Differentiation of three pairs of aconite alkaloid isomers from Aconitumnagarumvarlasiandrum by EIMS.pdf
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Differentiation of three pairs of aconite alkaloid isomers from Aconitumnagarumvarlasiandrum by EIMS
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
Rapid Commun. Mass Spectrom. 2006; 20: 157–170
Published online in Wiley InterScience (). DOI: 10.1002/rcm.2283
Differentiation of three pairs of aconite alkaloid isomers
from Aconitum nagarum var. lasiandrum by electrospray
ionization tandem mass spectrometry
Rui Li, Zhijun Wu, Fan Zhang and Lisheng Ding*
Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, PR China
Received 18 August 2005; Revised 31 October 2005; Accepted 7 November 2005
Three pairs of isomers of aconite alkaloids from Aconitum nagarum var. lasiandrum have been
investigated by electrospray ionization mass spectrometry (ESI-MS) and tandemmass spectrometry
(MS/MS) employing ion-trap and quadrupole time-of-flight mass spectrometers in positive mode.
Based on the differences of their fragmentation pathways and special fragment ions, three pairs of
isomers of aconite alkaloids were differentiated. In addition, fragmentation laws of some veatch-
ines and the discrepancy of fragmentation mechanisms between veatchine-type and aconitine-type
alkaloid were also concluded. In the case of veatchines, a radical would be formed by homolysis
of C18–C4 or C18–H bonds, followed by elimination of a series of C2H2 and C2H4. Moreover, the
retro-Diels-Alder (RDA) reaction occurred in the E-ring and double-electron transfer triggered by
the positive charge on C1 led to the formation of diagnostic ions at m/z 216. With regard to
aconitine-type alkaloids, the N-substituent is not eliminated easily. Although there is no carbonyl
group on some aconitine-type alkaloids, with hydroxyl and methoxyl on C15 and C16 respectively,
CO was readily eliminated through tautomerization. Copyright # 2005 John Wiley Sons, Ltd.
Aconitum nagarum var. lasiandrum (Ranuculaceae) is mainly
distributed in the Yunnan Province of China. Its roots can
relieve pain and dispel dampness. The roots of this species
have been used as a folk medicine in China for the treatment
of cold limb
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