以毛細管電泳螢光光譜法對尿液及藥錠中3,4-亞甲雙氧甲基安非他命(3,4-MDMA)及相關濫用藥物光學異構物之分析研究
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2006
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製備R-(-)-和S-(+)-3,4-MDMA的光學異構物，並以GC-MS鑑認其化學結構與純度之後，以此為標準品，做為毛細管電泳分離分析法時標準添加之用。本研究以毛細管電泳的方式成功分離了R-(-)-和S-(+)-3,4-MDMA及其相關的類似化合物，並探討電泳緩衝溶液中β-CD濃度、有機溶劑比例等電泳，以求得最佳化的分離條件。最後以此做為判定藥錠及尿液中(RS)-MDA和(RS)-MDMA的存在與否的方法，並找出R-(-)-和S-(+)-型藥錠中及尿液代謝物中彼此的相對存在量。
本研究分別比較了水相與非水相毛細管電泳/螢光偵測法在進行光學異構物的分離與在進行線上濃縮時的優缺點，並探討當緩衝溶液中添加不同濃度的ß-CD時，SDS-陰離子界面活性劑與CTAB-陽離子界面活性劑對電泳分離的影響。實驗選用R-(-)-/S-(+)型的MDMA及其相關狡詐家藥物(MDA, DMMDA, MBDB, BDB )做為測試樣品。實驗首先合成並分離了單一型的R-(-)-與S-(+)-MDMA 標準品，經GC/MS及旋光光譜儀鑑定無誤後，做為標準添加之用。電泳分離結果發現，對於水相毛細管電泳在進行光學異構物的分離時發現β-CD與CTAB所組成的溶液(β-CD與SDS所組成的緩衝溶液)對光學異構物的分離效果較佳，可使八種光學異構物達到完全分離的效果。對非水相電泳分離而言，當非水相緩衝溶液使用150 mM CTAB (MeOH：foramide = 7: 3; v/v)時，可使MDA、MDMA、DMMDA、MBDB完全分離。而當非水相緩衝溶液添加150 mM 的β-CD，可使R-(-)-與S-(+)-型等八種光學異構物達到完全分離的效果。實驗並成功鑑定了R-(-)-與S-(+)-MDMA在MDMA藥錠及吸食MDMA者尿液中各異構物存在的比例。此外，當比較水相與非水相毛細管電泳術對線上濃縮技術時發現，以sweeping-MEKC為電泳模式的最佳緩衝溶液條件為SDS 50mM 溶解於含有機修飾劑(MeOH：ACN：H2O = 30 : 7：63 ; v/v/v；pH=2；導電度=4.4ms/cm)的溶液的效果最好。最佳進樣長度為40 cm（毛細管總長87/92cm）時的偵測極限可達1 ppb。但是SDS不適合做為非水相sweeping-MEKC之用；以非水相-stacking的技術，偵測極限仍可達2.6 ×10-8 M。
The R-(-)- and S-(+)-isomers of 3,4-methylenedioxymethamphetamine (MDMA) and its metabolite 3,4-methylenedioxyamphetamine (MDA) were prepared, identified by GC/MS and then used as standards in a series of CE experiments. Using these R-(-)- and S-(+)-isomers, the distribution of (RS)-MDA and (RS)-MDMA stereoisomers in clandestine tablets and suspect urine samples were identified. Several electrophoretic parameters, such as the concentration of -cyclodextrin used in the electrophoretic separation and the amount of organic solvents required for the separation were optimized. A comparison of the use of aqueous and non-aqueous solutions in association with -cyclodextrin for the chiral separation of (R)- and (S)-3,4-methylenedioxymethamphetamine and related compounds is described. The (R)- and (S)-isomers of 3,4-methylenedioxymethamphetamine (MDMA) and its major metabolite 3,4-methylenedioxyamphetamine (MDA) were prepared. Under aqueous and non-aqueous solution conditions and based on the CZE and MEKC modes, the order of migration of (R)-MDA, (S)-MDA, (R)-MDMA and the (S)-MDMA enantioisomers were determined. Several electrophoretic parameters, including the concentration of -cyclodextrin (aqueous, 25 ~ 60 mM; non-aqueous, 20 ~ 150 mM) used in the electrophoretic separation and the amount of organic solvents required for the separation were optimized.
The R-(-)- and S-(+)-isomers of 3,4-methylenedioxymethamphetamine (MDMA) and its metabolite 3,4-methylenedioxyamphetamine (MDA) were prepared, identified by GC/MS and then used as standards in a series of CE experiments. Using these R-(-)- and S-(+)-isomers, the distribution of (RS)-MDA and (RS)-MDMA stereoisomers in clandestine tablets and suspect urine samples were identified. Several electrophoretic parameters, such as the concentration of -cyclodextrin used in the electrophoretic separation and the amount of organic solvents required for the separation were optimized. A comparison of the use of aqueous and non-aqueous solutions in association with -cyclodextrin for the chiral separation of (R)- and (S)-3,4-methylenedioxymethamphetamine and related compounds is described. The (R)- and (S)-isomers of 3,4-methylenedioxymethamphetamine (MDMA) and its major metabolite 3,4-methylenedioxyamphetamine (MDA) were prepared. Under aqueous and non-aqueous solution conditions and based on the CZE and MEKC modes, the order of migration of (R)-MDA, (S)-MDA, (R)-MDMA and the (S)-MDMA enantioisomers were determined. Several electrophoretic parameters, including the concentration of -cyclodextrin (aqueous, 25 ~ 60 mM; non-aqueous, 20 ~ 150 mM) used in the electrophoretic separation and the amount of organic solvents required for the separation were optimized.
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Keywords
毛細管電泳, MDMA, 螢光, 非水相, CTAB, 光學異構物