在分析過程中，樣品的前處理技術不僅影響實驗的結果且左右著整體實驗上時間及金錢的消耗，故如何去選擇一個快速、環保及符合經濟成本的前處理技術仍為現今最炙手可熱之話題，在此本論文提供兩種微萃取的技術分別連接於大氣壓基質輔助雷射脫離子阱附質譜儀及毛細管電泳儀。 第一個部分我們開發一新穎的一滴溶劑萃取一滴樣品之超微量萃取法(DDSME)結合大氣壓基質輔助雷射脫附離子阱質譜(AP-MALDI-Ion Trap)以快速分析水中、尿中及血中的尼福密酸(Niflumic Acid)，其中對於影響萃取的因子如有機溶劑、基質(α-cyano-4-hydroxy cinnamic acid, α-CHCA)濃度、萃取時間、水溶液的pH 值及鹽類添加效應逐一進行探討，在選用辛烷做為萃取溶劑、5000ppm 的α-CHCA、萃取時間十分鐘、pH 值為8.5 及不添加任何鹽類的最佳化的條件下，我們可測得水中、尿中及血中的偵測極限分別為0.1ng/mL、1ng/mL 及40ng/mL，此技術不僅提供一快速且高靈敏度的新萃取技術，並可作為藥物濃縮探針的有效方法。 第二部分我們利用一滴溶劑微萃取法(SDME)結合毛細管電泳儀對於不同基質中的三環系列藥物進行鑑別，萃取過程中欲分析物經由一滴溶劑微萃取法的有機溶劑萃取獲得，再藉由氮氣將溶劑吹乾並將欲分析物以毛細電泳所需緩衝溶液回溶，最後將樣品進樣以進行分析，其中萃取前水樣先經由氨水鹼化，藉此促進分析物萃取效率。在本研究中亦對五個影響萃取效率的因子(溶劑種類、萃取時間、磁石轉速、水溶液的pH 值及鹽類添加效應)分別進行探討，與傳統的液相-液相萃法取及固相萃取法相較之下此技術不僅操作簡易且符合經濟成本，此外完全無樣品殘留之顧慮，有效節約實驗成本及降低實驗過程中產生的對實驗人員的傷害和對環境的污染。 Excellent sample preparation techniques not only concern the fruitful results but also time and cost of experiments. Thus, it is a big challenge to develop a rapid and low cost of sample preparation method. There are two types of microextraction techniques developed in this thesis to couple with atmospheric pressure matrix assisted laser desorption mass spectrometry (AP-MALDI/MS) and capillary electrophoresis (CE) for analysis of drugs. The first one is a novel microextraction technique termed drop to drop solvent microextraction (DDSME) to couple to AP-MALDI/MS for the determination of niflumic acid in water, human urine and plasma. The effects of extraction solvent, concentration of α-cyano-4-hydroxy cinnamic acid, sampling time, pH and salt addition on the extraction efficiency were investigated and optimized. The best optimum conditions for the DDSME method were using octanol as extraction solvent, 5000 ppm of α-cyano-4-hydroxy cinnamic acid, 10 min of sampling time, pH of 8.5 and without salt addition. The limits of detection (LOD) of this method were in the range of 0.1 to 40 ng/ml. This method is not only a fast and sensitivity technique but also can be used as concentrating probe of drug. The second project is to combine the single drop microextraction (SDME) with capillary electrophoresis for the analysis of tricyclic antidepressant drugs in various matrixes including water and urine. These samples were extracted into organic solvent suspended in a stirred aqueous solution from the tip of a moicrosyringe needle. Nitrogen gas was used to remove the organic solvent, and then the buffer solution was used in capillary electrophoresis to re-dissolve samples. Prior to SDME, the aqueous solution was treated with ammonium hydroxide in order to promote extraction efficiency. The effects of extraction solvent, sampling time, sample agitation rate, pH and salt addition on the extraction efficiency were examined and optimized. This technique is simpler and cheaper than the traditional liquid-liquid extraction and solid phase extraction techniques.