HPLC-Q-TOF-MS分析注射用泮托拉唑钠中降解杂质

目的 优化注射用泮托拉唑钠有关物质检查方法,并用高效液相色谱-四级杆飞行时间质谱法(HPLC-QTOF-MS)对注射用泮托拉唑钠中降解杂质进行结构鉴定。方法 采用色谱柱 Waters Symmetry C₁₈(250 mm×4.6 mm,5 μm);流动相：10 mmol·L^-1乙酸铵(用乙酸调节pH至4.5)(A)-乙腈(B),梯度洗脱(0~20 min,B相20%;20~30 min,B相20%→40%;30~45 min,B相40%→30%;45.01~65 min,B相20%);流速：1.0 mL·min^-1;检测波长：289 nm;进样量：20 μL;柱温：35 ℃;离子源：ESI源;扫描模式：正离子模式。结果 优化后有关物质测定方法可有效分离各降解杂质。根据各降解杂质的二级质谱图以及高分辨数据,推测出了4个降解杂质的结构式。结论 所建立的色谱条件可有效检测注射用泮托拉唑钠中的有关物质,降解杂质结构式的确定为该产品稳定性研究提供了技术支持。     

A strategy for rapid discovery of traceable chemical markers in herbal prod-ucts using MZmine 2 data processing toolbox: A case of Jing Liqueur

Objective: The quality evaluation of herbal products remains a big challenge. Traceable markers are the core concept of the authentication of herbal products. However, the discovery of traceable markers is labor-intensive and time-consuming. The aim of this study is to develop a convenient approach to rapidly screen the traceable markers for herbal product authentication. Methods: Commercial Jing Liqueur and its 22 species of herbal ingredients were analyzed using HPLC-QTOF-MS and GC-MS to characterize nonvolatile and volatile chemicals. The acquired data were imported into MZmine 2 software for mass detection, chromatogram building, deconvolution and alignment. The aligned data were exported into a csv file and then traceable markers were selected using the built-in filter function in Excel. Finally, the traceable markers were identified by searching against online databases or publications, some of which were confirmed by reference standards. Results: A total of 288 chemical features transferred from herbal materials to Jing Liqueur product were rapidly screened out. Among them, 52 markers detected by HPLC-QTOF-MS were annotated, while nine volatile markers detected by GC-MS were annotated. Moreover, 30 of these markers were confirmed by comparing with reference standards. A chemical fingerprint consisting of traceable markers was finally generated to ensure the authentication and quality consistency of Jing Liqueur. Conclusion: A strategy for rapid discovery of traceable markers in herbal products using MZmine 2 software was developed.     

基于HPLC-QTOF-MS的环缩肽类rakicidins质谱裂解规律初探

目的和方法 采用高效液相色谱-四级杆-飞行时间质谱(HPLC-QTOF-MS)联用技术,建立了色谱分离、质谱检测的方法,对rakicidin同系物进行碰撞解离研究,推测其质谱裂解规律。结果 获得rakicidins在正离子模式下的质谱裂解规律。结论 该质谱裂解规律可应用于rakicidin及其同系物的快速结构解析、定量分析和药动学研究,以及应用于高通量、快速、高效筛选微生物来源的rakicidin类似物。     

Comprehensive metabolic profiling of Alismatis Rhizoma triterpenes in rats based on characteristic ions and a triterpene database

Alismatis Rhizoma (AR) is widely used in Chinese medicine, and its major bioactive components, triterpenes, reportedly possess various pharmacological activities. Therefore, it is very important to study the metabolism of triterpenes in vivo. However, the metabolism of AR triterpene extract has not been comprehensively elucidated due to its complex chemical components and metabolic pathways. In this study, an ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry method, which was based on the characteristic ions from an established database of known triterpenes, was used to analyze the major metabolites in rats following the oral administration of Alismatis Rhizoma extracts (ARE). As a result, a total of 233 constituents, with 85 prototype compounds and 148 metabolites, were identified for the first time. Hydrogenation, oxidation, sulfate and glucuronidation conjugation were the major metabolic pathways for triterpenes in AR. In addition, the mutual in vivo transformation of known ARE triterpenes was discovered and confirmed for the first time. Those results provide comprehensive insights into the metabolism of AR in vivo, which will be useful for future studies on its pharmacodynamics and pharmacokinetics. Moreover, this established strategy may be useful in metabolic studies of similar compounds.     

HPLC-QTOF-MS法鉴别雷公藤多苷工艺残渣中的化学成分

建立高效液相色谱串联四级杆飞行时间质谱法(HPLC-QTOF-MS)快速鉴定雷公藤多苷柱色谱工艺残渣化学成分。采用Zorbax SB-C₁₈色谱柱(4.6 mm×50 mm,1.8 μm),流动相为乙腈-0.2%甲酸溶液,梯度洗脱,采用ESI-Q-TOF检测,正离子模式扫描。根据色谱峰精确相对分子质量、碎片离子信息及液相色谱保留时间比较鉴别化合物。结果表明,采用HPLC-QTOF-MS法鉴定了雷公藤多苷工艺残渣中30个成分,包括15个生物碱类化合物,10个二萜类化合物,4个三萜类化合物,1个不饱和脂肪酸。本研究工作为雷公藤多苷工艺残渣的综合开发利用提供定性分析依据。     

HPLC法测定苯磺酸氨氯地平片的含量及其有关物质

目的：建立与质谱体系相兼容的高效液相色谱法测定苯磺酸氨氯地平片的含量及有关物质。方法：采用CAPCELL PAK C18色谱柱（250 mm×4.6 mm,5μm）,以甲醇-20 mmol·L-1醋酸铵溶液（60∶40）为流动相,检测波长为237 nm,流速为1.0 ml·min^-1,柱温35℃,进样量20μl。同时,采用液相色谱-四级杆飞行时间质谱联用（HPLC-QTOF MS）对氨氯地平的主要有关物质进行定性研究。结果：在该色谱条件下制剂中其他成分不干扰测定,杂质峰和氨氯地平峰达到有效分离度,苯磺酸氨氯地平在10-100μg·ml^-1范围内线性关系良好（r=0.999 8）,平均回收率为99.2%（RSD=1.0%,n=9）。HPLC-QTOF MS可以对氨氯地平的主要有关物质进行结构确证。结论：本法准确、可靠、重复性好,可用于控制苯磺酸氨氯地平片的质量。     

Metabolite Characterization of Penta-O-galloyl-??￠-D-glucose in Rat Biofluids by HPLC/QT of MS

Objective: To understand the in vivo metabolic fate of 1,2,3,4,6-Penta-O-galloyl-β-d-glucose(PGG)naturally existed in many medicinal herbs and food plants such as Rhus chinensis,Paeonia suffruticosa,Paeonia lactiflora and Mango.Methods: The metabolites of PGG in rat biofluids were characterized using high performance liquid chromatography combined with quadrupole time-of-flight tandem mass spectrometry(HPLC-QTOF-MS).Results: Ten metabolites in urine,five metabolites in feces and two metabolites in plasma,were observed when the rats were administrated with a single intravenous injection of PGG(20 mg/kg).Conclusion: PGG is firstly metabolized to gallic acid,then gallic acid undergoes sulfation,glucuronidation and methylation by rat liver.The determination of metabolites and the proposed metabolic pathway of PGG in vivo will be benefit to gain deeper insights into its pharmacological activities.