Chemical profiling of composite prescription caraway and quantification of three pairs isomeric components in caraway administered rat plasma by tandem mass spectrometry.

Caraway, a well-known traditional Uyghur medicine, has been used to treat vitiligo for centuries. Its biological effects on melanin synthesis of caraway have been investigated. However, beyond psoralen and isopsoralen alone, no further chemical component of caraway has been revealed. In this study, ultra-high performance liquid chromatography coupled with hybrid quadrupole orbitrap mass spectrometry was employed to comprehensively characterize the chemical components present in caraway. Based on accurate mass measurements, key fragmental ions and comparison with reference standards, 75 chemical components were identified in caraway. Moreover, a tandem mass spectrometry method was developed and validated for quantitative analysis of three pairs isomeric components, namely psoralen/isopsoralen, bavachin/isobavachalcone and bavachromene/isobavachromene in rat plasma. Psoralen, isopsoralen, bavachin, and isobavachalcone showed linearity with concentration ranging of 1.0-500.0 ng/ml. The linear ranges for bavachromene and isobavachromene were 0.2-500.0 ng/ml. The accuracies were in ranges of 85%-115% with coefficient of variation errors of less than 15%. Furthermore, the method was applied to quantify the three pairs isomeric components in rats after oral administration of caraway.

Chemical Profiling of Kaliziri Injection and Quantification of Six Caffeoyl Quinic Acids in Beagle Plasma by LC-MS/MS.

Vitiligo is a stubborn multifactorial skin disease with a prevalence of approximately 1% in the global population. Kaliziri, the seeds of Vernonia anthelmintica (L.) Willd., is a well-known traditional Uyghur medicine for the treatment of vitiligo. Kaliziri injections is a Chinese-marketed treatment approved by the China Food and Drug Administration for the treatment of vitiligo. The significant effects of Kaliziri injection have been thoroughly studied. However, chemical components studies and plasma quantification studies are lacking for Kaliziri injection. Ultra-high-performance liquid chromatography coupled with hybrid quadrupole orbitrap mass spectrometry was employed to comprehensively characterize the caffeoyl quinic acid derivatives present in Kaliziri injection. Based on accurate mass measurements, key fragmental ions and comparisons with reference standards, 60 caffeoyl quinic acid derivatives were identified in Kaliziri injections, including caffeoyl quinic acids, coumaroyl caffeoyl quinic acids, dicaffeoyl quinic acids, feruloyl caffeoyl quinic acids, and dicaffeoyl quinic acid hexosides. Moreover, an HPLC-MS/MS method was developed and validated for the quantitative analysis of 5-caffeoyl quinic acid, 4-caffeoyl quinic acid, 1,3-dicaffeoyl quinic acid, 3,4-dicaffeoyl quinic acid, 3,5-dicaffeoyl quinic acid and 4,5-dicaffeoyl quinic acid in beagle plasma. The quantitative HPLC-MS/MS method was applied to quantify these six major caffeoyl quinic acids in beagle plasma after the subcutaneous administration of Kaliziri injection. All of the six analytes reached their peak plasma of concentrations within 30 min.