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- 2018
柑橘种子类柠檬苦素的分析及质谱裂解途径——基于UPLC-Q-TOF-MS的新方法
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Abstract:
柑橘种子富含类柠檬苦素化合物，该类物质表现出多种生物活性.基于UPLC-Q-TOF-MS技术，优化出一种新的柑橘中类柠檬苦素化合物的定性定量检测方法.考察了流动相及流速、进样量、色谱柱温等条件的影响，优化得到分析方法.流动相为0.01%甲酸+H2O（A）以及乙腈（B），在洗脱程序为0~4.0 min，35%~55% B；4.0~5.0 min，55%~35% B，进样量1.0 μL，流速0.4 mL/min，柱温40℃的条件下，7种柑橘种子中诺米林、奥巴叩酮和柠檬苦素在5 min内得到最佳分离.通过与标准品的保留时间和质谱碎片比较，样品中诺米林、奥巴叩酮和柠檬苦素得到鉴定；研究了3种类柠檬苦素的MS/MS质谱裂解规律，并首次得出了诺米林的质谱裂解途径.此外，通过UPLC-PDA检测器，测定了7种柑橘种子中3种类柠檬苦素的质量比.结果显示，类柠檬苦素是一类很好的分类学标记物.
Citrus seeds have high contents of limonoids, which has been reported to show multiple bioactivities. In this work, an optimized method based on UPLC-Q-TOF-MS was applied to the separation and identification of nomilin, obacunone and limonin in citrus seeds of seven cultivars. The separation was achieved within 5 min with the column temperature set at 40℃, the flowing rate 0.4 mL/min and the injection volume 1.0 mL. The binary mobile phases consisted of 0.01% formic acid (A) and acetonitrile (B). The gradient elution was as follows:0-4 min, linear from 35% to 55% B; 4-5 min, from 55% to 35% B for washing and equilibration of the column. Nomilin, obacunone and limonin were identified by comparing the retention time and mass spectral fragmentation with the reference standards. The MS/MS fragmentation patterns of the three limonoids were investigated, and the fragmentation pathway of nomilin was proposed for the first time. In addition, the contents of the three limonoids in the seven different citrus seeds were determined by UPLC-PDA detector. The results showed the limonoids to be excellent taxonomic markers in citrus cultivars
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