林震煌Cheng-Huang Lin蕭瑤Yao Shiao2019-09-04不公開2019-09-042009http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN0696420507%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/100722本實驗以液相層析/紫外光吸收法及液相層析/電灑游離質譜法對十八種苯乙胺類及色胺類濫用藥物進行分離及偵測。整體的分析時間約 25 分鐘，液相層析所使用的沖提液為 0.1 % 甲酸水溶液 (pH=2.5) 和乙腈。液相層析/紫外光吸收法 (波長為 280 nm) 的偵測極限 (S/N = 3) 為 0.3~3 μg/mL。液相層析/電灑游離質譜法對十八種濫用藥物中一級胺、二級胺及三級胺分析樣品的偵測極限分別為 0.1 ~3.0、0.1~0.2 及 0.05~1.8 μg/mL。三級胺結構的分析物由於在電灑的過程中離子化效果較佳，故偵測極限較低。為了提升一級胺及二級胺分析物在液相層析質譜儀中的偵測極限，我們以醋酸酐作為衍生試劑將分析物進行衍生。在本研究中建立了十八種濫用藥物及經衍生後產物在電灑游離下的特徵斷裂譜峰。真實樣品的部分，取一健康者的尿液加入十八種混合的濫用藥物，以液液萃取及衍生作樣品前處理，並以液相層析/紫外光吸收法及液相層析/電灑游離質譜法進行分析，而實驗中的分離條件及偵測方法已最佳化。he optimal conditions for the separation and detection of a mixture of 18 phenethylamine/tryptamine derivatives were determined, using liquid chromatography/UV-absorption (LC/UV) and liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) methods, respectively. Complete separation could be achieved within ~25 min using gradient elution (A, 0.1% formic acid aqueous solution/pH, 2.5; B, acetonitrile). The limit of detection (LOD at S/N = 3) obtained by LC/UV-absorption (absorption wavelength, 280 nm) was in the range from 0.3 to 3 μg/mL. In contrast, when the LC/ESI MS method was used, the LODs for primary, secondary and tertiary amines were in the ranges 0.1-3.0, 0.1-0.2 and 0.05-1.8 μg/mL, respectively. The lower LOD obtained for a tertiary amine can be attributed to the fact that its ionization efficiency (during the ESI process) is better than the others. In order to improve the LOD of a primary/secondary amine, a derivatization procedure was used in which the chemical structure was altered to a secondary/tertiary amine, via a reaction with acetic anhydride. As a result, the LODs for primary/secondary amines could be significantly improved. The characteristic mass fragmentations of the 18 phenethylamine /tryptamine derivatives, as well as the products of the reaction with acetic anhydride, were investigated, and the data were reported. A urine sample was obtained by spiking urine from a volunteer with the 18 derivatives, and after liquid-liquid extraction the sample was examined by LC/UV and LC/ESI-MS, respectively. The extraction procedures used for the urine sample and the experimental conditions for the separation and detection were optimized.色胺類苯乙胺類液相層析質譜法TryptamineLC/MS