反相高效液相色谱柱前衍生荧光法测定肠粘膜中的谷氨酰胺

 以邻苯二甲醛及３－巯基丙酸为衍生试剂，５０ｍｍｏｌ／Ｌ磷酸缓冲液（ｐＨ７．０）－乙腈（９４∶６，Ｖ／Ｖ）为流动相，在ＬｉｃｈｒｏｓｏｒｂＲＰ１８（１５０ｍｍ×４．６ｍｍｉ．ｄ．，５μｍ）柱上，研究并建立了测定动物肠粘膜中谷氨酰胺（Ｇｌｎ）的柱前衍生荧光ＲＰ－ＨＰＬＣ法。样品与衍生剂按４∶１进行衍生反应，Ｅｘ＝２３０ｎｍ，Ｅｍ＝３８９ｎｍ；流速为２．０ｍＬ／ｍｉｎ。Ｇｌｎ的保留时间为３．１５８ｍｉｎ，检测限为２５μｍｏｌ／Ｌ（Ｓ／Ｎ＝３．５），线性范围为５０～３２００μｍｏｌ／Ｌ，ｒ＝０．９９９６。     

毛细管电泳在拮抗药物对氨基苯甲酸，对羟基苯甲酸和磺胺分析测…

本报道了一种用毛细管区带电泳法分离与测定对氨基苯甲酸、对羟基苯甲酸及磺胺类药物的新方法。电泳条件为：用２０ｍｍｏｌ／Ｌ硼砂－２０ｍｍｏｌ／ＬＨ３ＰＯ４－２０ｍｍｏｌ／Ｌβ－环糊精－４％乙醇作电泳液，Ｌ－抗坏血酸为内标，２８０ｎｍ为检测波长，样品由电进样方式１０ｋＶ／１０ｓ）引入毛细管（５１．２ｃｍ×５０μｍｉ．ｄ．，有效分离长度为３８．５ｃｍ）．在２４．５℃下，６ｍｉｎ内三可达基线分离（电泳电     

铂—钯共显色衍生络合物的高效液相色谱研究

研究了Ｐｄ（Ⅱ）和４，４＇－二（二乙氨基）苯硫酮（ＢＤＰＴＫ）共显色所生成的Ｐｔ（Ⅱ）络合物，于Ｎｕｃｌｅｏｓｉｌ Ｃ８柱上，用含３×１０＾－３ｍｏｌ／Ｌ ＣＳＡ和０．０２ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ３．５）的乙腈－丙酮－水（７２：５：２３，Ｖ／Ｖ）作流动相（１．０ｍｌ／ｍｉｎ）分离并检测。Ｐｔ的校正曲线的线性范围为０．２～３．０μｇ／ｍｌ，Ｐｔ检测限为０．７ｎｇ。此方法已应用于抗癌药物顺铂     

莨菪类生物碱毛细管电泳分析

采用毛细管区带电泳方法对阿托品（ＤＬ－莨菪碱）、东莨菪碱、山莨菪碱和樟柳碱进 行了系统分离，以 ５０ ｍｍｏｌ／Ｌ磷酸盐缓冲液（ｐＨ ８．０）－四氢呋喃（９：１，Ｖ／Ｖ）作背景电介质， 操作电压为１１ ｋＶ，柱温２４℃，电迁移进样５ ｋＶ×５ｓ，柱上２００ｎｍ检测，４种莨菪类生物碱 可在４０ ｃｍ×５０μｍ的石英毛细管柱上５．５ｍｉｎ之内实现基线分离。     

7—（对甲酰基苯偶氮）—8—羟基喹啉—5—磺酸的合成及其双波长分光光度…

７－（对甲酰基苯偶氮）－８－羟基喹啉－５－磺酸是一新显色剂，该试剂在微碱性介质中（ｐＨ＝７．５）与镓形成黄色络合物，络合物λｍａｘ＝３９２ｎｍ，摩尔吸光系数ε３９２＝２．２４×１０＾４Ｌ．ｍｃｌ＾－１．ｃｍ＾－１，同时在５００ｎｍ呈现负峰，用双峰双波长法测定镓ε３９２－５００＝６．８９×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，灵敏度是单波长法的三倍多，线性范围０～２．０×１０＾－６ｍｏｌ／Ｌ。用拟定     

反相HPLC测定钒,铌,钽的2—（2—吡啶偶氮）—5—二乙氨基苯酚配合物

以２－（２－吡啶偶氮０－５－二乙氨基苯酚（ＰＡＤＡＰ）为柱前衍生试剂，在含０．１％酒石酸的１０ｍｍｏｌ／Ｌ（ｐＨ３．５）ＨＡｃ－ＮａＡｃ缓冲溶液的甲醇／水（５０∶５０，Ｖ／Ｖ）中（５８０ｎｍ检测），在Ｃ１８柱上于１１ｍｉｎ内实现了Ｖ、Ｎｂ、Ｔａ的同时分离及测定，检出限（Ｓ／Ｎ＝３）杰０．３４、０．２９、７．３０ｎｇ／ｍＬ．该法灵敏度高，用于矿样分析所得民推荐值相行，标准加入回收率为９９．０％～１０     

铂－锇共显色衍生配合物的高效液相色谱研究

研究了Ｏｓ（Ⅱ）和４，４’二（二乙氨基）苯硫酮与Ｐｔ（Ⅱ）共显色所衍生的配合物，于ＮｕｃｌｅｏｓｉｌＣ＿８柱上，用含３×１０￣（－３）ｍｏｌ／ＬＤＬ－樟脑－１０－磺酸和０．０２ｍｏｌ／ＬＨＡｃ－ＮａＡｃ（ｐＨ３．５）的乙腈－丙酮－水（７２：５：２３，Ｖ／Ｖ）作流动相（１．０ｍＬ／ｍｉｎ）分离并检测。线性范围为０．２～４．０μｇ／ｍＬＰｔ；检测限为１．０ｎｇＰｔ。此方法已应用于抗癌药物顺铂和卡铂的分析。     

毛细管区带电泳法分离检测神经性毒剂降解产物

用毛细管区带电泳间接紫外检测法分离测定６种甲基膦酸单酯。以苯基膦酸为紫外添加剂 ,检测波长为２１０ｍｍ。优化后缓冲溶液组成为：２００ｍｍｏｌ／Ｌ硼酸－５ｍｍｏｌ／Ｌ苯基膦酸－０．１０ｍｍｏｌ／Ｌ ＤＤＡＢ－．２０％ＴｉｔｏｎＸ－１００（ｐＨ３．５５）。毛细管规格为７０ｃｍ＊７５μｍｉ．ｄ。以ＫＨ２ＰＯ４为内标定量,在１－３０ｍｇ／Ｌ浓度范围内６种甲基膦酸单脂标准回归曲线性关系良好,检测限为０．２５     

双臂套索冠醚双核铜（II）配合物的磁性质研究

测定了双臂套索冠醚双核铜（Ⅱ）配合物［Ｃｕ２Ｌ（ＯＨ）］（ＣｌＯ４）３Ｍｅ２ＣＯ（Ｌ－Ｎ，Ｎ＇－二（８－喹啉甲基）－１，４，１０，１３－四氧－７，１６－二氮环八环）的变温磁化率（４￣３００Ｋ），所加场强为５．０×１０＾５Ａ／ｍ，拟合了变温磁化率数据，得到Ｊ＝－２７９．４ｃｍ＾－２；加上分子场校正后，得Ｊ＝－２５７．７ｃｍ＾－１，Ｚｊ＇＝－３０．１ｃｍ＾－１。拟合结果表明，分子间存在反铁磁性交换作用     

单柱离子色谱法测定茶叶中草酸根和硫酸根的研究

本文研究单柱离子色谱分离测定茶叶中微量草酸根和硫酸根的方法。样品水浸泡，酸化液。上ＳｈｉｍＰａｒｓｋＩＣ－Ａ＿２柱分离，用２．０ｍｍｏｌ·Ｌ￣（－１）Ｈ－２Ｃ＿８Ｏ＿４／１．９ｍｍｏｌ·Ｌ￣（－１）Ｔｒｉ淋洗液洗脱，电导检测器检测，检测灵敏度为１．６Ｓ／ｃｍ，最低检出限０．０５μｇ／ｍＬ；线性范围Ｌ；相对标准偏差１．０６％；平均回收车９８．７２％９７．８８／。该法简便、快速、准确、灵敏、选择性好。     

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.     

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.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.