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Two undescribed piperidine racemates, (±)-caulophines A and B (1 and 2), a new N-containing xanthone derivative (3), together with six known piperidines, were isolated from the roots of Caulophyllum robustum Maxim. Their structures were determined by extensive spectroscopic techniques. Compounds 3 and 7 exhibited weak cytotoxicities against human palace cancer hela cell line with inhibitory rates of 32.2% and 39.7%, respectively, at the concentration of 40 μM.

Malonyl-triterpene saponins (MTSs) attract scientific attentions because of their structural diversities and valuable bioactivities. However, its thermal instability brings a huge amount of challenges for isolation and purification of this class of compounds. To our best knowledge, there has been no report on isolation and analysis of MTSs from genus Caulophyllum. In this study, a strategy combining data acquisition using an energy-resolved technique and the narrow widow extracted ion chromatograms as data mining method was developed for discovery and identification of MTSs in Caulophyllum robustum hair roots by ultra high liquid chromatography coupled to electrospray ionization Fourier transform mass spectrometry. The method was performed at an independent MS full scan using our bottom-up energies by in-source collision induced dissociations with 0, 25, 50 and 100 eV in both positive and negative modes. Precursor ion as well as fragment ion information was simultaneously collected from four energy-resolved MS spectra in a single run of 18 min. The fragmentation pathways of intact deprotonated, protonated and sodium ions of MTSs were proposed for the structural elucidation of Caulophyllum MTSs. A flowchart involving a stepwise procedure based on key fragments from ESI- /ESI+ -FT-MS(1, 1) to MS(1, 4) spectra was constructed for the identification of structural elements in the MTSs. As a result, a total of 23 MTSs were discovered and tentatively identified, which had not been reported from Caulophyllum species before. All of these were potentially new compounds. This study provides an excellent example for discovery and identification of MTSs in herb medicines. Copyright © 2016 John Wiley & Sons, Ltd.

A growth-regulating effect of triterpene glycosides of hederagenin (caulosides A, C, D, and G which were isolated from Caulophyllum robustum Maxim.) on a growth of roots of Cucumis sativus L. seedlings was studied. The efficacy of the growth-regulating action of the studied compounds was shown to depend on their chemical structure. Caulosides A and C had one carbohydrate chain. They inhibited the growth of roots of the Cucumis sativus L. seedlings in concentrations of 500 and 100 μg/mL by 10.3 and 20.4%, respectively. Caulosides D and G had two carbohydrate chains. These compounds did not inhibit the root growth in concentrations up to 500 μg/mL, but exhibited a slight stimulating effect (9.1 and 10.4%, respectively) in their concentrations of 100 and 250 μg/mL. The inhibiting effect of cauloside C was directed, for the first time, to the seedlings with an intensively growing main root.

The saponins in Caulophyllum robustum have not yet been fully characterized. Furthermore these saponins are often present in trace amounts and are structurally complex. Here, a simple direct infusion electrospray ion trap multiple-stage tandem mass spectrometry (DI-ESI-IT-MS(n)) method was described for the characterization of trace C. robustum saponins. Eight reference saponins from the C. robustum hairy root were investigated by DI-ESI-IT-MS(n) in positive ion mode. Some fragmentation approaches were proposed through analysis of the [M+Na](+) ions: (1) preferential cleavage of the C-28 ester glycosidic bond to provide complementary [Y0α+Na](+) and [Bα+Na](+) ions for bidesmosidic saponins; (2) diagnostically neutral loss of CO2 from free carboxyl groups at C-28 for monodesmosidic saponins; and (3) the ion intensity ratio between [C2β+Na](+) and [B2β+Na](+), which is sensitive to the structural differences between the two isomeric β-sugar chains (Glc → (2)Ara and Glc → (3)Ara). The DI-ESI-IT-MS(n) method was successfully used for the analysis of trace C. robustum saponins with [M+Na](+) ions at m/z 1745.6, 1729.5, 1583.7, 1567.7, 1421.7 and 1405.7. This article highlights the discovery and identification of complex α- and β-oligosaccharide moieties in Caulophyllum saponins by glycosidic product ions along with cross ring cleavage product ions. Five oligosaccharide moieties were unambiguously or tentatively identified as Rha → (4)Glc → (6)Glc → (4)Rha → (4)Glc → (6)Glc, Glc → (4)Glc → (6)Glc → (4)Rha → (4)Glc → (6)Glc, Rha → Glc → Glc (Glc) → (2,3)Ara, Glc → Glc (Glc) → (2,3)Ara and Glc (Glc) → (2,3)Ara. Accuracy of the analytical procedure was demonstrated by structural identification of two saponins isolated using 1D and 2D-NMR spectroscopy. The DI-ESI-IT-MS(n) method facilitates rapid discovery and analysis of trace Caulophyllum saponins and is a powerful and practical tool for structural characterization of complex oligosaccharide moieties in triterpene saponins.

Four new fluorenone alkaloids, caulophylline A-D (1–4), and one new dihydroazafluoranthene alkaloid, caulophylline E (5) were isolated from the roots of Caulophyllum robustum Maxim. Their structures were elucidated by spectroscopic analysis. Among the isolated alkaloids, Caulophylline E showed good scavenging effects against DPPH radical with IC50 of 39 μM.

Larval survival of four local populations ofEpilachna yasutomii in the southern part of Nagano Prefecture was evaluated on leaves of blue cohosh,Caulophyllum robustum, growing at two different sites, Takatoh and Nakatachi. Based on larval survival on leaves of TakatohC. robustum, TakatohE. Yasutomii was clearly distinguishable from the three populations in the Minami-Shinano area (Akasawa, Nakatachi and Tenryu). TakatohE. yasutomii developed successfully to emergence onC. robustum from both sites, while Minami-Shinano populations showed a very low survival rate when given TakatohC. robustum. Under controlled plant growth conditions, larval survival of AkasawaE. yasutomii was significantly reduced when givenC. robustum leaves, from either site, exposed to direct solar radiation, which suggested that larval survival was influenced by environmental conditions at the growing sites rather than genetic differences between the plant populations. In contrast, TakatohE. yasutomii developed well onC. robustum leaves from either site exposed to direct solar radiation. TakatohE. yasutomii appears to have some defensive mechanism that allows it to overcome a substance deterring larval development, which increases in leaves exposed to direct solar radiation.

Three new oleanane bidesmosidic triterpenoid saponins, named leiyemudanosides A–C (1–3) were isolated from the roots of Caulophyllum robustum Maxim. Their structures were established by chemical and detailed spectroscopic analysis as 3-O-α- l -arabinopyranosyl-caulophyllogenin-28-O-β- d -glucopyranosyl-(1 → 6)-β- d -glucopyranosyl ester (1), 3-O-β- d -glucopyranosyl-(1 → 3)-α- l -arabinopyranosyl-caulophyllogenin-28-O-α- l -rhamnopyranosyl-(1 → 4)-β- d -glucopyranosyl-(1 → 6)-β- d -glucopyranosyl ester (2), and 3-O-β- d -glucopyranosyl-(1 → 3)-α- l -arabinopyranosyl-echinocystic acid-28-O-α- l -rhamnopyranosyl-(1 → 4)-β- d -glucopyranosyl-(1 → 6)-β- d -glucopyranosyl ester (3), respectively.

A new fluorenone alkaloid (caulophine) was isolated from the radix of Caulophyllum robustum Maxim. (collected from the Qinling mountains) using cell membrane chromatography as the screening method. Caulophine was identified as 3-(2-(dimethylamino)ethyl)-4,5-dihydroxy-1,6-dimethoxy-9H-fluoren-9-one based on physicochemic and spectroscopic analyses, particularly by NMR spectroscopic data (i.e., COSY, HMQC, HMBC, NOESY). Caulophine possessed anti-myocardial ischemia activity.

A new population of the phytophagous ladybird, Epilachna yasutomii showing a relatively-wide food range was found in Nishitsugaru-gun, Aomori Prefecture. In the laboratory, adults and larvae both fed on leaves of Caulophyllum robustum, Panax japonicus, Hylomecon japonicum and potato (Solanum tuberosum). Due to the wide food range in the natural habita+, about 10% of adults had invaded an adjacent potato field.