臺灣博碩士論文加值系統

生化法為常用農藥快篩方式之一，利用農藥抑制乙醯膽鹼酶進行檢測，雖然能用於市場即時檢測農藥殘留，但無法篩檢所有農藥。嘉磷塞(Glyphosate, GLY)為一種有機磷農藥，普遍施用於基因改良黃豆，由於GLY為乙醯膽鹼酶弱抑制劑，目前現行生化法無法適用於檢測GLY殘留。因此，本研究開發兩種檢測GLY殘留方法，期以在食品安全監測上具實質性助益。本研究開發奈米金比色法(AuNPs colorimetry)檢測GLY，利用GLY和鉛離子之螯合效應，減弱鉛離子和AuNPs之間的靜電作用力，進而保留原本AuNPs顏色。比色法檢測結果顯示GLY濃度與AuNPs光吸收度具有良好負線性關係(R2 0.9964, LOD 0.0752 ppm)，AuNPs光吸收度隨GLY濃度上升而減弱。本研究針對AuNPs比色法亦開發微量農藥檢測儀器，以影像判讀比色法試片上GLY，可偵測到GLY濃度線性範圍介於0.1-1 ppm (R2 0.9645, LOD 0.025 ppm)。此外，本研究利用電化學方式開發分子印跡(Molecularly imprinted polymer, MIP)金電極，在電極表面修飾殼聚醣(Chitosan)，形成具有能吸附GLY之分子模腔，結合安培法(Amperometry, IT)檢測，可檢測GLY濃度線性範圍介於0.01-10 ppm (R2 0.8864, LOD 1.5 ppb)。利用MIP金電極-安培法檢測其他五種農藥，發現MIP金電極對於GLY具有專一性。本研究亦偵測黃豆樣本中GLY農藥殘留量，經水萃後，MIP金電極-安培法偵測結果呈現最佳線性濃度範圍為0.01-10 ppm (R2 0.9619, LOD 7.8 ppb)，涵蓋台灣衛生福利部食品藥物管理署(Taiwan Food and Drug Administration)法定GLY於各項農作物之容許殘留量(0.1-10 ppm)。本研究成功開發AuNPs比色法和MIP金電極-安培法能專一性檢測GLY，並且MIP金電極-安培法能檢測水萃黃豆樣本中GLY殘留，因此有助於提高農作物GLY殘留篩檢比率，促進食品安全。

The biochemical assay is one of the common screening methods for rapid pesticide detection by utilizing the attenuation of acetylcholinesterase. Although biochemical assay can be employed for real-time pesticide residue detection in the market, it is currently unable to screen for all commonly used pesticides. Glyphosate (GLY) is an organophosphorus pesticide frequently used in genetically modified soybeans. The current biochemical assay is not applicable for detecting residual GLY due to its weak inhibition of acetylcholinesterase. Therefore, this study developed two methods to detect residual GLY for food safety monitoring.This study developed an AuNPs colorimetry method to detect GLY by the chelation effect of GLY with lead ions to weaken the electrostatic interaction between lead ions and AuNPs and preserve the original color of the AuNPs. The results of AuNPs colorimetry method indicated a strong negative linear relationship between GLY concentration and AuNPs absorbance (R2 0.9964, LOD 0.0752 ppm) with AuNPs absorbance decreasing as GLY concentration increased. In addition, this study created a trace pesticide detection instrument for the AuNPs colorimetry method, capable of conductong image-based analysis of GLY on the AuNPs colorimetry test strip (linear range 0.1-1 ppm, R2 0.9645, LOD 0.025 ppm). Furthermore, this study introduced a molecularly imprinted material (MIP) gold electrode using an electrochemical approach, with the surface modification of chitosan to create molecularly imprinted cavities capable of adsorbing GLY for the detection of GLY (linear range 0.01-10 ppm, R2 0.8864, LOD 1.5 ppb). The MIP gold electrode performed its specificity for GLY detection when tested against five other pesticides. The MIP gold electrode was employed to detect GLY residues in soybean samples after water extraction, revealing a linear range of 0.01-10 ppm (R2 0.9619, LOD 7.8 ppb), which complies with the permissible GLY residue limits of agriculture crops established by the Taiwan FDA (0.1-10 ppm). This study successfully developed the AuNPs colorimetric method and MIP gold electrode for the specific detection of GLY, and in particular, the MIP gold electrode was capable of detecting GLY residues in water-extracted soybean samples. Consequently, these developments contributed to enhancing the screening ratio for GLY residues in agricultural crops for promoting food safety

摘要 iAbstract ii目錄 iii圖目錄 vi表目錄 viii第一章 前言 1第二章 文獻回顧 22.1 農藥使用現況 22.2 農藥環境分布 52.3 農藥生物危害 72.4 農藥分類 72.4.1 有機磷農藥 82.4.2 嘉磷塞 82.5 台灣農藥殘留檢測法 102.6 比色法之農藥殘留檢測 122.6.1 奈米粒子之農藥殘留比色法檢測 132.6.2 AuNPs結合鉛離子應用於檢測GLY 142.7 電化學農藥殘留檢測 152.7.1 分子印跡技術 162.7.2 分子印跡技術之農藥檢測 17第三章 研究目的 18第四章 材料與方法 194.1 實驗材料與設備 194.1.1 實驗材料 194.1.2 實驗儀器 194.1.3 實驗農藥 204.2 AuNPS合成 214.3 AuNPS之吸收光譜 214.4 Pb(NO3)2濃度對於比色法之影響 214.5 AuNPS比色法偵測GLY 214.6 AuNPS比色法偵測GLY之特異性 224.6.1 單一型特異性檢測 224.6.2 混和型特異性檢測 224.7 開發微量農藥檢測儀器 224.7.1 微量農藥檢測儀器檢測GLY 234.8 黃豆樣本製備 234.8.1 黃豆樣本中農藥萃取以水回溶 234.9 製備GLY分子印跡傳感器 244.9.1 電鍍液前處理 244.9.2 電沉積 244.10 電化學檢測GLY 254.10.1 CV檢測GLY 254.10.2 EIS檢測GLY 254.10.3 IT檢測GLY 254.10.4 MIP金電極-安培法檢測GLY之特異性 254.11 AuNPS比色法和電化學法偵測黃豆樣本中萃取農藥 264.11.1 AuNPS比色法偵測黃豆樣本中萃取農藥 264.11.2 MIP金電極-安培法偵測黃豆樣本中萃取農藥 26第五章 結果 275.1 AuNPS表徵 275.2 硝酸鉛濃度之最佳化條件 295.3 目標農藥之AuNPS比色法分析 305.4 鉛離子對於多種農藥之專一性分析 335.5 微量農藥檢測儀器偵測GLY 355.6 AuNPS比色法偵測黃豆樣本中農藥殘留 375.7 MIP金電極建構 385.7.1 MIP金電極表徵 395.8 MIP金電極檢測目標農藥 425.8.1 CV檢測GLY 425.8.2 EIS檢測GLY 435.8.3 IT檢測GLY 445.8.4 MIP金電極-安培法對於多種農藥之專一性分析 455.9 黃豆樣本中GLY水回溶萃取率 465.10 MIP金電極-安培法偵測黃豆樣本中萃取農藥 48第六章 討論 496.1 GLY螯合鉛離子調控AuNPS光吸收度 506.2 AuNPS比色法具專一性偵測GLY 526.3 金電極表面修飾殼聚醣以氫鍵作用力吸附GLY 536.4 MIP金電極-安培法檢測GLY 546.5 AuNPS比色法偵測黃豆樣本GLY殘留之侷限 566.6 MIP金電極以氫鍵作用力吸附黃豆樣本內GLY殘留 57第七章 結論 60參考文獻 61

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