環境荷爾蒙拓印光子晶體感測原件開發研究

Abstract

本研究結合分子拓印材料與光子晶體發展微型化光學型環境荷爾蒙感測原件，以 克服傳統儀器分析限制，達到高靈敏、快速、簡易操作、可即時現地分析的優勢。 研究中以無機ZrO2 為拓印基材，利用功能性單體以π-π作用力與氫鍵方式，將標的 分子模板於溶膠-凝膠反應中拓印於ZrO2 結構，待移除分子模板後，ZrO2 中的拓印 孔穴能以分子型態、尺寸與立體化學結構辨認標的分子，表現高度選擇性吸附能力， 作為感測原件的分子接受體可大幅降低環境樣品的基質干擾，提高感測靈敏度。結 合拓印高分子於光子晶體，可將分子濃縮事件以繞射光波長位移的方式轉譯成可讀 訊號，本研究以膠體晶體為模板，將拓印ZrO2 製備成反蛋白石光子晶體結構，根據 布拉格繞射定理，利用標的物與ZrO2 結合後晶體平均折射係數降低所造成的波長藍 移程度作為感測標的物濃度的依據。為提高有效吸附位址並克服分子於剛性ZrO2 結 構傳輸的限制，研究中導入有機高分子為中孔洞模板，製備層級式孔洞結構，並調 控光子晶體晶格常數，以提高波長位移變化量與讓繞射波長落於可見光區，達到目 測可讀的能力。相對於有機拓印材料，無機高分子具高度化學與機械穩定性，可提 供較高拓印程度，並對有機待測分子具較低非特定性吸附的優勢，本研究最後將更 進一步縮小量測點尺寸至1-2 釐米，並將不同分析物的感測點負載於單一載玻片上 製備感測晶片，完成同步多樣品分析的先進感測系統。

In this study, we combine a molecularly imprinted polymer with a photonic crystal to develop a miniaturized sensing device for detection of endocrine disrupting chemicals with high sensitivity and rapid response. In addition, its small size, light weight and high recognition ability enable in-situ and on-site analysis without complicated sample treatment processes. Inorganic ZrO2 material is used as the imprinted polymer in stead of conventional organic polymers because it exhibits higher chemical and mechanical stability, higher imprinting capability, and lower non-specific adsorption for organic compounds. The imprinting process involves with the formation of template-functional monomer complex in terms of π-π interaction and hydrogen bonding, followed by embedding the complex into the ZrO2 matrix through a sol-gel polymerization. After removal the templates, the imprinted cavities with the size, shape, and stereo-chemical similarity to the templates are left, which allow the ZrO2 polymer exhibiting high selectivity for the target binding and greatly inhibiting matrix interference. Imprinted ZrO2 photonic crystals with inverse opal structures are constructed through conducting the imprinted ZrO2 sol solution into the interstitial voids of polystyrene colloidal crystals, and then removing the templates through solvent extraction after gelation. Blue shift of the diffraction light turns the binding event into readable signals and reflects the concentrations of the targets. To increase the number of effective imprinted cavity and facilitate molecular diffusion in the ZrO2 matrix, additional organic templates are used to result the porous structure hierarchically. In addition, visual detection is achieved by increasing lattice parameters of the photonic crystal which augments the wavelength shifts and extends the diffraction into visible range. A microchip which composes of several analyzing spots with 1-2 mm in diameter is further fabricated. This upgrades the singing device to muti-analyte detection.