Reaction of Chlorogenic Acid with Sulfite and Its Application in Identification of Sulfur-fumigated Herbs / 中国实验方剂学杂志

ABSTRACT

Objective: To explore the structure and reaction sites of the reaction products of chlorogenic acid and sodium sulfite,and the chemical changes of chlorogenic acid in Lonicerae Japonicae Flos after sulfur fumigating. Method: Chlorogenic acid was reacted with sodium sulfite under mild conditions. Liquid chromatography-mass spectrometry-ion trap-time-of-flight (LC-MS-IT-TOF) and 1H nuclear magnetic resonance spectroscopy (1H-NMR) detection techniques were used to detect the reaction products,and the sulfur-fumigated and unsulfurized Lonicerae Japonicae Flos water extract was detected by LC-MS-IT-TOF. Result: After analyzing the mass spectrometry data of fragment ion,molecular cleavage and accurate molecular weight,according to the results of nuclear magnetic signals of chemical shift,peak intensity and peak splitting, the products of chlorogenic acid and sodium sulfite were preliminarily identified as chlorogenic acid α,β-unsaturated carbonyl addition product3-((3-(3,4-dihydroxyphenyl)-2-sulfopropyl)oxy)-1,4,5-trihydroxycyclohexane-1-carboxylic acid or 3-((3-(3,4-dihy droxyphenyl)-3-sulfopropyl)oxy)-1,4,5-trihydroxycyclohexane-1-carboxylic acid,and the same characteristic fragments were detected as the addition product in the sulfur fumigated Lonicerae Japonicae Flos,but not found in the unsulfurized. Conclusion: It is the first time to demonstrate the structure and reaction sites of chlorogenic acid and sulfurous acid reaction products,and detect the chlorogenic acid sulfite addition product in sulfur-fumigated Lonicerae Japonicae Flos. Although it is still unclear how the sulfite addition compound produced by sulphur Lonicerae Japonicae Flos affects the efficacy and toxicological activity of Lonicerae Japonicae Flos,we shall still pay attention to the changes of active ingredients in sulphuric medicinal materials. Besides,this study can also provide reference for the studies of chemical composition changes after sulfuration of traditional Chinese medicine containing α,β-unsaturated carbonyl structure.