α-酸糖蛋白手性柱对56种手性化合物的拆分

采用α-酸糖蛋白手性固定相(Chiral-AGP),固定流动相pH、流速,化合物样品浓度,考察酸性、碱性、中性手性化合物和21个氨基酸在α-酸糖蛋白手性柱上的拆分情况.应用高效液相色谱法,α-酸糖蛋白手性柱对上述手性样品拆分,一共有8个中性化合物、3个碱性化合物、6个酸性化合物和5个氨基酸得到手性对映分离.探讨了α-酸糖蛋白手性柱对酸性、中性、碱性样品的拆分能力并进行对比,结果证明α-酸糖蛋白手性柱拆分中性化合物和酸性化合物效果最好,拆分碱性化合物和氨基酸效果不好,为α-酸糖蛋白手性柱适合于拆分哪一类型的手性化合物提供参考.     

Δ5-3β-取代-5-甾烯并取代[17,16-c]吡唑(异噁唑)啉-5''''-酮类化合物的合成

3β-取代-5-甾烯-17-酮与碳酸二甲酯经克莱森缩合所得产物再分别与肼或羟胺反应,合成了几种新的△5-3β-取代-5-甾烯并-1'-取代[17,16-c]吡唑啉-5'-酮和△5-3β-取代-5-甾烯并[17,16-c]异噁唑啉-5'-酮化合物,其结构均经元素分析,IR和1H NMR确证.     

枸杞叶的黄酮类化学成分

枸杞叶是中国传统使用的滋养药物，应用高效液相色谱从枸札叶中分离和制备了5个黄酮类化合物，经光谱分析分别是5，7，3′－三羟基－6，4′，5′－三甲氧基黄酮（1），金合欢素（2），金合欢素－7－O－α－L－鼠李糖基（1→6）－β－D－葡萄糖苷（3），木犀草素（4），槲皮素－3－O－α－L－鼠李糖基（1→6)-β-D-葡萄糖苷（芦丁）（5）；并以槲皮素为内标测定了它们在枸杞中的含量，用油脂氧化向往 测定仪测定了它们的抗氧化活性，其中木犀草素是优良的天然抗氧化剂。     

Δ^5-3β-取代-5-甾烯并取代[17，16-c]吡唑（异嗯唑）啉-5′-酮类化合物的合成

3β-取代-5-甾烯-17-酮与碳酸二甲酯经克莱森缩合所得产物再分别与肼或羟胺反应，合成了几种新的Δ^5-3β-取代-5-甾烯并-1′-取代[17，16-c]吡唑啉-5′-酮和Δ^5-3β-取代-5-甾烯并[17，16-c]异噁唑啉-5′-酮化合物，其结构均经元素分析，IR和^1H NMR确证。     

6β-卤代-19-羟基-4-雄甾烯-3,17-双酮的分子内亲核取代反应

具有4-烯-3-酮结构的6β-卤代甾体化合物经强酸处理可以转变为大约1∶1的6β与6α卤代甾体化合物的混合物,混合物经分步结晶、柱层或薄层分离可以得到一定量的6α-卤代化合物。例如,6β-溴-4-雄甾烯-3,17-双酮在含有盐酸的甲醇中,45℃反应1小时,约50%的化合物转化为6α-溴代化合物。在寻     

红树尖瓣海莲内生真菌Penicillium sp.J41221的代谢产物及其抗菌活性研究

在生物活性指导下,从一株来源于药用红树尖瓣海莲的内生真菌Penicillium sp.(J41221)中分离鉴定了6个化合物,包括4个四环三萜类化合物和2个甾醇类化合物,结构分别为:11-羰基-12α-乙酰氧基-4,4-二甲基-24-甲烯基-5α-胆甾-8,14-二烯-2α,3β-二醇(1),12α-乙酰氧基-4,4-二甲基-24-甲烯基-5α-胆甾-8-单烯-3β,11β-二醇(2),12α-乙酰氧基-4,4-二甲基-24-甲烯基-5α-胆甾-8,14-二烯-3β,11β-二醇(3),12α-乙酰氧基-4,4-二甲基-24-甲烯基-5α-胆甾-8,14-二烯-2α,3β,11β-三醇(4),啤酒甾醇(5)和(3β,5α,6β,22E)-6-甲氧基麦角甾-7,22-二烯-3,5-二醇(6).其中化合物1为首次从生物中获得,且1和2的波谱数据迄今未见任何报道.抗菌活性结果表明,化合物2和4对金黄色葡萄球菌、大肠杆菌和四联球菌均显示一定的抑制活性,最小抑菌浓度(MIC)分别为5和4.86μmol/L.     

3个新呋喃黄酮的NMR研究

从厚果难血藤（Millettia pachycarpa Benth)根中分离得到3个呋喃黄酮类化合物,经NMR谱等分析研究,确定了它们的结构为：4H－呋喃并[2,3-h][1]苯并吡喃－4－酮,3－甲氧基－2－（3,4,5－三甲氧基苯基）（I）、4H－呋喃并[2,3-h][1]苯并吡喃－4－酮,3－甲氧基－2（3－甲氧苯基）（Ⅱ）、10,11二甲氧基－[2]苯并吡喃[4,3-b]-呋喃并[2,3-h][1]苯并吡喃－6（8H）－酮（Ⅲ）,皆未见文献报道,分别命名为厚果鸡血藤丙素（pachycarin C)、厚果难血藤丁素（pachycarin D)和厚果鸡血藤戊素（pachycarin E)。     

园果雪胆中雪胆甲素和雪胆乙素的结构

从葫芦科雪胆属园果雪胆的块根中分离到两种具有抗菌作用的苦味质,雪胆甲素和雪胆乙素,经质谱、紫外和红外吸收光谱、核磁共振谱分析以及化学降解反应证实甲素为19-失碳-9β-甲基-10α-2β,3α,16α,20,25-五羟基-Δ~5-羊毛甾烯-11,20-双酮-25-乙酸酯(Ⅱ_a)即葫芦素F(Ⅰ_c)的23,24-双氢-25-乙酸酯,乙素(Ⅱ_b)为葫芦素F(Ⅰ_c)的23,24-双氢化合物。     

活性白土催化松香反应产物的GC-MS分析

把活性白土上松香催化反应产物分离为酸性物和中性物,采用气相色谱-质谱联用技术(GC-MS)分别对各部分化学组成进行定性定量分析.结果表明,活性白土上松香主要进行脱氢、脱羧及裂解反应,其产物中的酸性物共分离出2个峰,主要成分是脱氢枞酸,含量为99.61%;中性物共分离出35个峰,初步鉴定出其中33个组分,大部分为甾族类化合物和环烯烃类化合物,主要成分是5α-雄甾烷、1,4-二甲基-7-(1-甲基乙烯基)-1,2,3,5,6,7,8,8a-八氢化-1S-(1α)-蓝烃、松香酸甲酯和(-)-石竹烯,含量分别为18.75%、13.00%、12.53%和11.74%.     

播娘蒿籽可溶有机质的分布特征及生物化学意义

播娘蒿籽经溶剂抽提得脂溶性物质,再经正己烷沉淀沥青质,得到可溶有机质.然后采用柱色谱分离方法,将可溶有机质分离为非极性馏分(2.5%)、弱极性馏分(37.3%)和极性馏分(60.2%).这3个馏分经气相色谱-质谱联用仪(GC-MS)分析,检测出7个系列、124种生物标志化合物,且以直链脂肪酸系列生物标志化合物相对丰度最高为特征.研究表明室温保存的播娘蒿籽易受到细菌-酶的降解作用,其各系列生物标志化合物的降解顺序为:正烷烃>五环三萜烷>甾烷>脂肪酸.     

Sterol sulfates from the Far Eastern holothurianCucumaria japonica

A chloroform-methanol extract of the musculocutaneous sac of the Far-Eastern holothurianC. japonica has yielded a fraction of sterol sulfates (13% of the weight of the extract, 0.8% of the weight of the dry biomass), the main components of which were derivatives of cholest-5-en-3β-ol, 24-methylene-, 24-ethyl-, and 24-ethylidenecholest-5-en-3β-ols, 5α-cholestan-3β-ol, and 24-methyl- and 24-methylene-5α-cholesten-3β-ol; among the minor components were found the sulfates of 24-ethyl-5α-cholestan-3β-ol of cholesta-5,22-dien-3β-ol, of a Δ⁵-C₃₀ sterol, and also of dienic and trienic C₂₆ sterols.     

5α-androstano [3,2-b]pyridines, 5α-androstano[17,16-b]pyridines and androst-4 and 5-eno[17,16-b]pyridines

A new synthesis of 5α-androstano[3,2-b]pyridin-17β-ol acetate (VIa) and 17-methyl-5α-androstano[3,2-b]pyridin-17β-ol (VIb), first reported by Shimizu, Ohta, Ueno, and Takegoshi, was achieved. The analogous 5α - androstano[17,16-b]pyridin-3β-ol (XII), 5α-androstano[17,16-b]pyridin-3-one (XIVa), and androst-4-eno[17,16-b]pyridin-3-one (XIVb) were also prepared. An illustration of the method follows. Condensation of 3β-hydroxy-5α-androstan-17-one (VIIa) with 3-(2-furyl)acrolein afforded 16-[3-(2-furyl)-2-propenylidene]-3β-hydroxy-5α-androstan-17-one (VIIIa), the oxime (IXa) of which was thermally cyclized to 5α-androstano[17,16-b]-6′-(2-furyl)pyridin-3β-ol (Xa). 3β-Hydroxy-5α-androstano[17,16-b]pyridine-6′-carboxylic acid (XI) was obtained by ozonolysis of Xa. Thermal decarboxylation of XI gave XII. Cinnamaldehyde was used in place of 3-(2-furyl)acrolein to give the corresponding phenylpyridines.     

Steroid alcohols from the ascidianHalocynthia aurantium

The total sterols have been isolated fromHalocynthia aurantium by column chromatography on silica gel. The following steroid alcohols have been identified in it with the aid of GLC, GLC-MS, and¹H NMR: 5α-cholestan-3β-ol, 24ξ-methylcholestan-3β-ol, 24ξ-ethylcholestan-3β-ol, 4ξ-methyl-24ξ-ethyl-5α-cholestan-3β-ol, cholest-5-en-3β-ol, 24ξ-methylcholest-5-en-3β-ol, 24ξ-ethylcholes-5-en-3β-ol, 5α-cholest-22-en-3β-ol, 24-nor-5α-cholest-22-en-3β-ol, cholesta-5,22-dien-3β-ol, 24ξ-methylcholesta-5,22-dien-3β-ol, 24-norcholesta-5,22-dien-3β-ol, 24-ethylcholesta-5,24(28)-dien-3β-ol, and 24-methylcholesta-5,24(28)-dien-3β-ol.     

Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing

Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n?=?67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical power and certainty to distinguish between the endo- or exogenous origin of a urinary steroid.     

Identification de stérols à chaînes latérales courtes dans l′éponge Damiriana hawaiiana

Identification of short side chain sterols in the sponge Damiriana hawaiiana The steroidal composition of the sponge Damiriana hawaiiana is examined. Twenty-seven components are identified. In addition to the C₂₆-C₂₉, Δ⁵-mono and diunsaturated sterols, the sponge contains sterols without side-chain: androsta-5, 16-dien-3β-ol( 1 ), androst-5-en-3β-ol( 2 ); sterols with a non-functionalized side-chain consisting of two, three, four, five and six carbon atoms: pregna-5, 20-dien-3β-ol( 5 ), pregn-5-en-3β-ol( 6 ), 23, 24-bisnor-chola-5, 20-dien-3β-ol( 7 ), 23, 24-bisnor-chol-5-en-3β-ol( 8 ), 24-nor-chol-5-en-3β-ol( 10 ), chol-5-en-3β-ol( 11 ), 26, 27-bisnor-cholest-5-en-3β-ol( 12 ), and sterols possessing a short oxygenated side-chain such as 3β-hydroxy-androst-5-en-17-one( 3 ), androst-5-en-3β, 17β-diol( 4 ) and 3β-hydroxy-26, 27-bisnor-22-trans-cholesta-5, 22-dien-24-one( 14 ). The probable biological or dietary origin rather than artifact production of these hitherto undescribed components from marine sources is supported by their relatively high concentration and their relative proportions, both very different from those expected for autoxidation.     

C-3 to C-2 Carbonyl Transposition via a Vinyl Chloride in Ring-A of Steroids

Transposition of a steroid C-3 ketone to the C-2 position was carried out through the 2-chloro-2-olefin. A convenient synthesis of 5α-androstan-2-on-17β-ol acetate is described.     

微波辅助合成罗库溴铵重要中间体

罗库溴铵(Rocuronium bromide,Org-9426,Esmeron,Zemuron)为非去极化型雄箔类肌肉松弛药,由荷兰欧加农公司研究开发,1994年批准上市.罗库溴铵因具有起效快、体内无蓄积、不良反应小等特点而被广泛用于临床外科手术中~([1-2]).     

Thiosteroids—XXXV : Diastereomers of steroidal thiolsulfinates

17β-Hydroxy-5α-androstan-2α,3α-anti(R)-episulfoxide on treatment with methanol and ethanol in the presence of a trace amount of sulfuric acid gave diastereomers of bis((2β-methoxy- and 2β-ethoxy-17β-hydroxy-5α-androstan-3α-yl) disulfide S-monoxides respectively. The absolute configuration of the compounds was established by their Grignard reactions leading to diastereomeric phenyl sulfoxides stereoaspecifically.     

Dissimilar behaviour of 3β, 16α-dihydroxy-5α-androstan-17-one Diacetate under Basic and Acidic Conditions

The base-catalysed rearrangement of 3β, 16α-dihydroxy-5α-androstan-17-one diacetate ( 1 ) in (D₆)benzene/ CD₃OD to 3β, 17β-dihydroxy-5α-androstan-16-one ( 3 ) is followed by ¹³C-NMR spectroscopy. By the same procedure, it is determined that in (D₆)benzene/CD₃OD, but under acid catalysis, 1 does not rearrange to 3 but yields the intermediate product 3β, 16α-dihydroxy-5α -androstan-17-one 17α -methyl hemiacetal ( 5 ).     

Ergosta-5,7,9(11), 22-tetraen-3β-ol and its 24ξ-Ethyl Homolog,Two New Marine Sterols from the Red Sea Sponge Biemna fortis

The steroidal components of a Red Sea sponge, Biemna fortis, were fractionated through reversed phase HPLC. and analyzed by a combination of physical methods, including high resolution GC./MS. and 360 MHz ¹H-NMR. The sponge contains five conventional Δ⁵-sterols, 1a – c , 1e , 1g , which comprise about 25% of the mixture and 2,5% of gorgosterol (1h) , a sterol never found before in Porifera. Three Δ^5,7,22-sterols were also present as major components in the mixture (～70%): cholesta-5,7,22-trien-3β-ol (2a) , ergosta-5,7,22-trien-3β-ol (2c) and (24R)-ethylcholesta-5,7,22-trien-3β-ol (2e) whereas two new tetra-unsaturated sterols were identified in minor amounts (2%): ergosta-5,7,9(11),22-tetraen-3β-ol (3c) and 24ξ-ethylcholesta-5,7,9 (11), 22-tetraen-3β-ol ( 3e or 3f ). NMR. spectroscopy made possible the assignment of a 24R configuration for all the C(24) substituted sterols isolated in sufficient amount from the mixture. The possible symbiotic, dietary or biosynthetic origins of these sterols are discussed.