京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18293号 / 工博第3885号 / 新制||工||1596(附属図書館) / 31151 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 秋吉 一成, 教授 赤木 和夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Functionalized poly(para-xylylene) (PPX) coatings can be useful for biomaterials applications due to their biocompatibility and useful chemistry for the immobilization of biomolecules. However, their application is not widespread due to the difficulty in synthesizing the corresponding precursors. Here, a two-step method for amine functionalization of [2.2]paracyclophane (PCP) via direct nitration and reduction is developed. Nitration at super acidic conditions and temperatures as low as -78 °C, improved the stability of PCP toward strong acids and successfully minimized side reactions such as oxidation and polymerization. This procedure resulted in quantitative yields of 4-nitro-PCP, which was successively reduced by Raney nickel catalysis with sodium borohydride. Compared to the many other reduction systems, this method is simple, inexpensive and applicable in large scales. Additionally, carboxylation of PCP using the Freidel-Crafts acylation was attempted and so far, we have been able to show the synthesis of intermediate acylated products. Then, through the chemical vapour deposition polymerization of amino-PCP amine-functionalized poly(para-xylylene) (PPX-A) thin films were coated on Si wafer substrates. The substrates coated with PPX-A showed a higher surface energy compared with those of coated with un-substituted or chlorine substituted PPX films. Furthermore, results of the surface characterization demonstrated that the CVD process was able to transfer the functionalities of the precursors to deposited polymer films without alteration. However, the stability of primary amine groups in air and aqueous solutions is a matter of concern. Aging of amino-PCP and corresponding PPX-A films showed a decrease in the amount of primary amines which was accompanied by the appearance and increase of oxygen, indicating that the decrease of available amine groups is associated with oxidation. Nevertheless, both aminated precursor and polymer films remained intact under argon. The method presented here has great potential for widespread application of PPX-A as a convenient biomaterial for microarrays and cell culture. / Thesis / Master of Science (MSc)

Functionalized reactive polymer coatings can be used in various biomaterials applications such as immunoassays and biomolecule immobilization. Poly(para-xylelene) is a relatively new biomaterial that has attracted attention over the past few decades in these areas due to its unique properties and biocompatibility. The introduction of functionalized, particularly aminated, poly(para-xylylene) will extend the application of these polymer coatings to a wide variety of biological studies. However, their application is not widespread due to the difficulty in synthesizing the corresponding precursors. Here, a two-step method for amine functionalization of [2.2]paracyclophane via direct nitration and reduction is developed. Nitration at super acidic conditions and temperatures as low as -78 °C, improved the stability of [2.2]paracyclophane toward strong acids and successfully minimized side reactions such as oxidation and polymerization. This procedure resulted in quantitative yields of 4-nitro[2.2]para-cyclophane, which was successively reduced by Raney nickel catalysis with sodium borohydride. Compared to the many other reduction systems, this method is simple, inexpensive and applicable in large scales. It does not require harsh reaction conditions and within short reaction times, delivers quantitative amounts of the reduced product. At the end, 4-amino[2.2]paracyclophane was collected in 77% overall yield. Additionally, carboxylation of [2.2]paracyclophane using the Freidel-Crafts acylation was attempted and so far, we have been able to show the synthesis of intermediate acylated products. The successful syntheses of products were verified by FT-IR, NMR and MS, and comparison of their solubility and physical properties showed significant changes upon substitution of the pristine [2.2]paracyclophane. Then, through the chemical vapour deposition polymerization of 4-amino[2.2]paracyclophane amine-functionalized thin films were coated on Si wafer substrates and their properties were compared with Parylene N and C, two well-known poly(para-xylylene) films. The substrates coated with amino-poly(para-xylylene) showed a higher surface energy compared with those of coated with un-substituted or chlorine substituted poly(para-xylylene) films. Furthermore, results of the surface characterization conducted by grazing angle reflectance IR spectroscopy and XPS, demonstrated that the CVD process was able to transfer the functionalities of the precursors to deposited polymer films without alteration. However, with the applied process parameters we obtained a higher functional density of amine groups on the surface. These polymer films can be deposited on a variety of substrates and be used as functional surfaces for a variety of applications. However, the stability of primary amine groups in air and aqueous solutions is a matter of concern. Aging of 4-amino-[2.2]paracyclophane and corresponding poly(para-xylylene) films in air and mili-Q water was studied via XPS and NMR spectroscopies. The results showed a decrease in the amount of primary amines with storage time in air or water for both aminated precursor and polymer. The kinetics for these changes, however, were not equal for the precursors and polymer films. The decay of amine groups was accompanied by the appearance and increase of oxygen, indicating that the decrease of available amine groups is associated with oxidation which can transform them to more stable amide and nitro compounds. In total, practical challenges involved in manufacture, durability and applications of amine-functionalized Parylene coatings are discussed and a reliable scheme for fabricating such films with high tunabiliy of the surface functional density is demonstrated. The highly practical method presented here provides great potential for widespread application of amine-functionalized poly(para-xylylene) as an outstanding biomaterial for microarrays, tissue engineering and cell culture studies. / Thesis / Master of Science (MSc)

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京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19406号 / 工博第4122号 / 新制||工||1635(附属図書館) / 32431 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 澤本 光男, 教授 赤木 和夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM