摘要
目的对降糖类中成药中发现的非法添加新物质格列波脲进行高分辨质谱确证,并对其质谱裂解机理进行初步研究,为其定性、定量与结构修饰提供参考依据。方法用高分辨质谱仪测定阳性样品及对照品的分子离子,然后对其质荷比进行对比确认;利用ESI^+离子阱液质联用仪测定三级质谱离子碎片,对结果进行裂解规律的分析。结果计算高分辨质谱测定结果的误差,格列波脲对照品和样品[M+H]^+均小于2 ppm,对照品和样品[M+Na]~^+均小于4 ppm。样品与对照品[M+H]^+三级质谱均相同,一级质谱为m/z 367.17;二级质谱分子离子碎片有m/z 349.17、170.11、196.13;m/z 349.17三级质谱的离子碎片有m/z 152.08、135.13;m/z 170.11三级质谱的离子碎片有m/z 152.07、109.02;m/z 196.13三级质谱的离子碎片有m/z 135.04、140.00、109.09、152.14。结论样品中目标物为格列波脲,其易裂解部位主要为苯磺酰脲基团与手性分子桥之间的酰胺键,其次是手性分子桥中的一分子水及甲基。
Objective To determine the MS molecular and ion fragments of glibornuride and to study MS fragment pathways in order to provide reference for qualitative and quantitative research. Methods High resolution mass spectrometry was used to determine and compare the molecular ion of positive and standard samples. ESI^＋ion trap liquid chromatograph / mass spectrometer was used to determine ion fragments before the MS fragment pathways were analyzed. Results According to calculation of the error of high resolution mass spectrometry determination results,the error of the glibornuride standard [M ＋ H]^＋and samples was less than 2 ppm,while the error of the standard and samples[M ＋ Na]^＋was less than 4 ppm. Mass spectrometry [M ＋ H]^＋of the sample and reference substance was the same,The molecular and ion fragments were m / z 367. 17 for MS,m / z 349. 17,170. 11,196. 13 for MS^2; and m/z 349. 17 was m/z 152. 08,135. 13; MS3 fragments of m / z 170. 11 was m / z 152. 07,109. 02; MS^3 fragments of m / z 196. 13 was 135. 04,140. 00,109. 09,152. 14 for MS^3. Conclusion The material detected in the samples is glibornuride. The MS fragment pathway is mainly the amido bond between the benzene sulfonyl urea groups and the chiral molecular bridge,followed by the water molecule and methyl in the chiral molecular bridge.
出处
《解放军药学学报》
CAS
CSCD
2015年第6期481-483,488,共4页
Pharmaceutical Journal of Chinese People's Liberation Army
关键词
降糖类中成药
非法添加
格列波脲
液质联用
裂解规律
hypoglycemic Chinese patent medicine
illegally added
glibornuride
liquid chromatograph / mass spectrometer
MS fragment pathways
