Acylated cyanidin 3-sambubioside-5-glucosides from the purple-violet flowers of Matthiola longipetala subsp. bicornis (Sm) P. W. Ball. (Brassicaceae)

A novel acylated cyanidin 3-sambubioside-5-glucoside was isolated from the purple-violet flowers of Matthiola longipetala subsp. bicornis (Sm) P. W. Ball. (family: Brassicaceae), and determined to be cyanidin 3-O-[2-O-(2-O-(trans-feruloyl)-β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] by chemical and spectroscopic methods. In addition, two known acylated cyanidin 3-sambubioside-5-glucosides, cyanidin 3-O-[2-O-(2-O-(trans-sinapoyl)-β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] and cyanidin 3-O-[2-O-(β-xylopyranosyl)-6-O-(trans-feruloyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside] were identified in the flowers.     

Isolation and Identification of Steroidal Saponins and Sapogenins from Aspidistra zongbayi K. Y. Lang et Z. Y. Zhu

Two steroidal saponins were isolated from the n-BuOH extract of the rhizome of Aspidistra zongbayi K. Y. Lang et Z. Y. Zhu. Their structures were elucidated as 3-O-{β-D-glucopyr-anosyl (l→2)-[β-D-xylopyranosyl (1→3)]-β-D-glucopyranosyl (l→4)-β-D-glactopyranosyl}-diosgenin (aspidistrin) and proto-aspidistrin by physical and chemical methods. Three steroidal sapogenins were isolated from the acid-treated n-BuOH extract. They were identified as△3.5 deoxyfigogenin, diosgenin and gentrogenin, β-sitosterol was isolated from the rhizome of this plant also.     

Bile acids. LXVIII. Allylic and benzylic photo-chemical oxidation of steroids

To provide 7-oxocholesterol derivatives in yields superior to those obtained by chemical oxidation, the preparation of steroidal allylic or benzylic ketones was studied. Air-induced oxidation was investigated with a highly selective low energy UV lamp in the presence of mercuric bromide. With this procedure cholesteryl acetate, 5-cholestene-3β, 27-diol diacetate, 24(R)-24-methyl-5-cholesten-3β-yl acetate, 24(R)-24-ethyl -5-cholesten-3β-yl acetate and 24(R)-24-ethyl-(22E)-cholesta-5, 22-dien -3β-yl acetate were oxidized to the allylic keto-derivative in good yields; estradiol-17β diacetate was similarly converted to the 6-oxo-product in improved yield. This method can be very useful in the synthesis of 7-oxocholesteryl acetate and its analogs and 6-oxoestratrienes.     

Study on Chemical Constituents of Gentianopsis barbata var. Stennocalyx H. W. Li ex T.N. Ho

Nine compounds were isolated from Gentianopsis barbata var. stennocalyx H. W. Li ex. T.N.Ho. Their structures are identified as 1-hydroxy4, 7, 8-trimethoxyxanthone (Ⅰ), 1, 7-dihydroxy-3, 8-dimethoxyxanthone (Ⅱ), 1, 7, 8-trihydroxy-3-methoxyxanthone (Ⅲ), 1-O-(β-D- xylopyranosyl-(1→6)-β-D-glucopyranosyl)-3, 7, 8-trimethoxyxanthone (Ⅳ), 1-O-(β-D-xylopy- ranosyl- (1→6)-β-D-glucopyranosyl)-7-hydroxy-3, 8-dimethoxyxanthone (Ⅴ), 1-O-(β-D-xylo- pyranosyl-(1→6)-β-D-glucopyranosyl)-7, 8-dihydroxy-3-methoxyxanthone (Ⅵ), luteolin-7-O- β-D-glucoside (Ⅶ), oleanolic acid (Ⅷ) and ursolic acid (Ⅸ) by means of chemical methods and UV, IR and NMR determinations respectively.     

Two-dimensional, 1H-n.m.r. study of peracetylated, reduced derivatives of three oligosaccharides isolated from human milk

The structures of the peracetylated derivatives of the following alditols obtained from oligosaccharides of human milk have been established by two-dimensional, J-resolved and J-correlated, ¹H-n.m.r. spectroscopy at 360 MHz: β- d-Galp-(1→3)-β- d-GlcpNAc-(1→3)-β- d-Galp-(1→4)- d-Glc-ol, α- l-Fucp-(1→2)-β- d-Galp-(1→3)-β- d-GlcpNAc-(1→3)-β- d-Galp-(1→4)- d-Glc-ol, and β- d-Galp-(1→3)-β- d-GlcpNAc-(1→3)-[β- d-Galp-(1→4)-β- d-GlcpNAc-(1→6)]-β- d-Galp-(1→4)- d-Glc-ol.     

Haemolytic activity and immunological adjuvant effect of a new steroidal saponin from Allium ampeloprasum var. porrum

A new steroidal saponin was isolated from the bulbs of Allium ampeloprasum L. var. porrum. On the basis of chemical evidence, comprehensive spectroscopic analyses, and comparison with known compounds, its structure was established as (3β,5α,6β,25R)-3-{(O-β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-(1→2)-O-[O-β-D-glucopyranosyl-(1→3)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranosyl)oxy}-6-hydroxyspirostan-2-one (1). Results of the present study indicated that 1 exhibited haemolytic activity in the in vitro assays, and immunological adjuvant activity on the cellular immune response against ovalbumin antigen.     

Two new eudesmane sesquiterpenoids from Daucus carota L.

Two new eudesmane sesquiterpenoids were isolated from the fruits of Daucus carota L. The structures were established based on the interpretation of high-resolution MS and 1D- and 2D-NMR data, the absolute configuration of compound 1 was determined by single-crystal X-ray diffraction. The new compounds were elucidated as (1βH, 3βH, 5βH, 7αH)-4α, 10α-dimethyl-7β-isopropyl-1α, 3α, 4β, 11-tetrahydroxy decahydronaphthalene (1) and (1βH, 3βH, 5βH, 7αH)-4α, 10α-dimethyl-7β-isopropyl-1α, 3α, 4β-trihydroxy decahydronaphthalene-11-O-β-d-glucopyranoside (2). The compound 1 showed significant antioxidant activity.     

A New Steroidal Glycoside from Ophiopogon japonicus (Thunb.) Ker-Gawl.

To study the chemical constituents from traditional Chinese herb Ophiopogon japonicus(Thunb.) Ker-Gawl., a new steroidal glycoside, named ophiopojaponin C (1), together with two known ones,was isolated by column chromatography. Spectroscopic and chemical evidence revealed the structures to be ophiopogenin 3-O-[α-L-rhamnopyranosyl(1→2)]-β-D-xylopyranosyl(1→4)-β-D-glucopyranoside (1),diosgenin 3-O-[2-O-acetyl-α-L-rhamnopyranosyl( 1 →2)] -β-D-xylopyranosyl( 1 →3)-β-D-glucopyranoside (2),and ruscogenin 1-O-[2-O-acetyl-α-L-rhamnopyranosyl(1→2)]-β-D-xylopyranosyl(1→3)-β-D-fucopyranoside(3).     

The Chemical Constituents of Swertia przewalskii Pissjauk.

Seven xanthonenoid compounds and a triterpenic acid have been isolated from Swertia przewalskii Pissjauk. Their structures were identified as 1,8-dihydroxy-3,7-dimethoxyxarthone(Ⅰ), 1,7-dihydroxy-3,8-dimethoxyxanthone (Ⅱ), oleanolic acid (Ⅲ), l-hydroxy-3,7,8-trimethoxyxanthone (Ⅳ), 1,7,8-trihydroxy-3-methoxyxanthone (Ⅴ), 8-0-[β-D-xylopyranosyl-(l--6)-β-D-glucopyranosyl]- 1,7-dihydr0xy- 3-methoxyxanthone (Ⅵ), 1-O- [β-D-xylopyranosyl-(1-6)-β-D-glucopyranosyl]-7,8-dihydroxy- 3-methoxyxanthone (Ⅶ) and 1-O- [β-D-xylopyranosyl-(1-6)-β-D-glucopyranosyl]-8-hydroxy-3,7-dimethoxyanthone (Ⅷ) respectively, by means of chemical and spectral methods or comparing with the authentic samples directly.     

Phenolic Glycosides with antiproteasomal activity from Centaurea urvillei DC. subsp. urvillei

A new flavanone glycoside, naringenin-7-O-β-d-glucuronopyranoside, and a new flavonol glycoside, 6-hydroxykaempferol-7-O-β-d-glucuronopyranoside were isolated together with 12 known compounds, 5 flavone glycoside; hispidulin-7-O-β-d-glucuronopyranoside, apigenin-7-O-β-d-methylglucuronopyranoside, hispidulin-7-O-β-d-methylglucuronopyranoside, hispidulin-7-O-β-d-glucopyranoside, apigenin-7-O-β-d-glucopyranoside, a flavonol; kaempferol, two flavone; apigenin, and luteolin, a flavanone glycoside; eriodictyol-7-O-β-d-glucuronopyranoside, and three phenol glycoside; arbutin, salidroside, and 3,5-dihydroxyphenethyl alcohol-3-O-β-d-glucopyranoside from Centaurea urvillei subsp. urvillei. The structure elucidation of the new compounds was achieved by a combination of one- (¹H and ¹³C) and two-dimensional NMR techniques (G-COSY, G-HMQC, and G-HMBC) and LC-ESI-MS. The isolated compounds were tested for their antiproteasomal activity. The results indicated that kaempferol, a well known and widely distributed flavonoid in the plant kingdom, was the most active antiproteasomal agent, followed by apigenin, eriodictyol-7-O-β-d-glucuronopyranoside, 3,5-dihydroxyphenethyl alcohol-3-O-β-d-glucopyranoside, and salidroside, respectively.     

古蔺雪胆中的新三萜皂苷

从采自四川汉源县的古蔺雪胆(Hemsleya penxianensis var.gulinensiks)中分到9个三萜皂苷化合物,通过化学反应和光谱方法鉴定了它们的结构。其中7个为已知化合物,分别为齐墩果酸-28-O-β-D-比喃葡萄糖苷(1),3-O-β-D-吡喃葡萄糖醛基齐墩果酸苷(3),3-O-β-D-吡喃葡萄糖醛基—齐墩果酸—28-O-α-L-吡喃阿拉伯糖苷(4),3-O-β-D-吡喃葡萄糖醛基—齐墩果酸—28-O-β-D-吡喃葡萄糖苷(5),3-O-α-L-阿拉伯糖基—(1→3)—β—D-吡喃葡萄糖醛基—齐墩果酸—28—O—β—D—吡喃葡萄糖苷(6),3—O—(6′—丁酯)—β-D-吡喃葡萄糖醛基—齐墩果酸—28-O-α-L-阿拉伯糖苷(7),3-O-(6′-丁酯)—β—D吡喃葡萄糖醛基—齐墩果酸—28-O-β-D-吡喃葡萄糖苷(8)。两个新化合物,即雪胆皂苷A(2)和雪胆皂苷B(9)。     

杜鹃属植物区系的研究

已知世界杜鹃属(Rhododendron)植物约967种（种下分类等级未计算在内）。本文基于植物区系学的观点,讨论了属内8个亚属：常绿杜鹃亚属、杜鹃亚属、马银花亚属、映山红亚属、羊踯躅亚属、云间杜鹃亚属、纯白杜鹃亚属、异蕊杜鹃亚属的系统位置、分布式样。分析了系统发育和地理分布上的时间、空间关系。认为常绿杜鹃亚属和杜鹃亚属是在本属植物起源后的早期阶段就沿不同途径迁徙、繁衍的两个演化枝。自第三纪以来,它们的性状发展多样,种系高度分化。在现存类群中最具原始性状的亚属是常绿杜鹃亚属,这个亚属的云锦杜鹃亚组Subsect.Fortunea,耳叶杜鹃亚组Subsect.Auriculata 保持较多原始性状。种的分布遍及欧洲、北美洲、亚洲、大洋洲(有1种),东亚种类最多,马来西亚次之。中国-喜马拉雅地区既是多度中心又是多样化中心,马来西亚仅是多度中心。大多数种为地方特有性分布,特有现象十分突出,东亚和马来西亚的特有种共约862种,占种总数的89%以上中国有6个亚属(Candidastrum,Mumeazalea不产)约562种,其中特有种约405种。分析第三纪的化石记录,杜鹃属在全球分布的时间、地点,杜鹃属保持原始或古老性状的类群的现代适生地,认为中国西南至中国中部最有可能是杜鹃属植物的起源地,始祖类群起源的时间会是在晚白垩纪至早第三纪。讨论了杜鹃属在第三纪至第四纪向北半球北部的传布,向亚洲西南、亚洲东南和向东亚的传布以及向大洋洲的传布。从杜鹃属在全球传布的现象和途径,看来现代分布格局形成的原因取决于三方面的因素：时间和窨历史对植物繁衍、传播有着重要制约作用,并受制于植物种系自身具有的遗传性和对环境强烈变化的反应能力。     

Cycloartane glycosides from Astragalus campylosema Boiss. ssp. campylosema

Four cycloartane glycosides, 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-3β,6α,16β,23α,25-pentahydroxy-20(R),24(S)-epoxycycloartane (1), 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-16-O-hydroxyacetoxy-23-O-acetoxy-3β,6α,25-trihydroxy-20(R),24(S)-epoxycycloartane (2), 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-3β,6α,23α,25-tetrahydroxy-20(R),24(R)-16β,24;20,24-diepoxycycloartane (3), 3-O-[α-l-arabinopyranosyl-(1 → 2)-β-d-xylopyranosyl]-25-O-β-d-glucopyranosyl-3β,6α,16β,25-tetrahydroxy-20(R),24(S)-epoxycycloartane (4), along with three known cycloartane glycosides were isolated from the MeOH extract of the roots of Astragalus campylosema ssp. campylosema. Their structures were established by the extensive use of 1D- and 2D-NMR experiments along with ESIMS and HRMS analysis. The occurrence of the hydroxyl function at position 23 (1-2) and of the ketalic function at C-24 (3) are very unusual findings in the cycloartane class.     

泡果荠属(十字花科)五新种

Haec species proxima H．changhuaensi Y. H．Zhang,a qua racemis longioribtus,laxioribus,siliculis longe obovoideis,stylis longlogioribus sub fructu c． 2 mm longis,seminibus superificie tuberculis minoribus dense munitis recedit．     

被子植物系统发育研究的现状与展望

为植物界最大的类群—被子植物建立一个能真正反映植物的进化历史和系统发育（phylogeny）的分类系统一直是许多植物系统学家和进化学家所向往的。到目前为止,已经提出的被子植物分类系统至少有二十多个。问题在于这样的分类系统能否说已符合于系统发育的要求？要回答这个问题,首先必须弄清系统发育的真正含义是什么。     

Steroidal saponins from the leaves of Cordyline fruticosa (L.) A. Chev. and their cytotoxic and antimicrobial activity

Three new steroidal saponins, spirosta-5,25(27)-diene-1β,3β-diol-1-O-α-l-rhamnopyranosyl-(1→2)-β-d-fucopyranoside (fruticoside H) 1, 5α-spirost-25(27)-ene-1β,3β-diol-1-O-α-l-rhamnopyranosyl-(1→2)-(4-O-sulfo)-β-d-fucopyranoside (fruticoside I) 2, and (22S)-cholest-5-ene-1β,3β,16β,22-tetrol 1-O-β-galactopyranosyl-16-O-α-l-rhamnopyranoside (fruticoside J) 3, together with the known quercetin 3-O-β-d-glucopyranoside, quercetin 3-O-[6-trans-p-coumaroyl]-β-d-glucopyranoside, quercetin 3-rutinoside, apigenin 8-C-β-d-glucopyranoside and farrerol, were isolated from the leaves of Cordyline fruticosa. Their structures were elucidated by spectroscopic techniques (¹H NMR, ¹³C NMR, HSQC, ¹H–¹H COSY, HMBC, TOCSY, NOESY), mass spectrometry (HRESIMS, Tandem MS–MS), chemical methods and by comparison with published data. Compounds 1 and 2 showed moderate cytotoxic activity against MDA-MB 231 human breast adenocarcinoma cell line, HCT 116 human colon carcinoma cell line, and A375 human malignant melanoma cell line, while compound 3 was not active. Compound 2 also showed a moderate antibacterial activity against the Gram-positive Enterococcus faecalis.     

Saponins from Astragalus hareftae (NAB.) SIRJ.

Four cycloartane- (hareftosides A–D) and oleanane-type triterpenoids (hareftoside E) were isolated from Astragalus hareftae along with fifteen known compounds. Structures of the compounds were established as 3,6-di-O-β-d-xylopyranosyl-3β,6α,16β,24(S),25-pentahydroxycycloartane (1), 3,6,24-tri-O-β-d-xylopyranosyl-3β,6α,16β,24(S),25-pentahydroxycycloartane (2), 3-O-β-d-xylopyranosyl-3β,6α,16β,25-tetrahydroxy-20(R),25(S)-epoxycycloartane (3), 16-O-β-d-glucopyranosyl-3β,6α,16β,25-tetrahydroxy-20(R),24(S)-epoxycycloartane (4), 3-O-[β-d-xylopyranosyl-(1→2)-O-β-d-glucopyranosyl-(1→2)-O-β-d-glucuronopyranosyl]-soyasapogenol B (5) by the extensive use of 1D- and 2D-NMR experiments along with ESI-MS and HR-MS analyses.     

Efficient Synthesis of O-Linked Glycopeptide by a Transglycosylation Using Endo α-N-Acetylgalactosaminidase from Streptomyces sp.

Galβ-(1→3)-GalNAc-linked hexapeptide was synthe-sized by a transglycosylation using Galβ-(1→3)-Gal-NAcβ-pNP as a donor and a serine-containing hexapeptide as an acceptor using endo GalNAc-ase from Streptomyces sp.. The Galβ-(1→3)-GalNAc residue was transferred to the hydroxyl group of the serine residue of the peptide. The total yield of the glycopeptide via this process was better than that of the chemoenzymatic method. This process was confirmed to be a versatile method for the synthesis of O-linked glycopeptides.     

New Cytotoxic Saponins from Lysimachia davurica Ledeb.

To investigate the saponins from whole plants of Lysimachia davurica Ledeb., two new saponins named davuricoside I （compound 1） and E （compound 2） were isolated. Their chemical structures were elucidated as 3β, 16α, 28, 29-tetrihydroxy-olean-12-en-3-O-β-D-glucopyranosyl-（1→2）-β-D-glucuronopyranoside （compound 1） and 3β, 16α, 29-trihydroxy-13, 28-epoxy-oleanane-3-O-β-D-glucopyranosyl-（1→2）-β-D-glucuronopyranoside （compound 2） on the basis of their one- and two-dimensional nuclear magnetic resonance and mass spectrometry data, and chemical methods. Compound 1 showed significant cytotoxic activity against human A2780 cells.