eprintid: 348 rev_number: 128 eprint_status: archive userid: 1 dir: disk0/00/00/03/48 datestamp: 2005-05-09 12:00:00 lastmod: 2020-06-16 04:30:42 status_changed: 2008-01-09 13:16:38 type: article metadata_visibility: show item_issues_count: 0 creators_name: Harrington, DJ creators_name: Soper, R creators_name: Edwards, C creators_name: Savidge, GF creators_name: Hodges, SJ creators_name: Shearer, MJ title: Determination of the urinary aglycone metabolites of vitamin K by HPLC with redox-mode electrochemical detection subjects: 5000 divisions: UCL note: Imported via OAI, 9:29:00 10th May 2005 abstract: We describe a method for the determination of the two major urinary metabolites of vitamin K as the methyl esters of their agyclone structures, 2-methyl-3-(3-3-carboxymethylpropyl)-1,4-naphthoquinone (5C-side-chain metabolite) and 2-methyl-3-(5-carboxy-3-methyl-2-pentenyl)-1,4-naphthoquinone (7C-side-chain metabolite), by HPLC with electrochemical detection (ECD) in the redox mode. Urinary salts were removed by reversed-phase (C18) solid phase extraction (SPE) and the predominately conjugated vitamin K metabolites hydrolysed with methanolic HCl. The resultant carboxylic acid aglycones were quantitatively methylated with diazomethane and fractionated by normal-phase (silica) SPE. Final analysis was by reversed-phase (C18) HPLC with a methanol-aqueous mobile phase. Metabolites were detected by amperometric, oxidative ECD of their quinol forms, which were generated by post-column coulometric reduction at an upstream electrode. The assay gave excellent linearity (r2 typically = 0.999) and high sensitivity with an on-column detection limit of <3.5 fmol (<1pg). The inter-assay precision was typically 10%. Metabolite recovery was compared to that of an internal standard (2-methyl-3-(7'-carboxy-heptyl)-1,4-naphthoquinone), added to urine samples just before analysis. Using this methodology we confirmed that the 5C- and 7C-metabolite were major catabolites of both phylloquinone (vitamin K1) and menaquinones (vitamin K2) in humans. We propose that the measurement of urinary vitamin K metabolite excretion is a candidate non-invasive marker of total vitamin K status. date: 2005-05 date_type: published oa_status: green primo: open primo_central: open_green article_type_text: Article doi: 10.1194/jlr.D400033-JLR200 lyricists_name: HODGES, STEPHEN lyricists_id: SHODG45 full_text_status: public publication: The Journal of Lipid Research volume: 46 number: 5 pagerange: 1053-1060 refereed: TRUE issn: 0022-2275 citation: Harrington, DJ; Soper, R; Edwards, C; Savidge, GF; Hodges, SJ; Shearer, MJ; (2005) Determination of the urinary aglycone metabolites of vitamin K by HPLC with redox-mode electrochemical detection. The Journal of Lipid Research , 46 (5) pp. 1053-1060. 10.1194/jlr.D400033-JLR200 <https://doi.org/10.1194/jlr.D400033-JLR200>. Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/348/1/Vit_K_metabs_JLR_2005.pdf