Silver-Plated Vitamins: A Method of Detecting Tocopherols and Carotenoids in LC/ESI-MS Coupling

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Abstract
In LC/MS, nonpolar substances in the majority of cases cannot be ionized by standard electrospray ionization (ESI) because they obviously lack a site for protonation or deprotonation. The ionization of carotenoids and tocopherols can be greatly enhanced by the addition of silver ions. The Ag+−carotenoid and Ag+−tocopherol adducts thus formed render these substances amenable to MS. α-, β-, γ-, and δ-tocopherol, α-tocopherol acetate, and the various isomers of lycopene and β-carotene were separated by C30 RP-HPLC and could be identified by on-line ESI-MS. A mixture of six different carotenoids was analyzed by scanning the mass range from m/z 500 to 800. The mass spectra of the peaks revealed that all carotenoids and most tocopherols were partially oxidized to radical cations.The detection limit for canthaxanthin was ∼500 fmol while that of β-carotene was below 300 fmol. An increase in sensitivity in the MRM mode can be attained by monitoring ions formed by loss of elemental silver from the adducts in the CID cell. Dichloromethane extracts of tomato, carrot, and vegetable juices, a vitamin drink, and a commercial infant food product were analyzed by LC/MS. After postcolumn argentation, from the mass-selective extracts of the TIC, the carotenoids and tocopherols present could be identified by their masses and their retention times. For all studies, a silver perchlorate solution with an overall concentration of 50 μg/mL was used.