电感耦合等离子体光谱法测定黄花棘豆中微量元素

1　引　　言黄花棘豆 (ＯｘｙｔｒｏｐｉｓＯｃｈｒｏｃｅｐｈａｌａＢｕｎｇｅ)为豆科棘豆属的一种多年生草本植物 ,广泛分布于我国西北部牧区 ,可导致家畜中毒、死亡。国外将棘豆属和黄花属中的一些有毒性植物统称为疯草 (ｌｏｃｏｗｅｅｄ) ,其引起的中毒症状相似 ,统称为疯草中毒综合症。国内外专家对其有毒成分进行了分析 ,对家畜疯草中毒症状 ,以及从病理学角度探讨其对生殖器官及其他各种脏器的影响做了研究 ,尚未见到对疯草中微量元素的分析报道。本文用高频电感耦合等离子体原子发射光谱法(ＩＣＰ ＡＥＳ)测定了疯草黄花棘豆中的微…     

红车轴草中刺芒柄花素的微波法提取工艺

红车轴草(Trifolium Pratense L．)为豆科多年生草本植物,异名红三叶,红菽草,三叶草等。全草含有刺芒柄花素(fommnonetin)和鹰嘴豆芽素A(bioehanin A)及相应的苷等8种主要异黄酮成分。这些成分具有抗肿瘤、解痉、降血脂、抗心律不齐、抗炎杀菌、植物雌激素样等作用。现有提取方法仅限于溶剂法及柱分离法。微波协同植物有效成分的提取比水溶液加热提取效率高,易控制,穿透力强,选择性高,提取成本低等。     

四齿四棱草根部的两个新二萜化合物

通过硅胶柱层析从我国特有属植物四齿四棱草(Schnabelia tetradonta)根部乙醇提取物中分离纯化出2个新的17(15→16)-移-20-降松香烷型二萜化合物,分别命名为四棱草内酯A和B.经波谱分析,将它们的结构确定为17(15→16)-移-20-降松香烷-12,16-环氧-7,17-二羟基-5(10),6,8,12,15-五烯-11,14-二酮-18(1)-内酯(1)和17(15→16)-移-20-降松香烷-12,16-环氧-7-羟基-5(10),6,8,12,15-五烯-11,14-二酮-18(1)-内酯(2).具有这种分子骨架的二萜化合物为首次报道.     

白花蛇舌草免疫多糖结构的研究

白花蛇舌草(Hedgotis diffusa willd)系茜草科(Rubiaceae)耳草植物,民间常用此草内服治疗小儿疳疾、毒蛇咬伤、癌肿及肠道疾病,外用治疗各种疮疥及跌打刀伤等症.本文首次报道从白花蛇舌草水溶性成份中分离得到一个具有免疫活性的多糖,并对它的结构进行了初步的探讨.     

藏药无茎芥的化学成分研究

藏药无茎芥(Pegaeophyton scapiflorun(Hook.f.et Thoms)Marq.et Shaw)为十字花科(Cruciferae)无茎芥属(Pe-gaeophyton Hayeket Hand-Wazz)植物,又名单花芥、高山辣根菜,为多年生草本,主要产于云南西北部、西藏、四川、青海等地,生长于海拔3500～5400米的高山草地[1].在藏族地区,藏医用无茎芥全草内服退热、治肺咯血、并解食物中毒,外用治刀伤[2,3].无茎芥属植物只有无茎芥一种植物,该植物的化学成分研究前人未见报道.     

中药紫珠中的二萜

紫珠(Callicarpa pedunculataR.Brown)为马鞭草科紫珠属植物,主要分布在我国南部地区,根、茎、叶及种子均可入药,有通经活血之功效[1].该属植物在中医临床上主要用于各种出血症,其中较常用的为紫珠,紫珠首载于<本草拾遗>,别名止血草,传说本药得之于某盗贼,故又称为"贼仔草"、"创伤草".经文献查阅,国内外对紫珠化学成分研究的报道较少,报道的化合物主要为黄酮、萜类成分[2-5].为了寻找紫珠中的活性成分,我们对紫珠的化学成分进行了研究.     

河口细叶黄皮化学成分研究

芸香科黄皮属植物(Clausena)多为乔木或小灌木植物,约23～25种,分布于印度西北至我国西南至台湾,南至印度尼西亚、大洋洲北部及巴布亚新几内亚;非洲西北部等.我国约12种,集中分布于西南及华南各省区;云南省有¨种[1],具有丰富的植物资源.本属药用植物在我国自古供药用,药理研究发现它们的粗提物具有保肝作用,在治疗急、慢性病毒性肝炎,降低由四氯化碳引起的降谷丙转氨酶(SGPT)升高等方面皆具有明显的活性,并有降血脂、解痉挛、抑菌等作用.因其显著的生理活性,近年来倍受国内外关注.黄皮属植物的化学成分研究,已报道约150多个化合物,主要为四降三萜类,香豆素及其甙类,苯丙素及其甙类,咔吧唑生物碱类等.     

高速逆流色谱分离与鉴定鹿药中黄酮类化合物

采用高速逆流色谱(HSCCC)与其它色谱联用的方法分离纯化鹿药中的化学成分,得到5个黄酮类化合物: 5,7,3′,4′-四羟基-3-甲氧基-8-甲基黄酮(1)、 8-甲基木犀草素(2)、 3′-甲氧基木犀草素(3)、 木犀草素(4)和槲皮素(5),它们均为首次自该种及该属植物中分离得到.HSCCC以V(氯仿)∶ V(甲醇)∶ V(水)=4∶ 3∶ 2混合液为溶剂,上相为固定相,下相为流动相, 分离纯化得到3个分别含化合物1, 4和5的主要部分,经HPLC检验纯度分别为98.3%, 96.7%和95.3%;还有1个含有化合物2和3的较纯部分,通过Sephadex LH-20柱色谱,以V(甲醇)∶ V(水)=1∶ 1混合液洗脱将二者分离.通过理化性质及紫外、红外、质谱、核磁等波谱分析确定化合物结构.     

具有二维超分子结构的{[Ni(oxbe)]2Mg(H2O)2}·2DMF·DMA的合成及晶体结构

合成了一种中心对称的草酰胺桥联异三核配合物{[Ni(oxbe)]2Mg(H2O)2}·2DMF·DMA[oxbe为N-(2-羧基苯)-N'-(2-氨乙基)不对称草酰胺(H3oxbe)的脱氢阴离子;DMF为N,N-二甲基甲酰胺;DMA为二甲胺].用单晶X射线衍射法测定了它的晶体结构,该晶体属单斜晶系,空间群C2/e,晶胞参数a=22.617(5)A,b=17.173(4)A,c=10.881(4)A,β=115.40(2)°,V=3818(2)A3,Ni2MgC30H44N8O13,Mr=866.46,Z=4,Dc=1.508g/cm3,μ(MoKα)=1.075mm-1,F(000)=1808,R=0.0660,wR=0.1772(I＞2б(I)),3755个可观察衍射点.该三核分子为中心对称结构,镁离子位于6个氧原子所构成的变形八面体的中心,两个镍离子则分别位于两端由N3O构成的近似平面四方场中,中心Mg2+与两端的Ni2+通过草酰胺阴离子桥联在一起.     

丝裂霉素C的酸解动力学研究

我们用高效液相色谱(HPLC)研究了抗生素类抗癌药物丝裂霉素C(MMC)的酸解反应动力学.MMC在酸性介质中水解,生成三种产物.该酸解反应属一级平行反应.本文给出了介质pH值、浓度和温度对酸解速率常数的影响规律.对高效液相色谱分离出来的酸解产物作了红外光谱和吸收光谱研究.还讨论了MMC酸解反应的机理.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.