2026-10-14T06:48:59Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33973579 2026-09-23T13:53:41Z category_1 category_4 category_12 category_13 category_272 category_873 category_39 category_46 category_734 category_64 category_69 portal_63 item_type_3 month_year_09_2026

Electrochemical Investigation of the Redox Behavior of Isoquinoline Alkaloid Emetine Carin Smith (22671758) JaVe Bonner (25097698) Emah Assimewlui (25097701) Keliah Tucker (25097704) Esdrizabeth Pereyra Cuello (25097707) Cassandra Sellers (25097710) Tosy King (25097713) Cameron Jamal Smith (25097716) Zoe Friedman (25097719) Weldejeworgis Gebrehiwot (18708542) Oladapo Bakare (2044063) Yue Li (102191) Uche Udeochu (22671755) Biophysics Biochemistry Cell Biology Genetics Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Ecology Immunology Biological Sciences not elsewhere classified Cancer Inorganic Chemistry tentative structural assignments resolution mass spectrometry physiologically relevant conditions glassy carbon electrode complementary spectroscopic evidence bioactive isoquinoline alkaloids rate studies showed dpv ), controlled 0 – 9 dependent studies two lower study establishes strongly influenced secondary product reported antiviral redox behavior protonation state predominantly diffusion potential processes potential electrolysis oxygen incorporation oxidative chemistry oxidative behavior mechanistic model mechanistic framework interfacial phenomena integrating electrochemistry incomplete understanding forming reactions fluorescence spectroscopy findings support electrochemical oxidation electrochemical investigation dependent toxicity containing products competing dehydrogenation antiparasitic properties amine functionalities Emetine is a biologically active isoquinoline alkaloid with reported antiviral, anticancer, and antiparasitic properties; however, its broader therapeutic application remains limited by dose-dependent toxicity and an incomplete understanding of its oxidative behavior. The electrochemical oxidation of emetine at a glassy carbon electrode (GCE) under physiologically relevant conditions was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), controlled-potential electrolysis (CPE), UV–Vis and fluorescence spectroscopy, and high-resolution LC–QTOF–MS/MS. DPV revealed three irreversible anodic oxidation processes centered near +0.90, +1.01, and +1.25 V versus Ag/AgCl. Scan-rate studies showed that the two lower-potential processes are predominantly diffusion-controlled, whereas the higher-potential process exhibits greater contributions from surface-associated and interfacial phenomena. pH-dependent studies (pH 4.0–9.1) demonstrated that emetine oxidation is strongly influenced by the protonation state and proceeds through a complex multistep irreversible mechanism. CPE generated multiple oxidation products, and subsequent high-resolution LC–QTOF–MS/MS analysis revealed ten emetine-associated products (P1–P10). Tentative structural assignments for P1–P8 encompassed dehydrogenated, oxygenated/dehydrogenated, and nitrogen-containing products, whereas P9 and P10 remained structurally unresolved. Together with complementary spectroscopic evidence, these findings support a mechanistic model in which emetine oxidation is initiated at amine functionalities and adjacent benzylic carbon centers, followed by competing dehydrogenation, oxygen incorporation, and secondary product-forming reactions. This study establishes a mechanistic framework for emetine electrooxidation and demonstrates the utility of integrating electrochemistry with high-resolution mass spectrometry to investigate the oxidative chemistry of bioactive isoquinoline alkaloids. 2026-09-23T00:00:00Z Dataset Dataset 10.1021/acsomega.6c06393.s002 https://figshare.com/articles/dataset/Electrochemical_Investigation_of_the_Redox_Behavior_of_Isoquinoline_Alkaloid_Emetine/33973579 CC BY-NC 4.0