臺灣博碩士論文加值系統

本研究以 2-(pentaflu orophenoxy)ethanol 與
2-chloroethanesulfonyl chloride 於二氯甲烷中, 以三乙基胺為催化
劑進行 elemination (dehydrohalogenation), 所得反應液經處理後再
與 piperidine 進行 Michael type addition, 而合成氣相層析用新衍生
試劑 2-(pentafluorophenoxy)ethyl 2-(piperidino)ethanesullfonate
(PFPES).PFPES 具有親電子性基團及三級胺基團, 利用衍生反應可將親
電子性基團 2-(pentafluorophenoxy)ethyl 標示到待測物上,以進行 GC-
ECD 之高感度分析 ,又殘存之 PFPES 可以酸洗轉換為水溶性之胺鹽而移
除, 因而降低過量 PFPES 對分離及檢測之干擾. 使用薄層層析法.探討
PFPES 之反應性,初步發現 PFPES 對有機物如正戊酸, valproic acid,
benzoic acid, 2-mercaptoethanol, thiophenol, phenol,
chloropamide 及 ethosuximide 以及陰離子如 I-, SCN-, CN- 及 NO2-
具有反應性.本研究進而選擇正戊酸及碘離子分別為勻相和兩相反應的模
式待測物,應用電子捕獲型氣相層析 (GC-ECD) 探討了其基本分析條件.所
得結果如下,(A)在甲苯勻相反應中,正戊酸 (VA) 以 18-crown-6 及碳酸
鉀為催化劑,於 70 與 PFPES 進行衍生反應,所得衍生物以 GC-ECD 進行
分析,結果顯示,其分析感度良好;VA 之定量範圍為 1-20 nmol (於 200
uL 溶液),偵測極限為 170 fmol (sample size: 0.6 uL).(B) 在甲苯及
水兩相反應中,碘離子由水層經 tetrahexylammonium bromide 轉移至甲
苯層,於 70 與 PFPES 進行衍生反應,所得衍生物以 GC-ECD 進行分析,結
果顯示,其分析感度甚佳;碘離子之定量範圍 0.05-1 nmol (於 200 uL 溶
液),偵測極限為 5 fmol (sample size:0.3 uL). 利用衍生反應配合 GC-
ECD,對 PFPES 在活性待測物之應用分析正在檢討中.

A new sulfonate reagent, 2-(pentafluorophenoxy)ethyl
2-(piperidino)ethanesulfonate (PFPES), was synthesized from
2-(pentafluorophenoxy)ethanol, 2-chloroethanesulfonyl chloride
and piperidine base on elemination (dehydrohalogenation) and
Michael type addition. The reagent consists of two moieties, i.
e., one with an electrophore (pentafluorophenoxy)for sensitive
detection after being tagged to an analyte; and the other with a
tertiary amino function (a substituted piperidine) that can be
removed after derivatization by acid treatment. This can
minimize the interference of excess PFPES in GC separation and
ECD detection. The reagent is reactive to n-valeric acid, va;
proic acid, benzoic acid, 2-mercaptoethanol, phenol, thiophenol
and chloropropamide in a homogenous reaction system; and PFPES
is also reactive to iodide, cyanide, nitrite and thiocyanate
anions in a biphasic system checked by thin layer
chromatography. Application of the reagent to the derivatization
of n-valeric acid and iodide anion as test analytes for
capillary GC-ECD was performed. The resulting derivatives are
highly responsive to an electron-capture detector. The linear
range for the determination of n-valeric acid was over 1-20 nmol
(each in 200 uL sample) with detection limit (S/N=3) of about
170 fmol per injection (0.6 uL); and the linear range for the
determination of iodide was over 0.05-1 nmol (each in 200 uL
sample) with a detection limit (S/N=3) of about 5 fmol per
injection (0.3 uL). Application of PFPES to the derivatization
and GC-ECD of active analytes is being investigated.