青龙衣中细胞毒活性成分的研究

利用各种化学及色谱技术从青龙衣中分离得到11个化合物,通过理化性质和波谱学手段分别鉴定为2-羟基-1,4-萘醌(2-hydroxy-1,4-naphthoquinone,1)、5-羟基-1,4-萘醌(5-hydroxy-1,4-naphthoquinone,2)、2,5-二羟基-1,4-萘醌(2,5-dihydroxy-1,4-naphthoquinone,3)、3,5-二羟基-1,4-萘醌(2,5-dihydroxy-1,4-naphthoquinone,4)、5,8-二羟基-1,4-萘醌(2,5-dihydroxy-1,4-naphthoquinone,5)、5-甲氧基-1,4-萘醌(5-methoxy-1,4-naphthoquinone,6)、5,7-二羟基色原酮(5,7-dihydroxychromone,7)、异香草酸(isovanillic acid,8)、没食子酸(gallic acid,9)、β-谷甾醇(β-sitosterol,10)和β-胡萝卜苷(β-daucosterol,11)。化合物3、4、6～8为首次从该属植物中分离得到,化合物1为首次从该植物中分离得到。细胞毒活性测试结果表明,化合物3和4对HepG2细胞表现出强的抑制作用,IC50值分别为5.0±0.6μmol/L和7.0±0.5μmol/L;2和5能显著抑制HL-60细胞的增殖,IC50值分别为9.3±1.2μmol/L和2.3±0.2μmol/L。     

降香中的酚性化合物

从降香(Dalbergia odorifera)中分离得到10个酚性化合物,运用波谱学方法分别鉴定为dalbergin(1),7-O-methylvestitol(2),syringaresinol(3),3,7-dihydroxy-2',4'-dimethoxyisoflavanone(4),3'-hydroxy-8-methoxyvestitol(5),2',6-dihydroxy-4'-methoxy-2-arylbenzofuran(6),3'-O-methylviolanone(7),pinocembrin(8),prunetin(9),mucronulatol(10)。其中化合物1具有乙酰胆碱酯酶抑制活性,化合物2~5为首次从降香中分离得到。     

隔山消化学成分的研究

从隔山消的石油醚部分分离得到6个芳香类化合物,分别鉴定为2,4-二羟基苯乙酮（1-（2,4-dihy—droxph—enyl）ethanone,1）、奎乙酰苯（acetylquinol,2）、对羟基苯乙酮（1-（4-hydroxyphenyl）ethanone,3）、4-羟基-3-甲氧基苯乙酮（1-（4-hydroxy-3-methoxyphenyl）ethanone,4）、2,4-二羟基-5-甲氧基苯乙酮（1-（2,4-dihydroxy-5-methoxyphenyl）ethanone,5）、3-羟基4-甲氧基苯甲酸（3-hydroxy-4-methoxy—benzoicacid,6）。除化合物2外,其余5个化合物均首次从该植物中分离得到。     

斑茅内生真菌Nigrospora sp.BM-2次级代谢产物研究北大核心CSCD

内生菌具有丰富的生物多样性,是潜力巨大的微生物新资源。内生菌的研究对于保护野生与濒危药用植物、拓展药用资源、新药研发等均有一定意义。从药用植物斑茅(Saccharum arundinaceum Retz.)的叶片中分离得到内生真菌Nigrospora sp. BM2,对其代谢产物化学成分进行研究,通过固体发酵,乙酸乙酯萃取得浸膏,其浸膏经硅胶柱层析,Sephadex LH-20,半制备型HPLC等分离手段分离得到10个化合物,经波谱学方法鉴定其结构分别为Pestalotiopyrones G(1)、Nigrosporapyrone D(2)、Pestalotiopyrones A(3)、Hydroxypestalopyrone(4)、Mellein(5)、6-hydroxymellein(6)、4-hydroxymellein(7)、5,8-dihydroxy-4-methyl-coumarin(8)、~1H-indole-3-carboxaldehyde(9)和Isosclerone(10)。体外细胞毒活性显示以上化合物对HepG2和Caski细胞均无明显抑制活性,其IC_(50)>100μM。除化合物1和5外,其余8个化合物均为首次从该属菌株的代谢产物中分离得到。     

斑茅内生真菌Nigrospora sp.BM-2次级代谢产物研究

内生菌具有丰富的生物多样性,是潜力巨大的微生物新资源。内生菌的研究对于保护野生与濒危药用植物、拓展药用资源、新药研发等均有一定意义。从药用植物斑茅(Saccharum arundinaceum Retz.)的叶片中分离得到内生真菌Nigrospora sp. BM2,对其代谢产物化学成分进行研究,通过固体发酵,乙酸乙酯萃取得浸膏,其浸膏经硅胶柱层析,Sephadex LH-20,半制备型HPLC等分离手段分离得到10个化合物,经波谱学方法鉴定其结构分别为Pestalotiopyrones G(1)、Nigrosporapyrone D(2)、Pestalotiopyrones A(3)、Hydroxypestalopyrone(4)、Mellein(5)、6-hydroxymellein(6)、4-hydroxymellein(7)、5,8-dihydroxy-4-methyl-coumarin(8)、~1H-indole-3-carboxaldehyde(9)和Isosclerone(10)。体外细胞毒活性显示以上化合物对HepG2和Caski细胞均无明显抑制活性,其IC_(50)100μM。除化合物1和5外,其余8个化合物均为首次从该属菌株的代谢产物中分离得到。     

艾纳香内生真菌Diaporthe sp.次生代谢产物

【目的】从艾纳香内生菌J1中获得活性次生代谢产物。【方法】对菌株J1进行ITS序列分子鉴定,综合运用多种色谱技术对其发酵产物进行分离纯化,结合波谱学技术对其进行结构表征。【结果】经构建系统进化树,鉴定菌株J1为Diaporthe sp.,从该菌株大米培养基中分离得到7个单体化合物,经鉴定分别为Dicerandrol A (1)、Dicerandrol B (2)、4,6-dihydroxy-1H-isoindole1,3(2H)-dione (3)、Cytochalasin H (4)、Cytochalasin J (5)、4,6-dihydroxy-2,3-dihydro-1H-isoindol-1-one (6)、Cerebroside C (7)。所有化合物均为首次从该菌中分得,化合物1对枯草芽孢杆菌Bacillus subtilis KCTC 1021具有非常强的抑制活性,MIC值为0.125μg/mL。【结论】Diaporthe sp.富含抑菌活性化合物,具有开发成微生物源农药潜力。     

两株多孔菌属担子菌菌丝体中的三萜成分

用组织分离法从采集于广东鼎湖山的2株多孔菌属担子菌子实体中分离得到2株菌丝体,并对菌丝体分别进行固体发酵培养,培养物经乙醇提取后,用柱层析分离得到4个化合物,用光谱法鉴定均为羊毛脂烷型三萜,它们分别是多孔菌酸C（polyporenic acid C）（1）、茯苓酸（pachymic acid）（2）、齿孔酸（eburicoic acid）（3）和硫磺菌酸（sulphurenic acid）（4）。其中化合物2为首次从多孔菌属中发现。     

马缨杜鹃茎的化学成分研究

利用各种色谱技术从马缨杜鹃(Rhododendron delavayi Franch.)茎中分离得到10个化合物。通过波谱学方法鉴定为异鼠李素(1),nectandrin B(2),resveratrol-3-O-β-D-glucoside(3),lysidiside N(4),19α-hydroxyasiatic acid(5),白桦脂酸(6),3β-hydroxylup-12-en-28-oic-acid(7),obtusalin(8),methyl 2,4-dihydroxy-6-methylbenzoate(9),2,5-dihydroxy-3-methoxytoluene(10)。化合物2～9为首次从该种植物中分离得到。     

山竺果壳的化学成分

从山竺（Garcinia mangostana）果壳中分离得到6个化合物,通过MS,1D NMR以及与文献对照鉴定它们为4个[口山]酮类化合物：α-rnangostin（1）,β-mangostin（2）,γ-mangostin（3）,5,9-dihydroxy-8-methoxy-2,2-dimethyl-7-（3-methylbut-2-envl）-2H,6H-pyrano-[3,2-b]-xanthen-6-one（4）,以及表儿茶素（epicatechin,5）和一个双苄类化合物egonol（6）。其中化合物5和化合物6为首次从该植物中分离得到。对化合物1～5进行抗HIV-1 RT活性筛选结果表明,化合物2和化合物5在浓度200μg/ml的条件下,其对HIV-1 RT抑制率分别为41．97％和47．72％;同一实验结果显示化合物1,3和4没有抑制HIV-1 RT作用。     

紫红獐牙菜口山酮及环烯醚萜类化合物的研究

采用各种柱色谱法对紫红獐牙菜的石油醚和正丁醇部位进行分离纯化,从石油醚部位分离鉴定得到6个化合物,利用理化性质和波谱学方法分别鉴定为oleanolic acid(1),swerchirin(2),sweriaperenine(3),bellidifo-lin(4),gentiacaulein(5)和1,7,8-trihydroxy-3-methoxyxanthone(6);从正丁醇部位分离鉴定得到9个化合物,分别鉴定为8-[(β-D-glucopyranosyl)oxy]-1,5-dihydroxy-3-methoxyxanthone(7),5-[(β-D-glucopyranosyl)oxy]-1,8-di-hydroxy-3-methoxyxanthone(8),7-[(β-D-xylopyranosyl)oxy]-1,8-dihydroxy-3-methoxyxanthone(9),8-[(β-D-gluco-pyranosyl)oxy]-1,3,5-trimethoxyxanthone(10),swertiamarin(11),tetrahydrosertianolin(12),8-hydroxy-10-hydro-sweroside(13),campestroside(14)以及uridine(15)。其中,化合物15首次从该属植物中得到,化合物9、10、12和13首次从该植物中分离得到。     

Glechomanolides and eudesmanolides from Smyrnium perfoliatum

In addition to five known sesquiterpenoids, six new compounds were isolated from Smyrnium perfoliatum. The new compounds were 1β-acetoxy-eudesma-3,7(11),8-trien-8,12-olide, 1β-acetoxyeudesma-4(15),7(11),8-trien-8,12-olide, 1β-10α;4α,5β-diepoxy-8β-isobutoxy-glechomanolide, 1β, 10α;4α,5β-diepoxy-8α-isobutoxy-glechomanolide, 1β,4α-dihydroxy-2α,3α-epoxy-eudesma-7(11),8-dien-8,12-olide, 1β,4α-dihydroxy-2α,3α-epoxy-8β-methoxy-eudesma-7(11)-en-8α,12-olide.     

Volatiles released by a Streptomyces species isolated from the North Sea

The North Sea Streptomyces strain GWS-BW-H5 was investigated by analyzing headspace extracts of agar-plate cultures (HE) or liquid cultures (LCE), obtained with a closed-loop stripping apparatus (CLSA), by GC/MS (Table 1). The volatile profile of the HE is dominated by the known volatiles (-)-geosmin (4) and 2-methyisoborneol (1). Small amounts of sesquiterpenes occur, which are present in a more-diverse structural variety and in higher quantities in the LCE. The different structures can be rationalized by few cationic intermediates along their biosynthetic pathway. The most-prominent difference between the two culture methods were the presence of the Me-branched gamma- and delta-lactones 31-38, not previously reported from nature, in the LCE. Major components were 10-methyldodecan-5-olide (34), 10-methyldodec-2-en-4-olide (36), and 10-methyldodec-3-en-4-olide (38). The structures of all new lactones were verified by synthesis. Furthermore, more volatiles in higher amounts were produced by the liquid culture than by to the agar plate culture. Since 36 showed inhibitory growth effects against strain GWS-BW-H5, growth inhibition against twelve other strains isolated from the same habitat was tested. Antagonistic activity against four of the strains was observed, with a slightly higher threshold level than found for penicillin G, which was used in control experiments (Table 2).     

Biotransformation of chinensiolide B and the cytotoxic activities of the transformed products

Biotransformation of chinensiolide B, 10α-hydroxy-1α,5α,15-H-3-oxoguaia-11(13)-en-6α,12-olide (1), yielded three selectively reduced products, 3β,10α-dihydroxy-1α,5α,15α-H-guaia-11(13)-en-6α,12-olide (2), 3α,10α-dihydroxy-1α,5α,15α-H-guaia-11(13)-en-6α,12-olide (3), and 3β,10α-dihydroxy-1α,5α,11β,15α-H-guaia-6α,12-olide (4) by the cell suspension cultures of Catharanthus roseus. 2 and 3 were also obtained from 1 incubated with cell cultures of a fungus Abisidia coerulea IFO 4011 and Platycodon grandiflorum, respectively. Among them, 2, 3 are two new compounds. The three products, 2–4, along with 1 were preliminarily evaluated for their in vitro cytotoxic activity against 3 cell lines (HepG2, WI-38 and VA-13) and all showed potent inhibitory effects on the cell proliferation. Of the four compounds, 3 was the most toxic to the three cell lines tested with IC₅₀ values of 22.7, 0.33 and 3.30 μM, respectively.     

离舌橐吾中艾里莫酚烷型倍半萜类化学成分的研究

为分析菊科橐吾属植物离舌橐吾Ligularia veitchiana(Hemsl.)Greenm中艾里莫酚烷型倍半萜类的化学成分,并对其进行抗肿瘤活性研究,实验综合运用硅胶柱色谱、反相硅胶柱色谱以及制备型高效液相等色谱方法,从其根茎的95%乙醇提取物的乙酸乙酯部位中分离得到了13个艾里莫酚烷型倍半萜类化合物,根据化合物的理化性质及其波谱学数据鉴定为:eremophilenolide(1),eremophila-7(11),9-dien-8-one(2),eremophil-6-en-11-ol(3),8-oxo-eremophil-6-en-11-one(4),(6α,8α)-6-hydroxyeremophil-7(11)-en-12,8-olide(5),8β-hydroxyeremophil-7(11)-en-12,8α-olide(6),6β-hydroxy-8α-methoxyeremophil-7(11)-12,8β-olide(7),2α-hydroxyeremophil-11-en-9-one(8),6β-methoxy-8β-hydroxyeremophil-7(11)-en-12,8α-olide(9),6β-hydroxyeremophil-7(11)-en-12,8β-olide(10),6β-hydroxy-8β-methoxyeremophil-7(11)-12,8α-olide(11), 6β,8β-dihydroxyeremophil-7(11)-en-12,8α-olide(12)和6β,8α-dihydroxyeremophil-7(11)-en-12,8β-olide(13)。其中,化合物5和10、7和11～13为三对非对映异构体。除化合物3和5外,所有化合物均为首次从该植物中分离得到。运用MTT法对所有化合物进行体外抗肿瘤细胞活性的筛选,结果表明其对胃癌细胞HGC-27和宫颈癌细胞Caski均未显示细胞毒作用。     

Humirianthenolides,new degraded diterpenoids from Humirianthera rupestris

The tuber of Humirianthera rupestris (Icacinaceae) contains the degraded diterpenoids 3β,20-epoxy-30α- hydroxy- 14-oxo-9β-podocarpan-19,6β-olide (humirianthenolide A), 3β,20-epoxy-3α,14α-dihydroxy-9β-podocarpan-19,6β- olide (humirianthenolide B), 3β,20; 16,14-diepoxy-3α-hydroxy-17-nor-15-oxo-9β-abiet-13-en-19,6β-olide (humirianthenolide C), 3β,20-epoxy-3α,14-dihydroxy-13-oxo-9β-podocarp-8(14)-en-19,6β-olide (humirianthenolide D), 3β,20-epoxy-3α-hidroxy-14-oxo-8α,9β-podocarpan-19,6β-olide (humirianthenolide E) and 3β,20-epoxy-3α,14β- dihydroxy-8α,9β-podocarpan-19,6β-olide (humirianthenolide F). ¹H NMR and ¹³C NMR spectroscopy were efrective for the determination of the humirianthenolide structures.     

Alisolide, alisols O and P from the rhizome of Alisma orientale

A nor-protostane, alisolide (1), a rearranged protostane, alisol O (2), and a 2,3-seco-protostane triterpene, alisol P (3), were isolated from the rhizomes of Alisma orientale, along with eight known protostane triterpenes. The structures were elucidated to be (17S)-3,11-dioxo-23-nor-protost-12-en-23(17)-olide, 3-oxo-11beta,23-dihydroxy-24,24-dimethyl-26,27-dinorprotost-13(17)-en-25-oic acid, and (20R,23S,24R)-23,24,25-trihydroxy-2,3-seco-protost-13(17)-en-3-oic acid 2,11beta-lactone, respectively, by interpretation of spectroscopic data.     

Microbial transformations of gelomulide G: a member of the rare class of diterpene lactones

Microbial transformation of gelomulide G (3beta,6beta-diacetoxy-8beta,14beta-epoxyabiet-13(15)-en-16,12-olide, 1) was carried out. Incubation of 1 with Aspergillus niger afforded two new metabolites, 3beta,6beta-diacetoxy-8beta,14beta-dihydroxyabiet-13(15)-en-16,12-olide (2) and 3beta,6beta-diacetoxy-14beta-hydroxyabieta-8(9),13(15)-dien-16,12-olide (3). While Cunninghamella elegans afforded the 14-epimer of 2, i.e., 3beta,6beta-diacetoxy-8beta,14alpha-dihydroxyabiet-13(15)-en-16,12-olide (4), along with 3beta-acetoxy-6beta-hydroxy-8beta,14beta-epoxyabiet-13(15)-en-16,12-olide (5). The structures of the transformed products 2-5 were deduced to be new on the basis of MS and NMR data.     

Sesquiterpenes and diterpenes from Ambrosia arborescens

Six compounds, eudesm-11(13)-en-4β,9β-diol, 15R,16-dihydroxy-3-oxoisopimar-9(11)-ene, 15S,16-dihydroxy-3-oxoisopimar-9(11)-ene, 1α-hydroxy-7-oxo-iso-anhydrooplopanone, 10α-hydroxy-11,13-dihydro-5-epi-psilostachyin, and 4β-hydroxypseudoguaian-12,6-olide 4-O-β-d-glucopyranoside, together with 12 known sesquiterpenes, were isolated from the leaves of Ambrosia arborescens. Structures were elucidated by 1D and 2D NMR spectroscopy including 1D-TOCSY, DQF-COSY, 2D-ROESY, HSQC, and HMBC experiments, as well as by ESI mass spectrometry. The absolute configuration of the 15,16-diol moiety in 15R,16-dihydroxy-3-oxoisopimar-9(11)-ene and 15S,16-dihydroxy-3-oxoisopimar-9(11)-ene was determined using Snatzke’s method. All compounds were evaluated for antiproliferative activity.     

Sesquiterpenoids from Curcuma wenyujin with anti-influenza viral activities

Five sesquiterpenoids, 1α,8α-epidioxy-4α-hydroxy- 5αH-guai-7(11),9-dien- 12,8-olide. (1), 8,9-seco-4β-hydroxy-1α,5βH-7(11)-guaen-8,10-olide (2), 8α-hydroxy-1α, 4β,7βH-guai-10(15)-en- 5β,8β-endoxide(3), 7β,8α-dihydroxy-1α,4αH-guai-10(15)-en-5β,8β-endoxide(4) and 7-hydroxy-5(10),6,8-cadinatriene-4-one(5), together with seven known analogs were isolated from the rhizomes of Curcuma wenyujin. Their structures and relative configurations were determined on the basis of spectroscopic methods including 2D NMR techniques, and the structures of 1 and 2 were confirmed by single-crystal X-ray diffraction experiment. Compounds 1–10 and 12 showed significant in vitro antiviral activity against the influenza virus A with IC₅₀ values ranged from 6.80 to 39.97 μM, and SI values ranged from 6.35 to 37.25.     

Modified ortho-cleavage pathway in Alcaligenes eutrophus JMP134 for the degradation of 4-methylcatechol

Abstract 2,4-Dichlorophenoxyacetate-grown cells of Alcaligenes eutrophus JMP134 [1] metabolized 4-methylphenoxyacetate via a modified ortho -cleavage pathway. 4-Carboxymethyl-4-methylbut-2-en-1,4-olide (4-methyl-2-enelactone), 4-carboxymethyl-3-methylbut-2-en-1,4-olide (3-methyl-2-enelactone) and 4-methyl-3-oxoadipate, were identified as intermediates.