UHPLC-ESI-qTOF-MS Analysis of Cyclopeptide Alkaloids in the Seeds of Ziziphus jujuba var. spinosa

Abstract

: An UHPLC-ESI-qTOF-MS analytical method was developed for cyclopeptide alkaloids in the seeds of Ziziphus jujuba var. spinosa (Semen Ziziphi Spinosae), which is a commonly used herb in Chinese and Korean traditional medicines. Considering the basicity of cyclopeptide alkaloids, a specific separation method was developed for an UHPLC system. The compounds were detected by DAD and ESI-qTOF-MS, and their fragmentation patterns were also acquired by MS E technologies. Peak-picking of major compounds was performed with nine previously isolated compounds and two reference standard compounds. Tandem MS fragmentation behaviors of type-Ia and -Ib cyclopeptide alkaloids were investigated with the acquired data to develop a strategy for dereplication of other cyclopeptide alkaloid compounds in Z. jujuba var. spinosa. Two more cyclopeptide alkaloids were tentatively identified with UHPLC-ESI-qTOF-MS using this method.

Bioactive compounds, antioxidant and antimicrobial activities of extracts from different plant parts of two Ziziphus Mill. species

“…Overall, various functional compounds such as vitamin C, amino acids, triterpene acids, polysaccharides, and polyphenols were previously reported in the Ziziphus genus [11,12]. Further, works on this genus allowed the isolation and identification of flavonoids [13,14], triterpene acids and derivatives such as saponins [15], alkaloids [16], indole derivatives [17], and fatty acids [5,18]. In fact, saponins, flavonoid C-glycosides and fatty acids in some of the species of the Ziziphus were responsible of plants sedative and hypnotic effects [19].…”

UHPLC-ESI-Orbitrap-HR-MS Analysis of Cyclopeptide Alkaloids From Ziziphus joazeiro

“…Alkaloids 1, 3 and 6 were found to have a type-Ia CPA core due to the observed loss of the styrylaminine moiety (C 8 H 9 NO, m/z 135), which is common for this type of CPA, as described in previous studies. 33 1) showed remarkably similar fragmentation patterns (Figure 4), indicating the presence of a C 3 H 7 moiety at R 3 , which corresponds to a valine or isovaline residue. However, since isovaline is not commonly found in Ziziphus CPAs, this residue is attributed to valine.…”

“…The fragmentation patterns of compounds 1 to 16 (Figure 2, see also Figures S1-S42) were proposed according to the rules of mass fragmentation under ESI conditions (Figure 3), and some models from the literature. [31][32][33] From the sixteen detected CPAs, three possess a type-Ia1, one a type-Ia2 and twelve a type-Ib cyclopeptide alkaloid core. As usual for cyclic peptides, the fragmentation process goes through the protonation of a nitrogen atom of an amide moiety, which weakens the nitrogencarbonyl bond of the amino acid.…”

Ziziphus jujuba Mill. var. spinosa (Bunge) Hu ex H. F. Chou Seed Ameliorates Insomnia in Rats by Regulating Metabolomics and Intestinal Flora Composition

“…In line with herbal records, modern pharmacology has confirmed that ZSS has sedative and hypnotic ( Jiang et al, 2007 ), antidepressant ( Shi et al, 2019 ), anxiolytic ( Li et al, 2019 ) and neuroprotective ( Park et al, 2019 ) effects. Previous studies have shown that ZSS contains many flavonoids ( Niu et al, 2010 ), saponins ( Du et al, 2019a ), alkaloids ( Kang et al, 2016 ), and fatty oils ( Xiao et al, 2018 ). Among them, flavonoids (such as spinosin) ( Wang et al, 2010 ) and saponins (such as jujuboside A ( Wang et al, 2015 ) and jujuboside B) were reported to have sedative and hypnotic effects and are believed to be the main active compounds for the treatment of insomnia in ZSS.…”