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Establishment of a High-Resolution Liquid Chromatography-Mass Spectrometry Spectral Library for Screening Toxic Natural Products.

Many natural products have biological effects on humans and animals. Poisoning caused by natural products is common in clinical toxicology cases. Liquid chromatography-high-resolution-mass spectrometry (LC-HRMS) has recently emerged as a powerful analytical tool for large-scale target screening, and the application of LC-HRMS can be expanded to evaluate potential natural product poisoning in clinical cases. We report the construction of an LC-HRMS spectral library of 95 natural products commonly implicated in poisoning, and an LC-HRMS assay was validated for definitive detection of natural products in urine and serum samples. For each compound, the limit of detection (LOD) was determined in the analytical range of 1.0 - 1000 ng/mL for urine samples and 0.50 - 500 ng/mL for serum samples. The mean (SD) of matrix effects for urine samples and that for serum samples were both -21% (22%), and the mean (SD) of recovery for serum samples was 89% (26%). The LC-HRMS assay was successfully applied to identify natural products in clinical cases. The spectral library parameters of each compound are provided in the supplementary material to aid other laboratories in identification of unknown natural toxins and development of similar methods on different mass spectrometry platforms.