卟啉试剂与稀土元素显色反应的分光光度法研究：（I）meso—四（对磺基…

本文研究了在ｐＨ１１．０的硼砂－ＮａＯＨ缓冲介质中，以Ｈｇ（Ⅱ）作催化剂，在乳化剂（ＯＰ）和溴化十六烷基三甲基铵（ＣＴＭＡＢ）协同作用下，ｍｅｓｏ－四（对磺基苯）卟啉（ＴＰＰＳ４）测定钇（Ⅲ）的显色反应，其摩尔吸光系数ε４１７为５．４６×１０＾６Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，钇浓度在０￣０．０３０μｇ／１０ｍＬ内符合比耳定律，在室温下显色迅速，１００倍重稀土不干扰，测定合成稀土混合样品中钇（Ⅲ）含     

用卡尔曼滤波-分光光度法测定无机铬的形态

利用Ｋａｌｍａｎ滤波技术和二溴苯基荧光酮－溴化十六烷基三甲基铵－Ｃ_２Ｈ_５ＯＨ分光光度测定体系,同时对Ｃｒ（Ⅲ）和Ｃｒ（Ⅳ）进行测定。Ｃｒ（Ⅲ）的表观摩尔吸光系数为１．９６ × １０~５ Ｌ· ｍｏｌ~（－１）·ｃｍ~（－１）,线性范围为０～ ４．０ ｘ１０－６ｍｏｌ／Ｌ;Ｃｒ（Ⅵ）的表观摩尔吸光系数为４．１６ ×１０~５Ｌ· ｍｏｌ~（－１）· ｃｍ~（－１）,线性范围为０～５．２×１０~（－１）ｍｏｌ／Ｌ。     

卟啉试剂与贵金属高灵敏显色反应的研究 Ⅴ.Ru(Ⅲ)-T(4-AOP)P-TritonX-100体系

本文研究了在Ｃｄ（Ⅱ）和ＴｒｉｔｏｎＸ－１００存在下，ｍｅｓｏ－四（４－乙酰氧基苯）卟啉［Ｔ（４－ＡＯＰ）Ｐ］与钌（Ⅲ）的显色反应。结果表明，在ｐＨ９．７～１０．３介质中，Ｒｕ（Ⅲ）与Ｔ（４－ＡＯＰ）Ｐ形成了灵敏度很高的稳定络合物，其表观摩尔吸光系数为７．０４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１。钌浓度在０～１．２μｇ／１０ｍＬ范围内服从比尔定律。络合物的摩尔比为Ｒｕ（Ⅲ）∶Ｔ（４－ＡＯＰ）Ｐ＝１∶１。在掩蔽剂存在下，方法有一定的选择性，应用于合成试样中钌的测定，结果满意。     

四（4—甲氧基—3—磺酸苯基）卟啉分光光度法测定微量铅

研究了水溶性卟啉５，１０，１５，２０－四（４－甲氧基－３－磺酸苯基）卟啉（Ｔ（４－ＭＯＰ）ＰＳ４）与铅的显色反应，在ｐＨ１１和酒石酸钾存在下铅与Ｔ（４－ＭＯＰ）ＰＳ４在室温时间形成１：１的配合物，其最大吸收波长在位于４６４．４ｎｍ，摩尔吸光系数为２．３×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，铅量在０～２０μｇ／２５ｍＬ，范围为符合比尔定律，工作工线回归方程Ａ＝０．０２６２＋０．０４３５ｃ相关系数ｒ     

2-羟基-3-羧基-5-磺酸基苯基重氮氨基偶氮苯与铊反应的分光光度法研究

于ｐＨ１０．０～１１．０的ＮＨ３－ＮＨ４Ｃｌ缓冲介质中，在ＴｒｉｔｏｎＸ－１００存在下，铊（Ⅲ）与２－羟基－３－羧基－５－磺酸基苯基重氮氨基偶氮苯（ＨＣＳ－ＤＡＡ）形成组成比为１∶３的红色配合物，其最大吸收波长和对比度分别为５１０ｎｍ和８０ｎｍ，表观摩尔吸光系数为１．５２×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，线性范围为０～０．７０ｍｇ／Ｌ，室温下显色反应立即完成，配合物至少稳定２ｈ。方法用于水样、烟叶和煤灰中痕量铊的分析，回收率为９０．０％～１０１．４％，５次测定的相对标准偏差不大于４．６％。     

钌（Ⅲ）－钼酸盐－罗丹明B离子缔合显色反应的研究及分析应用

钌（Ⅲ）钼酸盐－罗丹明Ｂ离子缔合显色体系分光光度测定钌，λｍａｘ为５７０ｕｍ，ε＝９．０５×１０５Ｌ·ｍｏｌ（－１）·ｃｍ（－１），相对标准偏差２．５％。线性范围０～１．２μｇ／２５ｍＬ。大量常见金属不干扰Ｒｕ的测定。方法用于某些岩矿和冶金产品中钉的测定，获得满意结果。     

硫代米蚩酮－乳化剂OP分光光度法测定微量铂的新体系

本研究工作发现：硫代米蚩酮（ＴＭＫ）可作光度法测定铂（Ⅳ）的新显色剂。与一般光度测铂方法不同，在最佳条件（１ｍＬ１％乳化剂ＯＰ，２ｍＬｐＨ２．２邻苯二甲酸氢钾－盐酸缓冲溶液，１．２ｍＬ０．５ｍｇ／ｍＬＴＭＫ乙醇溶液存在）下，只需在室温放置２０ｍｉｎ即显色完全，灵敏度高（ε＝１．６９×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）），对比度大（△λ）＝９５ｎｍ），线性范围较宽（０～１４μｇ／（２５ｍＬ），对含Ａｕ：ｐｔ＝１∶２．３～２．３∶１范围内的混合物在较宽波长范围（５１０～５８０ｎｍ）符合吸光度加和原理，可望用双波长分光光度法不经分离同时测定铂和金。     

催化动力学光度法测定痕量Cr（Ⅲ）

在弱酸性介质中,以２,２‘－联吡啶作活化剂,Ｃｒ（Ⅲ）强烈论过氧化氢氧化中性红褪色反应,催化反应的表观活化能为４９．８８ｋＪ·ｍｏｌ＾－１。据此建立了测定痕量Ｃｒ（Ⅲ）的催化动力学光度法。方法的检出限为２ｎｇ·ｍｌ＾－１,线性范围为０￣０．１μｇ·ｍｌ＾－１。通过测定模拟 １、矿井水样及电镀废水样中痕量Ｃｒ（Ⅲ）,结果满意。     

meso－四（3－氟－4－磺基苯）卟啉与钯（Ⅱ）显色反应的分光光度研究

本文对新多卤代水溶性ｍｅｓｏ－四（３－氟－４－磺基苯）卟啉与Ｐｄ（Ⅱ）的显色反应进行了研究，在ｐＨ４．８，有抗坏血酸存在，沸水浴中加热，形成稳定的１：１配合物，最大吸收波长在４０９ｎｍ处。工作曲线回归方程Ａ＝０．００１＋０．０６４ｘ，相关系数ｒ＝０．９９６４。摩尔吸光系数达１．７×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），Ｐｄ（Ⅱ）浓度在０～７．５μｇ／２５ｍＬ范围内符合比耳定律。灵敏度和选择性高于其它多卤代水溶性卟啉。对催化剂中钯含量的测定，获得满意的结果。     

meso－四（4－甲基－3－磺基苯）卟啉分光光度法测定痕量钯的研究

本文研究了Ｐｄ（Ⅱ）与ｍｅｓｏ－四（４－甲基－３－磺基苯）卟啉（Ｔ（４Ｍ３ＳＰ）Ｐ）的显色反应在表面活性剂十二烷基磺酸钠（ＳＤＳ）和抗坏血酸存在下，ｐＨ４８的ＨＡｃ－ＮａＡｃ介质中，沸水浴加热，Ｐｄ（Ⅱ）与Ｔ（４Ｍ３ＳＰ）Ｐ形成１∶１（Ｍ∶Ｌ）配合物配合物最大吸收波长４１４ｎｍ，表观摩尔吸光系数ε＝２０×１０５Ｌ·ｍｏｌ－１·ｃｍ－１钯量在０－２．２５μｇ／１０μＬ范围内符合比耳定律本法应用于催化剂中痕量钯的测定，结果满意     

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.