Quantitation of seven polyoxypregnane glycosides in Marsdenia tenacissima using reversed-phase high-performance liquid chromatography-evaporative light-scattering detection

A high-performance liquid chromatography coupled with an evaporative light scattering detector (HPLC-ELSD) has been developed for the simultaneous determination of seven polyoxypregnane glycosides, tenacissosides A, B, G, H, I and marsdenosides C, G, in the stem of Marsdenia tenacissima, a Chinese herbal medicine. With a C18 analytical column, the analytes were separated efficiently using methanol-water as the mobile phase in a gradient program. The method limits of detection ranged from ca. 0.3 microg for marsdenoside C to ca. 0.5 microg for marsdenoside G and the method limits of quantitation from 1.0 microg for marsdenoside C to 1.7 microg for marsdenoside G, respectively. The intra- and inter-day precisions of the method were evaluated and all were less than 4%. All the recoveries for the spiked analytes exceeded 90%. This method was successfully used to analyze 19 samples of the stem of M. tenacissima.     

Identification of polyoxypregnane glycosides from the stems of Marsdenia tenacissima by high-performance liquid chromatography/tandem mass spectrometry

A facile method based on high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC/(+)ESI-MSⁿ) has been established for the analysis of polyoxypregnane glycosides in the stems of Marsdenia tenacissima. The data reveals the ability of MSⁿ in the structural elucidation of polyoxypregnane glycosides including the nature of the polyoxypregnane core, the kinds of the substituents and the types of sugar residues. Offline Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is also performed to assign accurate elemental compositions. In this study, eighteen polyoxypregnane glycosides have been investigated. Among these components, five compounds are unambiguously identified as Marsdenoside K, Tencissoside A, B, C and D; two compounds are established as novel compounds based on mass spectral data; and the other eleven compound's structures are tentatively proposed. Furthermore, breakdown curves are constructed to distinguish five pairs of isomers among these eighteen compounds. As far as our knowledge, this is the first report on identification of polyoxypregnane glycosides in the stems of M. tenacissima by HPLC/ESI-MSⁿ directly, which could save time and material consuming efforts in traditional phytochemistry analyses.     

Two new C21 steroidal glycosides from Marsdenia tenacissima (ROXB.) WIGHT et ARN

Two new C(21) steroidal glycosides, tenacissoside L (1), tenacissoside M (2), were isolated from the stems of Marsdenia tenacissima (ROXB.) WIGHT et ARN. Their structures were elucidated, respectively, by means of chemical and spectral data, including ESI-MS, HR-ESI-MS, 1D-NMR and 2D-NMR.     

Three New Pregnane Glycosides from Marsdenia tinctoria

Three new pregnane glycosides, tinctorosides A–C ( 1 – 3 , resp.), together with one known pregnane glycoside, stephanoside B ( 4 ), were isolated from the stems of Marsdenia tinctoria R. Br . (Asclepiadaceae). Their structures were elucidated by extensive spectral methods, especially 2D‐NMR experiments (¹H,¹H‐COSY, HSQC, HMBC, TOCSY, HSQC‐TOCSY, and ROESY), and chemical evidence.     

Three New Polyoxypregnane Glycosides from Marsdenia tenacissima

Three new polyoxypregnane glycosides, marsdenosides I–K ( 1 – 3 ), were isolated from the stem of Marsdenia tenacissima. The structures were elucidated on the basis of in‐depth spectroscopic analyses, and by means of chemical evidence. Marsdenoside I ( = (3β,5α,11α,12β,14β,17α,20R)‐3‐[(2,6‐dideoxy‐4‐O‐(6‐deoxy‐3‐O‐methyl‐β‐D ‐allopyranosyl)‐3‐O‐methyl‐β‐D ‐arabino‐hexopyranosyl)oxy]‐8,20 : 11,20‐diepoxypregnane‐12,14‐diol; 1 ) is the first C₂₁ steroidal glycoside with a rigid cage. Also, the isolation of 1 demonstrated that tenacigenin A ( 1a ) is a true natural product as well, rather than an artifact.     

Polyoxypregnanes from the stems of Marsdenia tenacissima

From the stems ofMarsdenia tenacissima two new polyoxypregnanes were isolated, their structures were elucidated by 1D, 2D-NMR as 11α,12β-di-O-tigloyl-tenacigenin B （1） and tenacigenoside E （2）.     

Pregnane and pregnane tetraglycoside from Marsdenia roylei

Pregnane oligoglycoside, namely roylinine, and a pregnane derivative, namely marsgenin, have been isolated from chloroform-soluble extract of dried stem of Marsdenia roylei, and their structures were determined using 1H-NMR, 13C-NMR, 1H-1H COSY, HSQC, TOCSY and FABMS spectral techniques as well as chemical degradation and derivatisation.     

Two New C21 Steroids from Marsdenia tenacissima

Two new C21 steroids were isolated from the CHCI3 extract of the stem of Marsdenia tenacissima. On the basis of spectroscopic analysis and chemical methods, their structures were elucidated as 1713-tenacigenin B (2) and 3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(l→4)-β-D-oleandropyranosyl-tenacigenin C (3). The structure of the known aglycon tenacigenin C was revised as 5ct, 9ct, 1713-pregnane-313, 813, llct, 1213, 14β-pentanol-20-one. Compound 3 is the firstreported glycoside of tenacigenin C.     

The glycosides of Marsdenia erecta R. Br. I. Isolation, glycoside and aglycone. 325

Dried leaves of Marsdenia erecta R. Br. gave over 6% of a crude glycoside mixture, the main portion of which consisted of weakly polar material, soluble in ether or chloroform. By mild acid hydrolysis it yielded crude sugars and aglycones. The following four crist. sugars were isolated: D -cymarose, D -oleandrose and two bioses: pachybiose and marsectobiose (C₁₄H₂₄O₈, new). By PC. and TLC. the presence of digitoxose, canarose, thevetose and 3-O-methyl-6-deoxyallose could be demonstrated. The crude acyl-genin mixture contained β-sitosteryl-β-D -glucopyranoside and three highly hydroxylated pregnane derivatives: drevogenin-P, 17 β-marsdenin (C₂₁H₃₂O₆, new) and marsectohexol (C₂₁H₃₄O₆, new), all partly esterified with acetic, tiglic and benzoic acid. Five crist. acyl-genins (A1–A5) were isolated by chromatography, but most of them still were mixtures. After alkaline hydrolysis of the crude acyl-genins 6 acyl-free compounds were obtained. 4 of them were identical with the above mentioned substances, the other two: 17-iso-drevogenin-P and marsdenin (17 α-marsdenin) are formed from drevogenin-P and 17 β-marsdenin by isomerisation.     

A new C21 steroid glycoside from Marsdenia tenacissima

A new C21 steroid glycoside,11α-O-tigloyl-12-β-O-acetyl tenacigenin B 3-O-β-D-glucopyranosyl-（1→4）-β-D-glucopyr- anosyl-（1→4）-3-O-methyl-6-deoxy-β-D-allopyranosyl-（1→4）-β-D-oleandropyranoside（1）,named tenacissoside N was isolated from the stems of Marsdenia tenacissima.The structure of the glycoside was identified by HR-ESI-MS and NMR spectra.     

A new flavone from Malaysia Borneo Marsdenia tinctoria

Marsdenia tinctoria is an indigo producing plant commonly found in Borneo, Malaysia. In this present study, one new flavone kapitone (1) and three known compounds, that is 3,2’-dihydroxyflavone (2), 1-methylcyclobutene (3) and dimethyl isatoate (4) were isolated from the Malaysia Borneo M. tinctoria R. Br. (Apocynaceae). These compounds were isolated and characterised using extensive chromatographic and spectroscopic methods.     

A new pimarane from Mitrephora tomentosa

A new diterpenoid named (-)-8beta-hydroxypimar-15-en-18-oic acid was isolated, along with (-)-kaur-16-en-19-oic acid, 13,14-dihydrooropheic acid and beta-sitosterol, from the bark of Mitrephora tomentosa.     

A new bisabolene from Stevia tomentosa

The new sesquiterpene (1R,2R,3R,6R,7S)-1-acetoxy-2,3-dihydroxy-2,3-dihydrobisabolene (3) together with ten known terpenes and three known flavonoids were isolated from the aerial parts and from the roots of Stevia tomentosa. The structure of 3 follows from spectral studies, the relative chirality at C-3 follows from 1H NMR coupling constants comparison with the corresponding calculated values obtained by applying a generalized Karplus-type relationship to the dihedral angles of model compounds, and the absolute configuration is assumed in analogy to known (2R,3R,6R,7S)-2,3-epoxy-2,3-dihydrobisabolen-1-one (2).     

A New Triterpenoid Saponin from Anemone tomentosa

TherootsofAnemonetomentosa(Maxim.)PeiareusedasafolkmedicineforthetreatmentofdysenteriainChinal.Recently,twonewcoumarinsandnineknowncompoundswereisolatedfromtheethylacetateeXtractwhichexhibitedstrongantifeedantactivityagainstLeucaniaSeparataWailiee.Duringthefurtherinvestigationofthetitleplant,anewminorsaponin,tomentoside,togetherwithfourknownoneswasisolated.Tomentoside(5),amorphouspowder,[a]D-41.5(MeOH,c0.26).MolecularformulawasdeterminedasC,,H,,.O,.byHRFABMS,m/zf1497.7166([M-H]-),caf…     

Phenolic Compounds from Scorzonera tomentosa L.

From the subaerial parts of S. tomentosa L. (Asteraceae), two new dihydroisocoumarins, compounds 1 and 2 , a new phthalide, 3 , and a new stilbene derivative, 4 , were isolated, together with four known compounds, (±)‐hydrangenol ( 5 ), (?)‐hydrangenol 4′‐O‐β‐glucoside ( 6 ), (±)‐hydramacrophyllol A ( 7 ), and (±)‐hydramacrophyllol B ( 8 ). All secondary metabolites were identified on the basis of physicochemical, spectroscopic, and mass‐spectrometric data. The known compounds 5 – 8 were isolated for the first time from this species.     

Two New Flavonol Glycosides from Bridelia tomentosa

Bridelia tomentosa Bl., a small shrub in the Euphorbiaceae family, is widely distributed in Taiwan, Guangdong, Guangxi and Yunnan Provinces of south China. As a traditional medicine, it is used for curing neurasthenic, turbulence of emmenia, bite of dog, …     

通光散总苷的肿瘤细胞化疗增敏活性与质量控制方法研究

中药通光散(Marsdenia tenacissima)用于肿瘤治疗,研究其抗肿瘤或肿瘤化疗增敏活性提取物具有重要意义。研究发现,浓度为10μg/mL的通光散总苷对白血病K562、宫颈癌HeLa、肝癌HepG2、口腔上皮癌KB-3-1 4种人类肿瘤细胞的生长无影响,细胞活力均达到98%以上,以此为工作浓度联用紫杉醇处理肿瘤细胞,发现与单用紫杉醇组相比,联用后能够显著增强紫杉醇的体外抗肿瘤作用。对活性提取物开展的分析方法研究中,选择6种通光散苷元乙衍生物单体(化合物1~6)作为专属性对照品,采用Phenomenex Luna C18色谱柱,在230 nm下以甲醇-0.1%乙酸水进行梯度洗脱,获得了对通光散总苷中25个成分的良好色谱分离,以及对6种专属性指标成分的辨识;在色谱图中指标成分1~6的色谱峰面积之和为可检测成分总峰面积的43.39%。同时建立了通光散总苷中专属性指标成分1的含量测定方法。所得方法的峰面积精度、含量测定重现性、样品稳定性等数据的相对标准偏差(RSD)为0.16%~0.55%,样品测定的线性范围为0.86~6.45μg,方法回收率为100.4%±1.2%;测得指标成分1的含量为0.74%。