中国薯蓣属植物中的甾体皂苷及甾体皂苷元

中国薯蓣属(Dioscorea L.)植物含有约21种甾体皂苷元,其中大部分种类含有3β-羟基皂苷元,少数种类含有3α-羟基皂苷元。从薯蓣属13种植物中共分离出59个甾体皂苷成分,按化学结构可将这些甾体皂苷分为4种类型。约有17种薯蓣属植物含有甾体皂苷元(主要为薯蓣皂苷元),均为根茎组(Sect.Stenophora)种类。在查阅大量资料的基础上,对各种类所含的甾体皂苷元和甾体皂苷成分及各成分的化学结构进行了归纳和综述。     

(25R)-Isonuatigenin,an unusual steroidal sapogenin from Vestia lycioides

(25R)-Isonuatigenin, a ⁵-spirosten-3β,25-diol, was isolated from aerial parts of Vestia lycioides. Its structure was elucidated mainly by ¹H NMR and ¹³C NMR spectroscopy. A mixture of (25R)-nuatigenin and (25S)-isonuatigenin was also characterized. This is the first report on the natural occurrence of the two (25R)-isomers.     

Carbon-13 NMR spectroscopy of steroidal sapogenins and steroidal saponins

The ¹³C NMR chemical shifts of 130 naturally occurring steroidal sapogenins and saponin derivatives published up to 1983 are listed and a number of methods for signal assignment are explained. The utility of ¹³C NMR spectral analysis for the structure elucidation of these compounds is discussed.     

The occurrence of batatasins in the dioscoreaceae

The tubers and/or aerial bulbils of 13 species of Dioscorea, mostly of tropical origin, and one species each of Rajania and Tamus, were examined for the presence of batatasins. These phenolics have previously been reported in the temperate species D. opposite. One or more batatasins were found in either tubers or bulbils of most species examined, including taxa from both Old and New Worlds, and with annual or perennial tubers. Batatasin I was the most widespread in occurrence, followed by B-II, while B-III, B-IV and B-V were comparatively rare. Only the buibils of D. opposite contained all five batatasins.     

Steroidal saponins from Dioscorea floribunda: Structures of floribundasaponins A and B

Two steroidal saponins, floribundasaponins A and B isolated from the yams of Dioscorea floribunda, have been characterized as pennogenin-3-O-β-d-glucopyranoside and pennogenin-3-O-α-l-rhamnopyranosyl(1→4)-β-d-glucopyranoside.     

Dormantinol,a possible precursor in solanidine biosynthesis,from budding Veratrum grandiflorum

A new sapogenin, dormantinol, was isolated from budding Veratrum, and identified as (25S)-cholest-5-ene-3β,22α,26-triol by spectral analysis and its synthesis from dormantinone. Cholesterol was also identified in the budding Veratrum.     

The steroidal glycoalkaloid α-tomatine

The literature relating to chemical, biochemical and biological aspects of the steroidal glycoalkaloid, α-tomatine, is reviewed. The alkaloid, which can be used as a starting compound for the synthesis of steroidal hormones, is toxic to a wide range of living organisms. The significance of tomatine to plants which elaborate it is discussed and some possible uses of the compound are mentioned.     

Cardenagenin,a steroidal sapogenin from Calibanus hookerii

One new steroidal sapogenin with an open side chain was isolated from the rhizome of Calibanus hookerii. The structure has been determined by spectroscopic studies as 14α-hydroxy-calibagenin.     

Structure of barogenin from Solanum tuberosum

The budding tuber of Solanum tuberosum accumulated barogenin. Its structure was determined by chemical and spectroscopic studies as (25S)-3β, 26-dihydroxy-cholest-5-ene-16,22-dione, the (25S)-epimer of kryptogenin. The biogenetic relationship between barogenin and spirostanols is discussed.     

Structure of solanaviol,a new steroidal alkaloid from Solanum aviculare

A new alkaloid solanaviol ((22R, 25R)-spirosol-5-ene-3β,12β-diol) was isolated from Solanum aviculare in addition to solasodine as one of the main alkaloids. The structure of solanaviol was established by NMR spectroscopy, as well as by conversion into a known pregnane derivative and solasodine.     

广西蜘蛛抱蛋中一种甾体皂甙定性定量研究

为了进一步开发和利用广西甾体药源植物奠定基础 ,对广西蜘蛛抱蛋 (Aspidistra retusa K.Y.Langet.S.Z.Huang)块茎甾体皂甙化合物进行了提取分离。在分离得化合物中含量最高的甾体皂甙化合物 4经鉴定为 :偏诺甾体四糖皂甙 ,即 pennogenin-3-β-O-β-D-glucopyranosyl[-α-L-rhamno-pyranosyl(1 -2 ) ]-α-L-rham-no-pyanosyl(1 -4 ) -α-L-rhamnopyranosyl(1 -4 )。该化合物为首次从蜘蛛抱蛋属植物中分离得到。经 HPLC测定其在广西蜘蛛抱蛋中的含量为 1 .5 95 %。     

Distribution of stizolamine in some leguminous plants

The seeds of 38 species of 29 genera in 21 tribes of the Leguminosae were screened for stizolamine. It was detected in 19 species of the subfamily Lotoideae. Its occurrence in Lotoideae was wide (82% in tribes, 56% both in genera and species) but sporadic. The content was fairly varied (0·249–9540 nmol/g of seeds), the largest amount occurring in Stizolobium hassjoo.     

Homogeneous enzyme immunoassay of diosgenin and its glycosides

Homogeneous enzyme immunoassay has been used as a tool for the determination of diosgenin and its glycosides in plants. Diosgenin antisera was found to inhibit the activity of diosgenin hemisuccinate-horseradish peroxidase conjugate which was reversed by the addition of free diosgenin or its glycosides. The increase of enzyme activity was proportional to the quantity of the hapten over a certain range of hapten concentration. Thus, a minimum of 2.5 micrograms/ml of diosgenin and 11.5 micrograms/ml of diosgenin glycosides could be determined by this method. The results were comparable with those obtained by high-performance liquid chromatography and gravimetric methods.     

The co-occurrence of ecdysones with bufadienolides and steroidal saponins in the genus Helleborus

A method is described for the detection of ecdysones in small quantities of plant material. When applied to 14 taxa of Helleborus L., ecdysterone and 5 β-hydroxyecdysterone were detected and quantified in 11; the other 3, which are morphologically distinct, gave a negative result. The co-occurrence of ecdysones with bufadienolides and steroidal saponins is discussed. The isolation of the ecdysones from the aerial parts of H. orientalis hybrids is described.     

3-Desamino-3α-hydroxysolanocapsine—a steroidal alkaloid from Solanum aculeatum

A new steroidal alkaloid has been obtained from roots of Solanum aculeatum and its structure elucidated by IR, NMR and mass spectral studies as 3-desamino-3β-hydroxysolanocapsine.     

Intracellular distribution of the steroidal glycoalkaloid α-tomatine in Lycopersicon esculentum fruit

Pericarp tissue from green tomato fruits was homogenized and separated into organelle fractions by differential centrifugation. Tomatine was found mainly in the final (105 000g) supernatant, with small amounts in the microsomes. Expressed sap from intact tissue was also rich in the alkaloid. It is suggested that tomatine accumulates in the vacuoles and/or soluble phase of the cytoplasm and is possibly synthesized in microsomal organelles.     

Destabilization of liposome membranes by the steroidal glycoalkaloid α-tomatine

The effect of the steroidal glycoalkaloid α-tomatine on the leakage of peroxidase from liposomes was studied. At pH 7.2, the optimum pH for disruption, tomatine had little effect at concentrations less than 10μM but was increasingly disruptive at concentrations of 10–100μM. Liposome destabilization was pH-dependent declining with decreasing pH until at pH 5 lysis was achieved only at tomatine concentrations of 500–1000μM. At all pH values tested (pH 5–8), tomatine caused significant disruption only if the membrane contained sterol. The extent of membrane damage was correlated with the concentration of sterol in the liposomes but not with the nature of the sterol or of the phospholipid. These findings are inconsistent with claims that surface glycosidases, which convert the glycoside to the aglycone, are prerequisites for tomatine action and that the aglycone is the active moiety.     

Aculeamine,a solanocapsine-type steroidal alkaloid from Solanum aculeatum

A new solanocapsine-type alkaloid named aculeamine has been isolated from roots of Solanum aculeatum and its structure elucidated by physical methods including X-ray analysis as 22,26-epimino-22β-methoxy- 16α,23-epoxy-5α,22αH,25βH-cholestane-3β-ol. The corresponding 23β-ethoxy compound was also isolated as an artefact.