本研究使用離子選擇薄膜快速製作技術，並結合特殊的為結構設計，製作出具有不對稱感測面積的微流體晶片，並將其應用於食品之蔬菜檢測。本研究改良微流體晶片設計，使其封裝效能提升，增加晶片中薄膜的製程良率；也改良微流體感測晶片之銀/氯化銀電極製程，藉由自發性氯化反應，使製程不需要任何額外的儀器設備或是複雜的操作，僅透過銀的自發性化學反應即可完成電極的製作。本研究選用PMMA作為微流體晶片材質，因其成本低廉，且為熱塑性基材，適合發展可攜、拋棄式檢測裝置。
本研究使用不同設計之微結構阻塊，調整其薄膜兩側之感測面積比例，再利用電化學偵測原理，量測自發性氯化電極的電化學檢測效能。電化學循環伏安法結果顯示，自發性氯化電極的氧化還原能力良好，其氯化30秒鐘之銀/氯化銀電極，氧化還原電流為24.7 μA，高出市售銀/氯化銀電極約6.5倍的訊號。電位量測結果也證實，自發性氯化電極偵測硝酸根濃度範圍從10-4 M到1 M，具有良好的線性關係（R2=0.9992）。因此，於微流體晶片檢測中，使用前人已開發之快速自行封裝成膜技術，將硝酸根離子選擇薄膜封裝於感測晶片中，並透過其晶片微結構的設計，創造出不同感測之面積比，提升對於硝酸根離子的感測靈敏度。量測結果顯示，感測晶片於硝酸根濃度範圍10-5 M到1 M內，具有良好的線性關係（R2=0.9920），且樣品溶液與電解液的感測面積比值越高，可有較好的感測靈敏度。其中感測面積比為5：1之晶片，對於硝酸根濃度之感測靈敏度達 -57.0 mV/dec；相較於面積比為1：5之感測晶片，提升了約30%以上的感測度斜率。
在自動連續偵測時，進行濃度梯度量測，其結果顯示，本研究之感測晶片具有良好的再現性反應效能，但由於薄膜具有濃度滯留現象，因此本研究進一步探討反應時間，吸附型薄膜其吸附與脫附硝酸根離子所需要的反應時間不同，由量測結果得知，1 mM之硝酸根離子吸附於感測薄膜時，僅需花3.3秒鐘就可達到95%的反應平衡；而相同濃度之硝酸根離子的脫附反應時間，也只需要花11.4秒鐘即可達到95%的完全反應。最後，本研究也量測不同的干擾源，分別量測醋酸根離子、碳酸根離子以及亞硝酸根離子，探討其干擾離子於感測薄膜的影響，結果顯示這三種干擾離子對於本研究之感測晶片皆不會超過102倍的濃度訊號干擾。綜觀上述，本研究將硝酸根離子選擇薄膜整合於微流體系統，發展簡單製作、高效能且檢測對象範圍廣泛的電極感測晶片，並應用於檢測蔬菜中的硝酸鹽含量。

This research develops a rapid fabrication process of self-forming asymmetric polyvinylchloride (PVC) ion selective membrane in a microfluidic chip and using for nitrate ions detection in the vegetable samples. It is easily trapped the amount of polymer liquid with doping nitrate ionophores to form a thin ion selective membrane between microstructures utilizing surface tension force.Due to a large exposed ratio of the membrane surface areas, this method shows higher sensing performance than the traditional electrochemical detection. The Ag/AgCl electrode fabrication process is modified by using spontaneous chlorination reaction, which doesn’t need using any additional equipment or complex operation.
PMMA is a low cost material, which suitable for developing portable and disposable detection devices of the microfluidic chip. This study design different size of microstructures in the chip for adjusting sensing area ratio on both sides of the film to create an asymmetric membrane. In this system, the current response of cyclic voltammetry detection shows 6.5 times enhancement than the commercial system when the silver electrode treat with 1% FeCl3(aq) for 30 seconds. And the potential response of EC detection for detecting NaNO3(aq) shows a good linear response within the concentration range of 10-5 M to 1 M (R2=0.9920).
In addition, the higher sensing membrane area ratio shows better sensitivity for detecting nitrate ion in the buffer solution. When the sensing area ratio of 5 to 1 shows a linear response for nitrate ion detection in the concentration range from 10-5 M to 1 M. The good sensitivity for detecting nitrate ion is also achieved -57.0 mV/dec. In comparing to the sensing membrane area ratio of 1 to 5, the ratio of 5 to 1 shows an enhancement of the sensing efficiency of about 30% or more. During the continuous detection process, different concentrations of trace samples are injected into the sensing area sequentially. The method for cyclic detecting nitrate ion concentrations is measuring from low concentration to higher concentration and back to base concentration, which measuring the concentration in the range at 10-5 to 1 M per decade. This study of cyclic detecting nitrate ions concentration are in the range at 10-5 M to 1 M, and back to 10-5 M. Each concentration measured for 100 seconds. These results show microfluidic chip exhibit good reproducibility for nitrate ions detection. However, when the concentration in the current real sample is much higher than the next, the nitrate ions will dissolve in the next sample during the process of desorption, resulting in the retention phenomenon of concentration in continuous measurement.
The result also indicates that the response time of the adsorption and the desorption processes reach 95% of the maximum response takes 3.3 s and 11.4 s during detecting 1 mM of nitrate. At last, this study successfully integrates nitrate selective membrane into a microfluidic chip and develop a low cost yet high performance way for wide range nitrate concentration analysis. his microfluidic chip is capable of using the nitrate detection in the vegetables.

論文審定書 i
致謝 ii
中文摘要 iv
Abstract vi
目錄 viii
圖目錄 xi
表目錄 xiv
符號表 xv
簡寫表 xvii
第一章 緒論 1
1.1 研究背景 1
1.2 硝酸鹽 2
1.2.1 硝酸鹽檢測方法 5
1.3 離子選擇電極 8
1.3.1 離子選擇電極發展 9
1.3.2 市售離子選擇電極 10
1.3.3 離子選擇膜感測晶片 13
1.4 動機與目的 16
1.5 論文架構 17
第二章 工作原理 19
2.1 電化學 19
2.1.1 能斯特方程式 20
2.1.2 濃差電池系統 21
2.1.3 循環伏安法 23
2.2 離子選擇薄膜 24
2.2.1 液態薄膜 27
2.2.2 PVC薄膜 30
2.2.3 電極量測系統 32
2.3 硝酸根ISE 33
2.3.1 離子干擾 35
2.4 離子感測晶片 36
第三章 設計製作 37
3.1 微流體晶片 37
3.2 晶片設計與製作 39
3.2.1 感測電極 39
3.2.2 微流體管道 40
3.2.3 微結構設計 43
3.2.4 微流道製程 45
3.2.5 微晶片製作 49
3.3 實驗藥品 52
3.3.1 溶液配製 53
3.3.2 離子薄膜製備 54
3.3.3 蔬菜樣品配製 54
3.4 實驗架構 55
第四章 結果與討論 56
4.1 離子選擇電極 56
4.1.1 電極效能探討 56
4.1.2 氯化銀形貌 59
4.1.3 硝酸鹽對不同陽離子填充及待測液量測評估 61
4.1.4 硝酸根離子檢測 63
4.1.5 離子干擾評估 65
4.1.6 再現性效能 67
4.2 微流體感測晶片 69
4.2.1 微結構成膜 69
4.2.2 晶片效能 71
4.2.3 連續偵測 73
4.2.4 感測面積的影響 74
4.2.5 反應時間量測 77
4.3 蔬菜檢測 78
第五章 結論與未來展望 81
5.1 結論 81
5.2 未來展望 82
參考文獻 84
附錄 92
自述 96

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