title: Electrospray ionization mass spectrometry analysis of polyisoprenoid alcohols via Li+ cationization.
abstract: Direct analysis of polyisoprenoids by electrospray ionization mass spectrometry (ESI-MS) often produces poor results requiring off-line time and sample-consuming derivatization techniques. We describe a simple ESI-MS approach for the direct analysis of polyisoprenoids using several dolichols and polyprenols with different chain sizes as proof-of-principle cases. Lithium iodide is used to promote cationization by intense formation of [M+Li]+ adducts. Thus, detection of polyisoprenoids with mass determination can be performed with high sensitivity (limit of detection [LOD] approximately 100 rhoM), whereas characteristic collision-induced dissociations observed for both dolichols and polyprenols permit investigation of their structure. Using ESI(Li+)-MS and ESI(Li+)-MS/MS analysis, we screened for polyprenol products of an octaprenyl pyrophosphate synthase of Plasmodium falciparum and dolichols in a complex mixture of compounds produced by Leishmania amazonensis and P. falciparum.
authors.affiliation: Department of Parasitology, Institute of Biomedical Sciences, University of São Paulo, 05508-900 São Paulo, SP, Brazil.
authors.forename: Fabio Luiz
authors.initials: FL
authors.lastname: D'Alexandri
authors.forename: Fabio Cesar
authors.initials: FC
authors.lastname: Gozzo
authors.forename: Marcos Nogueira
authors.initials: MN
authors.lastname: Eberlin
authors.forename: Alejandro Miguel
authors.initials: AM
authors.lastname: Katzin
mesh_terms: D000438:Alcohols / Q000032:analysis* / Q000737:chemistry; D019883:Alkyl and Aryl Transferases / Q000378:metabolism; D000818:Animals; D002412:Cations / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D004286:Dolichols / Q000737:chemistry / Q000378:metabolism; D007454:Iodides / Q000737:chemistry*; D007891:Leishmania / Q000737:chemistry / Q000378:metabolism; D008094:Lithium / Q000737:chemistry*; D010963:Plasmodium falciparum / Q000737:chemistry / Q000378:metabolism; D011108:Polymers / Q000032:analysis* / Q000737:chemistry; D012680:Sensitivity and Specificity; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods; D013729:Terpenes / Q000032:analysis* / Q000737:chemistry
chemical_list: D000438:Alcohols; D002412:Cations; D004286:Dolichols; D007454:Iodides; D011108:Polymers; D013729:Terpenes; D008094:Lithium; D019883:Alkyl and Aryl Transferases; C048987:octaprenyl pyrophosphate synthetase