§ 瀏覽學位論文書目資料
系統識別號 U0002-1207200522270400
DOI 10.6846/TKU.2005.00852
論文名稱(中文) 電激發化學發光暨電化學偵測系統於農藥上的分析
論文名稱(英文) Development of Electrogenerated Chemiluminescent and Electrochemical System for Pesticides Determination
第三語言論文名稱
校院名稱 淡江大學
系所名稱(中文) 化學學系博士班
系所名稱(英文) Department of Chemistry
外國學位學校名稱
外國學位學院名稱
外國學位研究所名稱
學年度 93
學期 2
出版年 94
研究生(中文) 王俊勝
研究生(英文) Jun-Sheng Wang
學號 888170023
學位類別 博士
語言別 繁體中文
第二語言別
口試日期 2005-05-27
論文頁數 262頁
口試委員 指導教授 - 林孟山(mslin@mail.tku.edu.tw)
委員 - 王文竹
委員 - 陳壽椿
委員 - 黃承文
委員 - 傅明仁
關鍵字(中) 農藥
生化感測器
電化學
電激發化學發光
脈衝清除法
自動流注分析系統
關鍵字(英) Pesticide
Biosensor
Electrochemical
Electrogenerated chemiluminescent
Aryl acylamidase
Ammonium cerium(IV) nitrate
Pulse cleaning
Automatic flow injection analysis
第三語言關鍵字
學科別分類
中文摘要
本研究是利用電化學與電激發化學發光分析技術,開發農藥生化感測器及光電化學之偵測系統,結合的技術包括:生化感測器、電化學分析、電激發化學發光、流注分析以及脈衝再生自動化系統等等,用以解決農藥偵測上的困難。以電化學方法偵測農藥時,常見的問題有: 1. 種類繁多的農藥中許多是非電活性物種或 2. 具電活性之農藥易在電化學模式偵測後造成電極的毒化,使得分析結果無法再現的缺點。因此論文中針對含氮類、醯胺類及酚類等等,非電活性或易形成電極毒化的農藥進行分析與研究,以解決上述常在電化學農藥分析上遭遇的問題,使光暨電化學技術在農藥的分析上更趨彈性及完備。
首先是以酵素辨識系統來開發農藥偵測的研究,目的是發展非抑制型且具分析線性長之農藥生化感測器。研究是藉由醯胺類分解酵素 (Aryl acylamidase, EC 3.5.1.13) ,可選擇性辨識除草寧農藥的特性,先將除草寧農藥分解成苯胺類物質後,以拋棄式印刷電極配合微差脈衝電化學技術進行定量分析,此完成的電化學農藥生化感測器,有效延長了分析物操作濃度的線性範圍以及提高農藥分析的選擇性,改善了過去抑制型農藥生化感測器之偵測模式的缺點。
第二項的研究是利用化學反應前處理方式,將不具電活性或易毒化電極的物質做化性之改變後,再結合電化學農藥流注分析系統來偵測。研究是以硝酸鈰胺氧化劑先與 2,4,6-三氯酚農藥反應,生成還原氧化可逆的苯醌類氧化後產物,便可在低還原電位下偵測此苯醌類產物,並間接決定 2,4,6-三氯酚農藥的濃度,此結果成功避免了使用高的氧化電位,因此同時解決了干擾及電極表面毒化之偵測窘境。
第三項是利用自動化流注分析技術發展連續式脈衝電位之電極再生系統,來解決電化學偵測時常發生的電極毒化現象。研究將整合了連續式電壓脈衝產生程式、自製電位儀和自動化流注分析系統,已開發出可快速且簡易操作的電極毒化再生分析系統,研究以偵測易毒化電極之乙烯硫脲農藥當範例,成功改善易毒化物質過去以電化學偵測時,操作再現性不佳的問題。
最後開發非電活性物質之烷基胺類的偵測,研究使用在溶液環境中穩定性佳的發光物質 Ru(bpy)32+ ,利用它會與烷基胺類作用並產生光訊號的特性,用以開發烷基胺類尼古丁之電激發化學發光農藥分析系統。此系統成功地展現電激發化學發光分析系統之高靈敏特性,且顯示其具有快速及穩定性偵測含尼古丁農藥之水樣分析的優點。並利用電激發化學發光系統於易毒化電極之農藥分析的應用,以解決此物種利用電化學方法偵測時會毒化電極的問題。研究是選擇達諾殺為分析之農藥,此物質經電化學氧化後,易形成聚分子吸附在電極表面上而造成毒化,而以電激發化學發光分析系統來偵測此酚類化合物時,並無毒化現象的產生,此結果充分顯示本系統在農藥偵測上的優點。
綜合上述,本研究已成功利用電激發化學發光與電化學分析系統,結合酵素辨識、流注分析及自動化脈衝再生技術,開發了多個符合簡便、快速、選擇性佳、高靈敏度及高再現性的農藥分析系統,而此研究理念與偵測系統將可進一步應用於臨床、藥物及其他環境污染的分析,未來更可將其發展成可攜式之分析工具,以達到及時分析與居家檢測的最終目標。
英文摘要
The goal of this dissertation is to develop various schemes for pesticides determination based on biosensor, electrochemical, and electrogenerated chemiluminescent (ECL) system. The schemes offer solutions to measure non-electroactive species and to minimize electrode fouling.
We propose an enzyme based biosensor for propanil determination. The aryl acylamidase (EC 3.5.1.13) was modified onto disposable strip for biosensor development. The enzymatic reaction for propanil can produce 3,4-dichloroaniline which is detectable at oxidative potential. The results show both higher selectivity and longer linearity than inhibition based pesticide biosensors. 
A preoxidation treatment was used for 2,4,6-trichlorophenol detection. In this study, ammonium cerium (IV) nitrate was used as an oxidant to convert 2,4,6-trichlorophenol to 2,6-dichloro-1,4-benzoquinone. This product is easily reducted at -50 mV (vs. Ag/AgCl). The scheme shows high sensitivity and limited interferences for 2,4,6-trichlorophenol determination. 
A continuously automatic pulse scheme is used to clean the electrode fouling in oxidative detection scheme. This system is integrated with continuous pulse cleaning program, computerized potentiostat, and automatic flow injection analysis (AFIA). It was used to avoid the electrode surface poison from ethylene thiourea oxidation. The result shows good reproducibility for ethylene thiourea determination. 
At the last, the ECL scheme is based on the reaction of Ru(bpy)32+ and its related coreactant to detect nonelectroactive aliphatic amines. The Ru(bpy)32+ is a good luminescence that has both high qutumatic efficiency and stability. The rapid, stable and highly sensitive system was established to Nicotine and Dinoseb detection.
On the basis of above results, this dissertation has demonstrated several methods to solve the disadvantages of previous detection by using enzyme, chemical pretreatment, automatic pulse cleaning, and ECL system. Their merits include easy operation, prompt response, high selectivity, high sensitivity, and good reproducibility for pesticides determination.  In the future, the schemes can be applied to clinical, pharmaceutic, and environmental analysis. Otherwise, they will be developed to portable device for local and home-care applications.
第三語言摘要
論文目次
中文摘要	i
英文摘要	iii
圖目錄	v
表目錄	xiii
第一章  緒論	1
1-1 農藥偵測之重要性	2
1-2 生化感測器	33
1-2-1 感測器的組成元件	33
1-2-2 酵素為辨識元進行葡萄糖量測	37
1-2-3電極的修飾	40
1-2-4 干擾物排除技術	44
1-2-5 分析特性的提升	49
1-3 化學感測器	52
1-3-1 電極修飾方法	52
1-3-2修飾功能	58
1-4 脈衝式電極處理技術	61
1-5 自動化流注分析系統	67
1-6 電激發化學發光	71
1-7 本研究之目的	84
第二章 除草寧農藥生化感測器	87
2-1 簡介	87
2-1-1 除草寧農藥分析的重要性	88
2-1-2 除草寧農藥的偵測方法	88
2-2 實驗部分	91
2-2-1 儀器	91
2-2-2 藥品	92
2-2-3 實驗步驟	93
2-3 結果與討論	95
2-3-1 工作原理的探討	95
2-3-2 最佳化條件的探討	98
2-3-3 分析特性的探討	106
2-4 結論	109
第三章 2,4,6-三氯酚農藥化學偵測系統	110
3-1 簡介	110
3-1-1 2,4,6-三氯酚農藥分析的重要性	111
3-1-2 2,4,6-三氯酚農藥的偵測方法	112
3-2實驗部分	115
3-2-1 儀器	115
3-2-2 藥品	116
3-2-3 實驗步驟	117
3-3 結果與討論	118
3-3-1 工作原理的探討	118
3-3-2 最佳化條件的探討	126
3-3-3 分析特性的探討	134
3-4 結論	138
第四章 連續式脈衝電極再生系統於乙烯硫脲的偵測	139
4-1 簡介	139
4-1-1 乙烯硫脲分析的重要性	141
4-1-2 乙烯硫脲的偵測方法	142
4-2 實驗部分	144
4-2-1 儀器	144
4-2-2 藥品	146
4-2-3 實驗部分	146
4-3 結果與討論	147
4-3-1 工作原理的探討	148
4-3-2 最佳化條件的探討	150
4-3-3 分析特性的探討	165
4-4 結論	168
第五章 電激發化學發光之尼古丁農藥偵測系統	169
5-1 簡介	169
5-1-1 尼古丁農藥分析的重要性	170
5-1-2 尼古丁農藥的偵測方法	171
5-2 實驗部分	177
5-2-1 儀器	177
5-2-2 藥品	178
5-2-3 實驗步驟	182
5-3 結果與討論	182
5-3-1 工作原理的探討	182
2-3-2 最佳化條件的探討	184
5-3-3 分析特性的探討	200
5-4 結論	207
第六章 電激發化學發光之達諾殺類農藥偵測系統	208
6-1 簡介	208
6-1-1 達諾殺農藥分析的重要性	209
6-1-2 達諾殺農藥的偵測方法	209
6-2 實驗部分	212
6-2-1 儀器	212
6-2-2 藥品	213
6-2-3 實驗步驟	215
6-3 結果與討論	216
6-3-1 工作原理的探討	216
6-3-2 最佳化條件的探討	216
6-3-3 分析特性的探討	226
6-4 結論	228
第七章 總結	229
符號對照表	233
參考文獻	234

圖目錄
圖 (1-1) NAD(P)H 與Ru(bpy)32+ 之電激發化學發光反應機制。	78
圖 (1-2) Ru(bpy)32+ 和去氫酶之電極修飾示意圖。	79
圖 (1-3) 發光胺生化感測器之電激發化學發光反應機制圖。	80
圖 (2-1) 除草寧農藥生化感測器之印刷電極試片示意圖。	94
圖 (2-2) 除草寧生化感測器氧化偵測之反應機制圖。	95
圖 (2-3) 除草寧/aryl acylamidase 之微差脈衝伏安圖。分別取 15 μL 除草寧溶液其濃度為 (a) 150 和 (b) 0 μM ,滴於 Aryl acylamidase 酵素修飾 (3×10-3 units/strip) 之印刷電極上,偵測其氧化訊號之微差脈衝伏安圖;圖 (c) 則是未修飾酵素之印刷電極上偵測 150 μM 除草寧的微差脈衝伏安圖,其它操作條件: 0.1 M pH 7.0 磷酸緩衝溶液,電位區間 0 ~ 1.0 V ,而掃描速率為 50 mV/s 。........97
圖 (2-4) 除草寧與 Aryl acylamidase 酵素之反應時間探討。研究AAA 酵素分解除草寧的最佳操作時間,反應時間範圍在 10 ~ 180秒間,而其餘操作條件同圖 (2-3)。...........................................................99
圖 (2-5) 緩衝溶液之酸鹼值的探討。圖中顯示了除草寧生化感測器在酸鹼度為 pH 4 ~ 9 的反應溶液操作下,所得到的氧化電流訊號。除草寧與酵素的作用時間為 60 秒,其餘條件如圖 (2-4) 所示。...........................................................................................................101
圖 (2-6) 緩衝溶液電解質種類的探討。除草寧生化感測器之電解質探討,分別選擇了 Phosphate 、 Imidazole 、 Citric acid 、 Hepes 和 Tris 等電解質做研究,而緩衝溶液酸鹼值為 pH 7 ,其餘條件如圖 (2-5) 所示。...............................................................................103
圖 (2-7) 磷酸緩衝溶液濃度的探討。除草寧生化感測器之磷酸鹽緩衝
v
溶液濃度的探討,選擇的磷酸溶液濃度在 0.01 ~ 0.2 M 區間,研究電解質濃度對氧化電流訊號的影響。其餘條件如圖 (2-6) 所示。.....................................................................................104
圖 (2-8) 除草寧之濃度校正曲線。除草寧農藥生化感測器在 0.05 M, pH 7 之磷酸緩衝溶液下、酵素反應時間為 60 秒,連續測量除草寧濃度在 20 ~ 400 μM 間所得的氧化電流訊號響應圖,其餘條件如圖 (2-3)。...............................................................................................107
圖 (3-1) 2,4,6-三氯酚之循環伏安圖。圖中顯示濃度為 1.0 mM 之 2,4,6-三氯酚的第 1 圈 (a) 及第 10 圈 (b) 掃描後伏安圖,而 0.0 mM (c) 即不含 2,4,6-三氯酚之伏安圖。條件:在 0.05 M pH 3.0 之磷酸緩衝溶液及掃描速率 100 mV/s 下操作。	120
圖 (3-2) 偵測 2,4,6-三氯酚農藥的訊號再現性。圖中顯示經過硝酸鈰胺氧化處理 (a) 及未處理 (b) 的 2,4,6-三氯酚,在連續 20 次操作下,測量 100 mM 2,4,6-三氯酚農藥時,所獲得的訊號再現性圖,其它操作條件如圖 (3-1) 。	122
圖 (3-3) 2,4,6-三氯酚經硝酸鈰胺氧化後之循環伏安圖。圖中顯示 2,4,6-三氯酚經硝酸鈰胺氧化後所得的循環伏安圖,其三氯酚的濃度為 0.5 mM (a) 及 0.0 mM (b) ,而圖 (c) 是在空白緩衝溶液中操作之循環伏安圖。其餘操作條件如圖 (3-1) 所示。	123
圖 (3-4) 2,4,6-三氯酚經硝酸鈰胺氧化後之紫外光光譜圖。圖中顯示 2,4,6-三氯酚經硝酸鈰胺氧化後所得的紫外光光譜圖,其三氯酚的濃度為 25 mM (a) 及 0 mM (b) ,其餘操作條件如圖 (3-1) 所示。	124
圖 (3-5) 2,4,6-三氯酚電化學偵測系統之還原偵測反應機制圖。	125
圖 (3-6) 2,4,6-三氯酚偵測系統的施加電位探討。利用電化學流注分析系統於施加電位在 -100 ~ 300 mV 區間下,偵測 20μL 之 500 μM 三氯酚所得的還原電流訊號,其中載流液體為 0.05 M, pH 3 磷酸緩衝溶液,而流速為 1.0 mL/min 。	127
圖 (3-7) 2,4,6-三氯酚農藥分析系統之載流液體流速的探討。控制載體流速在 0.1 ~ 1.2 mL/min 間,評估其對偵測 2,4,6-三氯酚農藥之還原電流訊號的影響,此時的偵測電位為 -50 mV ,而其它操作條件如圖 (3-6) 所列。	129
圖 (3-8) 注射樣品體積的探討。分別注入 10 、 20 、 50 、 100 及 500 μL 體積之樣品,並偵測 2,4,6-三氯酚農藥之還原電流訊號,系統之流體流速控制在 1.0 mL/min ,其它操作條件如圖 (3-7) 所示。	131
圖 (3-9) 緩衝溶液之酸鹼值的探討。在緩衝溶液之酸鹼值分別為 pH 3 、 5 、 7 和 9 下,評估其對偵測 2,4,6-三氯酚農藥之還原電流訊號響應的關係;樣品體積為 20 
圖 (3-10) 2,4,6-三氯酚農藥偵測系統之濃度校正曲線。 2,4,6-三氯酚農藥偵測系統在最佳化操作條件下,連續測量濃度在 0.4 ~ 750 μM 間的 2,4,6-三氯酚農藥,所得的還原電流訊號響應,其緩衝溶液之酸鹼值為 pH 3 ,而其它最適化的操作條件如圖 (3-9) 。	136
圖 (4-1) 乙烯基二硫代胺基甲酸鹽代謝產生乙烯硫脲的途徑。	143
圖 (4-2) LabVIEW工作平台	145
圖 (4-3) 乙烯硫脲的循環伏安圖。在 (A) 0 及(B) 20 mM 乙烯硫脲之 0.05 M, pH 7 磷酸緩衝溶液中,所得之循環伏安圖,而圖中 (C) 為連續 20 圈掃描後之訊號圖,其掃描速率為 0.1 V/sec。	149
圖 (4-4) 偵測電位及電極再生脈衝電壓與時間的關係圖。	152
圖 (4-5) 脈衝強度的探討。於 +1.0 V下偵測 1.0 mM ETU 後,針對脈衝強度為 (0) no pulse 、 (1) 0 ~ 1.2 、 (2) 0 ~ 1.3 、 (3) 0 ~ 1.4 、 (4) 0V ~ 1.45 及 (5) 0 V ~ 1.5 V對毒化現象做處理,並偵測ETU 6次之相對標準偏差。操作條件為: 0.05 M, pH 7之磷酸緩衝溶液、流速 0.5 mL/min 、 注入樣品體積為 20 
圖 (4-6) 脈衝頻率的探討。系統以脈衝頻率分別為 0 、 5 、 10 、 15 、20 及 25 Hz ,作為處理偵測 1 mM 乙烯硫脲後的毒化電極,並觀察其氧化電流訊號的變化,脈衝強度為 0 ~ 1.4 V,其餘操作條件與圖 (4-5) 同。	156
圖 (4-7) 再生脈衝電壓施加時間的探討。系統脈衝處理時間分別為0 、5 、 10 、 15 、 20 、 25及30秒,作為處理偵測乙烯硫脲後的毒化電極,並觀察其氧化電流訊號的變化,脈衝頻率15 Hz ,其餘操作條件與圖 (4-6) 同。	157
圖 (4-8) 偵測乙烯硫脲之氧化電位的探討。在圖 (4-7) 的操作條件,且脈衝清除時間為 20 秒下,探討偵測電位分別為0.6 、 0.8 、 1.0 、 1.1及 1.2 V ( vs. Ag / AgCl, 3M KCl ) 時,所獲得的乙烯硫脲氧化電流訊號。	158
圖 (4-9) 溶液 pH 值探討。乙烯硫脲分析系統在 pH 值分別為 5 、 5.5 、6 、 6.5 、 7 、 8 及 9 之 0.05 M 磷酸緩衝溶液中,於偵測電壓為 1.0 V 下,偵測 ETU 所得的氧化電流訊號響應,其餘操作條件如圖 (4-8)。	160
圖 (4-10) 樣品注入體積的探討。乙烯硫脲分析系統在注入之樣品體積分別為 10 、 20 、 50 及 100 μL 下,酸鹼度為 pH 7之磷酸緩衝液中,偵測 ETU 所得的氧化電流訊號變化,其餘操作條件如圖
(4-9)。	161
圖 (4-11) 載流液體流速的探討。注入乙烯硫脲的體積為 20 μL下,對流體流速分別為 0.3 、 0.5 、 0.7 、 1.0 、 1.5 及 2 mL/min 做探討,比較 ETU 氧化電流訊號的變化,其餘操作條件如圖 (4-10)。	163
圖 (4-12) 乙烯硫脲之偵測校正曲線。在最佳化條件:脈衝強度0 ~ 1.4 V、頻率15 Hz 、施加時間20秒、偵測電位 +1.0 V 、 0.05M, pH 7 磷酸緩衝溶液、 20 μL之樣品體積、流體流速 0.5 mL/min下,連續偵測不同濃度 ETU 所得的濃度校正曲線。	166
圖 (5-1) ECL/ AFIA 之儀器裝置圖。	180
圖 (5-2) 電化學反應槽中的三電極系統裝置。	181
圖 (5-3) Ru(bpy)32+ 之結構。	181
圖 (5-4) 尼古丁之結構。	181
圖 (5-5) 尼古丁偵測系統之循環伏安圖及電激發化學發光圖。以循環伏安法在電位區間為 0.0 ~ 1.6 間,掃描速率 0.1 V/s 下,同時觀察 50 (a) 及 0 μΜ (b) 尼古丁溶液之光 (A) 及電化學電流訊號 (B) ,其他操作條件為:光電化學三電極反應槽是以 ITO 為工作電極、銀/氯化銀為參考電極和白金為輔助電極,而流注系統之載流液體為 0.1 M, pH 8 磷酸緩衝溶液內含 25 μΜ Ru(bpy)32+ mL/min 。	186
圖 (5-6) 尼古丁偵測系統之操作電位的探討。在電位區間為 1.0 ~ 1.5 間,偵測 50 μΜ 尼古丁反應所生成的光電流,其他操作條件為:光電化學三電極反應槽是以 ITO 為工作電極、銀/氯化銀為參考電極和白金為輔助電極,而流注系統之載流液體為 0.1 M, pH 8 磷酸緩衝溶液內含 0.1 mM Ru(bpy)32+ ,樣品迴路體積為 20 μL ,流速為 1 mL/min 。	187
圖 (5-7) 載流液體流速的探討。圖中顯示尼古丁偵測系統之載流液體流速變化對分析訊號的影響,流速變化控制在 0.6 ~ 1.1 mL/min 間,施加氧化電位為 1.4 V ,而其他的操作條件則如同圖 (5-6) 所示。	188
圖 (5-8) 緩衝溶液之酸鹼值的探討。圖為尼古丁偵測系統中緩衝溶液之酸鹼值改變對光電流訊號的影響,酸鹼值的探討在 pH 4 ~ 10 間,載流液體流速為 1.0 mL/min ,而其他的操作條件則如同圖 (5-7) 所示。	190
圖 (5-9) 緩衝溶液電解質種類的探討。圖中顯示尼古丁偵測系統在 Tris 、 Phosphate 、 Boric acid 、 Carbonate 等四種不同電解質緩衝溶液操作時,對產生光電流訊號的影響,溶液酸鹼值為 pH 8 ,而其他的操作條件則如同圖 (5-8) 所示。	194
圖 (5-10) 磷酸緩衝溶液濃度的探討。圖中顯示尼古丁偵測系統之磷酸緩衝溶液濃度改變對光電流訊號的影響,磷酸溶液濃度研究範圍在 0.01 ~ 0.15 M 間,而其他的操作條件則如同圖 (5-9) 所示。	195
圖 (5-11) 發光物質 Ru(bpy)32+ 濃度的探討。圖中顯示尼古丁偵測系統之磷酸緩衝溶液濃度改變對光電流訊號的影響,磷酸溶液濃度研究範圍在 0.01 ~ 0.15 M 間,而其他的操作條件則如同圖 (5-9) 所示。	196
圖 (5-12) 樣品迴路體積的探討。圖中顯示尼古丁偵測系統之樣品迴路體積改變對光電流訊號的影響,樣品體積分別為 10 、 20 、 50 和 100 µL ,磷酸緩衝溶液的濃度為 0.1 M ,而其他的操作條件則如同圖 (5-11) 所示。	197
圖 (5-13) 樣品迴路體積探討的真實訊號圖,其操作條件如圖 (5-12) 所述。	198
圖 (5-14) 尼古丁之電激發化學發光系統的濃度校正曲線。在 ITO 電極上施加 1.4 V ,於含有 0.1 mM, Ru(bpy)32+ 的 0.1 M, pH 8 磷酸緩衝溶液,樣品體積為 20 μL 及流體速度為 1.0 mL/min 之條件下偵測尼古丁,其濃度範圍在 2 ~ 300 μM 間所得的濃度校正曲線圖。	203
圖 (5-15) 尼古丁偵測系統之再現性的探討。在最佳化條件 (見圖 5-13) 下連續偵測 20 次 5 μM 之尼古丁,所得的訊號響應圖。	204
圖 (6-1) 達諾殺農藥混合劑之結構。	214
圖 (6-2) 達諾殺偵測系統之操作電位的探討。在電位區間為 1.1 ~ 1.8 間,偵測 500 μΜ 達諾殺反應所生成的光電流,其他操作條件:光電化學三電極反應槽是以 ITO 為工作電極、銀/氯化銀為參考電極和白金為輔助電極,而流注系統之載流液體為 0.1 M, pH 8 磷酸緩衝溶液內含 0.1 mM Ru(bpy)32+ ,樣品迴路體積為 10 μL ,流速為 1 mL/min 。	218
圖 (6-3) 樣品迴路體積的探討。圖中顯示達諾殺偵測系統之樣品迴路體積改變對光電流訊號的影響,樣品體積分別為 5 、 10 、 25 和 50 µL ,電壓施加為 1.55 V,而其他的操作條件則如同圖 (6-2) 所示。	220
圖 (6-4) 載流液體流速的探討。圖中顯示達諾殺偵測系統之載流液體流速變化對分析訊號的影響,流速變化控制在 0.9 ~ 1.7 mL/min 間,樣品體積為 10 µL ,而其他的操作條件則如同圖 (6-3) 所示。	221
圖 (6-5) 緩衝溶液之酸鹼值的探討。圖為達諾殺偵測系統中緩衝溶液之酸鹼值改變對光電流訊號的影響,酸鹼值的探討在 pH 5 ~ 9 間,載流液體流速為 1.5 mL/min ,而其他的操作條件則如同圖 (6-4) 所示。	223
圖 (6-6) 磷酸緩衝溶液濃度的探討。圖中顯示達諾殺偵測系統之磷酸緩衝溶液濃度改變對光電流訊號的影響,磷酸溶液濃度研究範圍在 0.01 ~ 0.2 M 間,而緩衝溶液酸鹼度為 pH 7 ,其他的操作條件則如同圖 (6-5) 所示。	224
圖 (6-7) 達諾殺之電激發化學發光系統的濃度校正曲線。在 ITO 電極上施加 1.55 V ,於含有 0.1 mM , Ru(bpy)32+ 的 0.1 M, pH 7 磷酸緩衝溶液,樣品體積為 10 μL 及流體速度為 1.5 mL/min 之條件下偵測達諾殺,其範圍在 2 ~ 1000 μM 間所得的濃度校正曲線圖。	227
表目錄
表(2-1)除草寧生化感測器之最佳化操作條件..............105
表(2-2)除草寧農藥生化感測器之分析特性................108
表(3-1)2,4,6-三氯酚農藥偵測系統之最佳化條件..........133
表(3-2)2,4,6-三氯酚農藥偵測系統之分析特性............137
表(4-1)乙烯硫脲分析系統之最佳化操作條件..............164
表(4-2)乙烯硫脲之分析特性............................167
表(5-1)尼古丁分析系統之最佳化操作條件................199
表(5-2)尼古丁偵測系統之分析特性......................205
表(5-3)尼古丁偵測方法的比較..........................206
表(6-1)達諾殺農藥混合物分析系統之最佳操作條件........225
表(6-2)達諾殺偵測系統之分析特性......................228
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