Cultivar to chemotype: characterizing complex botanicals with mass spectrometry metabolomics

Covering up to 2025 Plant products, including botanical dietary supplements, nutraceuticals, and herbal medicines, remain central to supporting human health and wellness. Their usage has been steadily increasing over the last few decades, which has also led to raised concerns about proper identification and characterization of plant materials. This information is crucial to evaluate the safety and efficacy of these botanical products and prevent misidentification or adulteration. While there are multiple analytical approaches to characterize botanicals, this review provides insight into how untargeted mass spectrometry metabolomics can profile these commonly complex mixtures and provide detailed datasets that are capable of taxonomically classifying samples, detecting adulteration, and providing insight into variation between plant materials and their nutritional, medicinal, or toxicological effects. We describe data analysis approaches for untargeted metabolomics, case studies on the various applications of this method for characterizing botanicals, and challenges that the growing field of mass spectrometry-based metabolomics is facing. The chosen topics reflect the current state of metabolomics analyses for complex systems with a look to the future of how to conceptualize botanical characterization.