Characterization of capsaicinoids and their analogues using feature-based molecular networking analysis

• Published in: Biotechnology and bioprocess engineering Vol. 30; no. 3; pp. 609 - 620
• Main Authors: Jang, Hyemi, Choi, Mira, Jang, Kyoung-Soon
• Format: Journal Article
• Language: English
• Published: Seoul The Korean Society for Biotechnology and Bioengineering 01.06.2025; Springer Nature B.V; 한국생물공학회
• Subjects: Annotations; Biotechnology; Capsaicin; Chemistry; Chemistry and Materials Science; Clusters; Cultivars; Disease resistance; Food processing; Fragmentation; Industrial and Production Engineering; Ionic mobility; Mass spectrometry; Mass spectroscopy; Metabolites; Natural products; Networking; Peppers; Pharmacology; Pungent principles; Quadrupoles; Research Paper; Scientific imaging; Social organization; Spices; 생물공학; Red pepper; Ion mobility Q-TOF; Long chain; Molecular network; vanillyl acylamide; Zucapsaicin; Capsaicinoid analogue
• ISSN: 1226-8372; 1976-3816
• DOI: 10.1007/s12257-025-00197-8

Capsaicinoids, a class of alkaloid compounds commonly found in Capsicum annuum, are known for their pungent properties. Recent studies have highlighted metabolites similar in structure and biological activities to known capsaicinoids but lacking the characteristic pungent stimuli. In this study, capsaicinoid-like compounds were investigated from untargeted tandem mass spectrometry (MS/MS) datasets of the ethanolic extracts of Korean local cultivars of red pepper (Subicho and Eumseong) and a phytophthora disease-resistance cultivar (Dokbulwang), obtained using hybrid trapped ion mobility quadrupole time-of-flight mass spectrometry. Feature-based molecular networking (FBMN) in the Global Natural Products Social molecular networking platform, along with an unsupervised substructure identification tool MS/MS Latent Dirichlet Allocation, was employed to characterize capsaicinoid-like clusters. Additionally, the Network Annotation Propagation, an in silico fragmentation tool, complemented the FBMN results. This analysis identified 82 novel capsaicinoid analogues, significantly improving annotation coverage from 6.1% to 24.4%, based on spectral library matching and collision cross-section (CCS) values. The study revealed distinct clusters of capsaicinoid-like compounds, including long-chain N -vanillyl-acylamides such as N -vanillyl-decanamide and zucapsaicin. These compounds were characterized by unique fragmentation patterns, CCS values, and retention times, indicating their structural similarities and differences with known capsaicinoids. The elucidation of these capsaicinoid analogues and their distribution in Korean red pepper cultivars enhances our understanding of the pungency of spices. This research contributes valuable insights into the diversity of capsaicinoid-like compounds, shedding light on their potential applications in various fields such as food science, pharmacology, and agriculture.