本研究主要利用不同金屬氧化物的氧化力及催化力開發環境及生醫相關的電化學檢測模式，並藉由流動注射分析、旋轉電極等系統配合各式電極表面修飾技術，建立具可行性的電化學偵測平台，用以發展具高度應用性之化學及生化檢測系統。
    各種金屬氧化物的氧化力順序首先藉由電位法在各種溶液環境中快速評估，其結果與安培法所得結果直接進行對照，顯示其具有高度相關性，而本實驗所建立的金屬氧化物的氧化力順序，可提供本研究、後續實驗及其他電化學分析領域的參考與應用。
    多巴胺在神經傳導機制中扮演相當重要的角色，但是體內的神經傳導物質極多，需兼具檢測上的高專一性，利用LiMn2O4對於多巴胺進行選擇性氧化之特性，可在雙電極的電化學流注分析系統中，建立低干擾的還原偵測模式，先以LiMn2O4進行氧化前處理，隨後再以空白玻璃碳電極施加還原電位偵測，不但能有效降低易氧化物質干擾，並能避免其他神經傳導物質的影響。
    尿酸為生理上重要的核酸代謝產物，透過Pb3O4修飾電極之氧化力及催化力，即可在流動注射系統下建立單電極還原偵測模式，實驗上藉由Pb3O4修飾電極進行氧化反應，並隨即電催化氧化後之中間產物進行還原偵測，能有效降低環境中易氧化物質的干擾，發展非酵素型高專一性的快速檢測模式。
    銨根為人體及環境之重要代謝物，利用Cu2O修飾電極之電催化特性，可在流注系統發展低電位氧化模式偵測，此機制亦可對於組織胺進行氧化模式偵測，或搭配共價修飾技術，結合creatinine deiminase酵素發展肌酸酐生化感測器，另外，在雙電極系統的上游電極修飾PbO2進行氧化前處理，可以避免環境中易氧化干擾物的影響。
    乳酸去氫酶(LDH)是重要的血液生化檢驗項目，主要透過NADH的量測進而定量酵素活性，利用Mn3O4修飾電極的電催化特性，搭配旋轉電極系統，對於NADH建立低電位的氧化偵測模式，並藉由塗佈Nafion®高分子薄膜，即可有效降低易氧化物質的干擾；此外，將NAD+藉由選擇性高分子薄膜固定於修飾電極上，即可利用定電位安培偵測模式，快速定量LDH的酵素活性。
    總而言之，本研究主要建立環境與生醫相關物質的檢測機制，藉由金屬氧化物的氧化及催化特性，發展簡易、靈敏、快速、低干擾的電化學檢測模式，有助於化學及生化感測器的發展，由於兼具實際應用的價值，可因應未來各種環境及生醫樣品的檢測需求；最後，本研究所建立的金屬氧化物氧化力表，也將提供未來在相關感測器開發及工業處理上的應用。

By using the chemical properties of metal oxides, the environmental and biomedical related electrochemical sensors have been developed in this research. The detecting schemes are based on the different oxidative or catalytic ability of metal oxide modified electrodes for ammonia ion, uric acid, creatinine, some well-known neurotransmitters, NADH and LDH, respectively. Either flow injection analysis system or rotating disk electrode system was used for the quantification of these analytes in this dissertation.
    At the beginning of this research, various metal oxide modified electrodes were quickly evaluated the sequence of oxidative strength by potentiometry under various solution conditions. The potential versus Ag/AgCl was recorded to contrast the amperometric response by flow injection analysis, and a good correlation was found between these two methods. Therefore, the sequence of oxidative strength among metal oxides can be easily consulted and used throughout this research.
    Dopamine, an important neurotransmitter in central nervous, was detected with limited interference in this experiment. The LiMn2O4 modified electrode was modified in upstream electrode to oxidize dopamine, and then the product was reduced in bare downstream glassy carbon electrode. This electrode can be easily fabricated by LiMn2O4 modified electrode and has the advantage of selective oxidation to avoid all the analogous neurotransmitters in biological applications.
    Uric acid, an important metabolite form nucleic acid, can get a reductive response on Pb3O4 modified electrode. This modified electrode was used to oxidize the uric acid and then catalyzed the reduction of above intermediate on the same modified electrode. This method can effectively reduce the interferences without enzyme modification in the biomedical application.
    Based on environmental and biomedical requirements, Cu2O was utilized to detect the ammonia ion in oxidative mode by flow injection analysis. This scheme was also used for histamine detection and the creatinine biosensor application. The creatinine deiminase for creatinine biosensor was modified onto the upstream of dual electrode. In order to obtain a limited interference system, PbO2 was used to pre-oxidize the easily oxidative compounds and also modified onto the upstream electrode in these biomedical or chemical sensors.
    Because of the importance of dehydrogenase based sensors, the Mn3O4 was used to catalyze the oxidation of NADH in steady-state amperometry by rotating disk electrode. And this system was employed for the LDH activity evaluation by several electrode modification processes. This scheme can provide the advantages of rapid way and limit interference to obtain the result of enzyme activity through permselective membrane and Nafion® coating electrodes.
    The results of these sensors can meet the requirements of biological and environmental applications. The unique strategies of metal oxide modified electrodes can provide the features of electrochemical schemes in various areas of analysis. And the sequence of oxidative strength among metal oxides can provide for the further application in other fields.

目錄 :
論文提要內容：	I
ABSTRACT:	III
目錄	I
圖目錄	I
表目錄	VII
第一章	緒論	1
1-1	化學感測器與生化感測器	2
1-1-1	感測器的發展與應用	3
1-1-2	化學感測器	5
1-1-3	化學修飾電極	6
1-1-4	修飾電極的特性與功能	11
1-1-5	生化感測器	13
1-1-6	生化感測器的分類	15
1-1-7	電化學生化感測器	18
1-1-8	電化學生化感測器在辨識元固定上的技術	22
1-1-9	干擾物的排除與分析特性提升技術	26
1-1-10	感測器的應用與發展	34
1-2	金屬氧化物	35
1-2-1	金屬氧化物的晶體結構	37
1-2-2	金屬、陶瓷與玻璃	38
1-2-3	複合材料、半導體材料及磁性材料	39
1-3	硼摻雜奈米鑽石電極	40
1-3-1	簡介	40
1-3-2	鑽石薄膜的特性	41
1-3-3	鑽石薄膜之合成	43
1-4	流動注射系統	47
1-4-1	簡介	47
1-4-2	流動注射分析系統的發展與原理	49
1-4-3	儀器組件之組成與選用	49
1-4-4	流動注射分析系統的應用技術	52
1-4-5	流動注射分析系統的未來發展	54
1-5	含氮化合物的重要性	55
1-5-1	簡介	55
1-5-2	環境的氮循環	55
1-5-3	人體的氮代謝	56
1-6	銨根與苯胺	57
1-6-1	簡介	57
1-6-2	銨根的重要性	58
1-6-3	苯胺的應用與毒性	59
1-7	尿酸與肌酸酐	60
1-7-1	簡介	60
1-7-2	尿酸的形成與代謝	60
1-7-3	肌酸酐的形成與代謝	63
1-8	神經傳導物質	66
1-8-1	簡介	66
1-8-2	單一神經元內的訊息傳導	67
1-8-3	神經元與神經元之間的訊息傳遞	69
1-9	菸鹼醯胺腺嘌呤雙核苷酸與去氫酶	72
1-9-1	簡介	72
1-9-2	菸鹼醯胺腺嘌呤雙核苷酸的重要性	72
1-9-3	乳酸脫氫酶	73
1-10	本研究之目的	74
第二章	金屬氧化物之氧化力評估	75
2-1	簡介	75
2-1-1	奈米金屬及金屬氧化物	75
2-1-2	金屬氧化物的反應性	76
2-1-3	氧化力	78
2-1-4	本實驗之研究目的	80
2-2	實驗部分	80
2-2-1	儀器	80
2-2-2	藥品	81
2-2-3	實驗步驟	81
2-3	結果與討論	83
2-3-1	電位法	83
2-3-2	安培法	88
2-3-3	金屬氧化物氧化力表	100
2-3-4	結論	102
第三章	以鋰錳氧化物修飾電極發展多巴胺化學感測器	104
3-1	簡介	104
3-1-1	多巴胺的發現與相關神經傳導物研究	104
3-1-2	多巴胺與其偵測	107
3-1-3	鋰錳氧化物及其應用	109
3-1-4	本實驗之目的	111
3-2	實驗部分	112
3-2-1	儀器	112
3-2-2	藥品	112
3-2-3	實驗步驟	113
3-3	結果與討論	115
3-3-1	本系統的偵測機制	115
3-3-2	金屬氧化物最佳化探討	117
3-3-3	系統操作條件最佳化	118
3-3-4	系統的分析特性探討	128
3-3-5	結論與未來展望	131
第四章	以四氧化三鉛修飾電極發展尿酸化學感測器	133
4-1	簡介	133
4-1-1	尿酸的發現及相關研究	133
4-1-2	尿酸的偵測	134
4-1-3	四氧化三鉛的性質及其應用	140
4-1-4	本實驗之目的	142
4-2	實驗部份	143
4-2-1	儀器	143
4-2-2	藥品	144
4-2-3	實驗步驟	144
4-3	結果與討論	147
4-3-1	金屬氧化物的最佳化	147
4-3-2	偵測機制探討	149
4-3-3	修飾電極的最佳化製備條件	157
4-3-4	操作條件最佳化	159
4-3-5	系統的分析特性探討	167
4-3-6	結論與未來展望	169
第五章	以一氧化二銅修飾電極檢測銨根及組織胺並應用於肌酸酐生化感測器	171
5-1	簡介	171
5-1-1	銨根的相關研究及偵測	172
5-1-2	組織胺的相關研究及偵測	179
5-1-3	肌酸酐的相關研究及偵測	183
5-1-4	一氧化二銅的性質及應用	188
5-1-5	本實驗之目的	191
5-2	實驗部份	192
5-2-1	儀器	192
5-2-2	藥品	192
5-2-3	實驗步驟	193
5-3	結果與討論：銨根化學感測器	196
5-3-1	金屬氧化物對於銨根偵測的催化特性評估	196
5-3-2	電化學偵測機制的探討	198
5-3-3	銨根感測器的最佳化製備條件探討	202
5-3-4	銨根化學感測器的操作條件最佳化	203
5-3-5	銨根化學感測器的分析特性	211
5-4	結果與討論：組織胺化學感測器	214
5-4-1	金屬氧化物對於組織胺的催化特性評估	214
5-4-2	電化學偵測機制的探討	216
5-4-3	組織胺感測器的最佳化製備條件探討	218
5-4-4	組織胺化學感測器操作條件最佳化	220
5-4-5	組織胺化學感測器的分析特性	226
5-5	結果與討論：肌酸酐生化感測器	230
5-5-1	金屬氧化物對於肌酸酐的催化特性評估	230
5-5-2	電化學偵測機制的探討	232
5-5-3	肌酸酐感測器的最佳化製備條件探討	235
5-5-4	肌酸酐生化感測器的操作條件最佳化	237
5-5-5	肌酸酐生化感測器的分析特性探討	243
5-6	結論與未來展望	247
第六章	以四氧化三錳修飾電極發展NADH化學感測器及乳酸脫氫酶生化感測器	249
6-1	簡介	249
6-1-1	菸鹼醯胺腺嘌呤雙核苷酸的相關研究及其偵測	250
6-1-2	乳酸脫氫酶的相關研究及其活性偵測	257
6-1-3	四氧化三錳的性質及應用	261
6-1-4	本實驗之目的	263
6-2	實驗部份	264
6-2-1	儀器	264
6-2-2	藥品	265
6-2-3	實驗步驟	266
6-3	結果與討論：NADH化學感測器	269
6-3-1	金屬氧化物的催化特性評估	269
6-3-2	電化學偵測機制探討	272
6-3-3	修飾電極的最佳化製備條件	275
6-3-4	操作條件最佳化	277
6-3-5	系統的分析特性探討	284
6-3-6	結論與未來展望	287
6-4	結果與討論：LDH酵素活性感測器	288
6-4-1	電化學偵測機制的建立	288
6-4-2	修飾電極的最佳化製備條件	291
6-4-3	操作條件最佳化	294
6-4-4	系統的分析特性探討	300
6-4-5	結論與未來展望	303
第七章	結論	305
符號對照表	309
參考資料：	311

圖目錄 :
( 1 ) 圖1-1  場效應電晶體元件應用於電位法的量測模式示意圖。	19
( 2 ) 圖1-2  環境中的氮循環示意圖。	55
( 3 ) 圖1-3  與尿酸相關的相關循環及代謝過程	62
( 4 ) 圖2-1  電位法量測之簡單示意圖及相關電極、儀器架設。	83
( 5 ) 圖2-2(A)  電位量測法中，金屬氧化物( PbO2 )組成探討，實驗在0.1 M pH 7的磷酸鹽下進行，並添加0.1 M 氯化鈉。	84
( 6 ) 圖2-2(B)  電位量測法中，氯化鈉電解質的添加濃度探討，實驗在0.1 M pH 7的磷酸鹽下進行，指示電極修飾90 % PbO2。	85
( 7 ) 圖2-3  電化學流動注射分析系統及其雙電極形式與運用。	88
( 8 ) 圖2-4  在安培法中，金屬氧化物( PbO2 )的組成探討，在施加–0.2 V的電位下，以0.1 M pH 7的磷酸鹽並添加0.1 M 氯化鈉的溶液進行實驗，而流速及樣品體積分別為0.75 mL/min及50 μL，注入0.5 mM的亞鐵氰化鉀進行分析。	90
( 9 ) 圖2-5  在安培法中，亞鐵氰化鉀分析濃度探討，以90 % PbO2修飾電極，在施加–0.2 V的電位下，以0.1 M pH 7的磷酸鹽並添加0.1 M 氯化鈉的溶液進行實驗，而流速及樣品注射體積分別為0.75 mL/min及50 μL。	91
( 10 ) 圖2-6  在安培法中，下游電極施加電位探討。以90 % PbO2修飾電極，分析0.5 mM亞鐵氰化鉀，以0.1 M pH 7的磷酸鹽並添加0.1 M 氯化鈉的溶液進行實驗，而流速及樣品體積為0.75 mL/min及50 μL。	93
( 11 ) 圖2-7  在安培法中，電解質流速探討。以90 % PbO2修飾電極，分析0.5 mM亞鐵氰化鉀，在–0.2V偵測電位，以0.1 M pH 7的磷酸鹽並添加0.1 M 氯化鈉的溶液進行實驗，而樣品體積為50 μL。	96
( 12 ) 圖2-8  在安培法中，分析物注射體積探討。以90 % PbO2修飾電極，分析0.5 mM亞鐵氰化鉀，在–0.2V偵測電位，以0.1 M pH 7的磷酸鹽並添加0.1 M 氯化鈉的溶液進行，而流速為0.75 mL/min。	97
( 13 ) 圖2-9  在安培法中，亞鐵氰化鉀的校正曲線及實際響應。以90 % PbO2修飾電極，分析0.5 mM亞鐵氰化鉀，在–0.2V偵測電位，以0.1 M pH 7的磷酸鹽並添加0.1 M 氯化鈉的溶液進行，而流速及樣品體積為0.75 mL/min及50 μL。	99
( 14 ) 圖2-10  pH 3的環境下，兩電化學技術所得氧化力的相關性。	101
( 15 ) 圖2-11  pH 7的環境下，兩電化學技術所得氧化力的相關性。	101
( 16 ) 圖2-12  pH 11的環境下，兩電化學技術所得氧化力的相關性。	102
( 17 ) 圖3-1  以空白玻璃碳電極對於5 mM多巴胺掃描的循環伏安圖，溶液配置於0.1 M pH 7電解質中，掃描速率為50 mV/s。	115
( 18 ) 圖3-2  上游修飾電極鋰錳氧化物之組成探討。偵測系統以50 μL注射體積、0.5 mL/min流速，在下游電極外加–0.1V電壓，以0.05M pH 6的磷酸鹽外加0.1M氯化鈉的溶液進行偵測。	119
( 19 ) 圖3-3  安培法量測中，下游電極偵測電位探討。偵測系統以50 μL注射體積、0.5 mL/min流速，在上游電極修飾90 % LiMn2O4，以0.05M pH 6的磷酸鹽外加0.1M氯化鈉的溶液進行偵測。	121
( 20 ) 圖3-4  安培法量測中，緩衝溶液pH值探討。偵測系統以50 μL注射體積、0.5 mL/min流速，在上游電極修飾90 % LiMn2O4，下游電極施加–0.1V工作電位，以0.05M的磷酸鹽外加0.1M氯化鈉的溶液進行偵測。	123
( 21 ) 圖3-5  在安培法量測中，電解質緩衝溶液之流速探討。偵測系統以50 μL注射體積，在上游電極修飾90 % LiMn2O4，下游電極施加–0.1V工作電位，以0.05M pH 6的磷酸鹽外加0.1M氯化鈉的溶液進行偵測。	126
( 22 ) 圖3-6 在安培法量測中，樣品取樣體積探討。偵測系統以0.5 mL/min流速，在上游電極修飾90 % LiMn2O4，下游電極施加–0.1V工作電位，以0.05M pH 6的磷酸鹽外加0.1M氯化鈉的溶液進行電化壆偵測。	127
( 23 ) 圖3-7  在安培法量測中，多巴胺的校正曲線及實際響應訊號。偵測系統以0.5 mL/min流速及50 μL注射體積，在上游電極修飾90 % LiMn2O4，下游電極施加–0.1V工作電位，以0.05 M pH 6的磷酸鹽外加0.1 M氯化鈉的溶液進行偵測。	129
( 24 ) 圖3-8  在流注系統中對於0.5 mM多巴胺進行定電位連續式偵測，觀察(a)飽和溶氧、(b)一般溶氧及(c)除氧環境下，訊號響應的變化。偵測系統以0.5 mL/min流速，在上游電極修飾90 % LiMn2O4，下游電極施加–0.1V工作電位進行偵測，並以0.05 M pH 6的磷酸鹽外加0.1 M氯化鈉作為電解質溶液。	131
( 25 ) 圖4-1  以空白玻璃碳電極對於0.5mM尿酸(B)及空白溶液(A)進行掃描的伏安圖，溶液條件為0.1 M pH 7磷酸鹽電解質溶液。	147
( 26 ) 圖4-2  尿酸在水溶液中進行氧化降解相關反應之結構變化示意圖。	150
( 27 ) 圖4-3  以流注系統搭配雙電極模式證明偵測機制。每次注射尿酸0.5mM，在緩衝溶液帶動下由左側電極流至右側電極，實線箭頭表示施加– 0.1 V偵測電位，虛線箭頭表示施加0.8 V氧化電位。	151
( 28 ) 圖4-4  以流注系統搭配單電極偵測模式在Pb3O4修飾電極上探討干擾物。每次注射不同分析樣品0.5 mM，實線箭頭表示施加–0.1 V偵測電位。	153
( 29 ) 圖4-5  以旋轉雙電極系統證明偵測機制可行性，以三種情況分別探討(A)空白環電極施加– 0.1 V偵測；(B)50 % Pb3O4修飾環電極施加– 0.1 V偵測；(C)空白盤電極施加0.8 V氧化處理電位，50 % Pb3O4修飾環電極施加– 0.1 V偵測。在0.1 M pH 6磷酸緩衝溶液下，轉速固定為625 rpm，連續注入尿酸0.5 mM進行分析。	155
( 30 ) 圖4-6  在本實驗中，尿酸還原偵測的電子傳遞機制示意圖。	156
( 31 ) 圖4-7  以循環伏安法探討尿酸偵測的可行性，修飾電極為50 % Pb3O4，靜置情況下連續添加0.5 mM尿酸分析物於0.1 M pH 6磷酸緩衝溶液中，掃描速率50 mV/s。	156
( 32 ) 圖4-8  Pb3O4修飾比例組成探討，在– 0.1 V工作電壓下注射尿酸進行分析，溶液為0.1 M pH 6磷酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與100 μL。	158
( 33 ) 圖4-9  系統偵測電位探討，以90 % Pb3O4修飾電極對於0.5 mM尿酸進行分析，溶液為0.1 M pH 6磷酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與100 μL。	160
( 34 ) 圖4-10  溶液酸鹼值探討，以90 % Pb3O4修飾電極在– 0.1 V施加電位下對於0.5 mM尿酸進行分析，溶液為0.1 M磷酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與100 μL。	162
( 35 ) 圖4-11  系統流速探討，以90 % Pb3O4修飾電極在– 0.1 V施加電位下對於0.5 mM尿酸進行分析，溶液為0.1 M pH 6磷酸鹽溶液，樣品注射體積為100 μL。	164
( 36 ) 圖4-12  系統注射分析樣品體積探討，以90 % Pb3O4修飾電極在– 0.1 V施加電位下對於0.5 mM尿酸進行分析，溶液為0.1 M pH 6磷酸鹽溶液，溶液流速為0.25 mL/min。	166
( 37 ) 圖4-13  本系統對於尿酸分析的校正曲線及實際響應訊號，以90 % Pb3O4修飾電極在– 0.1 V施加電位下，對於各種尿酸濃度進行分析，溶液為0.1 M pH 6磷酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與100 μL。	168
( 38 ) 圖5-1  以循環伏安法探討在50 % Cu2O修飾電極下(B)及空白玻璃碳電極下(A)的電化學行為，系統靜置於0.1 M pH 7磷酸鹽緩衝溶液中，掃描速率固定為50 mV/s。	199
( 39 ) 圖5-2  以循環伏安法探討在50 % Cu2O修飾電極下，偵測銨根的可行性，而系統靜置於0.1 M pH 10磷酸鹽緩衝溶液中，並連續添加1 mM氯化銨，掃描速率為50 mV/s。	200
( 40 ) 圖5-3  本實驗中利用Cu2O催化氨進行氧化偵測的電子傳遞機制示意圖。	201
( 41 ) 圖5-4  Cu2O修飾比例組成探討，在0.15 V工作電壓下注射0.5 mM氯化銨進行分析，溶液為0.05 M pH 10碳酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與20 μL。	202
( 42 ) 圖5-5  系統偵測電位探討，以60 % Cu2O修飾電極對0.5 mM氯化銨進行分析，溶液為0.05 M pH 10碳酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與20μL。	204
( 43 ) 圖5-6  緩衝溶液酸鹼值探討，以60 % Cu2O修飾電極對0.5 mM氯化銨進行分析，在操作電位150 mV下，溶液為0.05 M 的碳酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與20μL。	206
( 44 ) 圖5-7  系統流速探討，以60 % Cu2O修飾電極對0.5 mM氯化銨進行分析，在操作電位150 mV下，溶液為0.05 M pH 10的碳酸鹽溶液，樣品注射體積固定為20μL。	208
( 45 ) 圖5-8  注射樣品體積探討，以60 % Cu2O修飾電極對0.5 mM氯化銨進行分析，在操作電位150 mV下，溶液為0.05 M pH 10的碳酸鹽溶液，溶液流速固定為0.5 mL/min。	210
( 46 ) 圖5-9  銨根化學感測器的校正曲線及訊號響應圖，以60 % Cu2O修飾電極在150 mV施加電位下，對各種銨根濃度進行分析，溶液環境為0.05 M pH 10碳酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與20 μL。	212
( 47 ) 圖5-10  以循環伏安法探討在50 % Cu2O修飾電極下，偵測組織胺的可行性，而系統靜置於0.1 M pH 10磷酸鹽緩衝溶液中，並連續添加0.5 mM組織胺，掃描速率為50 mV/s。	217
( 48 ) 圖5-11  本實驗中利用Cu2O催化組織胺進行氧化偵測的電子傳遞機制示意圖。	217
( 49 ) 圖5-12  Cu2O修飾比例組成探討，在0.2 V工作電壓下注射0.5 mM組織胺進行分析，溶液為0.2 M pH 10磷酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與20 μL。	219
( 50 ) 圖5-13  系統偵測電位探討，以50 % Cu2O修飾電極對0.5 mM組織胺進行分析，溶液為0.2 M pH 10磷酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與20μL。	220
( 51 ) 圖5-14  溶液酸鹼值探討，以50 % Cu2O修飾電極對0.5 mM組織胺進行分析，在200 mV偵測電位下，溶液為0.2 M磷酸鹽溶液，流速與樣品注射體積則固定為0.5mL/min與20μL。	222
( 52 ) 圖5-15  系統流速探討，以50 % Cu2O修飾電極對0.5 mM組織胺進行分析，在200 mV偵測電位下，溶液為0.2 M pH 10磷酸鹽溶液，樣品注射體積固定為20μL。	224
( 53 ) 圖5-16  系統流速探討，以50 % Cu2O修飾電極對0.5 mM組織胺進行分析，在200 mV偵測電位下，溶液為0.2 M pH 10磷酸鹽溶液，溶液流速固定為0.5 mL/min。	226
( 54 ) 圖5-17  組織胺化學感測器的校正曲線及實際響應訊號，系統以50 % Cu2O修飾電極在200 mV施加電位下對各種組織胺濃度進行分析，溶液環境為0.2 M pH 10磷酸鹽溶液，流速與樣品注射體積為0.5 mL/min與20 μL。	227
( 55 ) 圖5-18  以氧化模式進行肌酸酐偵測的電子傳遞機制示意圖，本偵測系統利用creatinine deiminase結合Cu2O修飾電極所發展的生化感測器。	234
( 56 ) 圖5-19  creatinine deiminase修飾組成探討，在0.15 V工作電壓下注射0.5 mM肌酸酐進行分析，溶液為0.05 M pH 10碳酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與100 μL。	235
( 57 ) 圖5-20  固定酵素為0.5 unit下，1 % BSA及2 % glutaraldehyde交聯體積比例組成探討，在0.15 V工作電壓下注射0.5 mM肌酸酐進行分析，溶液為0.05 M pH 10碳酸鹽溶液，流速與樣品注射體積固定為0.5mL/min與100 μL。	237
( 58 ) 圖5-21  緩衝溶液酸鹼值探討，在最佳化電極製備條件下，對於0.5 mM肌酸酐進行分析，在操作電位150 mV下，溶液為0.05 M 的碳酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與100 μL。	239
( 59 ) 圖5-22系統流速探討，在最佳化電極製備條件下，對於0.5 mM肌酸酐進行分析，在操作電位150 mV下，溶液為0.05 M pH 10的碳酸鹽溶液，樣品注射體積固定為100 μL。	241
( 60 ) 圖5-23  注射分析樣品體積探討，在最佳化電極製備條件下，對於0.5 mM肌酸酐進行分析，在操作電位150 mV下，溶液為0.05 M pH 10的碳酸鹽溶液，溶液流速固定為0.5 mL/min。	243
( 61 ) 圖5-24  肌酸酐生化感測器的校正曲線，以60 % Cu2O修飾電極在150 mV施加電位下對各種肌酸酐濃度進行分析，溶液環境為0.05 M pH 10碳酸鹽溶液，流速與樣品注射體積固定為0.5 mL/min與100 μL。	244
( 62 ) 圖6-1  以循環伏安法探討在空白碳墨修飾旋轉玻璃碳工作電極下，對於空白緩衝溶液(A)及1 mM NADH(B)進行掃描，並觀察其電化學行為，系統靜置於0.1 M pH 7.5磷酸鹽緩衝溶液中，掃描速率為50 mV/s。	270
( 63 ) 圖6-2  本實驗中利用Mn3O4修飾電極催化NADH進行氧化偵測的電子傳遞機制示意圖。	273
( 64 ) 圖6-3  以循環伏安法探討在50 % Mn3O4修飾電極下，於0.1 M pH 7.5磷酸鹽緩衝溶液中，觀察NADH偵測的可行性；其中(A)為空白緩衝溶液，(B)到(E)為連續添加0.5 mM NADH所得，掃描速率固定為50 mV/s。	274
( 65 ) 圖6-4  Mn3O4修飾比例組成探討，在0.2 V工作電壓下注入0.1 mM NADH進行分析，溶液為0.1M pH 7.5磷酸鹽溶液，電極轉速為625 rpm。	276
( 66 ) 圖6-5  系統偵測電位探討，以70 % Mn3O4修飾電極對於0.1 mM NADH進行分析，溶液為0.1 M pH 7.5磷酸鹽溶液，電極轉速為625 rpm。	278
( 67 ) 圖6-6  抗壞血酸的偵測電位探討，以70 % Mn3O4修飾電極對於0.1 mM 抗壞血酸進行分析，其他操作條件同上圖所述。	279
( 68 ) 圖6-7  Nafion®覆蓋體積探討，以70 % Mn3O4修飾電極覆蓋不同體積的5 % Nafion®，在0.2 V施加電位下對於0.1 mM NADH(A)及抗壞血酸(B)進行分析，溶液為0.1 M pH 7.5磷酸鹽溶液，電極轉速為625 rpm。	280
( 69 ) 圖6-8  溶液酸鹼值探討，以70 % Mn3O4修飾電極，在0.2 V施加電位下對於0.1 mM NADH進行分析，配製各種pH的0.1 M磷酸鹽溶液，電極轉速固定為625 rpm。	281
( 70 ) 圖6-9  電極轉速探討，以70 % Mn3O4修飾電極，在0.2 V施加電位下探討各轉速下的訊號響應，溶液為0.1 M pH 7.5磷酸鹽，並對於相同的0.1 mM NADH溶液偵測。	284
( 71 ) 圖6-10  NADH化學感測器的校正曲線及實際響應，以70 % Mn3O4修飾電極在200 mV施加電位下連續添加50 mM NADH進行偵測，溶液環境為0.1 M pH 7.5磷酸鹽溶液，電極轉速625 rpm。	285
( 72 ) 圖6-11  以氧化模式進行LDH酵素活性量測的電子傳遞機制示意圖，本偵測系統透過定電位安培法建立LDH的直接量測模型。	291
( 73 ) 圖6-12  0.1 M NAD+修飾體積探討，在0.25 V工作電位下注射2 units LDH於添加有10 mM乳酸的10 mL 0.1 M pH 7.5磷酸鹽溶液中進行分析，電極轉速固定為625 rpm。	292
( 74 ) 圖6-13  1 % PEI修飾體積探討，在0.25 V工作電位下注射2 units LDH於添加有10 mM乳酸的10 mL 0.1 M pH 7.5磷酸鹽溶液中進行分析，電極轉速固定為625 rpm。	293
( 75 ) 圖6-14  1 % Glutaraldehyde修飾體積探討，在0.25 V工作電位下注射2 units LDH於添加有10 mM乳酸的10 mL 0.1 M pH 7.5磷酸鹽溶液中進行分析，電極轉速固定為625 rpm。	294
( 76 ) 圖6-15  系統偵測電位探討，以70 % Mn3O4為主的最佳化組成修飾電極，在各探討的工作電位下注射2 units LDH，並於添加有10 mM乳酸的10 mL 0.1 M pH 7.5磷酸鹽溶液中進行分析，電極轉速固定為625 rpm。	295
( 77 ) 圖6-16  溶液酸鹼值探討，以70 % Mn3O4為主的最佳化組成修飾電極，在0.25 V工作電位下注射2 units LDH，並於添加有10 mM乳酸的10 mL 0.1 M各pH下的磷酸鹽溶液進行分析，電極轉速固定為625 rpm。	297
( 78 ) 圖6-17  電極轉速探討，以70 % Mn3O4為主的最佳化組成修飾電極，在0.25 V工作電位下對於各種電極轉速進行探討，並注射2 units LDH於添加有10 mM乳酸的10 mL 0.1 M pH 7.5的磷酸鹽溶液進行分析。	300
( 79 ) 圖6-18  LDH酵素活性感測器的校正曲線及實際響應訊號，以70 % Mn3O4為主的最佳化組成修飾電極，在0.25 V工作電位下連續注射LDH酵素，並於添加有10 mM乳酸的10 mL 0.1 M pH 7.的磷酸鹽溶液進行分析，電極轉速固定為625 rpm。	301

表目錄 :
[ 1 ] 表2-1  以電位法對各種金屬氧化物在pH 3、7、11溶液下所得的電位響應值(單位：V)，實驗在0.1 M的磷酸鹽溶液下進行，並添加0.1 M 氯化鈉，金屬氧化物皆修飾90 %於指示電極上。	87
[ 2 ] 表2-2  安培法對各種金屬氧化物在各pH的量測結果(單位：μA)	100
[ 3 ] 表3-1  各種金屬氧化物對於各種分析物的偵測效果評估表。	117
[ 4 ] 表3-2  以本系統相較於其他強氧化劑修飾電極系統，對於多巴胺及各種干擾物的偵測響應比值，單位：%。	130
[ 5 ] 表4-1  固定50%組成條件的各種金屬氧化物修飾電極，在不同偵測電位下(vs. Ag/AgCl)，對於0.5mM的尿酸樣品進行分析。	148
[ 6 ] 表5-1  50 %組成的各種金屬氧化物修飾電極，在不同偵測電位下(vs. Ag/AgCl)，對於0.5 mM氯化銨進行分析；其他操作條件：0.1 M pH 7磷酸鹽緩衝溶液，樣品體積20μL，流速0.5 mL/min。	197
[ 7 ] 表5-2  銨根化學感測系統的最佳化製備、操作條件及系統分析特性。	213
[ 8 ] 表5-3  銨根化學感測系統的干擾物探討，並比較經PbO2氧化處理後的效果。	214
[ 9 ] 表5-4  50 %組成的各種金屬氧化物修飾電極，在不同偵測電位下(vs. Ag/AgCl)，對於0.5 mM組織胺進行分析；其他操作條件：0.1 M pH 7磷酸鹽緩衝溶液，樣品體積20μL，流速0.5 mL/min。	215
[ 10 ] 表5-5  組織胺化學感測系統的最佳化製備、操作條件及系統分析特性。	228
[ 11 ] 表5-6  組織胺化學感測系統的干擾物探討，並比較氧化處理的效果。	229
[ 12 ] 表5-7  50 %組成的各種金屬氧化物修飾電極，在不同偵測電位下(vs. Ag/AgCl)，對於0.5 mM肌酸酐進行分析；其他操作條件：0.1 M pH 7磷酸鹽緩衝溶液，樣品體積20μL，流速0.5 mL/min。	231
[ 13 ] 表5-8  在雙電極流動注射分析模式下，各式酵素固定方式對於肌酸酐偵測時靈敏度與再現性的比較與探討；其他操作條件：50 % Cu2O修飾電極、施加150 mV偵測電位、0.05 M pH 7磷酸鹽緩衝溶液，樣品體積100 μL，流速0.5 mL/min。	233
[ 14 ] 表5-9  肌酸酐生化感測系統的最佳化製備、操作條件及系統分析特性。	245
[ 15 ] 表5-10  肌酸酐生化感測系統的干擾物探討，並比較氧化處理後的效果。	246
[ 16 ] 表6-1  50 %組成的各種金屬氧化物修飾電極，在不同偵測電位下(vs. Ag/AgCl)，對於0.1 mM NADH進行分析；其他操作條件：0.1 M pH 7.5磷酸鹽緩衝溶液，轉速625 rpm。	271
[ 17 ] 表6-2  NADH化學感測器的最佳化製備、操作條件及系統分析特性。	286
[ 18 ] 表6-3  在旋轉電極系統中，各種NAD+固定方式對於LDH酵素偵測時靈敏度與再現性的比較與探討；其他操作條件：70 % Mn3O4修飾電極並覆蓋5 μL 5 % Nafion®及5 μL 0.1 M NAD+，在施加200mV偵測電位，625 rpm 轉速下，置於含有10 mM乳酸的0.1 M pH 7.5磷酸鹽溶液中偵測。	290
[ 19 ] 表6-4  LDH酵素活性感測器的最佳化製備、操作條件及系統分析特性。	302

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