High-performance liquid chromatography/electrospray tandem mass spectrometry was developed to distinguish isomers and compounds of similar structures with different configurations in the rhizomes of Z. cassumunar. Energy-resolved breakdown curves were utilized to differentiate four compounds. Compounds 2 (3R,4S) and 4 (3R,4R) were a pair of stereoisomers which could be distinguished easily by breakdown curves. The breakdown curve of compound 1 was identical to that of compound 2, which suggested that the configuration of compound 1 was (3R,4S) or (3S,4R). The breakdown curve of compound 3 was completely different from those of compounds 1, 2 and 4, and it might be that the configuration of the double bond of compound 3 was different from the other three compounds. Hence, the described method using breakdown curves has great potential in the distinguishing of isomers and compounds of similar structure with different configurations.
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