Two New Iridoid Esters from the Root and Rhizome of Valeriana jatamansi Jones

Two new iridoid esters, named valerjatadoids A and B ( 1 and 2 , resp.), together with three known iridoid esters, jatamanin O ( 3 ), jatamanvaltrate P ( 4 ), and jatamanvaltrate Q ( 5 ), have been isolated from the root and rhizome of Valeriana jatamansi Jones . The structures of the two new compounds were elucidated by spectroscopic analyses, including 2D‐NMR techniques.     

Iridoids from the Roots of Valeriana jatamansi

Three new iridoids, jatamanins N–P ( 1 – 3 ), along with the seven known iridiods 4 – 10 , were isolated from the roots of Valeriana jatamansi. Compound 1 is an unusual iridoid bearing two epoxy bridges between C(3) and C(6) and between C(1) and C(10), forming a unique cage‐like rigid skeleton. The structures of the new compounds were assigned on the basis of spectroscopic methods.     

Two New Iridoids from the Roots of Valeriana officinalis

Valeriana officinalis is the official species used in Europe as sedatives and tranquilizers for centuries. Two new iridoids, volvaltrates C and D ( 1 and 2 ) were isolated from the ethanol extract as a mixture from the roots of V. officinalis. Their structures were elucidated by spectroscopic evidence including MS, 1D and 2D‐NMR spectra.     

Anxiolytic potency of iridoid fraction extracted from Valeriana jatamansi Jones and its mechanism: a preliminary study

Valeriana jatamansi Jones (V. jatamansi) has been widely used for treating anxiety and its mechanism involves many aspects including GABA level. This study aimed to evaluate the anxiolytic potency of an iridoid fraction extracted from the radix and rhizomes of V. jatamansi. The iridoid fraction was extracted by using D101 resin; its major components were analysed preliminarily by thin layer chromatography, ultraviolet spectrophotometry and high-performance liquid chromatography; and its anxiolytic effects at 6 mg/kg (low-dose), 9 mg/kg (medium-dose) and 12 mg/kg (high-dose) were evaluated using the elevated plus maze test, the light–dark box test, the Vogel’s drinking conflict test, and the open field drink test. Its action mechanism was investigated using the ELISA. This study provided evidence on the anxiolytic potency of the iridoid fraction from V. jatamansi and revealed its action mechanism of regulating the GABA level.     

Mass spectrometric profiling of valepotriates possessing various acyloxy groups from Valeriana jatamansi

Valepotriates, plant secondary metabolites of the family Valerianaceae, contain various acyloxy group linkages to the valepotriate nucleus and exhibit significant biological activities. Identification of valepotriates is important to uncover potential lead compounds for the development of new sedative and antitumor drugs. However, making their structure elucidation by nuclear magnetic resonance (NMR) experiments is too difficult to be realized because of the overlapped carbonyl carbon signals of acyloxy groups substituted at different positions. Thus, the mass spectrometric profiling of these compounds in positive ion mode was developed to unveil the exact linkage of acyloxy group and the core of valepotriate. In this study, electrospray ionization tandem multistage mass spectrometry (ESI‐MS/MSⁿ) in ion trap and collision‐induced dissociation tandem MS were used to investigate the fragmentation pathways of four types of valepotriates in Valeriana jatamansi, including 5‐hydroxy‐5,6‐dihydrovaltrate hydrin (5‐hydroxy‐5,6‐dihydrovaltrate chlorohydrin), 5,6‐dihydrovaltrate hydrin (5,6‐dihydrovaltrate chlorohydrin), 5‐hydroxy‐5,6‐dihydrovaltrate and valtrate hydrin (valtrate chlorohydrin). The high‐resolution mass spectrum (HRMS) data of all the investigated valepotriates from quadrupole time‐of‐flight MS/MS were used as a supportive of the fragmentation rules we hypothesized from ion‐trap stepwise MSⁿ. As a result, the loss sequence of acyloxy groups and the abundance of key product ions, in combination with the characteristic product ions corresponding to the valepotriate nucleus, could readily differentiate the four different types of valepotriates. The summarized fragmentation rules were also successfully exploited for the structural characterization of three new trace valepotriates from V. jatamansi. The results indicated that the developed analytical method could be employed as a rapid, effective technique for structural characterization of valepotriates, especially for the trace compounds that could not be identified by NMR techniques. This study may also arouse interest for further structural analysis of other valepotriate‐containing type herbal medicines. Copyright © 2015 John Wiley & Sons, Ltd.     

Two New Iridoids from the Stem of Catalpa ovata

Two new iridoids, 6‐O‐[(E)‐feruloyl]jioglutin D ( 1 ) and 6‐O‐(4‐hydroxybenzoyl)jioglutin D ( 2 ), and six known compounds, minecoside ( 3 ), specioside ( 4 ), picroside II ( 5 ), picroside III ( 6 ), 4‐hydroxybenzoic acid ( 7 ), and martynoside ( 8 ), were isolated from the stem of Catalpa ovata. The structures of the new compounds were established on the basis of spectroscopic techniques, including 1D‐ and 2D‐NMR.     

毛细管电泳-电化学检测法测定蜘蛛香中多元酚类化合物

采用毛细管电泳 电化学检测法(CE ED)同时测定了蜘蛛香根中香叶木素、山奈酚、芹菜素、绿原酸 和咖啡酸等5种主要生物活性成分的含量,考察了运行缓冲液酸度、浓度、分离电压、氧化电位和进样时间等 实验参数对分离、检测的影响。在最佳实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为+ 950mV(vs.SCE),在50mmol/L的硼砂缓冲溶液(pH9.23)中,上述各组分在23min内能完全分离。5种组 分在两个数量级的范围内呈良好线性关系,检测下限(S/N=3)达1.7×10-4～1.8×10-5g/mL。该法已成功 地应用于蜘蛛香根中活性成分的分离检测,结果令人满意。     

Iridoids from the roots of Valeriana jatamansi and their biological activities

A new iridoid, jatamandoid A (1), and four known analogues (2-5) were isolated from the roots of Valeriana jatamansi. Their structures were elucidated on the basis of extensive spectroscopic analysis (IR, ESI-MS, HR-ESI-MS, 1-D and 2-D NMR). Five compounds were evaluated and compounds 1, 2 and 5 showed moderate neuroprotective effects against MPP(+)-induced neuronal SH-SY5Y cell death.     

Flexible and powerful strategy for qualitative and quantitative analysis of valepotriates in Valeriana jatamansi Jones using high‐performance liquid chromatography with linear ion trap Orbitrap mass spectrometry

Valeriana jatamansi Jones is an important medicinal plant and its quality is closely related to its region of origin. In the current study, we utilized a flexible and powerful strategy for comprehensive evaluation of the quality diversity for 15 regions in China. The method was based on a hybrid linear ion trap‐Orbitrap mass spectrometry platform. For structure characterization, fragmentation patterns were detected by analyzing a series of standard compounds using data dependent multistage mass spectrometry acquisition. A fragment ion database for valepotriates was established, and the acquired data were high throughput filtered by fragment ion search for compound identification. For quantitative purposes, we normalized the mass spectrometry data of 15 samples using SIEVE 2.0 and the differences in composition were analyzed using principal component analysis combined with hierarchical clustering analysis. The results identified a total of 92 compounds from Valeriana jatamansi Jones. Samples from Dali, Kunming, and Baoshan have better qualities and concentrations of the main active constituents. To verify our strategy, we compared the valtrate, acevaltrate, and baldrinal contents using high‐performance liquid chromatography with diode array detector. We developed and validated a comprehensive qualitative and quantitative analytical method to achieve quality control of Valeriana jatamansi Jones.     

Two New Sesquiterpenes from the Roots of Valeriana fauriei Briq.

A phytochemical investigation of the MeOH extract of Valeriana fauriei Briq . roots resulted in the isolation of two new sesquiterpenes, isovalerianin A (=(1β,4Z,6β,8α)‐8‐(acetyloxy)‐1,10‐dihydroxy‐6,11‐cyclogermacr‐4‐en‐15‐al=rel‐(1R,2Z,6S,7R,9R,10S)‐9‐(acetyloxy)‐6,7‐dihydroxy‐7,11,11‐trimethylbicyclo[8.1.0]undec‐2‐ene‐3‐carboxaldehyde; 1 ) and valerianin C (=(2α,3α,6α,8α)‐3‐(acetyloxy)‐2,4,8‐trihydroxyguai‐1(10)‐ene‐12,6‐lactone=rel‐(3R,3aS,4R,7S,8S,9R,9aR,9bR)‐8‐(acetyloxy)‐3a,4,5,7,8,9,9a,9b‐ octahydro‐4,7,9‐trihydroxy‐3,6,9‐trimethylazuleno[4,5‐b]furan‐2(3H)‐one; 2 ), together with six known compounds, i.e., camphor, methyl 4‐hydroxybenzoate, 2‐methoxybenzoic acid, benzoic acid, quercetin, and kaempferol. The structures of the compounds were established by detailed spectral analysis and comparison with previously reported data.     

Valtrate from Valeriana jatamansi Jones induces apoptosis and inhibits migration of human breast cancer cells in vitro

Abstract

Valtrate is a principle compound isolated from Valeriana jatamansi Jones, a traditional Chinese folk medicine originally used to treat various nervous disorders. Here, we found that valtrate exhibited significant anti-cancer activity in vitro, especially in human breast cancer cells, while displayed relatively low cytotoxicity to normal human breast epithelial cells (MCF 10A). Valtrate induced cell cycle arrest at G2/M stage and apoptosis in MDA-MB-231 and MCF-7 cells, with reduced expression of p-Akt (Ser 473), cyclin B1 and caspase 8, and increased expression of p21, p-cdc2, cleaved-caspase 3, cleaved-caspase 7 and poly (ADP-ribose) polymerase (PARP). In addition, valtrate inhibited cell migration through down-regulation of MMP-9 and MMP-2 expression. These results demonstrate that valtrate possesses anti-breast cancer activities via cell cycle arrest, apoptosis, and inhibition of cell migration, thus supporting valtrate as a potential antitumor agent.     

Quantification of Valerenic Acid in Valeriana jatamansi and Valeriana officinalis by HPTLC

A simple, rapid, cost-effective and accurate high performance thin layer chromatographic method has been developed for quantification of valerenic acid in Valeriana jatamansi and Valeriana officinalis which is one of the stable compounds of Valeriana officinalis and designated as a key marker compound. Valerenic acid makes substantial contribution to the sedative and spasmolytic activity of the essential oil and extract of Valeriana officinalis. Separation and quantification was achieved by HPTLC using ternary mobile phase of hexane: ethyl acetate: acetic acid (80:20:0.5 v/v) on precoated silica gel 60F₂₅₄ aluminium plates and densitometric determination was carried out after derivatization with anisaldehyde-sulphuric acid reagent at 700 nm, in absorption-reflectance mode. The calibration curves were linear in the range of (500 ng–2.5 μg). This is the first HPTLC report for the identification and quantification of valerenic acid in Valeriana jatamansi and Valeriana officinalis.     

Two New Antibacterial Iridoids from Patrinia rupestris

Patrinia rupestris has long been used as Chinese folk medicine for treatment of enteritis, appendicitis and hepatitis1. The chemical studies of this plant have not been reported till now, and iridoid containing chlorine has not been isolated from Patrinia…     

Iridoids from the Bark of Alstonia scholaris

Four new 11‐noriridoids named scholareins A–D ( 1 – 4 ), along with three known derivatives, isoboonein ( 5 ), alyxialactone ( 6 ), and loganin ( 7 ), were isolated from EtOH extracts of the bark of Alstonia scholaris by chromatographic methods. Their structures were identified by extensive mass‐spectrometric and spectroscopic (especially 2D‐NMR) experiments.     

Two New Indole Alkaloids from Emmenopterys henryi

Two new indole alkaloids, 5‐oxodolichantoside ( 1 ) and deglycocadambine ( 2 ), were isolated from the twigs and leaves of Emmenopterys henryi, together with four known indole alkaloids and five known iridoids. The structures of the new compounds were elucidated on the basis of extensive spectroscopic analyses, including 1D‐ and 2D‐NMR experiments, and confirmed by single‐crystal X‐ray diffraction studies. This is the first report on the isolation of indole alkaloids from this species. The indole alkaloids were evaluated for their cytotoxic activities against five human cancer lines.     

Iridoids and sesquiterpenoids with NGF-potentiating activity from the rhizomes and roots of Valeriana fauriei

A new iridoid glycoside, 10-isovaleryl kanokoside C (1), and a new sesquiterpene (2) together with two known compounds (3, 4) were isolated from the rhizomes and roots of Valeriana fauriei. Their structures were elucidated on the basis of spectroscopic analysis. Compounds 2 and 4 showed enhancing activity of nerve growth factor (NGF)-induced neurite outgrowth in PC 12D cells.     

Two New Constituents from Torricellia tiliifolia Stem Barks

A new iridoid, torrilliolide ( 1 ), and a new pyridine alkaloid, torricelline ( 2 ), were isolated from the stem barks of Torricellia tiliifolia. Their structures were determined by analysis of their spectroscopic data. Both compounds exhibited cytotoxicity against Spodoptera litura cell line.     

A rapid and highly sensitive UPLC-QTOF MS method for quantitative evaluation of Nardostachys jatamansi using Nardin as the marker

Nardostachys jatamansi DC. is a highly reputed Medhya and Nootropic (Learning and Memory) Ayurvedic medicinal plant. Its use as herbal medicine singly and as an ingredient of multi‐herbal formulations is fast increasing. In order to authenticate and evaluate it quantitatively, its standardization is highly warranted with respect to a reliable marker. In this connection a rapid and highly sensitive UPLC‐QTOF MS method has been developed. The analysis was carried out on an Acquity BEH C₁₈ column with gradient elution of methanol–water and 3 mm ammonium acetate using QTOF mass detector in negative ionization mode. The method was validated over a concentration range of 9.76–156.25 ng/mL nardin. The calibration curve is linear with the correlation coefficient (r) and coefficient of determination (R²) were 0.9997 and 0.9995 respectively. The LOD and LOQ were 3.050 and 9.277 ng/mL respectively. The recovery of nardin in the range 96.36–111.13% achieved from spiked samples was consistent and reproducible. The inter‐day and intra‐day assay precision of the analytes over the entire concentration range was less than 5%. The developed method required only 4 min for chromatography to authenticate and quantify the marker, viz. nardin in N. jatamansi samples, in addition to the sample preparation time. Copyright © 2010 John Wiley & Sons, Ltd.     

Chemical Diversity of Essential Oil of Valeriana jatamansi from Different Altitudes of Himalaya and Distillation Methods

Valeriana jatamansi is an important temperate herb that is used in the pharmaceutical and essential oil industries. In India, this species is now on the verge of extinction due to the over-exploitation of its rhizomes from its natural habitat. It is hypothesized that the variations in bioactive compounds in its essential oil are very high among the wild populations as well as cultivated sources. Thus, this study was conducted to evaluate the chemical profiling of essential oil of four wild populations (Rupena, Kugti, Garola, and Khani) and two cultivated sources (CSIR-IHBT, Salooni), which were distilled at three consecutive days. The variation in oil concentration in roots/rhizomes was found significant (p ≤ 0.05), and the maximum value (0.35%) was registered with the population collected from Kugti and Khani. In essential oil, irrespective of population and distillation day, patchouli alcohol was the major compound, which ranged from 19 to 63.1%. The maximum value (63.1%) was recorded with the essential oil obtained from Garola’s population and distilled on the first day. The percentage of seychellene was abruptly increased with subsequent days of extraction in all the populations. The multivariate analysis revealed that the essential oil profiles of Rupena, Kugti, Garola, and CSIR-IHBT populations were found to be similar during the first day of distillation. However, during the second day, Rupena, Kugti, Khani, and CSIR-IHBT came under the same ellipse of 0.95% coefficient. The results suggest that the population of Kugti is superior in terms of oil concentration (0.35%), with a higher proportion of patchouli alcohol (63% on the first day). Thus, repeated distillation is recommended for higher recovery of essential oil. Moreover, repeated distillation can be used to attain V. jatamansi essential oil with differential and perhaps targeted definite chemical profile.