镓—茜素紫极谱络合吸附波的研究

在含有０．０５ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ５．６）、０．１ｍｏｌ／Ｌ ＫＣＬ和１．５×１０＾－５ｍｏｌ／Ｌ茜素紫的溶液中，镓（Ⅲ）－茜素紫络合物在单扫示波极谱仪上产生一灵敏的导数极谱波，峰电位在－１．１１Ｖ（ｖｓ．ＳＣＥ），峰电流与镓（Ⅲ）浓度在２．０×１０＾－８ｍｏｌ／Ｌ。机理研究表明，峰电流是由吸附在电极表面的络合物中的中心离子和配位体同时还原而产生的。方法已应用于铝合金中镓的测定，结果     

锑—铜—茜素络合剂体系极谱行为的研究

在１．０ｍｏｌ／Ｌ甲酸－甲酸钠－０．０３ｍｏｌ／Ｌ邻苯二甲酸氢钾混合底液（ｐＨ３．５）中，锑－茜素络合剂（ＡＬＣ）络合物在单扫示波极谱上于一０．５３Ｖ（ｖｓ．ＳＣＥ）产生一极谱波，加入１．６×１０＾－３ｍｏｌ／ＬＣｕ（Ⅱ）后，灵敏度有较大提高，峰电流与锑浓度在２．０×１０＾－８～３．０×１０＾－６ｍｏｌ／Ｌ范围内呈线性关系，检测限达１．０×１０＾－８ｍｏｌ／Ｌ，研究了电极反应机理，方法应用于铜合金     

铟(Ⅲ)-7-(1-苯偶氮)-8-羟基喹啉-5-磺酸钠的配位吸附波及其应用

在ｐＨ４．５的 ０．０１５ ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ介质中，Ｉｎ铟（Ⅲ）－７－（１－苯偶氮）－８－羟基喹啉－５－磺酸钠（ＢＱ）在滴汞电极上于－０．６６５－０．７０ Ｖ（ｖｓ．ＳＣＥ）电位处得到络合物的吸附还原波，其一阶导数峰电流Ｉ＇ｐ与Ｉｎ（Ⅲ）浓度在４．０× １０~（－８）～３．５ × １０~（－６）ｍｏｌ／Ｌ范围内呈良好的线性关系，检测限为１．６ × １０~（－８）ｍｏｌ／Ｌ Ｉｎ（Ⅲ）．应用该法测定了铅粉和氢氧化铝样品中的微量铟，结果令人满意。对电极反应机理进行了探讨。     

镓(Ⅲ)-向红菲咯啉络合物极谱吸附波的研究及应用

在 ＰＨ＝４．２的 ０．０７ ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ介质中，Ｇａ（Ⅲ）－向红菲咯啉络合物在单扫描极谱仪上于－０．９８ Ｖ（ｖｓ．ＳＣＥ）处产生一灵敏的吸附还原波，其二阶导数波灵敏度高，波形好，峰电流 Ｉｐ与 Ｇａ（Ⅲ）在 ８．０×１０－８～３．０× １０－６ｍｏｌ／Ｌ的浓度范围内呈现良好线性关系，检出限为７．０×１０－８ｍｏｌ／ＬＧａ（Ⅲ）。用该法对粮食中的镓进行了测定，并对电极过程进行了研究。     

铟（Ⅲ）—2—硫基苯骈噻唑—7—碘—8—羟基喹啉—5—磺酸三元络合物吸附波研究

在ＨＣｌ－ＮａＡｃ介质（ｐＨ２．５）中，用单扫示波极谱法可获得高灵敏的Ｉｎ（Ⅲ）－２－巯基苯骈噻唑（ＭＢＴ）－７－碘－８－羟基喹啉－５－磺酸（Ｆｅｒｒｏｎ）三元络合物吸附波，峰电位在一－０．６４Ｖ（ｖｓ．ＳＣＥ），峰电流与铟浓度在７．０×１０＾－１０ｍｏｌ／Ｌ～８．８×１０＾－７ｍｏｌ／Ｌ之间呈线性关系，检出限可达３．０×１０＾－１０ｍｏｌ／Ｌ，测得电活性络合物的组成为Ｉｎ（Ⅲ）：ＭＢＴ：１∶１∶     

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     

铜（Ⅱ）锌（Ⅱ）－氟哌酸体系电化学行为及示波极谱法研究

铜（Ⅱ）和锌（Ⅱ）分别在０．１ｍｏｌ／ＬＫＨ＿２ＰＯ＿４－Ｎａ＿２ＨＰＯ＿４缓冲溶液（ｐＨ６．５）和０．２５ｍｏｌ／ＬＮＨ＿４Ｃｌ溶液中，与氟哌酸形成良好的络合吸附波，峰电位分别为－０．２６Ｖ和－１．２８Ｖ（ｖｓ；ＳＣＥ）；络合比分别为１：３和１：２；峰电流与铜（Ⅱ）和锌（Ⅱ）的浓度均在４．０×１０￣（－７）～５．０×１０￣（－６）ｍｏｌ／Ｌ范围内呈线性关系，检测限分别为７．０×１０￣（－８）和５．０×１０￣（－８）ｍｏｌ／Ｌ。用线性扫描和循环伏安法等手段研究体系的行为，表明均具吸附性，而铜（Ⅱ）－氟哌酸体系属络合物中铜（Ⅱ）的两电子还原的可逆过程。     

锡（Ⅱ）—1—苯基—3—甲基—4—苯甲酰基—吡唑啉酮—5—络合物吸附波的研究

在ｐＨ４．０的ＨＡｃ－ＮａＡｃ缓冲介质中，Ｓｎ（Ⅱ）与１－苯基－３－甲基－４－苯甲酰基－吡唑啉酮－５（ＰＭＢＰ）生成络合物，于－０．７４Ｖ（ｖｓ．ＳＣＥ）出现一灵敏的极谱峰。锡含量在４．２×１０－８ｍｏｌ／Ｌ～３．４×１０－６ｍｏｌ／Ｌ范围内与峰高呈线性关系，检出限为１．７×１０－８ｍｏｌ／Ｌ。用多种电化学方法研究了极谱波的性质及电极反应机理，证明该极谱波为络合吸附波，峰电流由中心离子Ｓｎ（Ⅱ）还原产生，络合物组成为Ｓｎ（Ⅱ）∶ＰＭＢＰ＝１∶１。试验了多种离子对峰电流的影响。方法已用于矿样中痕量锡的测定。     

镉-茜素紫-邻二氮菲体系的极谱行为及应用

用线性扫描示波极谱法研究了镉（Ⅱ）－茜素紫－邻二氮菲体系的极谱行为，发现在含有０．１ｍｏｌ／Ｌ ＫＣｌ、ｐＨ＝２．８５的ＨＡｃ的溶液中，镉（Ⅱ）－茜素紫－邻二氮菲体系产生－灵敏的极谱吸附波，共峰电位为－０．６４Ｖ（ｖｓ．ＳＣＥ），峰电流与镉（Ⅱ）的浓度在５．０＊１０＾－８－１．０＊１０＾－６ｍｏｌ／Ｌ的范围内呈一性关系；检出限为３．０＊１０＾－８ｍｏｌ／Ｌ。研究了电极反应机理，并用建立的方法成功地测定了废水样中的镉。     

钒－槲皮素－氯酸盐体系极谱催化波的研究

在醋酸盐缓冲底液中，钒能与槲皮素形成络合物，并吸附在汞电极上，在氯酸盐存在下，在Ⅴ（Ⅳ）还原至Ⅴ（Ⅲ）过程中，形成催化波。用单扫二阶导数极谱法测定时，钒浓度在１．０×１０￣（－９）～５．０×１０￣（－６）ｍｏｌ／Ｌ与峰高有正比关系，检出下限为５．０×１０￣（－１０）ｍｏ１／ｍＬ。测得电活性络合物的组成为Ⅴ（Ⅳ：Ｑｕ＝１：２。平行催化反应的速率常数Ｋ＝１．５×１０￣（４）（ｍｏｌ／Ｌ）￣（－１）ｓ（－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.