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Covalent Binding of Acetone to Aminophospholipids in Vitro and in Vivo
Author(s) -
KUKSIS ARNIS,
RAVANDI AMIR,
SCHNEIDER MICHAEL
Publication year - 2005
Publication title -
annals of the new york academy of sciences
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.712
H-Index - 248
eISSN - 1749-6632
pISSN - 0077-8923
DOI - 10.1196/annals.1333.049
Subject(s) - chemistry , acetone , adduct , chromatography , electrospray ionization , mass spectrometry , ion , electrospray , covalent bond , in vivo , biochemistry , organic chemistry , microbiology and biotechnology , biology
A bstract : We have determined the ions characteristic of acetone adducts of reference aminophospholipids and have used them as markers for identification of acetone adducts of aminophospholipids in commercial lecithin, acetone extracts of tissue lipids, and in plasma and red blood cells of diabetic subjects. The acetonation products were determined by normal‐phase high‐performance liquid chromatography (HPLC) with on‐line electrospray‐mass spectrometry, and electrospray/collision‐induced dissociation in the negative ion mode. The major acetone complexes of PtdEtn and PtdSer were identified as the diacetone derivatives [PtdEtn+116‐H 2 O] − and [PtdSer+116‐H 2 O] − , respectively, although ions corresponding to monoacetone [PtdEtn+58‐H 2 O] − and doubly dehydrated diacetone adducts [PtdSer+116‐2x18] − were also observed. Upon increase of the capillary exit voltage (CapEx) from −160 to −300 V, new ions appeared with the original retention time but with 58 masses (one acetone molecule) lower than the mass of the parent compounds, along with fragment ions corresponding to lysoGPE+40 and free fatty acids. Scanning of chloroform/methanol extracts of red blood cell lipids of two of five diabetic subjects examined yielded elevated levels (in relation to nondiabetic subjects) for ions corresponding to the diacetone adducts [M+98] − of the major molecular species of PtdEtn and PtdSer. Because of possible overlap with major molecular species of PtdIns, the identification of the acetonated PtdSer in diabetic blood requires further confirmation.