臺灣博碩士論文加值系統

PART I
　　本研究第一部分以親水性單體hydroxyethylmethacrylate (HEMA)、poly(ethylene glycol) methacrylate (PEGMA, Mn=360)，與新型可分解性交聯劑N, N’-bisacrylyl cystamine (BACy)，以自由基聚合法製備具可分解性之水凝膠，與傳統隱形眼鏡用交聯劑ethylene glycol dimethylacrylate (EGDMA) 製備之水凝膠材料進行一系列的研究，如含水率、藥物釋放、透光率、水接觸角、SEM、機械強度、交聯密度…等進行探討。並利用二硫鍵氧化還原之特性，將水凝膠中之二硫鍵還原為硫醇，使水凝膠達到分解的效果，探討分解前後性質之變化及其相關之應用。HEMA及PEGMA分別和新型可分解性交聯劑 (BACy) 與傳統隱形眼鏡組成之交聯劑 (EGDMA) 共聚合得到HPB及HPE系列水凝膠，由初步成果得知以下幾點：HPB系列水凝膠其平衡含水率最高達36%，高於HPE系列水凝膠之29%，藥物釋放方面，每公克HPB系列水凝膠之咖啡因吸附量達1.60毫克，在48小時內累積釋放率達99%，皆高於HPE系列水凝膠之最高吸藥量1.17毫克及累積釋放率90%；HPB系列水凝膠剪切模數G值為459.8 kPa低於HPE系列凝膠552.1 kPa，其值越低表示材料較柔軟。將HB水凝膠以半胱胺酸水溶液分解後，藥物累積釋放量提升約15%，驗證水凝膠經過一定程度的分解使整體結構變得鬆散。本研究第二部分以3-[tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) 將HPB1及HPE1水凝膠之表面疏水化，形成具有兩種聚合物特性之interpenetrating polymer network (IPN) 雙層水凝膠，依照TRIS濃度其樣本代號為HPB1T-0.1、HPB1T-0.5及HPE1T-0.1、HPE1T-0.5。其中HPB1與HPB1T-0.5水凝膠相比其水接觸角度增加25.9°，其他水凝膠基礎性質如含水率、藥物釋放、透光率、機械強度沒有明顯的差異，說明除了表面疏水化之外仍能保有原水凝膠之特性。

PART II
　　本研究以氫鍵作用力為主要核心，輔以其他機制設計可自癒的多重動態交聯凝膠，並透過材料破壞前後的伸長量觀察其自癒效果。聚丙烯醯胺 (Acrylamide) 主鏈上豐富的羰基 (C=O) 與一級胺 (NH2) 能夠提供大量的分子間氫鍵，故選擇丙烯醯胺單體作為提供氫鍵作用力的主要來源。從初步的實驗結果得知，自聚合的圓柱形丙烯醯胺樣本截成兩半後，兩破壞面接觸一段時間即產生一定的作用力，使材料克服重力而不會掉落。
　　為提升自癒的強度，試著在丙烯醯胺系統中導入二硫鍵與硫醇間的氧化還原機制；二硫鍵與硫醇的氧化還原屬於共價鍵的生成，而共價鍵的鍵能強度遠高於氫鍵，預期能夠達到更好的自癒強度。然而實驗結果卻不如預期，聚合系統中氧化還原對引發自由基的過程，間接使硫醇被氧化成磺酸，導致聚丙烯醯胺完全失去自癒的現象。
　　最後我們導入金屬配位的概念，期望以金屬離子與高分子鏈上的配體產生配位鍵；N-Vinylpyrrolidone (VP) 在還原奈米銀粒子製程中，是常見的金屬螯合劑。基於此，將丙烯醯胺與VP共聚合，希望能夠透過VP與銀離子產生配位的能力增強自癒效果，效果卻沒有明顯差距。

PART I
In this study, a novel degradable hydrogel (HPB) which was used as contact lenses material was prepared by free radical polymerization with N, N’-bisacrylyl cystamine (BACy) as crosslinker, hydroxyethylmethacrylate (HEMA) and poly(ethylene glycol) methacrylate (PEGMA, Mn=360) as monomer. These degradable hydrogels were compared with the hydrogel (HPE) which used ethylene glycol dimethylacrylate (EGDMA) as crosslinker for the hydrogel properties, such as water content, drug release, transmittance of visible spectrum, water contact angle, construction of the hydrogel, mechanical properties, degree of crosslinking. In addition, the disulfide bond redox reactions to reduce disulfide containing hydrogel. Explore the changes of the properties before and after decomposition and their related applications. From the results, the equilibrium water content of HPB series hydrogels achieved 36% and higher than 29% of HPE series hydrogels. In terms of drug-releasing, HPB series hydrogels had drug-absorption of 1.60 mg /g and released 99% drugs in 48 hr, higher than 1.17 mg /g and 90% drug release capacity of the HPE series hydrogels. And the shear modulus of HPB series hydrogels reached to 459.8 kPa lower than HPE series hydrogels 552.1 kPa. When HB hydrogels was degraded by cysteine, its drug-release capacity reduced 15%. The results of the drug-release experiment explained the construction of HB hydrogels were more friable. The second part of this study, we modified the surface of the HPB1 and HPE1 series hydrogels with 3-[tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS). And the interpenetrating polymer network (IPN) double layer hydrogel with two polymer properties was formed. The samples were labeled HPB1T-0.1, HPB1T-0.5 and HPE1T-0.1, HPE1T-0.5 according to the TRIS concentration. Which HPB1 and HPB1T-0.5 hydrogel compared to its water contact angle increased by 25.9°. Other hydrogel properties such as water content, drug release, transmittance of visible spectrum, mechanical properties, there were not obvious difference. The results of hydrogel properties indicated that the properties of the raw hydrogel could be maintained in addition to the surface hydrophobicity.

PART II
In this study, hydrogen bond as the main core, supplemented by other mechanisms designed to a dynamic cross-linked hydrogel can self-healing. And the self-healing effect was observed by the amount of extended. The rich carbonyl (C=O) and primary amine (NH2) on the polyacrylamide backbone provide a large amount of intermolecular hydrogen bonds. So the acrylamide monomer is selected as the primary source of hydrogen bonds. From the preliminary experimental results, it was found that the self-polymerized cylindrical acrylamide samples were cut in half, and the two failure surfaces were touched to a certain period of time to make the material overcome gravity and not fall. In order to improve the self-healing ability, try to introduce the redox mechanism between the disulfide bond and the mercaptan in the acrylamide system. The oxidation and reduction of disulfide bonds and mercaptans are covalent bonds, and the bond strength of covalent bonds is much higher than that of hydrogen bonds, and it is expected to achieve better self-healing strength. However, the experimental results are not as expected, the redox system in the process of the polymerization, mercaptans were indirectly oxidized into sulfonic acid. Resulting in complete loss self-healing effected of polyacrylamide. Finally, we introduced the concept of metal coordination into self-healing hydrogels. We expected to use metal ions and ligand on the polymer chain to produce coordination bonds.
N-Vinylpyrrolidone (VP) is a common metal chelator in the reduction of silver nanoparticle processes. Based on this, acrylamide was copolymerized with VP, expected that through the VP and silver ions to produce the ability to enhance the coordination of self-healing effect, but the effect was no significant gap.

PART I
CONTENTS
CHAPTER 1 2
INTRODUCTION 2
CHAPTER 2 4
EXPERIMENTAL 4
2.1 Materials 4
2.2 Synthesis of N, N’-bisacrylyl cystamine (BACy) 5
2.3 Preparation of degradable and undegradable poly(HEMA-co-PEGMA) hydrogels 7
2.3.1 Hydrophobization of glass surface 7
2.3.2 Preparation of degradable poly(HEMA-co-PEGMA) hydrogels 9
2.3.3 Preparation of undegradable poly(HEMA-co-PEGMA) hydrogels 12
2.4 Preparation of IPN poly(HEMA-co-PEGMA) hydrogels 15
2.4.1 Preparation of degradable IPN poly(HEMA-co-PEGMA) hydrogels 15
2.4.2 Preparation of undegradable IPN poly(HEMA-co-PEGMA) hydrogels 17
2.5 Degradation of the hydrogels in cysteine solution 21
2.6 Measurement of swelling ratio 22
2.7 Measurement of water content 22
2.8 Drug release experiment 23
2.9 Measurement of visible light spectral transmittance 24
2.10 Measurement of water contact angle 24
2.11 Morphologies 24
2.12 Measurement of physical properties 25
CHAPTER 3 26
RESULTS and DISCUSSION 26
3.1 Degradable and undegradable poly(HEMA-co-PEGMA) hydrogels 26
3.1.1Characterization of BACy 26
3.1.2 Effect of different crosslinker on swelling kinetics 28
3.1.3 Drug release behavior of HPB and HPE series hydrogels 31
3.1.4 Drug release behavior of HB and degraded HB hydrogels 34
3.1.5 Visible light spectral transmittance of HPB and HPE series hydrogels 37
3.1.6 Water contact angle of HPB and HPE series hydrogels 39
3.1.7 Interior Mophologies of HPB and HPE series hydrogels 41
3.1.8 Mechanical Properties of HPB and HPE series hydrogels 43
3.2 IPN poly(HEMA-co-PEGMA) hydrogels 45
3.2.1 Effect of IPN on swelling kinetics 45
3.2.2 Drug release behavior of IPN series hydrogels 48
3.2.3 Visible light spectral transmittance of IPN series hydrogels 51
3.2.4 Water contact angle of IPN series hydrogels 53
3.2.5 Interior Mophologies of IPN series hydrogels 55
3.2.6 Mechanical Properties of IPN series hydrogels 57
CHAPTER 4 59
CONCLUSIONS 59
4.1 Degradable and undegradable poly(HEMA-co-PEGMA) hydrogels 59
4.2 IPN poly(HEMA-co-PEGMA) hydrogels 60
REFERENCE 61

LIST OF SCHEMES
Scheme 2.1 Synthesis of N, N’-bisacrylyl cystamine (BACy) 6
Scheme 2.2 Hydrophobization of glass surface 8
Scheme 2.3 Fragmentation of DEAP 10
Scheme 2.4 Polymerization of degradable poly(HEMA-co-PEGMA) hydrogels 11
Scheme 2.5 Polymerization of undegradable poly(HEMA-co-PEGMA) hydrogels 13
Scheme 2.6 Polymerization of the surface layer of the degradable poly(HEMA-co-PEGMA) hydrogels 16
Scheme 2.7 Polymerization of the surface layer of the undegradable poly(HEMA-co-PEGMA) hydrogels 18
Scheme 2.8 Redox of the SS/SH 21

LIST OF FIGURES
Fig 2.1 Illustration of moulds 14
Fig 2.2 Illustration of IPN hydrogels 20
Fig 2.3 The illustration of drug release experiment 23
Fig 3.1.1 FT-IR spectra of BACy 27
Fig 3.1.2 Swelling ratio in a function of time for HPB and HPE series hydrogels in distilled water at 25℃ 29
Fig 3.1.3 Water content in a function of time for HPB and HPE series hydrogels in distilled water at 25℃ 30
Fig 3.1.4 Caffeine release profile loading at 25℃ and releasing at 25℃ for the HPB and HPE series hydrogels in distilled water 32
Fig 3.1.5 The amount of caffeine loaded in HPB and HPE series hydrogels 33
Fig 3.1.6 Caffeine release profile loading at 25℃ and releasing at 25℃ for HB and degraded HB (R-HB) series hydrogels in distilled water 35
Fig 3.1.7 The amount of caffeine loaded in HB and degraded HB (R-HB) series hydrogels 36
Fig 3.1.8 The visible light spectral transmittance of HPB and HPE series hydrogels 38
Fig 3.1.9 Water contact angle of HPB and HPE series hydrogels 40
Fig 3.1.10 SEM microphotograph of cross-sectional of HPB and HPE series hydrogels 42
Fig 3.2.1 Swelling ratio in a function of time for IPN series hydrogels in distilled water at 25℃ 46
Fig 3.2.2 Water content in a function of time for IPN series hydrogels in distilled water at 25℃ 47
Fig 3.2.3 Caffeine release profile loading at 25℃ and releasing at 25℃ for IPN series hydrogels in distilled water 49
Fig 3.2.4 The amount of caffeine loaded in IPN series hydrogels 50
Fig 3.2.5 The visible light spectral transmittance of IPN series hydrogels 52
Fig 3.2.6 Water contact angle of IPN series hydrogels 54
Fig 3.2.7 SEM microphotograph of cross-sectional of IPN series hydrogels 56

LIST OF TABLES
Table 2.1 Composition of degradable ande undegradable poly(HEMA-co-PEGMA) hydrogels 14
Table 2.2 Composition of the surface of degradable and undegradable IPN poly(HEMA-co-PEGMA) hydrogels 19
Table 3.1 Mechanical properties of HPB and HPE series hydrogels 44
Table 3.2 Mechanical properties of IPN series hydrogels 58

PART II
CONTENTS
CHAPTER 1 65
INTRODUCTION 65
CHAPTER 2 67
EXPERIMENTAL 67
2.1 Materials 67
2.2 Preparation of dynamic crosslinked hydrogels based on hydrogen bonds 68
2.3 Preparation of multiple dynamic crosslinked hydrogels based on hydrogen bonds and disulfide exchange reaction 69
2.4 Preparation of multiple dynamic crosslinked hydrogels based on hydrogen bonds and coordination complex 73
2.5 Self-healing test 77
CHAPTER 3 78
RESULTS and DISCUSSION 78
3.1 Dynamic crosslinked hydrogels based on hydrogen bonds 78
3.2 Multiple dynamic crosslinked hydrogels based on hydrogen bonds and disulfide exchange reaction 81
3.3 Multiple dynamic crosslinked hydrogels based on hydrogen bonds and coordination complex 84
CHAPTER 4 87
CONCLUTIONS 87
REFERENCE 88

LIST OF SCHEMES
Scheme 2.1 Polymerization of dynamic crosslinked hydrogels based on hydrogen bonds 68
Scheme 2.2 The reduced reaction of the BACy by TCEP∙HCl 70
Scheme 2.3 The polymerization of multiple dynamic crosslinked hydrogels based on hydrogen bonds and disulfide exchange reaction 71
Scheme 2.4 The coordination of the VP and Ag+ 74
Scheme 2.5 The polymerization of multiple dynamic crosslinked hydrogels based on hydrogen bonds and coordination complex 75
Scheme 3.1 The mechanism of the dynamic crosslinked hydrogels based on hydrogen bonds 80
Scheme 3.2 The mechanism of multiple dynamic crosslinked hydrogels based on hydrogen bonds and disulfide exchange reaction 83
Scheme 3.3 The mechanism of multiple dynamic crosslinked hydrogels based on hydrogen bonds and coordination complex 86

LIST OF FIGURES
Fig 3.1 Heterogeneous polymerization of the poly(AAm) 79
Fig 3.2 Self-healing of poly(acrylamide) 79
Fig 3.3 The polymerization of the C-AM and AM series hydrogels 82
Fig 3.4 Self-healing of multiple dynamic crosslinked hydrogels based on hydrogen bonds and coordination complex 85

LIST OF TABLES
Table 2.1 composition of multiple dynamic crosslinked hydrogels based on hydrogen bonds and disulfide exchange reaction 72
Table 2.2 The composition of multiple dynamic crosslinked hydrogels based on hydrogen bonds and coordination complex 76
Table 3.1 The self-healing efficiency of the AVP series hydrogels 85

PART I
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