毛细管电泳-柱端安培检测测定莲子心中荷叶碱、芦丁和金丝桃甙的含量

采用毛细管电泳-柱端安培检测测定莲子心中荷叶碱、芦丁和金丝桃甙的含量．研究了检测电位、运行缓冲液浓度和pH值,分离电压和进样时间对分离和检测的影响．以微碳圆盘电极（Ф=0.5ram）为工作电极,检测电位为＋0．95V（vs．Ag／AgCl）,pH为7．25的50mmol／L Na2B4O7和100mmol／L NaH2PO4缓冲液为运行液,当分离电压为15kV时,3种分析物在15min内完全分离．荷叶碱、芦丁和金丝桃甙的检出限（S／N=3）分别为0．02μg／mL、0．05μg／mL和0．04μg／mL．该方法已成功地应用于莲子心中上述3种活性成分的测定．     

毛细管电泳法测定复方鱼腥草片中的绿原酸和槲皮素

建立了毛细管电泳法分析复方鱼腥草片中绿原酸和槲皮素的方法,通过研究缓冲溶液酸度和浓度、工作电压和进样时间的影响优化了分析条件。在优化的条件下,15min内实现了两种分析物质的良好分离。绿原酸和槲皮素峰高和质量浓度分别在0．05～0．80g／L和0．05～1．00g／L范围内成良好线性。基于迁移时间和峰高的重复性(RSD)分别为：绿原酸,1．91％和4．32％;槲皮素,2．30％和3．18％。绿原酸和槲皮素的检出限(S／N=3)分别为0．014g／L和0．015g／L。通过分析实际样品并做加样回收实验进一步验证了该方法的可行性。     

杜仲及其保健品中生物活性成分的毛细管电泳/电化学检测

采用毛细管电泳/电化学检测法(CE/ED)同时分离测定了杜仲叶、杜仲皮及市售杜仲保健品中芦丁、抗坏血酸、金丝桃甙、绿原酸、槲皮素等多种生物活性成分的含量,考察了运行缓冲液酸度和浓度、分离电压、氧化电位和进样时间等实验参数对分离、检测的影响。在最优化条件下,以300μm碳圆盘电极为检测电极,检测电位为 950 mV(vs.SCE),50 mmol/L硼砂的运行缓冲液(pH9.0)中,上述各组分在20 min内可基本实现基线分离。各组分浓度与峰电流在3个数量级范围内呈良好线性,检出限(S/N=3)在3.3×10-5~9.6×10-5g/L范围。该方法已成功地应用于杜仲及其保健品中生物活性成分的测定,结果令人满意。     

毛细管电泳电化学检测法测定烟草中的多元酚

采用毛细管电泳电化学检测法同时测定了烟草中的多元酚,即芦丁、绿原酸,槲皮素和咖啡酸。考察了工作电极的氧化电位、运行缓冲溶液浓度和pH值,分离电压和进样时间对分离和检测的影响。在优化条件下,以300μm直径的碳圆盘电极为工作电极,检测电位为+0.9 V(vs.SCE),在50 mmol/L硼酸盐(pH 8.4)的运行缓冲液中,被测物浓度与峰电流在三个数量级范围内呈良好线性,检出限为2×10-7或5×10-7g/mL。方法有着良好的重现性,被测组分的迁移时间和峰高的相对标准偏差(RSDs)小于4%(n=7)。单次测定可在16 min内完成,已用于实际样品多元酚的测定,样品处理简单,无须预富集。     

毛细管电泳法测定单胺氧化酶活性

应用毛细管电泳技术,建立了快速测定单胺氧化酶（MAO）活性的方法。研究对分离缓冲液pH值、浓度、毛细管表面改性剂十四烷基三甲基溴化铵（TTAB）浓度等影响因素进行优化,探讨了方法的可行性,确立了最佳分离条件。以70cm×50μm（i．d．）未涂敷熔融石英毛细管为色谱分离柱,运行电压15kv,运行缓冲液：0．5mmol／LTTAB,磷酸盐缓冲液（50mmol／L,pH 10．5）;紫外检测波长：214nm。MAO催化犬尿胺（Kyn）反应的产物4-羟基喹啉（4-HQ）的浓度和峰面积的线性范围为5～1000μmol／L,相关系数为0．9997,相对标准偏差（RSD）小于5．6％（n=5）,检出限为2μmol／L（S／N=3）。实验证明,此方法可以用于生物样品中MAO催化活性的检测。     

地骨皮中生物活性成分的毛细管区带电泳-安培检测方法研究

采用毛细管区带电泳-安培检测法(CZE-AD)同时分离测定了中药地骨皮中刺槐素、莨菪亭、山奈酚、对香豆酸、香草酸、木犀草素和槲皮素等多种生物活性成分,考察了运行液酸度和浓度、分离电压、氧化电位和进样时间等实验参数对分离、检测体系的影响。在最佳实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为950 mV(vs.SCE),在80 mmol/L的硼砂缓冲溶液(pH 9.0)中,7组分在24 m in可实现基线分离。7组分峰电流与其浓度在1.0×10-3~1.0×10-1范围内呈良好线性,检出限(S/N=3)达3.5×10-5~6.0×10-5g/L。该方法成功地应用于中药地骨皮中生物活性成分的含量检测。     

牡丹皮中有效成分丹皮酚的毛细管电泳快速检测新方法

采用毛细管电泳高频电导法对丹皮酚进行了快速分离检测。对电泳介质的种类及浓度、操作电压和进样时间等影响因素进行了优化。最佳条件为：分离介质1．0mmol／LH3BO3-3．0mmol／L三乙胺-10％CH，OH（pH=8．0），分离电压20．0kV，25．0cm位差虹吸进样8．0s。在该条件下。可在4min内实现对丹皮酚的分离检测。线性范围为2．0～105μg／mL，检出限为0．3μg／mL。成功测定了中药牡丹皮中的丹皮酚，回收率达94％～99％。方法简便、快速、灵敏，可用于药物分析。     

毛细管电泳安培法测定田基黄中的芦丁与槲皮素

建立了毛细管电泳电化学分离检测田基黄中生物活性成分芦丁和槲皮素的方法。考察了检测电极电位、缓冲液浓度、pH、运行电压和进样时间对分离的影响。以40 cm长,50μm内径的石英毛细管作为分离通道,运行缓冲液为25 mmol/L硼砂(pH 9.2)溶液,分离电压12 kV,0.3 mm直径的铂圆盘电极为检测电极,检测电位1.00 V(vs.Ag/AgCl),芦丁和槲皮素在10 min内得到良好分离。在上述实验条件下,芦丁和槲皮素分别在8.2×10-6~5.2×10-4mol/L与6.8×10-6~7.2×10-4mol/L范围内与峰面积呈良好线性关系,检出限分别为9.0×10-7mol/L(S/N=3)和4.7×10-7mol/L(S/N=3)。方法已应用于田基黄药材提取物成分分析。     

尼索朗对映体的高效毛细管电泳电导拆分

使用自行设计的毛细管电泳柱端电导检测系统,以未涂层融硅石英毛细管(75μm×45 cm)为分离柱,用非水介质对尼索朗对映体进行了拆分。研究了缓冲溶液浓度和酸碱度、非水介质、手性拆分剂(β-CD)等因素对分离的影响。以V(甲醇):V(甲酰胺)=8:2溶液为非水介质,5 mmol/L NaAc 2 mmol/L HAc为缓冲溶液,分离电压为15 kV,在8．0～160 mg/L范围内,峰高与浓度呈良好的线性关系,线性同归方程:y= 9．4 36．8x,线性相关系数R=0．996 3,检出限为1．6 mg/L。     

吲哚美辛的毛细管电泳测定法研究

建立了制剂和体液中吲哚美辛的毛细管电泳高频电导分析法,并用于吲哚美辛肠溶片、复方吲哚美辛酊及血清、尿液中吲哚美辛含量的测定。对电泳介质的种类、浓度以及操作电压和进样量等影响因素进行了优化。实验采用3.0mmol／L乳酸＋0．68mol／L乙醇为电泳介质,分离电压为20.0kV,可在10min内实现对吲哚美辛的分离检测。在最佳实验条件下,吲哚美辛的线性范围为0.05μg／mL—100μg／mL,检出限为0．01μg／mL,回收率92.0％-105．1％。     

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.