Application of mass spectrometry in the study of the material basis of Chinese herbal decoctions

Decoction, a classic dosage form of Traditional Chinese Medicine (TCM), has been employed since the era of Yi Yin. The inherently complex composition of individual herbal medicines, coupled with interactions among constituents during co-decoction, results in an exceedingly complicated chemical profile of decoctions. This complexity renders the elucidation of their material basis and pharmacological mechanisms a central challenge in the modernization of TCM. Mass spectrometry (MS), owing to its high sensitivity and resolution, has emerged as a pivotal technique for deciphering the material basis of decoctions. This review provides an overview of MS and its commonly hyphenated techniques. It systematically summarizes key applications of MS in decoction research, encompassing: 1) decoction process studies (including decoction method investigation and self-assembled nanoparticle research); 2) quality control aspects (including fingerprinting, quality marker identification, and consistency evaluation between decoctions and formula granules); and 3) research on pharmacologically active substances (including spectrum-effect relationship, network pharmacology, metabolomics, pharmacokinetics, serum pharmacochemistry and serum pharmacology, and Chinmedomics studies). This review aims to provide a reference for future research and development of TCM decoctions. Green Analytical Chemistry (GAC) and White Analytical Chemistry (WAC), as forefront paradigms in analytical science, emphasize environmental friendliness and comprehensive practical utility, respectively. Furthermore, this review assesses the applications of MS in decoction studies from the perspectives of greenness and whiteness, thereby offering robust support for the sustainable promotion and standardized application of MS technologies in this field. • First systematic review of MS for studying the material basis of TCM decoctions. • Novel framework covering decoction preparation, quality control, and pharmacodynamic material basis. • Pioneering greenness and whiteness assessment of MS in specific applications.