疏花毛萼香茶菜中一新的对映-贝壳杉烷型二萜

从疏花毛萼香茶菜（Ｉｓｏｄｏｎ ｅｒｉｏｃａｌｙｘ ｖａｒ．ｌａｘｉｆｌｏｒａ）叶中分离得到一新的对映－贝壳杉烷型二萜,命名为疏花丁素（１）,通过波谱方法鉴定了它的结构。此外,还分离得到６个已知对映－贝壳杉烷型二萜化合物：疏花甲素（２）,毛萼晶Ａ－Ｃ（３－５）和Ｑ（６）,毛萼乙素（７）,以及ｃｉｒｓｉｍａｒｉｔｉｎ（８）和２α－羟基乌索酸（９）。     

旱生香茶菜中三个新的对映-贝壳杉烷型二萜

从旱生香茶菜（ｌｓｏｄｏｎ ｘｅｒｏｐｈｉｌｕｓ）叶中分离得到３个新的对映－贝壳杉烷型二萜,旱生香茶菜素Ｇ,Ｈ和Ｌ０通过波谱方法鉴定它们的结构。     

毛萼香茶菜中的新二萜化合物——毛萼晶P

从毛萼香茶菜的叶的甲醇提取物中分离得到两个二萜化合物,ｃｏｅｔｓｏｉｄｉｎＡ和毛萼晶Ｐ,它是目前从香茶菜属分离到的仅有的两个Ｂ环具有α,β－不饱和酮结构的对映－贝壳杉烷型二萜事物,其中毛萼晶Ｐ为新化合物     

胶粘香茶菜素的化学结构

从胶粘香茶菜叶的乙醚提取物中分得两个二萜化合物‘经各项光谱数据和化学反应确定,其中一个为四环二萜化合物,对映-贝壳杉烷-16β,17-二醇(ent-kauran-16β,17-diol)(1);另一个为三环二萜对映-异海松烷型(ent-isopimarane type)新化合物,命名为胶粘香茶菜素(glutinosin)(2)。对映-异海松烷型二萜化合物的分离和鉴定,对于从化学上阐明香茶菜属植物中大量存在的对映-贝壳杉烯型四环二萜化合物的生源关系有一定的学术意义。     

细锥香茶菜化学成分的研究

从细锥香茶菜（Ｒａｂｄｏｓｉａｃｏｅｔｓａ（Ｂｕｃｈ．Ｈａｍ．ｅｘＤ．Ｄｏｎ）Ｈａｒａ）的叶中分离到９个化合物,通过波谱分析阐明其结构,其中１个为新的二萜酸———７α,１２α,１４β三羟基１５酮对映贝壳杉１８羧酸,命名为细锥香茶菜酸（ｃｏｅｔｓａｎｏｉｃａｃｉｄ）。另外８个化合物分别为二氢昆明香茶菜丙素、昆明香茶菜丙素、白柔毛香茶菜甲素、大萼香茶菜丙素、４羟基Δ８,９（Ｚ）鞘氨醇２′羟基正二十（二十一二十六）碳酸酰胺、乌苏酸、２α,３β二羟基乌苏酸和胡萝卜甙。神经酰胺类化合物系首次从该属植物中分离得到。     

毛萼香茶菜中的三个新的对映—贝壳杉烷型二萜

从采自云南省江川县的毛萼香茶菜的甲醇提取物中分离得到３个新的６,７－螺断－对映－贝壳杉烷型二萜;表毛萼甲素,毛萼晶Ｎ和毛萼晶Ｏ,同时还分离到２个已知化合物,毛萼甲素及毛萼晶Ｌ,并修正了毛萼甲素的结构。     

细叶香茶菜中两个新的对映-贝壳杉烷二萜化合物

从云南中甸产细叶香茶菜(Isodon tenuifolia (W. W. Smith) Kudo)的地上部分分离得到6个化合物, 它们的结构通过波谱方法得到鉴定。其中化合物1和2为新的对映-贝壳杉烷二萜化合物, 即细叶香茶菜甲素(3β,6α,15β-trihydroxy-1α,7β-diacetoxy-11β,16β-epoxy-ent-kaurane) (1) 和细叶香茶菜乙素(1α,6α,11β-trihydroxy-3β,7β-diacetoxy-ent-kaur-16-en-15-one) (2)。     

细叶香茶菜中两个新的对映—贝壳杉烷二萜化合物

从云南中甸产细叶香茶菜 (Isodontenuifolia (W .W .Smith)Kudo)的地上部分分离得到 6个化合物 ,它们的结构通过波谱方法得到鉴定。其中化合物 1和 2为新的对映_贝壳杉烷二萜化合物 ,即细叶香茶菜甲素 (3β ,6α ,15 β_trihydroxy_1α ,7β_diacetoxy_11β ,16 β_epoxy_ent_kaurane) (1)和细叶香茶菜乙素 (1α,6α ,11β_trihydroxy_3β,7β_diacetoxy_ent_kaur_16_en_15_one) (2 )。     

大萼香茶菜中的二萜化学成分研究

为研究大萼香茶菜(Isodon macrocalyx )的化学成分,该文采用硅胶、ODS、Sephadex LH-20、反相C₁₈半制备高效液相等色谱方法对大萼香茶菜地上部分进行分离纯化,并利用¹H NMR、¹³C NMR和HR-ESI-MS等波谱数据,以及结合 参考文献,鉴定了这些化合物的结构。结果表明:从大萼香茶菜地上部分分离得到13个二萜,它们分别是19-羟基陶塔酚(1)、macrophynin E(2)、inumakoic acid(3)、inumakiol D(4)、4β-carboxy-19-nortotarol(5)、(-)-lambertic acid(6)、2-oxo-5-fagonene(7)、isodoterniofiln B(8)、长管贝壳杉素E(9)、长管香茶菜素A(10)、牛尾草素H(11)、16S-dihydrolongikaurin A(12)和ent-3S,16S,17-trihydroxy-kauran-2-one(13)。所有得到的二萜均为首次从该植物中分离得到。     

胶粘香茶菜的化学成分

胶粘香茶菜(I.glutinosa C.Y.Wu et H.W.Li),为唇形科(Labiatae)香茶菜属(Isodon)植物,产于云南西北部及四川西南部,海拔2000-2300m的河谷两岸山坡砾石地或干燥灌丛中。从云南丽江产胶粘香茶菜中,已分离和鉴定了2种不同结构类型的二萜成分,为进一步比较不同地区产该种植物在化学成分上的差异,我们对大理苍山产胶粘香茶菜进行了研究。由2316g茎叶得149g提取物,然后经硅胶柱层析,依次用氯仿、氯仿-乙酸乙脂(8:2→4:6),乙酸乙酯梯度洗脱,除分离和鉴定了β-谷甾醇(β-sitosterol),胡萝卜甙(β-sitosterol-D-glucoside),乌苏酸(ursolic acid),山植酸(crataegolic acid)和丁二酸(butanedioic acid)外,还得到迄今从香茶菜属植物中分离得到的氧化程度最低的一个对映-贝壳杉烯型四环二萜类化合物:对映-贝壳杉烷-16β,17-二醇(ent—Kauran-16β,17-diol)(1)(2.8g)和具有抑制革兰氏阳性菌生长活性的松香烷(abitane)型二萜pisiferic acid(2)(1.2g)。pisiferic acid(2)系首次从该属植物中得到。     

肋果茶中的萜类化学成分研究

从肋果茶(Sladenia celastrifolia)95％乙醇提取物的乙酸乙酯部位中分离得到15个萜类化合物,经波谱学方法分别鉴定为sladeniafolin A(1),grasshopper ketone (2),(3S,5R,6S,7E,9R) -7-megastigmene-3,6,9-triol (3),hedytriol (4),(3S,5R,6R,7E,9R) -3,5,6,9-tetrahydroxy-7-megastigmene(5),1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien -2-one (6),2α,3α,19α,23-tetrahydroxyurs-12-en-28-oic acid (7),2α,3β,19α,23-tetrahydroxyurs-12-en-28-oic acid(8),pomolic acid(9),3-O-acetyl pomolic acid(10),ursaldehyde (11),camarolide (12),3β-hydroxyurs-11-en-13β(28) -olide (13),3β-hydroxy -11α,12α-epoxy-urs-13β,28-olide (14)和28-0-β-D-glucopyranosyl euscaphic acid (15).以上化合物均首次从该植物中分离得到,其中1为新的C9裂环烯醚萜.     

猴头菌子实体化学成分研究

利用柱色谱技术从猴头菌(Hercium erinaceus)干燥子实体的甲醇提取物中分离得到11个化合物,经波谱技术分别鉴定为:D-赤藓糖醇(1)、D-阿拉伯糖醇(2)、1-O-β-D-吡哺葡萄糖基-(2S,4E,8E,2'R)-2-N-(2'-羟基十六烷酰)-9-甲基-4,8-sphingadienine(3)、3β-羟基-麦角甾-5,7,22-三烯(4)、3β-羟基-5α,8α-过氧化麦角甾-6,22-二烯(5)、硬脂酸(6)、油酸(7)、hericenone F(8)、hericenone C (9)、hericenone E(10)和hericene A(11).研究结果表明,hericenones型酚类物质在猴头菌子实体中含量丰富,化合物3是从猴头菌子实体中首次分离得到的脑酰胺类物质.     

Selective sweeps at the organophosphorus insecticide resistance locus, Rop-1, have affected variation across and beyond the α-esterase gene cluster in the Australian sheep blowfly, Lucilia cuprina

A major theoretical consequence of selection at a locus is the genetic hitchhiking of linked sites (selective sweep). The extent of hitchhiking around a gene is related to the strength of selection and the rate of recombination, with its impact diminishing with distance from the selected site. At the Rop-1 locus of the sheep blowfly, Lucilia cuprina, polymorphisms at two different sites within the LcαE7 gene encode forms of the protein that confer organophosphorus insecticide resistance. To assess the impact of selection at these two sites on variation around LcαE7, we sequenced regions within six other genes along chromosome IV across isogenic (IV) strains of L. cuprina. High levels of linkage disequilibrium, characterized by low haplotype number (K) and diversity (H), and significant R(2) values were observed for two genes, LcαE1 and LcαE10, both members of the same α-esterase gene cluster as LcαE7. A significant R(2) value was also observed for a gene predicted to be the next closest to LcαE7, AL03, but not for any of the other genes, LcRpL13a, Lcdsx, or LcAce. Skews in the site frequency spectra toward high-frequency variants were significant for LcαE1 (Fay and Wu's H = -2.91), LcαE10 (H = -1.85), and Lcdsx (H = -2.00). Since the selective sweeps, two forms of likely returning variation were observed, including variation in microsatellites in an intron of LcαE10 and a recombination event between LcαE7 and LcαE10. These data suggest that two incomplete soft sweeps have occurred at LcαE7 that have significantly affected variation across, and beyond, the α-esterase gene cluster of L. cuprina. The speed and impact of these selective sweeps on surrounding genomic variation and the ability of L. cuprina to respond to future environmental challenges are discussed.     

Cytotoxic steroids from Monascus purpureus-fermented rice

Bioassay-guided fractionation of an EtOH extract of Monascus purpureus-fermented rice led to the isolation of two new steroids (22S, 23R, 24S)-20β,23α,25α-trihydroxy-16,22-epoxy-4,6,8(14)-trienergosta-3-one (1), the first example of a steroid possessing both a conjugated triene ketone system and a fused 4H-furan ring side chain within one molecule, and (22E, 24R)-3β,5α-dihydroxyergosta-23-methyl-7,22-dien-6-one (2), as well as two known compounds (22E, 24R)-3β,5α-dihydroxyergosta-7,22-dien-6-one (3) and (22E, 24R)-6β-methoxy-ergosta-7,22-diene-3β,5α-diol (4). Their structures were assigned by detailed interpretation of HRESIMS, 1D and 2D NMR spectroscopic data. The absolute stereochemistry of 1 was determined by single-crystal X-ray crystallography while the absolute stereochemistry of 2 was established by CD. Compounds 1-4 showed cytotoxic activity against the lung adenocarcinoma (A549) with IC(50) values of 0.08, 0.94, 12.6 and 13.5 μM, respectively. In addition, compounds 1 and 2 exhibited moderate activities against human ovarian cancer (A2780), with IC(50) values of 2.8 and 5.1 μM.     

Analysis of tubulin alpha-1A/1B C-terminal tail post-translational poly-glutamylation reveals novel modification sites

Tubulin-α(1A/1B) C-terminal tail (CTT) has seven glutamic acid residues among the last 11 amino acids of its sequence that are potential sites for glutamylation. Cleavage of C-terminal tyrosine resulting in the detyrosinated form of tubulin-α(1A/1B) is another major modification. These modifications among others bring about highly heterogeneous tubulin samples in brain cells and microtubules, play a major role in directing intracellular trafficking, microtubule dynamics, and mitotic events, and can vary depending on the cell and disease state, such as cancer and neurodegenerative disorders. Identified previously using primary mass spectrometry (MS) ions and partial Edman sequencing, tubulin-α(1A/1B) glutamylation was found exclusively on the E(445) residue. We here describe the analysis of tubulin-α(1A/1B) glutamylation and detyrosination after 2-DE separation, trypsin and proteinase K in-gel digestion, and nanoUPLC-ESI-QqTOF-MS/MS of mouse brain and bovine microtubules. Tyrosinated, detyrosinated, and Δ2-tubulin-α(1A/1B) CTTs were identified on the basis of a comparison of fragmentation patterns and retention times between endogenous and synthetic peptides. Stringent acceptance criteria were adapted for the identification of novel glutamylation sites. In addition to the previously identified site at E(445), glutamylation on mouse and bovine tubulin-α(1A/1B) CTTs was identified on E(441) and E(443) with MASCOT Expect values below 0.01. O-Methylation of glutamates was also observed.     

三种毒菌的化学成分研究

本文对三种毒菌的化学成分进行了研究。从光盖伞(Psilocybe spp)分离鉴定了4个化合物,经波谱分析鉴定为:(22E,24R)-麦角甾-7,22-二烯-3β-十八烷酸酯(1)、β-胡萝卜苷(2)、(22E,24R)-5α,6α-环氧麦角甾-8,22-二烯-3β,7α-二醇(3)、色氨酸(4);从假褐云斑鹅膏(Amanita pseudoporphyria)分离鉴定了4个化合物:(22E,24R)-3β-羟基-5α,8α-过氧化麦角甾-6,22-二烯(5)、(22E,24R)-麦角甾-7,22-二烯-3β,5α,6β-三醇(6)、1-O-β-D-吡喃葡萄糖基-(2S,3R,4E,8E,2′R)-2-N-(2′-羟基棕榈酰)-9-甲基-4,8-脱氢鞘氨醇(7)、1-O-β-D-吡喃葡萄糖基-(2S,3R,4E,8E,2′R)-2-N-(2′-羟基十八烷酰)-9-甲基-4,8-脱氢鞘氨醇(8);大青褶伞(Chlorophyllum molybdites)发酵菌丝体分离鉴定了4个化合物:5、6、(22E,24R)-5α,6α-环氧麦角甾-8(14),22-二烯-3β,7α-二醇(9)、(22E,24R)-麦角甾-7,22-二烯-3β-醇(10)。除化合物9外其它化合物均为首次从以上相应毒菌中分离得到。     

南海柳珊瑚鳞海底柏化学成分的研究

本文对南海柳珊瑚鳞海底柏Melitodes squarnata Nutting进行了化学成分的研究.通过用工业乙醇:二氯甲烷(2∶1)进行了提取,采用硅胶柱色谱、Sephadex LH-20凝胶色谱、高效液相半制备色谱和薄层制备等方法对鳞海底柏的化学成分进行了分离,并利用波谱分析技术和文献对照鉴定其结构.从鳞海底柏中分离得到了17个化合物,分别鉴定为:malonganenone E(1),malonganenone D(2),nuttingin A(3),腺嘌呤核苷(4),1,3,7-三甲基黄嘌呤(5),2'-脱氧胸腺嘧啶核苷(6),3-甲基-6-次黄嘌呤(7),2'-脱氧尿苷(8),(22E,24R)-ergosta-8 (14),22-dien-3β,5α,6β,7α-tetrol(9),(22E)-胆甾-5,22-二烯-3β-醇(10),胆甾醇(11),(2S,3S,4R)-N-hexadecanoyl-2-amino-1,3,4-eicosanetriol( 12),(2S,2'R,3R,4E,8E)-N-2'- Hydroxytetradecanoyl-2-amino-9-methyl-4,8-octadecaa-diene-1,3-diol(13),鲨肝醇(14),十六烷基甘油醚(15),三油酸甘油酯(16)和4-hydroxy-2,3-dimetlhy1-2-nonen-4-olide(17).     

The dietary fatty acid 10E12Z-CLA induces epiregulin expression through COX-2 dependent PGF(2α) synthesis in adipocytes

Conjugated linoleic acids (CLAs) are a group of dietary fatty acids that are widely marketed as weight loss supplements. The isomer responsible for this effect is the trans-10, cis-12 CLA (10E12Z-CLA) isomer. 10E12Z-CLA treatment during differentiation of 3T3-L1 adipocytes induces expression of prostaglandin-endoperoxide synthase-2 (Cyclooxygenase-2; COX-2). This work demonstrates that COX-2 is also induced in fully differentiated 3T3-L1 adipocytes after a single treatment of 10E12Z-CLA at both the mRNA (20-40 fold) and protein level (7 fold). Furthermore, prostaglandin (PG)F(2α), but not PGE(2), is significantly increased 10 fold. In female BALB/c mice fed 0.5% 10E12Z-CLA for 10 days, COX-2 was induced in uterine adipose (2 fold). In vitro, pharmacological COX-2 inhibition did not block the effect of 10E12Z-CLA on adipocyte-specific gene expression although PGF(2α) was dose-dependently decreased. These studies demonstrate that PGF(2α) was not by itself responsible for the reduction in adipocyte character due to 10E12Z-CLA treatment. However, PGF(2α), either exogenously or endogenously in response to 10E12Z-CLA, increased the expression of the potent mitogen and epidermal growth factor (EGF) receptor (EGFR) ligand epiregulin in 3T3-L1 adipocytes. Blocking PGF(2α) signaling with the PGF(2α) receptor (FP) antagonist AL-8810 returned epiregulin mRNA levels back to baseline. Although this pathway is not directly responsible for adipocyte dependent gene expression, these results suggest that this signaling pathway may still have broad effect on the adipocyte and surrounding cells.     

Potentiation of paclitaxel effect by resveratrol in human breast cancer cells by counteracting the 17β-estradiol/estrogen receptor α/neuroglobin pathway

Neuroglobin (NGB), an antiapoptotic protein upregulated by 17β-estradiol (E2), is part of E2/estrogen receptor α (ERα) pathway pointed to preserve cancer cell survival in presence of microenvironmental stressors including chemotherapeutic drugs. Here, the possibility that resveratrol (Res), an anticancer plant polyphenol, could increase the susceptibility of breast cancer cells to paclitaxel (Pacl) by affecting E2/ERα/NGB pathway has been evaluated. In MCF-7 and T47D (ERα-positive), but not in MDA-MB 231 (ERα-negative) nor in SK-N-BE (ERα and ERβ positive), Res decreases NGB levels interfering with E2/ERα-induced NGB upregulation and with E2-induced ERα and protein kinase B phosphorylation. Although Res treatment does not reduce cell viability by itself, this compound potentiates Pacl proapoptotic effects. Notably, the increase of NGB levels by NGB expression vector transfection prevents Pacl or Res/Pacl effects. Taken together, these findings indicate a new Res-based mechanism that acts on tumor cells impairing the E2/ERα/NGB signaling pathways and increasing cancer cell susceptibility to chemotherapeutic agent.     

黑柄炭角菌的化学成分

从黑柄炭角菌(Xylaria nigripe)子实体中分离得到10个化合物,通过波谱分析等方法分别鉴定为(22E,24R)-麦角甾-5,7,22-三烯-3β-醇(1)、5α,8α-过氧-(22E,24R)-麦角甾-6,22-二烯-3β-醇(2)、脑苷酯B(3)、脑苷酯D(4)、stearic acid(5)、甘油的亚油酸三酯(trilinolein,6)、α-kojibiose(7)、D-阿洛糖醇(8)、L-氨基丙酸(9)和尿囊素(10)。所有化合物均为首次从该子实体中分离得到。