On-Line Coupling of High-Performance Liquid Chromatography to Atmospheric Pressure Chemical Ionization Mass Spectrometry (HPLC/APCI-MS and MS/MS). The Pollen Analysis ofHippeastrum x hortorum (Amaryllidaceae)

Abstract

A H2O/MeOH extract of the pollen of Hippeastrum x hortorum (Amaryllidaceae) was analyzed. A mixture of different compounds (at the most 84) was found, namely the geometrically ((E,E), (E,Z), (Z,E), and (Z,Z) and structurally isomeric N,N′‐dicoumaroyl (=N,N′‐bis[3‐(4‐hydroxyphenyl)prop‐2‐enoyl]), N,N′‐diferuloyl (=N,N′‐bis[3‐(4‐hydroxy‐3‐methoxyphenyl)prop‐2‐enoyl]), N,N′‐disinapoyl (=N,N′‐bis[3‐(4‐hydroxy‐3,5‐dimethoxyphenyl)prop‐2‐enoyl]), N‐coumaroyl‐N′‐feruloyl, and N‐feruloyl‐N′‐sinapoyl derivatives of spermidine (=4‐azaoctane‐1,8‐diamine=N‐(3‐aminopropyl)butane‐1,4‐diamine). Their structures were proven by using on‐line‐coupled high‐performance liquid chromatography and atmospheric‐pressure chemical‐ionization mass spectrometry (HPLC‐UV(DAD)/APCI‐MS and MS/MS), UV‐induced (E)⇌(Z) photoisomerization, and catalytic hydrogenation, as well by comparing their spectra and chromatographic behavior with those of synthetic standards. According to the physicochemical properties of these natural compounds, a proposed biological function is discussed.

Studies into the phenolic patterns of different tissues of pineapple (Ananas comosus [L.] Merr.) infructescence by HPLC-DAD-ESI-MS n and GC-MS analysis

“…2d). [37]. Due to the occurrence of (E/Z)-and/or regio-isomers, a great number of isomeric hydroxycinnamic acid polyamines having identical molecular weight may exist [37].…”

“…Due to the occurrence of (E/Z)-and/or regio-isomers, a great number of isomeric hydroxycinnamic acid polyamines having identical molecular weight may exist [37]. Since the fragment ions at m/ z 147 and 207 indicating p-coumaroyl and sinapyl residues were not detected, compounds 49, 53, 54 and 57 were assigned to isomeric N,N′-diferuloylspermidines [37]. Four isomeric N,N′-diferuloylspermidines with almost identical mass spectra have recently been reported in elderberry (Sambucus nigra L.) inflorescence [38].…”

A Novel Polyamine Acyltransferase Responsible for the Accumulation of Spermidine Conjugates in Arabidopsis Seed

“…Diagnostic fragments at m/z 426 and at m/z 443 suggested the substitution of N 1 and N 8 by sinapoyl groups and the substitution of C 49 of the N 1 sinapoyl moiety by a hexose group ( Figure 1C). The weak signal for a fragment at m/z 72 (<2%) also confirmed the substitution of N 1 and N 8 by sinapoyl groups (Parr et al, 2005) since acyl migration may account for low levels of this fragment (Youhnovski et al, 1998). Within the Brassicaceae, N 1 ,N 8 -disubstituted spermidine derivatives have been identified in the seeds of Lunaria annua (Sagner et al, 1998) and Brassica napus (Baumert et al, 2005), respectively.…”

Metabolome Analysis of Biosynthetic Mutants Reveals a Diversity of Metabolic Changes and Allows Identification of a Large Number of New Compounds in Arabidopsis

“…The same applies to two novel hydroxycinnamoyl spermidine conjugates that were annotated as N,N#-bis(sinapoyl)spermidine (T13) and a corresponding O-hexoside N-sinapoyl-N#-(4-hexosyloxy-3,5-dimethoxycinnamoyl)spermidine (T14). The reported CID mass spectrum of N,N#-bis(sinapoyl)spermidine identified in pollen of Hippeastrum 3 hortorum was in good agreement with that obtained from compound T13 (Youhnovski et al, 1998). Unfortunately, the acylation pattern of the spermidine backbone cannot be deduced from CID mass spectra due to intramolecular transamidation reactions occurring under mass spectral conditions (Bigler et al, 1996).…”