来江藤的苯丙素类配糖体成分

从云南民间药用植物来江藤(Brandisia hancei Hook．f．)的全草中分离到10个化合物,分别鉴定为3,4-二羟基苯乙醇基-O-α-L-鼠李吡喃糖基(1→3)-β-D-(4-O-咖啡酰基)-半乳吡喃糖苷(1),3,4-二羟基苯乙醇基-O-α-L-鼠李吡喃糖基(1→3)-β-D-(2-O-乙酰基-4-O-咖啡酰基)-半乳吡喃糖苷(2),acteoside(3),2’-acetylacteoside(4),poliumoside(5),2’-acetylpohumoside(6),mussaenoside(7),luteolin-7-O-β-D-glucoside(8),luteolin(9)和mannitol(10)。化合物1-6为苯丙素配糖体成分,其中化合物2为新化合物,化合物1为首次从该属植物中获得。关键词：来江藤;苯丙素类配糖体;3,4-二羟基苯乙醇基-O-α-L-鼠李吡喃糖基(1→3)-β-D-(2-O-乙酰基-4-O-咖啡酰基)-半乳吡喃糖苷。     

Isomartynoside,a phenylpropanoid glycoside from Galeopsis pubescens

The structure of isomartynoside, a new phenylpropanoid glycoside, isolated along with the known martynoside from Galeopsis pubescens, has been elucidated on the basis of chemical and spectral data as 3-hydroxy-4-methoxy-β-phenylethoxy-O-α-L-rhamnopyranosyl-(1 → 3)-6-O-feruloyl-β-D-glucopyranoside.     

Isoangoroside C, a phenylpropanoid glycoside from Scrophularia scorodonia roots

A new phenylpropanoid glycoside isoangoroside C was isolated from the roots of Scrophularia scorodonia. Its structure was determined on the basis of spectral data as: 3-hydroxy-4-methoxy-beta-phenylethoxy-O-alpha-L-arabinopyranosy l-(1-->6)alpha L-rhamnopyranosyl-(1-->3)-4-O-Z-feruloyl-beta-D-glucopyranoside. Additionally, one known phenylpropanoid, angoroside C, and five known iridoid glycosides, harpagoside, bartsioside, 8-O-acetyl-harpagide, aucuboside and harpagide were isolated and identified.     

Total synthesis of syringalide B, a phenylpropanoid glycoside

The first total synthesis of syringalide B, 2-(4-hydroxyphenyl)ethyl 4-O-[(E)-feruloyl]-beta-D-glucopyranoside, is described. The hydroxyl groups were protected with allyloxycarbonyl (Aoc) and allyl groups, which successfully prevent the migration of the feruloyl group during the deblocking procedure.     

Trichotomoside: a new antioxidative phenylpropanoid glycoside from Clerodendron trichotomum

The structure and antioxidant properties of a new natural glycoside, trichotomoside (1), isolated from Clerodendron trichotomum, were investigated. Trichotomoside was identified as 2-(3-hydroxy-4-methoxyphenyl)ethyl 3-O-(2,3-di-O-acetyl-alpha-L-rhamnopyranosyl)-4-O-[(2E)-3-(3-hydroxy-4-methoxyphenyl)prop-2-enoyl]-beta-D-glucopyranoside. The compound was active towards intracellular reactive oxygen species (ROS) and exhibited DPPH-radical-scavenging effects. The radical-scavenging activity of 1 was found to protect the viability of Chinese hamster lung fibroblasts (V79-4 cells) exposed to H2O2 and gamma-irradiation.     

Effects of verbascoside,a phenylpropanoid glycoside from lemon verbena,on phospholipid model membranes

Phenylpropanoid glycosides are water-soluble compounds widely distributed, most of them deriving from medicinal herbs. Among them, verbascoside or acteoside has exhibited a wide biological activity, being free radical scavenging the most representative one. Moreover, antitumor, antimicrobial, anti-inflammatory, anti-thrombotic and wound healing properties have been previously described. Herein, the interaction of verbascoside with phospholipid membranes has been studied by means of differential scanning calorimetry, fluorescence anisotropy and dynamic light scattering. Verbascoside showed stronger affinity for negatively charged membranes composed of phosphatidylglycerol (PG) than for phosphatidylcholine (PC) membranes. This compound promoted phase separation of lipid domains in PC membranes and formed a stable lipid complex with and approximate phospholipid/verbascoside ratio of 4:1. Despite its hydrophilic character, verbascoside's caffeoyl moiety was located deep into the hydrophobic core of PC membranes and was almost inaccessible to spin probes located at different depths in PG membranes. This compound affected the ionization behavior of the PG phosphate group and most likely interacted with the vesicles surface. The presence of verbascoside decreased the particle size in PG unilamellar vesicles through the increase of the phospholipid head group area. A localization of verbascoside filling the upper region of PG bilayers close to the phospholipid/water interface is proposed. These effects on membranes may help to understand the mechanism of the biological activity of verbascoside and other similar phenylpropanoid glycosides.     

Synthesis of a benzyl-protected analog of arenarioside, a trisaccharide phenylpropanoid glycoside

A benzyl-protected analog of the phenylpropanoid glycoside arenarioside, (4-benzyloxyphenyl)ethyl alpha-L-rhamnopyranosyl-(1-->3)-4-O-[(E)-3,4-di-O-benzyl-caffeoyl]-[beta-D-xylopyranosyl-(1-->6)]-beta-D-glucopyranoside (22), was synthesized through two different routes from D-glucose. This is the first approach on the synthesis of a trisaccharide phenylpropanoid glycoside, although the benzyl-protecting group in the backbone of the arenarioside analog could not be removed by conventional debenzylation procedures.     

Staggered arrangement and sequential dehiscence of anthers in didynamous stamens facilitate reproductive fitness of Brandisia hancei

Didynamous stamens are separated into two pairs of different length, and the implication of this arrangement has not been well understood. The functional advantages of didynamous stamens were investigated in Brandisia hancei. Change of stamens during floral aging was recorded; the quantity, viability, and siring ability of pollen grains were tested; the anther arrangement was manipulated into four types based on stamen category and number, and fruit set and number of seeds per fruit were measured. Didynamous stamens exhibited staggered anther arrangement, and pollen sacs dehisced gradually. There was no difference for quantity, viability, and siring ability of pollen grains between the two pairs of anthers. Seed production after the removal of one long and one short stamen was higher than that of two long or two short stamens. Through prolonging pollen presentation and promoting delayed self-pollination, staggered arrangement and sequential dehiscence of anthers in didynamous stamens facilitate reproductive fitness of B. hancei.     

Growth discrepancy between filament and style facilitates self‐fertilization in Brandisia hancei (Paulowniaceae)

Self‐pollination has been hypothesized to be beneficial in environments where pollinators are rare as it can provide reproductive assurance. This study presents evidence for an autonomous self‐fertilization mechanism in the winter flowering plant, Brandisia hancei. To determine changes in the spatial separation of stigma and anthers, the length of style and stamens was recorded. Additionally, pollination treatments were carried out to test fruit‐set and seed production. Brandisia hancei is herkogamic in the early flowering stages. However, different growth rates of the filament and style lead to contact of stigma and anthers in the later stages, thereby facilitating self‐pollination. The highest seeds number is produced under an out‐crossing scenario but plants produce a considerable number of seeds even when purely selfed. Although pollinators are scarce, autonomous selfing alleviates the pollen limitation in B. hancei. Self‐fertilization in B. hancei seems to be an adaptive strategy to ensure reproduction when pollinators are scarce.     

Rubiginoside, a farnesyl glycoside from Lepisanthes rubiginosa.

Chemical investigation of the methanolic fraction of Lepisanthes rubiginosa bark has led to the isolation and characterisation of a new tetrasaccharide derivative of farnesol named rubiginoside along with known triterpenoid saponins.     

A new phenylpropanoid glycoside from the bark of Streblus ilicifolius (Vidal) Corner

A new compound, pheglycoside A (1), along with four known aromatic glycosides (2-5) and three known lignan glycosides (6–8) were isolated from Streblus ilicifolius (Vidal) Corner. The structure of compound 1 was determined by spectral analyses, including HRESIMS, 1D, and 2D NMR (COSY, HSQC, and HMBC) experiments. The absolute configuration of compound 1 was determined using the CD spectrum and experiment data. From the present investigation, all these compounds were isolated for the first time from S. ilicifolius. It is interesting that phenylpropanoid glycoside and aromatic glycosides are reported for the first time in the genus Streblus. The chemotaxonomic significance of these compounds was summarized.     

Lignans from the stems and leaves of Brandisia hancei and their effects on VEGF-induced vascular permeability and migration of HRECs and DLAV formation in zebrafish

In our continuing search for novel antiangiogenic agents, a new lignan glycoside, (7R,8R)-1-(4-O-β-d-glucopyranosyl-3-methoxyphenyl)-2-{2-methoxy-4-[1-(E)-propene-3-ol]-phenoxyl}-propane-1,3-diol (1), along with three known lignans (2–4), were isolated from the 80% EtOH extract of Brandisia hancei stems and leaves. These isolates (1–4) were subjected to an in vitro bioassay to evaluate their effects on vascular endothelial growth factor (VEGF)-induced vascular permeability and migration of human retinal endothelial cells (HRECs). Of the compounds tested, compound 1 resulted in the greatest reduction in VEGF-induced vascular permeability by about 31.5% at 10 μM compared to the VEGF-treated control. In the migration assay, compounds 1 and 2 significantly decreased VEGF-induced HREC migration. Furthermore, zebrafish embryos treated with compounds 1 and 2 showed mild reductions of dorsal longitudinal anastomotic vessel (DLAV) formation.     

Helmanticine,a phenylpropanoid from Thapsia villosa

Helmanticine, a new phenylpropanoid esterified by angelic and 2,3-dihydroxy-2-methylbutyric acids, was isolated from Thapsia villosa and its full structure established by spectroscopic methods and chemical transformations. Hydrocarbons, 12-nonacosanone, sitosterol and latifolone were also isolated.     

Balanitoside, a furostanol glycoside, and 6-methyldiosgenin from Balanites aegyptiaca.

In addition to a known spirostanol glycoside, balanitin-3, and a new sapogenol, 6-methyldiosgenin, a new furostanol saponin, balanitoside has been isolated from the fruits (mesocarp) of Balanites aegyptiaca. The structure of the glycoside has been determined as 26-O-beta-D-glucopyranosyl-3 beta, 22,26-trihydroxy-furost-5-ene 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D- glucopyranosyl-(1-->4)-beta-D-glucopyranoside, on the basis of spectroscopic and chemical evidence.     

Glochidioside,a triterpene glycoside from Glochidion heyneanum

A new triterpenoid glycoside, glochidioside, has been isolated from Glochidion heyneanum. Its structure has been established as 3β[(O-β-D-glucopyranosyl-(1 → 3)-O-α-L-arabinopyranosyl)oxy]-16β-benzoyloxy-olean-12-ene-21β,23,28-trio     

Ipopurpuroside,a new glycoside from Ipomoea purpurea

A new glycoside, ipopurpuroside, has been isolated from Ipomoea purpurea. The results of acid hydrolysis together with chemical and spectroscopic analyses have shown that it consists of glucose, rhamnose and 6-deoxy-D-glucose glycosidically linked to ricinoleic acid. The acyl group removed by alkaline hydrolysis was identified as methylbutyric acid. The carboxyl group of ipopurpuroside is esterified.     

Reaction of hydroxyl radical with phenylpropanoid glycoside and its derivatives by pulse radiolysis

The reaction of hydroxyl radical with 1 phenylpropanoid glycoside (PPG), cistanoside C, and its 3 derivatives: 1-0-β-D-2-(p-hydroxyphenyl)-ethanyl-glucose, 6-O-(E)-femloyl-glucose and 6-O-(E)-p-hydroxy-cinnarnoylglucose isolated from folk medicinal herbs was investigated by pulse radiolysis technique respectively. The reaction rate constants were determined by analysis of built-up trace of absorption at λ_max of specific transient absorption spectra of PPG and its derivatives upon attacking · OH. All four compounds react with · OH at close to diffusion controlled rate (1. 03 × 10⁹-19.139 × 10⁹ L · mol⁻¹ · s⁻¹), suggesting that they are effective · OH scavengers. The results demonstrated that the numbers of phenolic hydroxyl groups of PPG and its derivatives are directly related to their scavenging activities. By comparing the reaction rates of · OH with 1-O-β-D-2-(p-hydroxyphenyl)-ethanyl-glucose, 6-O-(E)-feruloyl-glucose or 6-O-(E)-p-hydroxy-cinnomoyl-glucose, it is evident that the phenylethyl group is more impofiant than phenylacryloyl group for scavenging · OH.     

Physocalycoside,a new phenylethanoid glycoside from Phlomis physocalyx Hub.-Mor

A new phenylethanoid tetraglycoside, physocalycoside (2), was isolated from the aerial parts of Phlomis physocalyx. Its structure was identified as 3-hydroxy-4-methoxy-beta-phenylethoxy-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)]-4-O-feruloyl-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside, on the basis of spectroscopic evidence. In addition, one known iridoid glucoside, lamiide (1) and five known phenylethanoid glycosides, wiedemannioside C (3), verbascoside (= acteoside) (4), leucosceptoside A (5), martynoside (6), and forsythoside B (7) were also characterized. Compounds 2-7 demonstrated radical scavenging properties towards the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical.     

Two phenylpropanoid glycosides from Leonurus glaucescens.

Two new phenylpropanoid glycosides, leonosides A and B, and two known glycosides lavandulifolioside and verbascoside, were isolated from the aerial parts of Leonurus glaucescens. On the basis of chemical and spectral evidence, leonosides A and B were shown to be beta-(3,4-dihydroxyphenyl)-ethyl-O-alpha-L-arabinopyranosyl-(1---- 2)-alpha-L- rhamnopyranosyl-(1----3)-4-O-feruloyl-beta-D-glucopyranoside and beta-(3-hydroxy, 4-methoxyphenyl)-ethyl-O-alpha-L-arabinopyranosyl-(1----2)- alpha-L-rhamnopyranosyl-(1----3)-4-O-feruloyl-beta-D-glucopyranosi de, respectively.