毛细管胶束电动色谱法分离测定胆红素亚组分

 用毛细管胶束电动色谱法成功地分离和定量测定了血清及胆汁中α，β，γ及δ等４种胆红素亚组分。二牛磺酸胆红素浓度在５１０μｍｏｌ／Ｌ以下时，峰面积与浓度呈良好的线性关系，二牛磺酸胆红素浓度即使为１．５μｍｏｌ／Ｌ时仍可检测出明显的定量峰。用一份２５５μｍｏｌ／Ｌ的二牛磺酸胆红素标准液进行重复性检测，第１次定量结果为２６０μｍｏｌ／Ｌ，出峰时间１６ｍｉｎ；第５０次电泳结果为２３８μｍｏｌ／Ｌ，出峰时间１６．７ｍｉｎ。     

碳纤维汞膜微电极1.5次微分伏安法测定米托蒽醌的研究

米托蒽醌（ＭＸＴ）能吸附在碳纤维汞膜微电极表面，阴极溶出时，产生一个灵敏的１．５次微分溶出峰，其峰电流和米托葱酿的浓度在１．０×１０－５ｍｏｌ／Ｌ～１．３×１０－９ｍｏｌ／Ｌ范围内具有良好的线性关系，经３ｍｉｎ的富集，检出限可达１．０×１０－１０ｍｏｌ／Ｌ，据此建立了测定ＭＸＴ的灵敏的新方法，本文讨论了实验条件，并对血样中的ＭＸＴ进行了测定。     

胆绿素的溶出伏安法研究及胆红素的间接测定

本对胆绿素的吸附溶出分析法进行了研究，发现胆绿素在Ｎａ２ＨＰＯ４－Ｎａ３ＰＯ４（０．１ｍｏｌ／Ｌ，ｐＨ１１．５）缓冲溶液中可在－０．８３Ｖ（ｖｓ，ＳＣＥ）左右产生灵敏的吸附溶出峰，该峰可检测出低至５×１０＾－９ｍｏｌ／Ｌ胆绿素。在通常条件下，通过０．５ｍｉｎ预富集后溶出，可使峰高提高约一个数量级。应用此法间接测定了小牛血清中的胆红素含量。     

金在脱乙酰壳多糖学修饰电极上的电化学行为及分析应用

用脱乙酰壳多糖化学修饰电极为工作电极，阳极溶出伏安法测定痕量金。在ｐＨ１￣２的ＫＣｌ－ＨＣｌ底液中，超始电位０．２０Ｖ，终止电位１．３０Ｖ，富集时间５ｍｉｎ，以－０．１／ｓ扫速阳极溶出，峰电位在１．００Ｖ（ｖｓ．ＳＣＥ），Ａｕ（Ⅲ）浓度在０．１０ｍｇ／Ｌ￣１０ｍｇ／Ｌ范围内与峰高呈线性关系。在富集１０ｍｉｎ时，可检测０．２５ｍｉｇ／ＬＡｕ，大大提高了测定灵敏度，用于矿样测定，无需分离，结果满意。用     

穿心莲内酯的电化学研究

用单扫描示波极谱法在０．０５ｍｏｌ／ＬＮＨ４ＣＬ＋０．２５ｍｏｌ／ＬＮＨ３．Ｈ２Ｏ中，穿心链内酯有一灵敏的还原峰，２５℃时，峰电位为－１．６０Ｖ（ｖｓ．ＳＣＥ），峰电流与浓度在０．０１～１．２ｍｇ／Ｌ和１．４～２６ｍｇ／Ｌ范围内有良好的线性关系，检测限为６ｎｇ／ｍＬ。用本法测定天然中药穿心链中总内酯的含量，其结果令人满意。实验证明穿心链内酯的电极过程为可逆的逐级电子过程，Ｈ２Ｏ２可催化该还原峰，另     

丙酸睾丸素的吸附阴极溶出伏安法研究

在ｐＨ为６．０的Ｂ－Ｒ缓冲溶液中，丙酸睾丸素于电位－１．４Ｖ（ｖｓ．ＳＣＥ）左右处出现一个灵敏的附阴溶出峰。经５ｍｉｎ富集后，阴极溶出峰电流与浓度在１．３８×１０＾－＾８－７．３×１０＾－＾８ｍｏｌ／Ｌ范围内成线笥关系，该方法用于注射液中丙酸睾丸素含量测定，回收率８０％－８６％。检测下限为４．１×１０＾－＾９ｍｏｌ／Ｌ。     

一阶导数差示脉冲极谱法用于甲硝唑的定量研究

本实验运用一阶导数差示脉冲极谱法对甲硝唑及其制剂进行了定量研究。在０．００１ｍｏｌ／Ｌ氯化钾－０．００１ｍｏｌ／Ｌ盐酸－水（１＋０．２＋４８）的底液中，甲硝唑于－０．８００Ｖ（ｖｓ Ａｇ／ＡｇＣｌ）处出现一良好的一阶导数差示脉冲极谱峰，在５０～３００μｇ／ｍＬ范围内，药物浓度与其导数峰幅值呈线关系，检测限为８．０×１０＾－８ｍｏｌ／Ｌ。本法操作简便，快速，灵敏，结果准确。     

金在脱乙酰壳多糖化学修饰电极上的电化学行为及分析应用

用脱乙酰壳多糖化学修饰电极为工作电极，阳极溶出伏安法测定痕量金。在ｐＨ１～２的ＫＣｌ－ＨＣｌ底液中，起始电位０．２０Ｖ，终止电位１．３０Ｖ，富集时间５ｍｉｎ，以０．１Ｖ／ｓ扫速阳极溶出，峰电位在１．００Ｖ（ｖｓ．ＳＣＥ），Ａｕ（Ⅲ）浓度在０．１０ｍｇ／Ｌ～１０ｍｇ／Ｌ范围内与峰高呈线性关系。在富集１０ｍｉｎ时，可检测０．０２５ｍｇ／ＬＡｕ，大大提高了测定灵敏度，用于矿样测定，无需分离，结果满意。用紫外光谱和拉曼光谱研究了该法的电极过程机理。     

铁的单点络合滴定法研究

本研究了Ｆｅ＾３＋的单点络合滴定法，导出了定量关系式，比较了以铂电极为指示电极和以ＰＶＣ膜四氯络铁（Ⅲ）阴离子电极为指示电极时电位测量的稳定性及所得的分析结果。在Ｆｅ＾３＋浓度为１．０００×１０＾－３ｍｏｌ／Ｌ时，１８次实验的平均值为１．０２×１０＾－４ｍｏｌ／Ｌ，相对偏差小于１．７％；Ｆｅ＾３＋在５．０×１０＾３ｍｏｌ／Ｌ以上时，相对偏差小于０．１％；其浓度小于１０＾－３ｍｏｌ／Ｌ而大于５×１     

金橙G螯合形成树脂分离富集地质样品中的微量贵金属

主要研究了金橙Ｇ螯合形成树脂分离富集地质样品中金、铂、钯的最佳实验条件。在柱高大于１６ｃｍ，０．１ｍｏｌ／Ｌ ＨＣｌ介质的样品溶液以小于或等于０．５ｍＬ／ｍｉｎ流速过柱，用０．１ｍｏｌ／Ｌ ＨＣｌ的３％硫脲溶液以小于或等于０．５ｍＬ／ｍｉｎ流速洗脱金、铂、钯（和铑），都能同时定量富集。用火焰原子吸收光谱法测定，回收率均在９５％￣１１０％之间。经地质样品加标准回收实验，结果令人满意。证明这种以磺酸基     

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.