Fragmentation reactions of molecular ions and dications of indoleamines

被引:7
作者
Cardoso, AM [1 ]
Correla, AJF [1 ]
机构
[1] Univ Aveiro, Dept Quim, P-3810 Aveiro, Portugal
来源
EUROPEAN MASS SPECTROMETRY | 1999年 / 5卷 / 01期
关键词
indolamines; doubly-charged ions; kinetic energy release; two-dimensional mass spectrometry;
D O I
10.1255/ejms.244
中图分类号
O64 [物理化学(理论化学)、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号
070203 ; 070304 ; 081704 ; 1406 ;
摘要
The combination of techniques such as two-dimensional mass spectrometry and mass analysed ion kinetic energy spectrometry (with and without collision gas) in the study of gas-phase ion chemistry of indole, gramine, tryptamine and serotonine enabled us to establish the fragmentation pathways of their singly- and doubly-charged molecular ions generated by electron impact. The measurement of the kinetic energy released in the charge separation reactions of the molecular dications produced information on the intercharge distance on the transition state for the fragmentation, assuming that it arises entirely from the coulombic energy released, For the singly-charged molecular ions of indoleamines, loss of the neutral molecule CH2=NR (R = H or CH3), by hydrogen transfer from the amino (or methyl) group to the indole nucleus, is the only fragmentation occurring in the third field-free region of the mass spectrometer, Upon collision of the molecular ion with He gas, a competing process of bond cleavage by loss of the radical (CH2NH2)-C-. (or N-.(CH3)(2) for gramine) is observed for tryptamine and serotonine, The doubly-charged ions dissociate by elimination of neutral molecules or radicals to generate doubly-charged fragment ions or by charge separation reactions. The intercharge distance, calculated from the kinetic energy released in the fragmentation, was, whenever possible, correlated with charge location in the ion.
引用
收藏
页码:11 / 18
页数:8
相关论文
共 34 条
[1]   The importance of charge-separation reactions in tandem mass spectrometry of doubly protonated angiotensin II formed by electrospray ionization: Experimental considerations and structural implications [J].
Adams, J ;
Strobel, FH ;
Reiter, A ;
Sullards, MC .
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 1996, 7 (01) :30-41
[2]   SOME ASPECTS OF DOUBLY-CHARGED ION CHEMISTRY OF AROMATIC-AMINES AND DIAMINES [J].
AST, T ;
BEYNON, JH .
ORGANIC MASS SPECTROMETRY, 1973, 7 (05) :503-513
[3]   CHARGE LOCALIZATION - DOUBLY-CHARGED ION REACTIONS IN TOLUENE [J].
AST, T ;
BEYNON, JH ;
COOKS, RG .
ORGANIC MASS SPECTROMETRY, 1972, 6 (07) :741-&
[4]   ION KINETIC ENERGY SPECTRA OF SOME AROMATIC HYDROCARBONS [J].
BEYNON, JH ;
CAPRIOLI, RM ;
BAITINGE.WE ;
AMY, JW .
ORGANIC MASS SPECTROMETRY, 1970, 3 (04) :455-+
[5]  
BEYNON JH, 1996, CHEM COMMUN, P717
[6]  
BEYNON JH, 1972, ORG MASS SPECTROM, V16, P273
[7]   STEREOCHEMICAL STUDIES OF COMPLEX-MOLECULES BY COLLISIONALLY INDUCED DECOMPOSITION OF DOUBLY CHARGED IONS - NUPHAR ALKALOIDS [J].
BORTOLINI, O ;
CURCURUTO, O ;
TRALDI, P ;
IWANOW, A ;
WROBEL, JT .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1991, (03) :287-289
[8]   CHARGE LOCALIZATION .1. ION KINETIC ENERGY SPECTRA OF ORTHO-PHENYLENEDIAMINE, META-PHENYLENEDIAMINE AND PARA-PHENYLENEDIAMINE [J].
CAPRIOLI, RM ;
BEYNON, JH ;
AST, T .
ORGANIC MASS SPECTROMETRY, 1971, 5 (04) :417-&
[9]   2-DIMENSIONAL MASS-SPECTRA OF 2-PHENYLETHYLAMINES [J].
CARDOSO, AM ;
CORREIA, AJF .
JOURNAL OF MASS SPECTROMETRY, 1995, 30 (09) :1255-1259
[10]  
Cooks RG., 1973, Metastable Ions