Mass spectrometric structure determination of spider toxins: arginine-containing acylpolyamines from venoms of Brazilian garden spider Nephilengys cruentata.
A new strategy to characterize glutaminergic blocker acylpolymines stored in a spider venom with mass spectrometry is described. The crude spider venom extracts are amenable to direct MALDI mass spectrometry analysis which provides a rapid and accurate means of measuring the molecular weights of acylpolyamines without the isolation of individual samples. Compared with the previously developed mu-column HPLC/MS method, this procedure provides more efficient detection and identification of complex venom constituents. Twenty-five acylpolyamines were detected from Brazilian garden spider Nephilengys cruentata crude venom extracts by both HPLC/MS and MALDI-mass spectrometry. These acylpolyamine structures were determined by high-energy collision induced dissociation MS/MS method. Most of the compounds were classified into the previously reported generalized structures types A to D, which were found from the venom of Nephilengys borbonica. The structures of four acylpolyamines (M + H)+, m/z 623, 646, 688, and 745, which were not contained in the venom of Nephilengys borbonicare were determined to have arginine at the polyamine chain terminal and were named NPTX-622, -645, -687, and -744, respectively.
Palma
M S
MS
Suntory Institute for Bioorganic Research, Osaka, Japan.
Itagaki
Y
Y
Fujita
T
T
Hisada
M
M
Naoki
H
H
Nakajima
T
T
D000818:Animals; D001120:Arginine / Q000032:analysis / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D009682:Magnetic Resonance Spectroscopy; D011073:Polyamines / Q000302:isolation & purification*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013111:Spider Venoms / Q000032:analysis / Q000737:chemistry*
D011073:Polyamines; D013111:Spider Venoms; D001120:Arginine