摘要
本研究以2,2,6,6-四甲基-4-嘧啶氮氧自由基(TEMPO)作為穩定自由基，利用穩定自由基法以過氧化二苯甲醯(BPO)作為起始劑合成聚4-氯甲基苯乙烯(polychloromethylstyrene, PCMS)，再以其作為巨起始劑與苯乙烯單體合成出具有疏水鏈段之團連共聚物，並利用具有生物活性的尼可丁醇醯胺(nicotinamide)進行改質反應，合成出具有離子性且具氧化還原活性的高分子(q-PCMS-b-PS)，之後將改質後高分子粒子分散於溶液中，加入氧化劑(H2O2)、還原劑(Na2S2O3)與葡萄醣測量其穿透度，探討溶液中之穿透度對濃度之變化。並以聚乙烯醇為基材分別製備高分子複合膜，分別以氧化劑(H2O2)、還原劑(Na2S2O3)與葡萄醣溶液測其液滴接觸角之變化性來作探討複合膜之氧化還原性質。以尼可丁醇醯胺改質後高分子粒子分散在水中，其溶液穿透度會隨著所加入之還原劑增加而下降，其分散在磷酸緩衝溶液中並添加葡萄糖氧化酵素，當加入葡萄糖時則會隨著溶液葡萄糖濃度增加造成高分子聚集之現象，另外以氧化還原劑測試聚乙烯醇複合膜，當還原劑濃度提升，複合膜液滴接觸角則增加，當改以含氧化劑液滴時，複合膜液滴接觸角則相對的減少。推測是還原劑Na2S2O3或葡萄糖溶液與高分子之尼可丁醇醯胺官能基反應，使高分子鏈段型態改變進而造成液滴接觸角改變。而添加q-PCMS-b-PS於1.5%PVA溶液所製備的修飾電極，電極表面上修飾有帶正電荷之以尼可丁醇醯胺改質後的團連共聚物，提供電極與電解質間之離子傳導特性。於支持電解質中添加K3Fe(CN)6後，於0.2V~0.4V左右會有氧化還原波峰出現，而加入不同濃度K3Fe(CN)6所得到之電流強度亦會隨濃度增加而有增大之趨勢。
並列摘要
Polychloromethylstyrene, PCMS, macro-initiators were synthesized by a stable free radical polymerizations in the presence of 2,2’,6,6’-teramethyl-1-piperidinyloxy (TEMPO) and benzoyl peroxide initiator (BPO); then the TEMPO-capped PCMS were extended by polymerization with styrene monomers to synthesize PCMS-b-PS block copolymers. The PCMS and block copolymers were further modified by nicotinamide to prepare quaternized PCMS, q-PCMS, and q-PCMS-b-PS block copolymers; then functional particles will be formed. The particle size can be varied with redox reagent. Adding reductant into the solution with the functional particles results in precipitate. The polymers were further blended with PVA solution, and the mixture was cast on a screen-printed electrode (SPE) and dried to form a modified electrode. The contact angle of a drop with oxidant or reductant by the film was observed by an optical microscope. It was found that the contact angle depends on the oxidant and reduced state of the drop. It shows a better wetting property on the modified PVA film for the reduced state than that of oxidant rate of drop. The oxidoreduction property of the film made of the q-PCMS-b-PS block copolymers is more sensitive than that of q-PCMS homopolymers. Cyclic voltammograms of K3Fe(CN)6 at various concentrations were studied in electrolyte at pH 7.0 by the modified electrode. It was found that the anodic and cathodic peak currents increase with concentration of the K3Fe(CN)6.