高效液相色谱法测定朝鲜淫羊藿中淫羊藿甙的含量

采用高效液相色谱法测定朝鲜建羊藿中淫羊藿成的含量,色谱柱为Shim-PackCLC-ODS柱,流动相为乙睛-水（30:70）,检测波长270um。在此条件下,淫羊藿式与其它黄酮醇咸的色谱峰分离完全。方法回收率为976％,RSD为1.2％,操作简便,结果可靠,为淫羊藿药材的质量控制提供了新的方法。     

朝藿甙－C的分离和结构

从朝鲜淫羊蕾的地上部分分离得到４个化合物。经化学和光谱方法鉴定它们为：５，７，３＇－三羟基－４＇－甲氧基－８－异戊烯基黄酮醇－３－Ｏ－α－Ｌ－鼠李吡喃糖甙（Ⅰ）、ＩｃａｒｉｓｉｄｅＣ１（Ⅱ）、Ｅｐｉｍｅｄｏｋｏｒｅａｎｏｓｉｄｅ－Ⅰ（Ⅲ）和Ｄｅｓｍｅｔｈｙｌｉｃａｒｉｔｉｎ（Ⅳ）。其中Ⅰ是未见报道的新化合物，命名为朝藿甙－Ｃ；Ⅱ、Ⅲ和Ⅳ首次从该植物中获得。     

朝藿甙E的分离和结构

从朝鲜淫羊藿的地上部分分离到２个化合物，经化学和光谱方法鉴定它们为５，７－二羟基－４＇－甲氧基－８－异戊烯基黄酮－３－Ｏ－β－Ｄ－（２－Ｏ－乙酰基）－葡萄吡喃糖基－（１－３）－α－Ｌ－（４－Ｏ－乙酰基）－鼠李吡喃糖基－７－Ｏ－β－Ｄ－葡萄吡喃糖甙（Ｉ）和β－乐淫羊藿素（Ⅱ），其中Ｉ是未见报道的化合物命名为朝藿甙－Ｅ，Ⅱ为首次从该植物中获得。     

固体表面室温燐光法测定淫羊藿甙

１引言 淫羊蕾甙（ｉｃａｒｉｉｎ）为中草药淫羊蕾的主要有效成分,有增加冠脉血流量的作用。淫羊蕾甙的测定方法有薄层扫描法,高效液相色谱法等。固体表面室温光法是一种微量技术与痕量分析相结合的分析方法,而建羊蕾甙的室温光法的研究未见文献报道。本文以Ｄｄ（Ａｃ）２为重原子微扰剂,以聚酰胺膜作基质时,能诱导出淫羊藿甙的ＲＴＰ发射。其激发波长为３００ｎｍ（弱峰）和４００ｎｍ（强峰）,发射波长为５００ｎｍ。淫羊藿甙含量在１．３５～６７５ ｎｇ／斑范围内与ＲＴＰ强度呈良好的线性关系,检出限达０,０６ ｎｇ／斑。该…     

高效液相色谱法测定箭叶淫羊藿中淫羊藿苷的含量

箭叶淫羊藿用70%乙醇回流提取,取部分提取液直接干燥得淫羊藿提取物,以高效液相色谱法测定箭叶淫羊藿中淫羊藿苷的含量,色谱柱为InertsilODS-3柱,流动相为乙腈-水(27∶73),检测波长为270nm。在此条件下,淫羊藿苷与其它黄酮醇苷的色谱峰分离完全,平均回收率为99.46%。该法可用于淫羊藿药材的质量控制。     

应用色质联机对淫羊藿多糖结构的研究

淫羊藿多糖(Epimedium polysaccharide,EPS)能够刺激机体免疫系统,增强免疫应答功能,同时,淫羊霍多糖还有刺激骨髓DNA合成的作用.近年来对淫羊藿甙及淫羊藿总黄酮的研究较多,而对淫羊藿多糖的研究较少.用化学实验方法研究淫羊藿多糖的结构,存在时间长、实验步骤多等问题.寻找快速、准确的测试手段,对研究淫羊藿多糖的结构有着重要的意义.本文从淫羊藿茎叶中提取水溶性多糖,经甲基化后,再经色质联机(GC-MS)分析,初步确定了糖苷的键型,并用化学实验方法进行了验证.     

淫羊藿炮制前后UPLC-PDA-MS 的指纹图谱研究

建立了朝鲜淫羊藿和柔毛淫羊藿药材的超高效液相色谱(UPLC)指纹图谱分析方法, 实验结果表明, 两个品种的指纹图谱差别较大, 朝鲜淫羊藿标出35 个共有峰, 质谱鉴定了26 个峰, 柔毛淫羊藿标出13 个共有峰, 质谱鉴定了9个峰; 研究了朝鲜淫羊藿和柔毛淫羊藿炮制前后UPLC 指纹图谱的变化规律, 指纹图谱发生了五处变化. 该法快速、简便, 重现性好, 从整体上显示淫羊藿药材和炮制品的特征, 为淫羊藿的生品和炮制品的质量控制提供了有效手段.     

工业制备高效液相色谱法制备淫羊藿中的黄酮系列对照品

淫羊藿甙和朝藿定A、B、C是淫羊藿中重要的活性成分,本研究应用工业制备高效液相色谱从淫羊藿粗提物中分离制备了这4个成分。淫羊藿粗提物经大孔吸附树脂粗分离获得相应的组分后,利用工业制备高效液相色谱完成精制纯化。采用自装填Chromatorex C18制备柱(220 mm×77 mm, 10 μm),乙腈-水(26:74或30:70, v/v)为流动相进行洗脱,在35 min内,实现了这4种成分的基线分离及规模制备。从300 g粗提物(总黄酮含量约20%)中获得淫羊藿甙33 g、朝藿定C 4.6 g、朝藿定B 3.7 g和朝藿定A 0.6 g,产品纯度均达到98%以上。此方法通过两步分离即可实现这4种成分的完全分离,具有快速高效、产品纯度高的特点,适于淫羊藿中淫羊藿甙、朝藿定A、B、C系列对照品的规模制备。     

固体表面室温烯光法测定淫羊藿甙

1引言 淫羊藿甙(cariin)为中草药淫羊藿的主要有效成分,有增加冠脉血流量的作用.淫羊甙的测定方法有薄层扫描法,高效液相色谱法等.固体表面室温燐光法是一种微量技术与痕量分析相结合的分析方法,而淫羊藿甙的室温燐光法的研究未见文献报道.本文以cd(c)2为重原子微扰剂,以聚酰胺膜作基质时,能诱导出淫羊藿甙的RTP发射.其激发波长为300nm(弱峰)和400nm(强峰),发射波长为500nm.淫羊藿甙含量在1.35～675ng/斑范围内与RTP强度呈良好的线性关系,检出限达0.06ng/斑.该法具有操作简便,灵敏度高,线性范围宽,取样量少的特点.     

毛细管电泳法测定淫羊藿甙的pK_a值及其在中药淫羊藿中的含量

 利用毛细管电泳中不同 pH条件下有效淌度 (μeff)与缓冲溶液中氢离子的浓度 ([H+])的非线性关系以及1/ μeff与缓冲溶液中 [H+]的线性关系 ,测定了淫羊藿甙的离子淌度 (μA- )和pKa 值 ;考察了在有机改性剂存在的情况下 ,随缓冲溶液中有机改性剂浓度的增加 ,淫羊藿甙的 pKa 值的变化情况。在缓冲溶液为V(2 4mmol/L磷酸盐 )∶V(乙醇 ) =70∶30时 ,对中药淫羊藿中淫羊藿甙的含量进行了定量测定 ,结果发现校正峰面积 (Y)与淫羊藿甙的质量浓度 (X ,g/L)的线性相关方程为Y =6 96× 10 -3 + 17 0X ,线性范围为 0 0 32g/L～ 0 35 4g/L。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.