| 摘要: | 本計畫擬研究含皮質類固醇與可洛貝他索(clobetasol)衍生物之測定，建立生物感測器之研究，其目標如下： 第一年：利用層析分析法篩選市售藥品和化妝品中含皮質類固醇(fluprednisolone, chloroprednisone acetate, clobetasol propionate, clohetasone butyrate, prednisone and prednisolone)的藥物。研究在有氧和無氧、各種溶劑、酸、鹼和熱的條件下，照射不同波長 (254 nm 和310 nm)，皮質類固醇的分解和光化學反應。設計一組光反應器 (photo-reactor)置放在液相層析儀管柱與偵測器之間，進行衍生物 (post-column online photochemistry derivatization)之測定。利用液相層析儀-紫化光感測器和氣相層析儀-質譜 儀方法，研究皮質類固醇的穩定性、抗氧化性效力和可能的光化學反應產物。 第二年：在這個研究計畫，使用不同的方法與不同的組成分，合成年子組合 (ion association) 和分子刻印聚合物膜 (molecularly imprinted polymers (MIPs)，以建構對氯倍他索 (clobetasol)的特異性識別電位感測器。MIPs膜分別以沉澱聚合法和電合成法製造。電合成法即在金和銀電極上，以clobetasol作為模板，電化學聚合含硫醇基化合物。利用循環伏安法 (CV)和電化學交流阻抗光譜法 (EIS)監測電聚合的過程。利用紅外線反射吸收光譜、掃描電子顯微鏡和流動式注射系統，評估影響薄膜感測器分析的效能之參數。 第三年： 在這研究計畫，先以化學合成法製得石墨烯氧化物(GO)，再以電化學法還原GO， 形成石墨烯。利用電化學交流阻抗光譜法 (EIS) Nyquist圖，判定還原態和氧化態GO， 作為電極材料及其電化學性能。電沉積金、銀和鈀鹽在玻璃碳電極(GCE)，再與石墨烯反應，製作“三明治式”石墨烯/奈米金屬/ GCE複合電極。用X-射線光電子能譜 (XPS)， 拉曼光譜和透射電子顯微鏡(TEM)，確認所有這些分子共價鍵結到石墨烯的表面上。設計一個流動式電解槽通過石墨烯/奈米金屬/GCE感測器，用於測定和吸附研究。在感測器以不同的參數，如電解質、pH與流速，對感測器在流動式電解槽之影響。此系統可同時獲得藥物和生物體液中皮質類固醇的電位、電流變化值，與電流對時間關係圖。
The project is proceeding with the construction study of biosensor system of corticosteroid and clobetasol derivatives in cosmetics and drugs. The objects are the following as: First year: Screening the content of corticosteroids (fluprednisolone, chloroprednisone acetate, clobetasol propionate, clohetasone butyrate, prednisone and prednisolone) in drugs and commercial containing corticosteroids cosmetic products are studied using a chromatographic method. The degradation and photochemistry study of corticosteroids are investigated in aerobic as well as in anaerobic condition with different irradiation wavelengths (254 nm and 310 nm) in various solvent, acidic, basic and heat condition. Design a photo-reactor placed between the liquid chromatography column and detector, and determination of derivatives after post-column online photochemistry derivatization. The corticosteroids stability, antioxidation effectiveness and possible photochemical reaction products were investigated by LC-UV and GC-MS methods. Second year: In this research project, different methods to synthesis ion association and molecularly imprinted polymers membranes with different compositions are tested to construct the potentiometric sensor for specific recognition of clobetasol. The molecularly imprinted polymer is synthesized by precipitation polymerization, and electropolymerization of containing mercapto group compound on a gold and silver electrode in the presence of clobetasol as a template. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) measurements are used to monitor the process of electropolymerization. The potentiometric sensor with membranes electrode is characterized by infrared reflection absorption spectroscopy and scanning electron microscope and used in flow injection system for analysis performance. Third year: In this research project, chemically synthesized graphene oxide (GO), and electrochemical reduction of GO to form graphene. They are used as electrode materials and their electrochemical properties are systematically characterized using electrochemical impedance spectroscopy (EIS) to obtain the electronic transfer properties, based on Nyquist diagrams. Preparation of “sandwich–type” Graphene- Metal nano/GCE composite electrode is modified gold, silver and palladium toward biosensing of corticosteroids. Investigation by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) all confirm that these molecules were covalently grafted to the surface of graphene. Design a flow – through Graphene- Metal nano/GCE sensor for measure and adsorption studies. The response of the Graphene- Metal nano/GCE composite electrode to different parameters such as electrolyte, pH and flow rate in the flow cell was evaluated. Simultaneous measurements of potential-current or current-time transients allowed investigated of corticosteroids in pharmaceutical preparations and biological fluids. |
