A novel derivatization reagent possessing a bromoquinolinium structure for biological carboxylic acids in HPLC-ESI-MS/MS
A novel derivatization reagent possessing a bromoquinolinium structure for biological carboxylic acids in HPLC-ESI-MS/MS
复制标题
DOI：
10.1002/jssc.201300083
复制
发表时间：
2013-06-01
影响因子：
3.1
通讯作者：
Toyo'oka, Toshimasa
中科院分区：
文献类型：
--
作者：
Mochizuki, Yuko;Inagaki, Shinsuke;Toyo'oka, Toshimasa
合成了一种新的溴代喹啉试剂1-（3-氨丙基）-3-溴代喹啉溴化物（APBQ），用于羧酸的分析。以胆汁酸和游离脂肪酸为生物样品中的代表性羧酸，建立了一种简单实用的柱前衍生化方法。在N，N-二环己基碳二亚胺和吡啶作为活化剂的存在下，APBQ与羧酸在60 ℃下有效地反应60 min。由于APBQ在结构中具有溴原子，因此由于质谱中的特征溴同位素模式，很容易实现一系列羧酸的鉴定。APBQ还具有季胺结构，因此带正电荷的衍生物主要用于羧酸的高灵敏度检测。该方法已成功地应用于人体血浆中生物羧酸的选择性测定。在拟定程序下，通过HPLC-MS合理测定了胆汁酸（鹅去氧胆酸和脱氧胆酸）以及几种饱和（硬脂酸和棕榈酸）和不饱和游离脂肪酸（油酸和亚油酸）。基于人血浆和唾液的分析结果，所提出的方法似乎适用于生物样品中一系列羧酸的定性和定量分析。
A novel bromoquinolinium reagent, i.e. 1-(3-aminopropyl)-3-bromoquinolinium bromide (APBQ), was synthesized for the analysis of carboxylic acids. A simple and practical precolumn derivatization procedure using the APBQ in RP chromatography and MS (HPLC-MS) has been developed using bile acids and free fatty acids, as the representative carboxylic acids in biological samples. The APBQ efficiently reacted with carboxylic acids at 60 degrees C for 60 min in the presence of N,N-dicyclohexylcarbodiimide and pyridine as the activation reagents. Because the APBQ possesses a bromine atom in the structure, the identification of a series of carboxylic acids was easily achieved due to the characteristic bromine isotope pattern in the mass spectra. The APBQ also has a quaternary amine structure, thus the positively charged derivatives are predominate for the highly sensitive detection of carboxylic acids. The APBQ was successfully applied to the selective determination of biological carboxylic acids in human plasma. The bile acids (chenodeoxycholic acid and deoxycholic acid) and several saturated (stearic acid and palmitic acid) and unsaturated free fatty acids (oleic acid and linoleic acid) were reasonably determined by HPLC-MS under the proposed procedure. Based on the results of analyses of human plasma and saliva, the proposed procedure using APBQ seems to be applicable for the qualitative and quantitative analyses of a series of carboxylic acids in biological samples.