嘉磷塞 (glyphosate) 為一種全球廣泛使用的有機磷除草劑，能有效的殺死草本、木本、闊葉等多種植物。一些研究表明，嘉磷塞已被發現存在於水體、食品、甚至是人體等環境中，使得可能導致長期的生物累積並對人類或生物體造成極大傷害，因此，開發一種簡單、靈敏、並具有選擇性的嘉磷塞分析方法對於環境和食品安全評估具有重要意義。本研究結合分離方法和分析技術，提供了一種檢測嘉磷塞的創新策略。提出以檸檬酸溶膠-凝膠法改質的氧化鑭 (c-La2O3-300) 吸附樣品中的嘉磷塞，並分離去除非待測物的雜質後，再以0.5 mM次氯酸鈉 (NaClO) 水解成甘胺酸 (glycine)，最後使用經典的茚三酮反應 (ninhydrin) 衍生生成藍紫色產物，以UV-Vis分光光度計在570 nm處測定嘉磷塞濃度。該方法降低了吸附時間以及吸附劑的用量之外，也成功透過吸附手法排除樣品所含的其他干擾雜質進而提升量測準確度，並克服水解步驟引發ninhydrin衍生弱化的問題。檢測適用線性範圍為0.5–100 μM，偵測極限達0.52 μM，量測真實樣品回收率介於85–114%，方法已成功應用於檢測水體及食品當中的嘉磷塞。

Glyphosate is a commonly and widely applied organic phosphorus herbicide in the agricultural field. Its excellent performance also can effectively kill a variety of plants, including herbaceous, woody, and broad-leaved plants. Several studies have shown that glyphosate can be found in various environments such as water, food, and even human bodies. This may lead to long-term bioaccumulation and harm to humans or living organisms. Therefore, the development of a simple, sensitive, and selective analytical method for glyphosate is significant in environmental and food safety assessments. In this study, we provide an innovative strategy that combines a separation method and analytical technique to detect glyphosate. First, glyphosate was adsorbed onto citric acid sol-gel method modified lanthanum oxide (c-La2O3-300) from samples. After separating materials and removing impurities, the glyphosate on c-La2O3-300 was hydrolyzed by 0.5 mM NaClO to form glycine, which could be derivatized with ninhydrin to produce Ruhemann’s Purple coloures complex and measured glyphosate concentration by using UV-Vis spectrophotometer at 570 nm. In addition to reducing adsorption time and the amount of adsorbent, this study also successfully increased measurement accuracy by eliminating impurities in the adsorption step and overcoming the weak derivatization effect between ninhydrin reaction and hydrolysis step. The linear range was 0.5–100 μM, the limit of detection (LOD) was 0.52 μM, and real samples recovery were 85–114%. This method has been successfully applied to detect glyphosate in water and food samples.

目錄
摘要.................................................................I
Abstract............................................................II
誌謝................................................................III
目錄................................................................IV
圖目錄..............................................................VII
表目錄..............................................................XII
第一章 前言...........................................................1
1.1 簡介..........................................................1
1.2 研究動機......................................................2
第二章 文獻回顧.......................................................3
2.1 嘉磷塞類農藥...................................................3
2.1.1 農藥簡介與分類............................................3
2.1.2 嘉磷塞農藥的發展背景與危害.................................5
2.2 嘉磷塞的量測方法...............................................7
2.3 茚三酮 (Ninhydrin) 反應.......................................10
2.4 鑭吸附材料....................................................12
2.4.1製備方法：檸檬酸-溶膠凝膠法 (citric acid sol-gel method)...14
2.5 吸附原理......................................................15
2.5.1 物理吸附 (physisorption) 與化學吸附 (chemisorption).......15
第三章 研究方法......................................................17
3.1 實驗裝置......................................................17
3.1.1 紫外光可見光光譜儀 (UV-Vis spectrophotometer).............17
3.1.2試管震盪器................................................18
3.1.3 離心機...................................................18
3.1.4 其他儀器.................................................18
3.2 實驗之藥品與配製方式...........................................19
3.2.1 實驗藥品.................................................19
3.2.2 藥品配製.................................................20
3.3 實驗分析流程..................................................22
3.3.1 配製ninhydrin顯色試劑步驟.................................22
3.3.2 量測甘胺酸 (glycine) 檢量線的實驗步驟......................23
3.3.3 以檸檬酸溶膠-凝膠法製備的氧化鑭 (c-La2O3-300)..............24
3.3.4 量測嘉磷塞濃度的實驗步驟 (未添加材料吸附步驟)...............25
3.3.5 量測嘉磷塞濃度的實驗步驟 (有添加材料吸附步驟)...............26
3.2.6 萃取真實樣品中嘉磷塞的步驟及量測...........................27
第四章 結果與討論.....................................................28
4.1 Ninhydrin衍生反應最佳化條件....................................29
4.1.1 Ninhydrin反應pH最佳化....................................30
4.1.2 Ninhydrin濃度最佳化......................................32
4.2 NaClO水解效率探討.............................................34
4.2.1 NaClO水解時間最佳化.......................................35
4.2.2 NaClO水解濃度最佳化.......................................36
4.2.3 過高濃度NaClO對ninhydrin反應的顯色影響....................39
4.3 改質氧化鑭 (c-La2O3) 吸附嘉磷塞條件探討.........................43
4.3.1 c-La2O3吸附後清洗次數.....................................44
4.3.2 c-La2O3鍛燒溫度最佳化.....................................45
4.3.3 c-La2O3吸附pH條件最佳化...................................47
4.3.4 c-La2O3吸附劑劑量........................................48
4.3.5 農藥中異丙胺鹽成分之探討..................................49
4.4 影響吸附因素..................................................54
4.4.1 水體體積.................................................54
4.4.2 嘉磷塞與磷酸根之競爭效應..................................56
4.4.3 共存離子干擾.............................................58
4.5 分析方法確效..................................................60
4.6 真實樣品......................................................61
4.6.1 水體樣品分析結果..........................................62
4.6.2 食品樣品分析結果..........................................64
第五章 結論..........................................................65
第六章 未來展望.......................................................66
參考文獻.............................................................67
Supporting Information – 1..........................................77
Supporting Information – 2..........................................78
Supporting Information – 3..........................................80
Supporting Information – 4..........................................81
Supporting Information – 5..........................................86
The Author..........................................................87

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