大丽轮枝菌YMF1.02083的化学成分研究

从大丽轮枝菌(Verticillium dahliae)YMF1.02083发酵液的甲醇提取物中分离得到3个化合物。经质谱、核磁共振波谱分析,鉴定其为(9Z,11E,13E)-9,11,13-octadecatrienoic acid(Ⅰ)、4-hydroxy-benzene-ethanol(Ⅱ)和(3β,5α,6α,22E)-3-hydroxy-5,6-epoxy-7-one-8(14),22-dien-ergosta(Ⅲ);这3个化合物在浓度为200μg·mL~(-1)时,对秀丽隐杆线虫(Caenorhabditis elegans)均无毒杀活性。     

耳叶紫菀化学成分及生物活性研究

首次对耳叶紫菀(Aster auriculatus Franch)全草的化学成分及生物活性进行研究,采用柱层析(CC)对植物中的提取物进行分离提纯,并利用现代波谱方法(1H-NMR,13C-NMR,MS等)分析鉴定,确定化合物的结构并对其生物活性进行筛选。从该植物的氯仿部分分离得到8个倍半萜类化合物,它们的结构分别鉴定为:Ilicic acid(1),(7R,10S)-selina-4,11(13)-dien-3-on-12-oic acid(2),2-oxo-isocostic acid(3),1β,5α-diangeloyloxy-eudesm-(15)-ene(4),1β,6α-dihydroxyeudesm-4(15)-ene(5),4(15)-eudesmene-1β,7α-diol(6),Furanoligularenone(7),(4αR,5S,8αR)-4α,5,6,7,8,8α-Hexahydro-8α-hydroxy-3,4α,5-trimethylnaphtho[2,3-b]furan-2(4H)-one(8)。并采用杯碟法对以上8个化合物进行生物活性筛选,通过观测各供试菌抑菌圈的半径,发现化合物2、化合物4对大肠杆菌(Escherichia coli)有较强的抑制作用,所有化合物均为首次从该植物中分离得到。     

N-杂环卡宾银配合物的合成与表征

由N-杂环卡宾配体L(L=1,3-双(苄基)苯并咪唑盐酸盐)与Ag2O反应,得到银卡宾配合物(1),通过核磁、元素分析对化合物进行全面表征。并采用溶剂挥发法得到化合物(1)的单晶,利用X-射线单晶衍射测定和研究了化合物(1)的晶体结构,晶体结构数据:单斜晶系,空间群P2(1)/c,a=9.144(8),b=9.518(9)°,c=20.789(19)°,α=90°,β=94.307(13)°,γ=90°,Z=4,V=1804(3)3。     

红树植物老鼠簕根化学成分的研究

采用硅胶柱色谱、Sephadex LH-20柱色谱、高效液相色谱分离化合物,通过波谱技术确定所得化合物的结构。从老鼠簕根乙醇提取物中分离得到11个化合物,分别鉴定为:2-benzoxazolinone(1),4-hydroxy-benzoxazolinone-2(3H)-one(2),benzoxazolinone-2(3H)-one(3),4-O-β-D-glucopyranosyl-benzoxazolinone-2(3H)-one(4),benzoxazolinone-2(3H)-one(5),4-hydroxy-3,5-dimethoxybenzoic acid(6),erigeside C(7),glucosyringic acid(8),(2R)-2-O-β-D-glucopyranosyl-2H-1,4-benzoxazin-3(4H)-one(9),7-chloro-(2R)-2-O-β-D-glucopyranosyl-2H-1,4-benzoxazin-3(4H)-one(10),(2R)-2-O-β-D-glucopyranosyl-5-hydroxy-2H-1,4-benzoxazin-3(4H)-one(11)。化合物5~8为首次从该植物中分离得到。     

狭瓣鹰爪花枝叶中化学成分研究

综合运用硅胶柱色谱、反相硅胶柱色谱、Sephadex LH-20凝胶柱色谱以及制备型高效液相等色谱分离技术,对番荔枝科鹰爪花属植物狭瓣鹰爪花Artabotrys hainanensis枝叶中的化学成分进行系统研究。结合理化性质和多种现代波谱技术,并通过与文献进行对照,鉴定了从狭瓣鹰爪花枝叶90%乙醇提取物的中分离得到6个化合物,分别鉴定为:5-羟基-7,8-二甲氧基二氢黄酮(1)、litseachromolaevane A(2)、liguducin A(3)、1β-hydroxy-4(15),5E,10(14)-germacratriene(4)、(9E,11Z)14-hydroxyoctadecan-9,11-dienoic acid(5)和benzyl benzoate(6)。其中化合物1为黄酮类化合物,化合物2-4为倍半萜类化合物,化合物5为脂肪酸类化合物,化合物6为芳酸类化合物,所有化合物均为首次从鹰爪花属植物中分离得到。     

苦味西葫芦果实木脂素类成分研究

采用色谱技术对苦味西葫芦果实的抗炎活性部位的化学成分进行分离,应用1HNMR、13CNMR确定化合物的结构.从正丁醇萃取部位分离得到4个木脂素化合物:Larisiresinol 4'-O-β-D-glucopyranoside(Ⅰ)、( )-5'-Methoxyisolarisiresinol 3α-O-β-D-glucopyranoside(Ⅱ)、Lyoniside(Ⅲ)、Isolariciresinol-9-O-β-D-xylopyranoside(Ⅳ).化合物Ⅰ、Ⅱ、Ⅲ和Ⅳ均为首次从南瓜属植物中分离得到.     

山茱萸果肉化学成分研究

研究了山茱萸(Cornus officinalis)果肉的化学成分,分离得到单体化合物。对山茱萸成熟果实渗漉提取,利用硅胶、Sephadex LH-20柱色谱和重结晶等方法分离纯化化合物,通过理化性质和现代波谱分析技术鉴定化合物结构。结果表明:从山茱萸果肉中分离并鉴定得到6个单体化合物。化合物分别鉴定为槲皮素(Quercetin,1)、咖啡酸(Caffeic acid,2)、没食子酸(Gallic acid,3)、没食子酸乙酯(Ethyl gallate,4)、齐墩果酸(Oleanoic acid,5)、β-谷甾醇(β-Sitosterol,6)。     

(E)-2-(1-萘亚胺)苊酮席夫碱的合成及晶体结构

以1,2-苊二酮和甲萘胺为原料合成标题化合物,其结构经1HNMR、MS和单晶X-射线衍射技术表征。实验结果表明,该化合物晶体为单斜晶系,P21/c空间群,化合物分子式为C22H13NO,分子量为307.33,晶胞参数为a=0.825 90(11)nm,b=1.551 4(2)nm,c=1.202 39(16)nm,α=90.00°,β=100.342(4)°,γ=90.00°,V=1.515 6(3)nm3,Z=4,CCDC:1035525。     

2-甲基-4-(4-(吡啶-4-乙炔基)苯基)-3-丁炔-2-醇的合成及结构表征

由1,4-二碘代苯出发,经过两步Sonogashira偶联反应合成标题化合物2-甲基-4-(4-(吡啶-4-乙炔基)苯基)-3-丁炔-2-醇。通过1 H NMR、13 C NMR核磁共振、X射线单晶衍射等手段对化合物的结构进行了表征。结果表明,该化合物属于单斜晶系,空间群为P2(1)2(1)2(1)。晶体学参数:a=0.060754(15)nm,b=0.081700(19)nm,c=0.32073(7)nm,α=90.00°,β=90.00°,γ=90.00°,V=15.920(7)nm3,Z=8。     

4种12-烯-28-乌索酸的分离以及结构鉴定

从山梨猕猴桃(Actinidia rufa plands ex miq)根分离得到4种三萜类化合物,经光谱(IR, MS,1DNMR和2DNMR)确认为2α, 3β, 19α, 23, 24-五羟基-12-烯-28-乌索酸(1),2β,3α,24-三羟基-12-烯-28-乌索酸(2),2α,3β,24-三羟基-12-烯-28-乌索酸(3)和2β,3α,23-三羟基-12-烯-28-乌索酸(4).     

新疆白麻药用成分的提取与表征

以新疆白麻Poacynum pictum(Schrenk)Baill叶为原料,采用溶剂萃取及色谱技术从新疆白麻叶中共分离并鉴定了11个化合物的结构,并通过理化常数、MS、1H NMR和13C NMR等现代波谱技术鉴定其化学结构,分别为羽扇醇棕榈酸酯(1)、异莨菪亭(2)、正十六烷酸(3)、正二十六烷酸(4)、β-谷甾醇(5)、槲皮素(6)、槲皮素-3-O-β-D-吡喃葡萄糖苷(7)、金丝桃苷(8)、Δ′-异戊烯-3-O-β-D-吡喃葡萄糖苷(9)、丁香树脂醇-β-D-吡喃葡萄糖苷(10)和蔗糖(11)。其中化合物2为首次从属中分离得到。     

Osteoprotective Effects of Loganic Acid on Osteoblastic and Osteoclastic Cells and Osteoporosis-Induced Mice

Osteoporosis is a common disease caused by an imbalance of processes between bone resorption by osteoclasts and bone formation by osteoblasts in postmenopausal women. The roots of Gentiana lutea L. (GL) are reported to have beneficial effects on various human diseases related to liver functions and gastrointestinal motility, as well as on arthritis. Here, we fractionated and isolated bioactive constituent(s) responsible for anti-osteoporotic effects of GL root extract. A single phytochemical compound, loganic acid, was identified as a candidate osteoprotective agent. Its anti-osteoporotic effects were examined in vitro and in vivo. Treatment with loganic acid significantly increased osteoblastic differentiation in preosteoblast MC3T3-E1 cells by promoting alkaline phosphatase activity and increasing mRNA expression levels of bone metabolic markers such as Alpl, Bglap, and Sp7. However, loganic acid inhibited osteoclast differentiation of primary-cultured monocytes derived from mouse bone marrow. For in vivo experiments, the effect of loganic acid on ovariectomized (OVX) mice was examined for 12 weeks. Loganic acid prevented OVX-induced bone mineral density loss and improved bone structural properties in osteoporotic model mice. These results suggest that loganic acid may be a potential therapeutic candidate for treatment of osteoporosis.     

两个多羟基甾醇的分离与结构鉴定

研究刺柳珊瑚Echinogorgia sp的化学成分。各种色谱方法进行分离纯化,理化性质和光谱数据鉴定结构。从中国南海硇洲岛刺柳珊瑚Echinogorgia sp中分离得到两个多羟基甾醇：胆甾-3β,5α,6β,11β-四醇;胆甾-22（23）-烯-3β,5α,6β,11β-四醇,这些化合物均为首次从该属珊瑚中获得。     

Evaluation of Antioxidant and Free Radical Scavenging Capacities of Polyphenolics from Pods of Caesalpinia pulcherrima

Thirteen polyphenolics were isolated from fresh pods of Caesalpinia pulcherrima using various methods of column chromatography. The structures of these polyphenolics were elucidated as gallic acid (1), methyl gallate (2), 6-O-galloyl-d-glucoside (3), methyl 6-O-galloyl-β-d-glucoside (4), methyl 3,6-di-O-galloyl-α-d-glucopyranoside (5), gentisic acid 5-O-α-d-(6'-O-galloyl)glucopyranoside (6), guaiacylglycerol 4-O-β-d-(6'-O-galloyl)glucopyranoside (7), 3-methoxy-4-hydroxyphenol 1-O-β-d-(6'-O-galloyl) glucopyranoside (8), (+)-gallocatechin (9), (+)-catechin (10), (+)-gallocatechin 3-O-gallate (11), myricetin 3-rhamnoside (12), and ampelopsin (13). All isolated compounds were tested for their antioxidant activities in the 1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl, and peroxynitrite radicals scavenging assays. Among those compounds, 11, 12, and 2 exhibited the best DPPH-, hydroxyl-, and peroxynitrite radical-scavenging activities, respectively. Compound 7 is a new compound, and possesses better scavenging activities towards DPPH but has equivalent hydroxyl radical scavenging activity when compared to BHT. The paper is the first report on free radical scavenging properties of components of the fresh pods of Caesalpinia pulcherrima. The results obtained from the current study indicate that the free radical scavenging property of fresh pods of Caesalpinia pulcherrima may be one of the mechanisms by which this herbal medicine is effective in several free radical mediated diseases.     

氧雄龙的合成

以甲基表雄醇为起始原料,环保高效地合成了氧雄龙。首先采用环保的温和氧化剂2-iodoxybenzoicacid(IBX)在65～70℃,氧化甲基表雄醇直接合成α,β-不饱和羰基甾体-17α-甲基-1-睾酮;经-30～-40℃臭氧化后,用氢氧化钠溶液碱性水解得到17β-羟基-17α-甲基-1-氧代-1,2-开环-A-失碳-5α-雄甾-2-含氧羧酸;最后在0～10℃,经硼氢化钠碱性条件下还原后,调节pH=1～2,内酯化反应合成了目的物。3步操作的产率分别为72%、69%及86%。中间体和目的物经红外光谱、核磁共振氢谱、质谱及元素分析确证了其化学结构。     

Improved Chemical Synthesis,X-Ray Crystallographic Analysis,and NMR Characterization of (22R)-/(22S)-Hydroxy Epimers of Bile Acids

We report an improved synthesis of the (22R)- and (22S)-epimers of 3α,7α,12α,22-tetrahydroxy-5β-cholan-24-oic acid and 3α,7α,22-trihydroxy-5β-cholan-24-oic acid from cholic acid (CA) and chenodeoxycholic acid (CDCA), respectively. The principal reactions involved were as follows: (1) oxidative decarboxylation of the bile acid peracetates with lead tetraacetate, and (2) subsequent Reformatsky reaction of the 23,24-dinor-22-aldehydes with ethyl bromoacetate in the presence of activated Zn as a catalyst with the reaction temperature maintained precisely at 75 °C. The absolute configuration of the chiral center at C-22 of each epimer was established by single-crystal X-ray diffraction data using its ethyl ester-peracetate derivative. The ¹H- and ¹³C-NMR spectra that permit the (22R)- and (22S)-epimers to be distinguished are reported as well as the specific ¹H shift effects induced by C₅D₅N. Bile acids having hydroxyl groups at C-22 are present in a variety of animal biles, previously have been difficult to identify, and are known to have distinctive physicochemical and biological properties.     

Separation and Purification of Bioactive Flavonol Glycosides from Hedyotis diffusa Willd by High-Speed Counter-Current Chromatography

Three flavonoid glycosides including quercetin-3-O-[2″-O-(6″′-O-E-sinapoyl)-β-D-glucopyranosyl]-β-D-glucopyranoside(I), quercetin-3-O-[2″-O-(6″′-O-E-feruloyl)-β-D-glucopyranosyl]-β-D-glucopyranoside(II) and quercetin-3-O-[2″-O-(6″′-O-E-feruloyl)-β-D-glucopyranosyl]-β-D-galactopyranoside(III) were isolated and purified from Hedyotis diffusa Willd by high-speed counter-current chromatography (HSCCC). This run was carried out with a two-phase solvent system composed of n-hexane–ethyl acetate–n-butanol–methanol–1.0% acetic acid (1:1:3.5:1:4.5, v/v) by eluting the lower phase as the mobile phase with a flow-rate at 2.0 ml/min. Consequently, 29.6 mg of I, 35.1 mg of II, 41.3 mg of III with purities of over 95% were obtained from 200 mg of the crude extracts in a single run in less than 130 min. The structure of the isolated compounds was confirmed by MS, ¹H NMR, and ¹³C NMR analysis.     

Constituents of human meconium: II. Identification of steroidal acids with 21 and 22 carbon atoms

Monohydroxylated acid fraction isolated from human meconium was found to contain, in addition to C₂₀ and C₂₄ acids identified previously, three C₂₂ bile acids-(20S)-3α-hydroxy-23,24-bisnor-5β-cholan-22-oic, (20S)- and (20R)-3β-hydroxy-23,24-bisnor-chol-5-en-22-oic, and one C₂₁ acid-3β-hydroxypregn-5-en-21-oic. These compounds were identified by capillary gas chromatography-mass spectrometry and by comparison with standards. It is postulated that these C₂₂ acids, as well as the two monohydroxylated C₂₄ bile acids (lithocholic and 3β-hydroxychol-5-enoic) are produced in the maternal intestine by microbial flora and transferred to the fetus through the placenta.     

Progesterone inclusion into cyclodextrin-functionalized mesoporous silica

SBA-15 type mesoporous silica has been modified to produce a covalent bond with β-cyclodextrin by two different synthetic approaches to obtain an hybrid system able to work as a drug delivery system for progesterone. In the first approach, SBA-15 silica was first let to react with 3-glycidyloxypropyltrimethoxysilane to produce an epoxide ring functional group on mesoporous silica. The latter was then reacted under basic conditions with mono-6-deoxy-6-mercapto-β-cyclodextrin (β-CDCH₂SH), prepared in its turn in two steps from β-cyclodextrin (β-CD) through monotosylation to give β-CDCH₂OTs followed by thiolation with thiourea. In the second approach, a silica suitably functionalized with a terminal thiol group (obtained by the reaction of SBA-15 silica with 3-mercaptopropyltrimethoxysilane) was reacted with β-CDCH₂OTs. The obtained materials were characterized by X-Ray powder diffraction, nitrogen adsorption, ¹³C Cross Polarization Magic Angle Spin Nuclear Magnetic Resonance (¹³C CP/MAS NMR). Progesterone was loaded on the materials producing complete filling of mesopores and cyclodextrin cavities. Its release was studied at different pH values. Only one of the two progesterone-loaded delivery device is able to retain the drug in the system during the first period at acid pH (2 h) and release it after pH increase.