知母中甾体皂苷类成分的研究(英文)

从中药知母(Anemarrhena asphodeloides Bge.)的70%乙醇提取物中分离得到6个化合物,经波谱学方法和与已知样品对照鉴定为:3-O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranosyl-(3β,5β)-pregn-16(17)-ene-20-one(1)、timosaponin AIII(2)、timosaponin BIII(3)、22-hydroxy-5β-furost-3β,15α-diol-3-O-β-D-glucopyranosyl(1→2)-β-D-galactopyranoside(4)、timosaponin G(5)、β-daucosterol(6)。其中化合物1为新天然产物,命名为知母孕甾A,是知母中首次发现的C21甾体类化合物,经HR ESI-MS、1D NMR、2D NMR确定其结构,并首次对其核磁数据进行归属。     

钟花报春花的化学成分研究(Ⅱ)

从钟花报春花Primula sikkmensis Hook.中分离得到5个化合物,通过波谱分析其结构分别鉴定为5-羟基黄酮(1),2-苯基色原酮(2),5,8-二羟基黄酮(3),2’-羟基黄酮(4),3’-羟基-黄酮-4’-O-β-D-吡喃葡萄糖苷(5)。其中化合物1～4首次从该属植物中分离得到,化合物5首次从该植物中分离得到,并首次对3的NMR数据进行了归属。     

粗枝崖摩中一个新的三萜

从粗枝崖摩(Amoora dasyclada (How et T.Chen)C.Y.Wu)中分离到5个化合物.通过波谱方法鉴定为:24,25-epoxy-tirucall-7-ene-3,23-dione(1),24,25,26,27-tetranortirucall-7-ene-3-oxo-23(21)-lactone(2),taraxerone(3),taraxerol(4)andβ-sitosterol(5).其中化合物1为一个新的三萜,3～5为首次从该植物中分离得到.化合物2是首次从天然植物中分离得到的一个四降三萜,对它的碳谱和氢谱数据进行了全归属.此外化合物2在碳7位上的双键和14位上的甲基并未发生变化,以前文献中没有报道过与此类似的四降三萜,据此进一步讨论了四降三萜的生物合成路径.     

墨西哥落羽杉中三个活性双黄酮研究

从墨西哥落羽杉 (Taxodiummucronatum)枝叶中分离得到 3个化合物 ,通过MS、1DNMR、 2DNMR以及与参考文献比较的方法鉴定它们分别为 3个已知双黄酮 ,即 :a mentoflavone (1) ,podocarpusflavoneA (2 ) ,4′ ,7 dimethylamentoflavone (3)。本文还对文献中amentoflavone的C - 2 和C - 6 的碳谱数据归属进行了修正。体外生物活性筛选结果表明 ,这 3个双黄酮均为组织蛋白酶B的抑制剂 ,其IC50 值分别为 1 75、 1 6 8和 0 5 5 μmol/L ;这 3个双黄酮均显示一定的细胞毒活性 ,其中化合物 1对肿瘤细胞株BGC 82 3的IC50 值为 3 5 1μmol/L ,化合物 2对肿瘤细胞株HT 2 9的IC50 值为 11 16 μmol/L ,化合物 3对肿瘤细胞株A5 49、BEL 74 0 2、DU14 5、HT 2 9的IC50 值分别为 7 74、 17 16、 12 4 2、 14 5 4μmol/L。其中双黄酮为组织蛋白酶B的新型天然抑制剂     

大果大戟的化学成分

从大果大戟的根部首次分离得到11个化合物。利用波谱方法鉴定为β-香树素(1),β-香树素乙酸酯(2),3β-乙酰化羽扇豆烯醇(3),baccatin(4),2个caffeic mters(5a,5b),棕榈酸-1-甘油酯(6),棕榈酸(7),东莨菪内酯(8),β-谷甾醇(9)和胡萝卜甙(10)。其中5a,5b是第一次在大戟属中得到;并对5a,5b的碳谱和氢谱数据进行了全归属。     

云南拟单性木兰的化学成分

从云南拟单性木兰（Parakmeria yunnanensis Hu)的干燥嫩枝中首次分离得到6个化合物,它们的结构经各种波谱数据分别鉴定为云南拟单性木兰素A（parakmerinA,1),eupomatenoid-7(2),eupomatenoid-5(3),槲皮素（quercetin,4),芦丁（rutin,5)及丁香苷（syrigin,6),其中化合物1为一新的eupomatene型木脂素,其结构为2,3－二氢－2a-(4-羟基－3－甲氧基苯基）3β－甲基－5[E]－烯丙基苯并呋喃,对化合物2级3进行了首次^13C NMR归属。     

脉叶虎皮楠的生物碱成分研究

从脉叶虎皮楠(Daphniphyllum paxianum)的枝干中分离并鉴定了四个生物碱,分别为daphnilactone A(1)、daphnicyclidin D(2)、daphniphylline(3)、daphnicyclidin H(4).其中首次对化合物1的碳谱数据进行了归属.     

粉防己根的化学成分及抗肝纤维化活性研究CSCD

研究粉防己根的化学成分和抗肝纤维化活性。采用硅胶、Sephadex LH-20、ODS和半制备HPLC对粉防己根的乙醇提取物进行分离纯化得到13个化合物。根据化合物的理化性质和波谱数据鉴定其结构,分别为cyclanoline(1)、coclaurine(2)、5-hydroxymethyl-1-[2-(4-hydroxyphenyl)-ethyl]-1H-pyrrole-2-carbaldehyde(3)、isosalsoline(4)、thalifoline(5)、northalifoline(6)、2-甲基-3-羟基吡啶(7)、(+)-lyoniresinol(8)、icariside B5(9)、丁香酸(10)、对羟基苯乙酸(11)、对羟基苯甲酸(12)、对羟基苯乙酸甲酯(13)。化合物1~13为首次从该植物中分离得到,在千金藤属植物中化合物3、4、6~9也未见报道。初步评价了化合物1~13的抗肝纤维化活性,化合物2、5、6、10~12对TGF-β1诱导的LX-2细胞增殖具有显著抑制作用。     

南海海绵Dysidea sp.的化学成分研究

从我国南海陵水地区采集的一种未定种海绵Dysideasp中首次分离到7个化合物,经MS,NMR等光谱技术,确定了结构分别为胆固醇(1),过氧化麦角甾醇(2),cholesl-7-en-9a,11α-epoxy-3β,5α,6β,19-tetraol-6-monoacetate(3),甲基尿嘧啶(4),尿嘧啶(5),甲基尿嘧啶脱氧核糖核苷(6),尿嘧啶脱氧核糖核苷(7)。其中化合物3的^1H NMR和^13C NMR数据通过二维NMR实验首次得到了全归属。     

瑞香狼毒根中的一个新化合物(英文)

从瑞香狼毒根中分离得到了7个化合物,根据理化性质和波谱数据鉴定为:3-丁酰基-4-氨基肉桂酸乙酯(1)、阿魏酸(2)、香草酸(3)、姜黄素(4)、5'-去甲氧基-姜黄素(5)、3'-羟基-4'-O-β-D-葡萄糖苷黄酮(6)、3-甲氧基-4-O-β-D-葡萄糖苯甲酸(7),其中化合物1~3,6~7为首次从该植物中分离得到,化合物1为新化合物。     

Chemical constituents from Celastrus aculeatus Merr.

Phytochemical investigation of Celastrus aculeatus Merr. led to the isolation of nine compounds. Their structures were identified to be dulcitol (1), β-sitosterol (2), n-tritriacontane (3), nimbidiol (4), pristimerin (5), p-hydroxybenzoic acid (7), vanillic acid (8), 3, 5-dimethoxy-4-hydroxybenzoic acid (9) and a new compound named pristimerol (6) on the basis of mass and NMR spectra. This is the first report of phenolic acids (compounds 7–9) from C. aculeatus Merr. We present the HR-MS, 1D NMR (¹H, ¹³C NMR, DEPT) and 2D NMR (HMBC) data of the new compound (6).     

藏药红花绿绒蒿的化学成分

从红花绿绒蒿(Meconopsis punicea)植物地上部分中分离得到17个化合物,通过MS和NMR等方法将它们的结构分别鉴定为karachine(1)、valachine(2)、二氢血根碱(dihydrosanguinarine,3)、威尔士绿绒蒿定碱((?)-mecambridine,4)、原鸦片碱(protopine,5)、马齿苋酰胺E(oleracein E,6)、anhydroberberillic acid(7)、小糪碱(berberine,8)、阿苞碱(alborine,9)、木犀草素(luteolin,10)、小麦黄素(tricin,11)、二氢槲皮素(dihydroquerce-tin,12)、洋芹素(apigenin,13)、大风子素(hydnocarpin,14)、小麦黄素7-O-β-D-葡萄糖苷(tricin 7-O-β-D-glucopyr-anoside,15)、对羟基桂皮酸(p-coumaric acid,16)和尿嘧啶(uracil,17)。其中,化合物1~3、7、15和17为首次从该属植物中分离得到;6、8、11和14为首次从该种植物中分离得到,采用二维NMR技术首次归属了化合物1和2的1H和13C NMR信号。     

A compound representing the D-glycerate terminus of the methylglucose-containing polysaccharide of Mycobacterium smegmatis.

In order to study the structure of the methylglucose-containing polysaccharide (MGP) of Mycobacterium smegmatis by NMR spectroscopy, we have prepared the model compound O-alpha-D-glucopyranosyl-(1 leads to 2)-D-glyceric acid. This compound, which represents the aglycon-containing terminus of MGP, was made from leucorse [O-alpha-D-glucopyranosyl-(1 leads to 5)-D-fructopyranose] by successive treatment with sodium borohydride, lead tetraacetate, and hypobromite. The structure of O-alpha-D-glucopyranosy.-(1 leads to 2)-D-glyceric acid was confirmed by chemical and enzymic methods. 13C and 1H NMR spectra of this compound, together with spectra of several disaccharides, were obtained for future reference in the polysaccharide study. The nine resonances in the 13C spectrum were assigned by comparison with the spectrum of methyl alpha-D-glucopyranoside. Analysis of the 1H NMR spectrum showed that the two methylene protons on C-3 of the glycerate moiety were less equivalent in the sodium salt than in the acid. This may be attributable to hydrogen bonding between the carboxylate and the hydrogen atom of the glycerate 3-hydroxyl group.     

灵芝菌丝体中一个三萜类化合物的核磁归属及活性初探

通过液体振荡-静置两阶段发酵获得灵芝菌丝体,并采用硅胶柱色谱层析、反相柱层析和甲醇重结晶的方法,从中分离得到4个三萜类化合物。根据NMR、MS等波谱数据分析,化合物分别被鉴定为lanosta-7,9(11),24-trien-3α-acetoxy-26-oic acid（1）、灵芝酸R（2）、灵芝酸T（3）和灵芝酸S（4）,其中化合物1的核磁信号全归属为首次报道。4个三萜类化合物均具有较好的抑制肿瘤细胞L1210及K562增殖的活性,且化合物1的体外抗肿瘤活性为首次证实,其对肿瘤细胞L1210及K562增殖的半数抑制浓度IC₅₀分别为22.17μmol/L和54.79μmol/L。     

Re-characterization of three conjugated linolenic acid isomers by GC-MS and NMR

Conjugated linolenic acids (CLN) refer to a group of octadecatrienoic acids with three conjugated double bonds. Minor positional and geometrical differences among CLN isomers make their separation and identification difficult. We have used GC-MS and NMR to study three common CLN isomers namely alpha-eleostearic acid, beta-eleostearic acid and punicic acid, finding that some signals of olefinic carbon atoms in NMR spectra were mistakenly assigned in the literature. The present study was therefore undertaken to re-characterize the location of CC double bonds and assign the chemical signals of proton and carbon atoms using (1)H NMR, (13)C NMR, (1)H-(1)H two-dimensional correlation spectra ((1)H-(1)H COSY) and (13)C-(1)H two-dimensional correlation spectra ((13)C-(1)H COSY). The geometrical structure of double bonds in these three CLN isomers was identified using homonuclear decoupling technique.     

1H NMR studies on the CuA center of nitrous oxide reductase from Pseudomonas stutzeri.

1H NMR spectra of the CuA center of N2OR from Pseudomonas stutzeri, and a mutant enzyme that contains only CuA, were recorded in both H2O- and D2O-buffered solution at pH 7.5. Several sharp, well-resolved hyperfine-shifted 1H NMR signals were observed in the 60 to -10 ppm chemical shift range. Comparison of the native and mutant N2OR spectra recorded in H2O-buffered solutions indicated that several additional signals are present in the native protein spectrum. These signals are attributed to a dinuclear copperII center. At least two of the observed hyperfine-shifted signals associated with the dinuclear center, those at 23.0 and 13.2 ppm, are lost upon replacement of H2O buffer with D2O buffer. These data indicate that at least two histidine residues are ligands of a dinuclear CuII center. Comparison of the mutant N2OR 1H NMR spectra recorded in H2O and D2O indicates that three signals, c (27.5 ppm), e (23.6 ppm), and i (12.4 ppm), are solvent exchangeable. The two most strongly downfield-shifted signals (c and e) are assigned to the two N epsilon 2H (N-H) protons of the coordinated histidine residues, while the remaining exchangeable signal is assigned to a backbone N-H proton in close proximity to the CuA cluster. Signal e was found to decrease in intensity as the temperature was increased, indicating that proton e resides on a more solvent-exposed histidine residue. One-dimensional nOe studies at pH 7.5 allowed the histidine ring protons to be definitively assigned, while the remaining signals were assigned by comparison to previously reported spectra from CuA centers. The temperature dependence of the observed hyperfine-shifted 1H NMR signals of mutant N2OR were recorded over the temperature range of 276-315 K. Both Curie and anti-Curie temperature dependencies are observed for sets of hyperfine-shifted protons. Signals a and h (cysteine protons) follow anti-Curie behavior (contact shift increases with increasing temperatures), while signals b-g, i, and j (histidine protons) follow Curie behavior (contact shift decreases with increasing temperatures). Fits of the temperature dependence of the observed hyperfine-shifted signals provided the energy separation (Delta EL) between the ground (2B3u) and excited (2B2u) states. The temperature data obtained for all of the observed hyperfine-shifted histidine ligand protons provided a Delta EL value of 62 +/- 35 cm-1. The temperature dependence of the observed cysteine C beta H and C alpha H protons (a and h) were fit in a separate experiment providing a Delta EL value of 585 +/- 125 cm-1. The differences between the Delta EL values determined by 1H NMR spectroscopy and those determined by EPR or MCD likely arise from coupling between relatively low-frequency vibrational states and the ground and excited electronic states.     

Physicochemical and biological properties of 6(1),6(3),6(5)-tri-O-alpha-maltosyl-cyclomaltoheptaose (6(1),6(3),6(5)-tri-O-alpha-maltosyl-beta-cyclodextrin)

A unique multibranched cyclomaltooligosaccharide (cyclodextrin, CD) of 6(1),6(3),6(5)-tri-O-alpha-maltosyl-cyclomaltoheptaose [6(1),6(3),6(5)-tri-O-alpha-maltosyl-beta-cyclodextrin, (G(2))(3)-betaCD] was prepared. The physicochemical and biological properties of (G(2))(3)-betaCD were determined together with those of monobranched CDs (6-O-alpha-D-glucopyranosyl-alpha-cyclodextrin (G(1)-alphaCD), 6-O-alpha-D-glucopyranosyl-beta-cyclodextrin (G(1)-betaCD), and 6-O-alpha-maltosyl-beta-cyclodextrin (G(2)-betaCD)). NMR spectra of (G(2))(3)-betaCD were measured using various 2D NMR techniques. The solubility of (G(2))(3)-betaCD in water and MeOH-water solutions was extremely high in comparison with nonbranched betaCD and was about the same as that of the other monobranched betaCDs. The formation of an inclusion complex of (G(2))(3)-betaCD with stereoisomers (estradiol, retinoic acid, quinine, citral, and glycyrrhetinic acid) depends on the cis-trans isomers of guest compounds. The cis isomers of estradiol, retinoic acid, and glycyrrhetinic acid were included more than their trans isomers, while the trans isomers of citral and quinine fit more tightly than their cis isomers. (G(2))(3)-betaCD was the most effective host compound in the cis-trans resolution of glycyrrhetinic acid. Among the branched betaCDs, (G(2))(3)-betaCD exhibited the weakest hemolytic activity in human erythrocytes and showed negligible cytotoxicity in Caco-2 cells up to 200 microM. These results indicate unique characteristics of (G(2))(3)-betaCD in some biological responses of cultured cells.     

Proton nuclear magnetic resonance spectroscopy of horseradish peroxidase isoenzymes: correlation of distinctive spectra with isoenzyme specific activities

High-resolution proton NMR spectra are reported for the paramagnetic ferric native and cyano complexes of the five major horseradish root peroxidase (HRP) isoenzymes (A1, A2, A3, B, and C). Axial imidazole resonances are observed in the native and cyano-complex spectra of all the isoenzymes, thus indicating the presence of a common axial histidine ligand. Proton NMR spectra outside the usual diamagnetic region are identical for sets of A1 and A2 isoenzymes and for the B and C isoenzyme set. Variation in heme residue chemical shift positions may be controlled in part by porphyrin vinyl side chain-protein interactions. Diverse upfield spectra among the isoenzymes reflect amino acid substitutions and/or conformational differences near the prosthetic group, as signals in this region must result from amino acid residues in proximity to the heme center. Acid-base dependence studies reveal an "alkaline" transition that converts the native high-spin iron (III) porphyrin to the low-spin state. The transition occurs at pH 9.3, 9.4, 9.8, and 10.9 for respective HRP A1, A2, A3, and C isoenzymes, respectively. Significantly, this ordering also reflects specific activities for the isoenzymes in the order A1 = A2 greater than A3 greater than B = C. Identical proton NMR spectra for A1/A2 and B/C isoenzyme sets parallel equivalent specific activities for members of a particular set. Proton NMR spectra thus appear to be highly sensitive to protein modifications that affect catalytic activity.     

31P NMR of phospholipid glycerol phosphodiester residues

Saponification of extracted tissue phospholipids yields a set of isolated glycerol 3-phosphoryl phospholipid polar headgroups from which semi-quantitative 31P NMR spectra can be obtained. The resonance signals from these molecules, which frequently have been reported as uncharacterized phosphate signals observed in perchloric acid extracts of tissue, can be used as an aid in the characterization of isolated phospholipids and of tissue phospholipid 31P NMR profiles. 31P NMR chemical-shift values of the resonances at pH 7 in water and relative to 85% phosphoric acid are: glycerol 3-phosphocholine (-0.13 delta), glycerol 3-phosphoethanolamine (0.42 delta), glycerol 3-phospho(monomethyl)ethanolamine (0.29 delta), glycerol 3-phospho(dimethyl)ethanolamine (0.16 delta), glycerol 3-phosphoserine (0.14 delta), glycerol 3-phosphoinositol (-0.07 delta), glycerol 3-phosphoglycerol (0.92 delta), bis(glycerol 3-phospho)glycerol (0.79 delta), serine ethanolamine phosphodiester (-0.46 delta), glycerol 3-phosphate (0.60 delta; 4.29 delta at pH 10) glycerol 2-phosphate (0.15 delta; 3.92 delta at pH 10). In addition, analysis of extracted cancer tissue phospholipid samples yielded a new and uncharacterized polar headgroup fragment with a chemical-shift value of 0.29 delta that is independent of sample pH.     

Synthesis of some acrylophenones with N-methylpiperazine and evaluation of their cytotoxicities

In this study, the compounds having acrylophenone structure, 1-aryl-2-(N-methylpiperazinomethyl)-2-propen-1-one dihydrochlorides, were synthesized and their chemical structures were identified with ¹H NMR, ¹³C NMR and HRMS spectra. The cytotoxicities of the compounds were tested towards Ca9-22 (human gingival carcinoma), HSC-2 (human oral squamous carcinoma), HSC-3 (human oral squamous carcinoma) and HSC-4 (human oral squamous carcinoma) cell lines as tumor cell lines and HGF (gingival fibroblasts), HPLF (periodontal ligament fibroblasts) and HPC (pulp cells) cell lines as non-tumor cell lines. PSE of the compound TA2, which has a methyl substituent on phenyl ring, pointed out the compound TA2 as a leader compound to be considered.