Identification and characterization of flavonoids from semen zizyphi spinosae by high-performance liquid chromatography/linear ion trap FTICR hybrid mass spectrometry

Abstract

Semen zizyphi spinosae (SZS) has been used to treat insomnia and anxiety for thousands of years. In this paper, a novel high-performance liquid chromatography coupled with the photodiode array detector/linear ion trap-MS(n) (HPLC-PDA/LTQ-MS(n)) method was established to separate and identify flavonoids from the extract of SZS. Separation was performed on an HYPERSIL C(18) column by gradient elution using CH(3)CN/H(2)O-CH(3)COOH as the mobile phase at a flow rate of 0.8 ml/min. UV spectral data, accurate molecular weights, and multi-stage MS/MS fragmentation information were obtained. Electrospray ionization/MS/MS fragmentation patterns were proposed. Nineteen flavonoid glycosides were identified or tentatively characterized based on their retention time, UV spectral data, accurate molecular weights, and mass fragmentation behavior. The method was useful for separation and identification of the flavonoid components from SZS and could be applied to other complex samples, especially for minor constituents.

Identification of the metabolites after oral administration of extract of ziziphi spinosae semen to rats or dogs by high‐performance liquid chromatography/linear ion trap FTICR hybrid mass spectrometry

“…Moreover, the product ions at 367 ([Y 0 − CH 6 O 3 + H] + ), 313 ([Y 0 + 0,2 X 0 + H] + ), 337 ([Y 0 − C 2 H 8 O 4 + H] + ), 397 ([Y 0 − 2H 2 O + H] + ) and 379 ([Y 0 − 3H 2 O + H] + ) were detected in the MS 3 spectrum of the ion at m/z 433. These results were consistent with those of saponarin (Niu et al ., ). Thus, compound 5 was identified as saponarin.…”

“…In the MS 2 spectrum, the most abundant fragment ion at m/z 429 ([M À H 2 O + H] + ) was formed by the loss of H 2 O, and the product ions at m/z 381, 351, 411 and 393 were generated by the loss of CH 6 O 3 , C 2 H 8 O 4 , 2H 2 O and 3H 2 O, respectively, from the saccharide group attached to the C6 position of the aglycone. The characteristic ion at m/z 327 ([ 0,2 X 0 + H] + ) in the MS 2 spectrum was observed owing to the internal cleavage of the glucose at C6 by the loss of a C 4 H 8 O 4 (120 Da) residue, which was the characteristic loss of the sugar moiety of C-glycosylation (Ferreres et al, 2003;Niu et al, 2010…”

“…Extracts of ZSS and its constituents have been reported to exhibit a wide spectrum of biological activities, including antiinsomnia and anti-anxiety (Fang et al, 2010;Rong et al, 2008). Previous studies have shown that the main constituents of ZSS are flavonoids such as spinosin (Cheng et al, 2000;Niu et al, 2010;Otsuka et al, 1978;Yoshikawa et al, 1997), and modern pharmacological studies have demonstrated that flavonoids are the main bioactive compounds for the treatment of insomnia (Cheng et al, 2000;Guo et al, 1998).…”

Extraction methods and sedative–hypnotic effects of polysaccharide and total flavonoids of Cordyceps militaris

“…All of the mice were kept at [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] C and 40%-60% humidity and were fed a standard laboratory feed diet with water available ad libitum. All of the mice in each group were intragastrically administered successively for 30 days according to the doses described above.…”

“…Along with polysaccharides, cordycepin and adenosine, there is a high content of flavonoids [17] in C. militaris. Studies have shown that flavonoids are the main substantial basis of the sedative and hypnotic effects of many Chinese herbs, such as Semen Ziziphi Spinosae [18] and Epimedium [19]. The underlying mechanisms of the action of these Chinese herbs are associated with neurotransmitters, such as g-aminobutyric acid (GABA), glutamate (Glu), acetylcholine (ACh) 5-hydroxytryptamine (5-HT).…”