figure 58. Recyclability and reusability of the PCL-PPy/Cu film against MO for up to 5 cycles. 177
Figure 59. Pore-selectively functionalized HCP films via the modified BF method and their applications in biology, medical, sensor application, and catalysis. (PSFF:... 182