為解決疏水性矽酮(silicone)隱形眼鏡接觸眼球之不舒適感及脂質沾黏之問題，本研究採用共聚合以及層接式自組裝的方式來提高隱形眼鏡的親水性及含水量。本研究以矽酮為隱形眼鏡基材，利用氧電漿來活化表面，進行甲基丙烯酸二甲胺乙酯(DMAEM) [2-(dimethyl amino)ethyl methacrylate]接枝，於膜表面產生-NH3+基團，然後分別以透明質酸(hyaluronic acid, HA)與幾丁聚醣(chitosan, CS)以及海藻酸鈉(sodium alginate, AL)與幾丁聚醣，進行層接式自組裝形成多層聚集結構。經由染料確認幾丁聚醣、海藻酸、透明質酸接枝量會隨著固化層增加而有增加趨勢。接觸角會因透明質酸及海藻酸密度增加而降低，使得親水性提高。因(HA-CS)及(AL-CS)量增加更降低PDMS-HEMA薄膜的蛋白質吸附。此外層接式自組裝層對PDMS-HEMA的含水量、透氧率、透光率，均無明顯的影響。

This work is to increase the hydrophilicty of silicone polymer in order to reduce its uncomfortableness and protein adsorption as a contact lens. The hydrophilic was improved through copolymerization followed by layer-by-layer self-assembly. After copolymerization, the silicone copolymer was treated with plasma to activate the surface, followed by grafting with 2-(dimethylamino)ethylmethacrylate (DMAEM) to introduce amino groups to the surface. Afterward, polyelectrolyte multi-layer of hyaluronic acid (HA) and chitosan (CS) was assembled through layer-by-layer self-assembly. Similar procedure was performed to form multi-layer of sodium alginate (AL) and chitosan. The results showed that the resulting silicone copolymer exhibited increased hydrophilicity and decreased protein adsorption. Furthermore, the light transmittance, oxygen permeability, tensile strength and modulus of the silicone copolymer were not significantly affected by the polyelectrolyte multi-layer.

[1] 張朝凱, "近視雷射手術大揭密," 眼睛保健聖經, 2007.
[2] 吳志凌, "隱形眼鏡自動光學檢測系統之設計與開發," 2007.
[3] 許瓊文, "嬌生攻下五成眼鏡族市場的秘密," 今周刊, vol. 期518, pp. PP.112-113, 2006.
[4] Bes, Laurence Huan, Kim Khoshdel, Ezat Lowe, Martin J. McConville, Christopher F. Haddleton, and D. M., "Poly(methylmethacrylate-dimethylsiloxane) triblock copolymers synthesized by transition metal mediated living radical polymerization: bulk and surface characterization," European Polymer Journal, vol. 39, pp. 5-13, 2003.
[5] Y. Berdichevsky, J. Khandurina, A. Guttman, and Y. H. Lo, "UV/ozone modification of poly(dimethylsiloxane) microfluidic channels," Sensors and Actuators B: Chemical, vol. 97, pp. 402-408, 2004.
[6] W. O. and L. D., "Hydrophilic Gels for Biological Use," nature, vol. 185, pp. 117-118, 1960.
[7] Y. I. V., L. E., O. D. P., S. E. M., and M. G. F., "Synthesis and characterization of a model extracellular matrix that induces partial regeneration of adult mammalian skin," Sci., vol. 86, pp. 933-937, 1989.
[8] S. A. Barenberg, "Abridged report of the committee to survey the needs and opportunities for the biomaterials industry," Journal of Biomedical Materials Research, vol. 22, pp. 1267-1291, 1988.
[9] Hoffman and A. S., "Hydrogels for biomedical applications," Advanced Drug Delivery Reviews, vol. 54, pp. 3-12, 2002.
[10] 陳進富, "淺談水膠在生醫之應用," 化工科技與商情, vol. 38期, pp. 38-43, 2002.
[11] P. NA, M. HJ, and L. LM, "The structure of highly crosslinked poly(2-hydroxyethyl methacrylate) hydrogels.," J Biomed Mater Res., vol. 4, pp. 397-411, 1985.
[12] H. J. Choi and M. Kunioka, "Preparation conditions and swelling equilibria of hydrogel prepared by γ-irradiation from microbial poly(γ-glutamic acid)," Radiation Physics and Chemistry, vol. 46, pp. 175-179, 1995.
[13] W. R. Gombotz and S. F. Wee, "Protein release from alginate matrices," Advanced Drug Delivery Reviews, vol. 31, pp. 267-285, 1998.
[14] F. Yokoyama, I. Masada, K. Shimamura, T. Ikawa, and K. Monobe, "Morphology and structure of highly elastic poly(vinyl alcohol) hydrogel prepared by repeated freezing-and-melting," Colloid and Polymer Science, vol. 264, pp. 595-601, 1986/07/01 1986.
[15] D. W. Lim and T. G. Park, "Stereocomplex formation between enantiomeric PLA–PEG–PLA triblock copolymers: Characterization and use as protein-delivery microparticulate carriers," Journal of Applied Polymer Science, vol. 75, pp. 1615-1623, 2000.
[16] Wichterle O. and L. D., "Hydrophilic Gels for Biological Use," Nature Biotechnology, vol. 185, pp. 117-118, 1960.
[17] R. Bettini, P. Colombo, and N. A. Peppas, "Solubility effects on drug transport through pH-sensitive, swelling-controlled release systems: Transport of theophylline and metoclopramide monohydrochloride," Journal of Controlled Release, vol. 37, pp. 105-111, 1995.
[18] H. Cicek and A. Tuncel, "Immobilization of α-chymotrypsin in thermally reversible isopropylacrylamide-hydroxyethylmethacrylate copolymer gel," Journal of Polymer Science Part A: Polymer Chemistry, vol. 36, pp. 543-552, 1998.
[19] L. Hovgaard and H. Brondsted, "Dextran hydrogels for colon-specific drug delivery," Journal of Controlled Release, vol. 36, pp. 159-166, 1995.
[20] T. Coviello, M. Grassi, G. Rambone, E. Santucci, M. Carafa, E. Murtas, F. M. Riccieri, and F. Alhaique, "Novel hydrogel system from scleroglucan: synthesis and characterization," Journal of Controlled Release, vol. 60, pp. 367-378, 1999.
[21] A. J. Kuijpers, G. H. M. Engbers, T. K. L. Meyvis, S. S. C. de Smedt, J. Demeester, J. Krijgsveld, S. A. J. Zaat, J. Dankert, and J. Feijen, "Combined Gelatin−Chondroitin Sulfate Hydrogels for Controlled Release of Cationic Antibacterial Proteins," Macromolecules, vol. 33, pp. 3705-3713, 2000/05/01 2000.
[22] N. A. Peppas and R. E. Berner Jr, "Proposed method of intracopdal injection and gelation of poly (vinyl alcohol) solution in vocal cords: polymer considerations," Biomaterials, vol. 1, pp. 158-162, 1980.
[23] A. K. Bajpai, S. K. Shukla, S. Bhanu, and S. Kankane, "Responsive polymers in controlled drug delivery," Progress in Polymer Science, vol. 33, pp. 1088-1118, 2008.
[24] Y. Qiu and K. Park, "Environment-sensitive hydrogels for drug delivery," Advanced Drug Delivery Reviews, vol. 53, pp. 321-339, 2001.
[25] X. Zhou, L. Weng, Q. Chen, J. Zhang, D. Shen, Z. Li, M. Shao, and J. Xu, "Investigation of pH sensitivity of poly(acrylic acid-co-acrylamide) hydrogel," Polymer International, vol. 52, pp. 1153-1157, 2003.
[26] A. Mamada, S. T. Tanaka, y. D. Kungwatchakun, and M. Irie, "Photoinduced Phase Transition of Gels," Macromolecules, vol. 23, pp. 1517-1519, 1990.
[27] J.-i. Anzai, A. Uneo, H. Sasaki, K. Shimokawa, and T. Osa, "Photocontrolled Permeation of Alkali Cations through Poly(viny chloride)/Crown Ether Membrane," Markmol. Chem., vol. 4, pp. 731-734, 1983.
[28] K. Ishihara and I. Shinoham, "Photoinduced Permeation Control of Proteins Using Amphiphilic Azoaromatic Polymer Membrane," Polymer Science, vol. 22, pp. 515-518, 1984.
[29] M. G. Kodzwa, M. E. Staben, and D. G. Rethwisch, "Photoresponsive control of ion-exchange in leucohydroxide containing hydrogel membranes," Journal of Membrane Science, vol. 158, pp. 85-92, 1999.
[30] I. C. Kwon, Y. H. Bae, and S. W. Kim, "Electrically erodible polymer gel for controlled release of drugs," Nature, vol. 354, pp. 291-293, 1991.
[31] A. Khokhlov, S. Starodubtzev, and V. Vasilevskaya, "Conformational transitions in polymer gels: Theory and experiment," in Responsive Gels: Volume Transitions I. vol. 109, K. Dušek, Ed., ed: Springer Berlin Heidelberg, 1993, pp. 123-171.
[32] C. Dong-June, I. Yoshihiro, and I. Yukio, "An insulin-releasing membrane system on the basis of oxidation reaction of glucose," Journal of Controlled Release, vol. 18, pp. 45-53, 1992.
[33] T. A. Horbett, B. D. Ratner, J. Kost, and M. Singh, "A Bioresponsive Membrane for Insulin Delivery," in Recent Advances in Drug Delivery Systems, J. Anderson and S. Kim, Eds., ed: Springer US, 1984, pp. 209-220.
[34] 齐备, 隐形眼镜手册: 上海科学技术出版社, 1998.
[35] R. E. B. 原著 Richard P. Franz, ，主譯瞿佳, 隐形眼镜基础: 上海科学技术出版社, 1994.
[36] 瞿佳 and 呂帆, 隐形眼镜学: 上海科学技术出版社, 1997.
[37] J. M. Goddard and J. H. Hotchkiss, "Polymer surface modification for the attachment of bioactive compounds," Progress in Polymer Science, vol. 32, pp. 698-725, 2007.
[38] D. S. Bag, V. P. Kumar, and S. Maiti, "Chemical modification of LDPE film," Journal of Applied Polymer Science, vol. 71, pp. 1041-1048, 1999.
[39] Y. Wang, J.-H. Kim, K.-H. Choo, Y.-S. Lee, and C.-H. Lee, "Hydrophilic modification of polypropylene microfiltration membranes by ozone-induced graft polymerization," Membrane Science, vol. 169, pp. 269-276, 2000.
[40] I. L. J. Dogue, R. Forch, and N. Mermilliod, "Plasma-induced hydrogel grafting of vinyl monomers on polypropylene," Journal of Adhesion Science and Technology, vol. 9, pp. 1531-1545, 1995/01/01 1995.
[41] D. L. Angst and G. W. Simmons, "Moisture absorption characteristics of organosiloxane self-assembled monolayers," Langmuir, vol. 7, pp. 2236-2242, 1991/10/01 1991.
[42] D. G., H. J. D., and S. J., "Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces " Thin Solid Films, vol. 210/211, pp. 831-835, 1992.
[43] A. F. Xie and S. Granick, "Local Electrostatics within a Polyelectrolyte Multilayer with Embedded Weak Polyelectrolyte," Macromolecules, vol. 35, pp. 1805-1813, 2002/02/01 2002.
[44] S. L. Cooper, T. A. Speckhard, K. K. S. Hwang, C. Z. Yang, and W. R. Laupan, "Properties of segmented polyurethane zwitterionomer elastomers," Journal of Macromolecular Science, Part B, vol. 23, pp. 175-199, 1984/04/01 1984.
[45] T. A. Speckhard and S. L. Cooper, "Ultimate Tensile Properties of Segmented Polyurethane Elastomers: Factors Leading to Reduced Properties for Polyurethanes Based on Nonpolar Soft Segments," Rubber Chemistry and Technology, vol. 59, pp. 405-431, 1986/07/01 1986.
[46] C. Li, X. Yu, T. A. Speckhard, and S. L. Cooper, "Synthesis and properties of polycyanoethylmethylsiloxane polyurea urethane elastomers: A study of segmental compatibility," Journal of Polymer Science Part B: Polymer Physics, vol. 26, pp. 315-337, 1988.
[47] Y. Camberlin and J. P. Pascault, "Quantitative DSC evaluation of phase segregation rate in linear segmented polyurethanes and polyurethaneureas," Journal of Polymer Science: Polymer Chemistry Edition, vol. 21, pp. 415-423, 1983.
[48] 王朝陽, 趙耀明, 王浚, and 李雄武, "異佛爾酮二異氰酸酯溶液擴鏈合成聚乳酸類藥物緩試劑," 精細化工, vol. 23, p. 913, 2006.
[49] A. Pizzi, B. Mtsweni, and W. Parsons, "Wood-induced catalytic activation of PF adhesives autopolymerization vs. PF/wood covalent bonding," Journal of Applied Polymer Science, vol. 52, pp. 1847-1856, 1994.
[50] K. V.Y., B. V.A., L. E.P., and Y. T.E., Plastic Massy:Chemical Abstracts, vol. 27, 1981.
[51] I. Sava, M. Bruma, B. Schulz, F. Mercer, V. N. Reddy, and N. Belomoina, "Synthesis and properties of silicon-containing polyamides," Journal of Applied Polymer Science, vol. 65, pp. 1533-1538, 1997.
[52] 蔡濟懋, "以具耐鹼性且可與反應性染料結合之水性聚氨基甲酸酯形成人造皮-探討其減量與染色性," 2003.
[53] J.-S. Yang, Y.-J. Xie, and W. He, "Research progress on chemical modification of alginate: A review," Carbohydrate Polymers, vol. 84, pp. 33-39, 2011.
[54] D. L. French and K. J. A.-M. Himmelstein, John W., "Physicochemical aspects of controlled release of substituted benzoic and naphthoic acids from CarbopolR gels Journal of Controlled Release," Controlled Release, vol. 37, pp. 281-289.
[55] W. R. Gombotz and S. Wee, "Protein release from alginate matrices," Advanced Drug Delivery Reviews, vol. 31, pp. 267-285, 1998.
[56] A. D. Augst, H. J. Kong, and D. J. Mooney, "Alginate Hydrogels as Biomaterials," Macromolecular Bioscience, vol. 6, pp. 623-633, 2006.
[57] M. Van Beek, L. Jones, and H. Sheardown, "Hyaluronic acid containing hydrogels for the reduction of protein adsorption," Biomaterials, vol. 29, pp. 780-9, Mar 2008.
[58] B. Thierry, F. M. Winnik, Y. Merhi, and M. Tabrizian, "Nanocoatings onto Arteries via Layer-by-Layer Deposition:  Toward the in Vivo Repair of Damaged Blood Vessels," Journal of the American Chemical Society, vol. 125, pp. 7494-7495, 2003/06/01 2003.
[59] M. B. Huglin and M. B. Zakaria, "Observations on the homogeneity of crosslinked copolymers prepared by γ-irradiation," Polymer, vol. 25, pp. 797-802, 1984.
[60] D. Luensmann and L. Jones, "Protein deposition on contact lenses: the past, the present, and the future," Cont Lens Anterior Eye, vol. 35, pp. 53-64, Apr 2012.
[61] A. M. Zamore, "Process foe producing an implantable apparatus comprising a biomedical device coated with crosslinled TPU," USP 6,558,732, 2003.