近幾年來，由於白金奈米顆粒具有獨特的物理化學以及電催化特性，許多學者嘗試將此奈米材料應用於製備生物感測器上。本研究目標主要是合成出以白金為主的雙金屬奈米觸媒，並實際應用於製備電化學式感測平台，希望藉由此平台能製備出高性能的電化學生物感測器。本研究分為兩大主題：首先是以雙氧水為主的第一代葡萄糖感測器，另一主題則是直接催化葡萄糖為主的第四代葡萄糖感測器。
(I). 在第一個主題，主要以修飾Watanabe法將兩種雙金屬奈米顆粒(PtM, M = Ir, Pd)成功地沈積在多層壁奈米碳管上(PtM/MWCNTs)，並具有良好的分散性，同時本研究也利用XRD、TEM、 ICP以及 XAS進行材料上物理化學的分析。雙氧水電化學感測器的製備方式是以Nafion包覆奈米金屬觸媒修飾於玻璃碳電極表面，發現以Pt-Pd/MWCNTs所製備出的雙氧水感測器性能比Pt-Ir/MWCNT來的好，並也利用XAS來證明電子傳遞效應對雙氧水催化能力的影響。另外，從電化學測試上發現以Pt-Pd/MWCNTs所製備出的雙氧水感測器俱有良好的再現性、儲存安定性以及抗干擾能力，最後並將Pt-Pd/MWCNTs此奈米金屬觸媒應用於製備葡萄糖感測試片，製備方式首先將觸媒溶液滴覆在Au/Ti薄膜微型試片的工作電極表面上，再以靜電吸引的方式將酵素層 (CS-GA-GOx) 修飾於觸媒層之上；所製備出的葡萄糖感測試片可量測之線性範圍為0.5 mM~22 mM ( R2 = 0.996)，其靈敏度為49.9 μA mM-1 cm-2，並發現此感測試片具有良好的再現性以及穩定性，並也有良好的抗干擾能力。
(II). 在第二主題，主要利用白金-金殼核奈米金屬顆粒 (Aurod@Pt) 製備出一高感度非酵素型電流式葡萄糖感測器；此奈米金屬顆粒也以XRD、TEM、UV-vis以及 XPS等儀器來分析此奈米顆粒物理化學等特性。此葡萄糖感測器製備方式是以Nafion包覆奈米金屬觸媒直接固定於玻璃碳電極表面(Nafion/Aurod@Pt/GCE)。由此修飾電極與Nafion/Ptdendrite/GCE之結果比較發現，其催化葡萄糖氧化的能力較好，並且白金於電極上的承載量較少(1.48×10-5 gPt/cm2)，代表此殼核結構之奈米金屬觸媒，可以較少白金量達到較佳的催化效果。同時也發現此感測電極可以較低的施加電位進行催化反應，也同時具有良好的再現性與抗干擾能力。

In recent years, several studies have demonstrated that Pt NPs have excellent prospects for use in biosensors owing to their physical and chemical properties. They facilitate electron transfer and increase the sensor’s surface area, thus achieving enhanced mass transport with good biocompatibility. The goal of this research was to synthesize Pt-based bimetallic nanocatalysts for high -performance electrochemical sensing platforms with wide linear ranges, high sensitivities, fast response times, good biocompatibility, stability, and selectivity. Two kinds of glucose electrochemical biosensors with important clinical significance and applications were selected for study and development; namely, first generation (H2O2-based) and fourth generation (enzyme free) glucose biosensors, associated with diabetes management and/or prevention.
The following research topics have been addressed in this dissertation:
(I). A new highly catalytic and intensely sensitive amperometric sensor based on PtM (where M=Pd,Ir) bimetallic nanoparticles (NPs) for the rapid and accurate estimation of hydrogen peroxide (H2O2) by electrooxidation in physiological conditions is reported. PtPd and PtIr NPs-decorated multiwalled carbon nanotube nanocatalysts (PtM/MWCNTs) were prepared by a modified Watanabe method, and were characterized by XRD, TEM, ICP, and XAS. The sensors were constructed by immobilizing PtM/MWCNTs nanocatalysts in a Nafion film on a glassy carbon electrode. The PtPd sensor showed a better performance in H2O2 sensing than did the PtIr counterpart. Explanations were sought from XAS measurements to explain the reasons for differences in sensor activity. In addition, the PtPd/MWCNTs nanocatalyst sensor electrode also exhibited excellent reproducibility and stability. Along with these attractive features, the sensor electrode also displayed very high specificity to H2O2 with complete elimination of interference from UA, AA, AAP and glucose. The biosensor was constructed by immobilizing the PtPd-MWCNTs catalysts in a Nafion film on a Au/Ti micro-strip working electrode surface. An inner Nafion film coating was used to eliminate common interferents such as UA, AA and AAP. Finally, a enzyme layer (CS-GA-GOx) was fabricated by electrostatic adsorbed method. The sensitivity determined using the slope of the calibration plot between 0.5 and 22 mM ( R2 = 0.996) was found to be, on an average, 49.9 μA mM-1 cm-2. In addition, the biosensor exhibited high reproducibility, good storage stability and satisfactory anti-interference ability. The applicability of the biosensor to actual serum sample analysis was also evaluated.
(II). A new highly catalytic and intensely sensitive amperometric sensor based on bimetallic heteronanostructures, consisting of a dendritic Pt shell and rod-shaped structured Au cores (Aurod@Pt), i.e. bimetallic nanoparticles, for the rapid and accurate estimation of glucose by direct electro-oxidation under physiological conditions is reported. The physicochemical characteristics of the bimetallic Aurod@Pt nanocatalysts were investigated using XRD, TEM, UV-vis, and XPS. The glucose sensor was constructed in a simple manner by immobilizing Aurod@Pt bimetallic nanoparticles, in a Nafion film, on a glassy carbon electrode (Nafion/Aurod@Pt/GCE). The amount of Pt used, to form the catalytic sensing system, is extremely small (1.48×10-5 gPt/cm2), yet it shows unusually high sensor activity for the electrochemical oxidation of glucose compared with Nafion/Ptdendritic/GCE. The Nafion/Aurod@Pt/GCE was found to exhibit a low working potential, fast amperometric response, high sensitivity, good reproducibility and long-term stability, a very high specificity to glucose with complete elimination of interference from UA, AA, AAP, and chloride ions; thereby indicating it can reliably provide efficient signal transduction in an enzyme-free glucose biosensor.

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