臺灣博碩士論文加值系統

本論文旨在探討隱形眼鏡之組成分對其物理及生物性質的影響。本論文分為三部分進行探討。第一部分係以3-（甲基丙烯醯氧基）丙基三（三甲基甲矽烷氧基）矽烷（3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, TRIS），N，N-二甲基丙烯醯胺（N,N-dimethylacrylamide, DMA），1-乙烯基-2-吡咯烷酮（1-vinyl-2-pyrrolidinone, NVP）和甲基丙烯酸2-羥乙酯（2-hydroxyethylmethacrylate, HEMA）聚合而成軟式鏡片。所得之鏡片進行的測試包括平衡水含量（EWC），氧氣透過性（Dk），透光度，接觸角，機械測試，蛋白質吸附和細胞毒性。結果顯示，配方中的TRIS濃度會提升Dk而降低EWC，而DMA和NVP均有助於水膠的親水性。Dk的最大值為74.9 barrer，對應於EWC為44.5%，接觸角為82°。此外，L929纖維母細胞均能在所有水凝膠上生長，顯示無細胞毒性。總之，本研究中的矽水膠具有良好的氧透過性，勁度和光學透明性以及抗蛋白質吸附性。因此，這些矽水膠可用於製造隱形眼鏡。
第二部分係由聚二甲基矽氧烷（polydimethylsiloxane, PDMS）和原矽酸四乙酯（tetraethyl orthosilicate, TEOS）以溶膠 - 凝膠法合成矽氧烷奈米粒子（SiNPs）。 然後再將這些SiNPs與HEMA和NVP混合，以光起始聚合法合成水膠隱形眼鏡。 所得之鏡片進行的測試包括動態光散射（DLS），透射電子顯微鏡（TEM），掃描電子顯微鏡（SEM），EWC，Dk，透光度和接觸角。 SiNPs的平均直徑為336 nm。 結果顯示，增加SiNPs的含量，可提升p(HEMA-co-NVP)-SiNPs鏡片的Dk，但不影響其EWC。 對於含有1.2 wt% SiNPs的鏡片，Dk的最大值為71 barrer，而其最高EWC達到73%。因此，這種新方法可用於製造軟鏡片。
第三部分係以DMA、NVP和SiNPs合成軟式鏡片。所有樣品的物理和生物化學性質的測試包括SEM，EWC，Dk，透光度，接觸角，機械性質，蛋白質吸附和細胞毒性等。結果顯示，SiNPs的加入增加了Dk而不影響鏡片的EWC。含1.2 wt%的SiNPs，p(DMA-co-NVP)-SiNPs的Dk為94.8 barrer，而其EWC維持在85.14%。特別是，DNS12的接觸角約40°。另外，蛋白質吸附主要取決於帶負電的SiNPs。SiNPs含量越高，樣品的人血清白蛋白（HSA）越低，和溶菌酶沉積越高。此外，L929纖維母細胞能在所有水膠樣品上生長，顯示無細胞毒性。總之，SiNPs與水膠的組合具有高Dk，而不會顯著影響透光度。因此這一種組成可於製造軟式隱形眼鏡。

This thesis is aiming to investigate the effect of the composition on the physical and biological properties of silicone contact lenses. This thesis is divided into three parts to conduct the investigation. In the first part, soft lenses were synthesized by the polymerization of 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane (TRIS), N,N-dimethylacrylamide (DMA), 1-vinyl-2-pyrrolidinone (NVP), and 2-hydroxyethylmethacrylate (HEMA). The physical and biochemical characterizations of silicone hydrogel lenses were measured by methods comprising equilibrium water content (EWC), oxygen permeability (Dk), optical transparency, contact angle, mechanical test, protein adsorption, and cytotoxicity. The results indicated that the TRIS concentration in all formulations enhanced Dk and decreased the EWC, whereas both DMA and NVP contributed to the hydrophilicity of the hydrogels. The maximum value of Dk was 74.9 barrer, corresponding to EWC of 44.5% as well as a contact angle of 82°. Furthermore, L929 fibroblasts grew on all these hydrogels, suggesting non-cytotoxicity. Generally, the silicone hydrogels in this study presented good oxygen permeability, stiffness, and optical transparency as well as anti-protein adsorption. Consequently, these silicone hydrogel polymers would be feasible for making contact lens.
In the second part, silicone nanoparticles composites (SiNPs) were synthesized by the combination of tetraethyl orthosilicate (TEOS) and polydimethylsiloxane (PDMS) via the sol-gel reaction. Before the polymerization of hydrogel lenses, these SiNPs were blended with HEMA and NVP monomers. All samples were subject to characterization consisting of dynamic light scattering (DLS), transmission electron microscope (TEM), scanning electron microscope (SEM), EWC, Dk, optical transparency, and contact angle. SiNPs has the average diameter of SiNPs of 336 nm. The result showed that the different mixing concentrations of SiNPs composites increased Dk, but did not influence the EWC of p(HEMA-co-NVP)-SiNPs lenses. The maximum of Dk was 71 barrer for p(HEMA-co-NVP) sample containing 1.2 wt% of SiNPs whereas its highest EWC attained 73%. These results demonstrate a novel approach for producing soft lenses.
In the third part, soft lenses were synthesized by the polymerization of DMA, NVP, and SiNPs. The physical and biochemical properties of all samples were analyzed based on methods such as SEM, EWC, Dk, optical transparency, contact angle, mechanical properties, protein adsorption, and cytotoxicity. The results indicated that the addition of SiNPs increased the Dk without influencing the EWC of the soft lenses. With 1.2 wt% of SiNPs, the Dk of p(DMA-co-NVP)-SiNPs was 94.8 barrer whereas its EWC remained at 85.14%. In particular, DNS12 displayed a contact angle around 39.65°. Additionally, protein adsorption primarily depended on the negatively charged SiNPs. Higher SiNPs content led to lower human serum albumin (HSA) and higher lysozyme deposition on all samples. Moreover, L929 fibroblasts grew on all hydrogel samples, suggesting non-cytotoxicity. Generally, the combination of SiNPs with hydrogels exhibited high Dk, without influencing importantly the optical transparency, moduli. These results may be applicable as ophthalmic biomaterials in for soft contact lens.

Abstract
Acknowledgments
Index
List of figures
List of tables
Abbreviation list
Chapter 1: Introduction - 1 -
1.1 Background of the study. - 1 -
1.2 Motivation and objectives of study - 2 -
Chapter 2: Literature review - 4 -
2.1 Contact lens’s development - 4 -
2.2 Contact lens classification - 5 -
2.2.1 Hard contact lens - 6 -
2.2.1.1 Hard PMMA lens - 6 -
2.2.1.2 Gas permeable rigid lens .- 6 -
2.2.2 Soft contact lens - 7 -
2.2.2.1 Hydrogel lens - 8 -
2.2.2.2 Silicone hydrogel lens - 9 -
2.3 Special properties of soft contact lens material - 11 -
2.3.1 Water retention - 11 -
2.3.2 Oxygen permeability - 12 -
2.3.2.1 Oxygen permeability - 12 -
2.3.2.2 Oxygen transmissibility - 14 -
2.3.3 Optical transparency - 15 -
2.3.4 Surface wettability - 15 -
2.3.5 Protein adsorption on contact lens - 17 -
2.3.6 Mechanical properties - 19 -
2.4 Materials introduction - 20 -
2.4.1 DMA - 20 -
2.4.2 NVP - 21 -
2.4.3 HEMA - 22 -
2.4.4 TRIS - 23 -
2.4.5 PDMS - 23 -
2.4.6 TEOS - 25 -
2.4.7 EGDMA - 25 -
2.5 Photoinitiator crosslinking mechanism - 26 -
Chapter 3: Synthesis and characterization of silicone contact lenses based on TRIS-DMA-NVP-HEMA hydrogels - 28 -
3.1 Experimental section - 28 -
3.1.1 Materials - 28 -
3.1.2 Equipment apparatus - 28 -
3.1.3 Experimental steps - 29 -
3.1.4 Physical and biocompatibility characteristic testing - 30 -
3.1.4.1 Equilibrium water content - 31 -
3.1.4.2 Oxygen permeability - 31 -
3.1.4.3 Optical transparency - 31 -
3.1.4.4 Contact angle - 31 -
3.1.4.5 Mechanical strength - 32 -
3.1.4.6 Protein adsorption - 33 -
3.1.4.7 Cytotoxicity - 34 -
3.2 Result and discussion - 35 -
3.2.1 Equilibrium water content - 36 -
3.2.2 Oxygen permeability - 36 -
3.2.3 Optical transparency - 38 -
3.2.4 Contact angle - 39 -
3.2.5 Mechanical properties - 40 -
3.2.6 Protein adsorption - 41 -
3.2.7 Cytotoxicity - 43 -
3.2.8 Comparison with commercial lenses - 46 -
Chapter 4: Effect of silicone nanoparticles on the ophthalmic performance of hydrogel contact lenses - 48 -
4.1 Experimental section - 48 -
4.1.1 Materials - 48 -
4.1.2 Equipment apparatus - 48 -
4.1.3 Experimental steps - 49 -
4.1.3.1 Preparation of silicone nanoparticles - 49 -
4.1.3.2 Preparation of SiNPs hydrogel samples - 50 -
4.1.4 Physical characteristic testing - 52 -
4.1.4.1 Elemental analysis and size of particles - 52 -
4.1.4.2 Equilibrium water content - 52 -
4.1.4.3 Optical transparency - 53 -
4.1.4.4 Contact angle - 53 -
4.1.4.5 Oxygen permeability - 53 -
4.2 Result and discussion - 53 -
4.2.1 Size and elemental composition of particles - 54 -
4.2.2 Optical transparency - 56 -
4.2.3 Equilibrium water content - 56 -
4.2.4 Contact angle - 57 -
4.2.5 Oxygen permeability - 57 -
Chapter 5: Synthesis and characterization of soft contact lens based on the combination of SiNPs with hydrophobic and hydrophilic monomers - 62 -
5.1 Experimental section - 62 -
5.1.1 Materials - 62 -
5.1.2 Equipment apparatus - 62 -
5.1.3 Experimental steps - 63 -
5.1.3.1 Preparation of silicone nanoparticles - 63 -
5.1.3.2 Preparation of SiNPs hydrogel samples - 64 -
5.1.4 Physical and biocompatibility characteristic testing - 65 -
5.1.4.1 Equilibrium water content - 65 -
5.1.4.2 Oxygen permeability - 65 -
5.1.4.3 Optical transparency - 66 -
5.1.4.4 Contact angle - 66 -
5.1.4.5 Mechanical strength - 66 -
5.1.4.6 Surface morphology - 66 -
5.1.4.7 Protein adsorption - 66 -
5.1.4.8 Cytotoxicity - 67 -
5.2 Result and discussion - 67 -
5.2.1 Equilibrium water content - 67 -
5.2.2 Oxygen permeability - 68 -
5.2.3 Optical transparency - 69 -
5.2.4 Contact angle - 70 -
5.2.5 Mechanical properties - 71 -
5.2.6 Surface morphology - 72 -
5.2.7 Protein adsorption - 73 -
5.2.8 Cytotoxicity - 74 -
Chapter 6: Conclusion - 78 -
References - 80 -

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