Key Laboratory of Combinatorial Biosynthesis and Drug Discovery, Ministry of Education, School of Pharmaceutical Sciences, Wuhan University, Wuhan, China.
J Sep Sci. 2013 Jan;36(2):341-9. doi: 10.1002/jssc.201200678. Epub 2012 Dec 18.
A nonaqueous CE-IT MS with a nanospray ionization interface method was developed for the identification and quantification of tetrandrine (TET), fangchinoline (FAN), and sinomenine (SIN) using berberine as internal standard. The TET, FAN, and SIN standard solutions were directly infused into IT-MS for collecting MS(1-3) spectra. The major fragment ions of analytes were confirmed and possible main cleavage pathways of fragment ions were studied. A bare fused-silica capillary was used for separation of the analytes. A sheath liquid (50% aqueous methanol containing 0.2% acetic acid) to the capillary effluent with a nanoelectrospray ionization interface was added. Separation buffer comprised 80 mM solution of ammonium acetate, in a mixture of 70% methanol, 20% ACN, and 10% water, which also contained 1% acetic acid. The CE-MS method was validated for linearity, sensitivity, accuracy, and precision, and then used to determine the content of the above components. The detection limits of TET, FAN, and SIN are 0.05, 0.08, and 0.15 μg/mL, respectively. The precision was no more than 4.67% and the mean recovery of the analytes were 95.36-99.24%. This method was successfully applied to determine TET, FAN, and SIN in real samples radix Stephaniae tetrandrae and rhizomes of Menispermum dauricum.
建立了一种非水毛细管电泳-电喷雾串联质谱（CE-IT-MS）联用分析方法，以小檗碱为内标物，用于同时检测和定量粉防己碱（TET）、蝙蝠葛碱（FAN）和青风藤碱（SIN）。TET、FAN 和 SIN 标准溶液直接注入到 IT-MS 中，采集 MS(1-3)谱。对分析物的主要碎片离子进行了确认，并研究了可能的主要碎片离子裂解途径。采用裸熔融石英毛细管进行分离。将含有 0.2%乙酸的 50%甲醇水溶液作为鞘液添加到毛细管流出液中。分离缓冲液由 80 mM 乙酸铵溶液组成，甲醇、乙腈和水的比例分别为 70%、20%和 10%，其中还含有 1%乙酸。对该 CE-MS 方法进行了线性、灵敏度、准确度和精密度的验证，然后用于测定上述成分的含量。TET、FAN 和 SIN 的检测限分别为 0.05、0.08 和 0.15 μg/mL。精密度不超过 4.67%，分析物的平均回收率为 95.36-99.24%。该方法成功应用于测定粉防己和防己中的 TET、FAN 和 SIN。
