溴水氧化氰根光度法测定微量氰化物

在磷酸介质中,氰根被饱和溴水氧化为溴化氰,剩余的溴水用磺基水杨酸除去。溴化氰与碘化钾反应生成单质碘,碘与淀粉显色,从而测定氰化物。其最大吸收波长λｍ ａｘ＝ ５６５ｎｍ ,ＣＮ－ 在０～１５μｇ／２５ｍ Ｌ范围内呈良好线性关系,表观摩尔吸光系数为３．１×１０４Ｌ·ｍ ｏｌ－ １·ｃｍ － １。已用于测定废水中的氰化物。     

4-(H酸偶氮)-1-苯基-3-甲基吡唑酮光度法测定铝

研究了新试剂４－（Ｈ酸偶氮）－１－苯基－３－甲基吡唑酮（ＨＡＰＭＰ）与铝的显色反应,在ｐＨ４．６的ＨＡｃ－ＮａＡｃ缓冲介质中,ＣＴＭＡＢ存在下,ＨＡＰＭＰ和Ａｌ（Ⅲ）反应生成２∶１红色络合物,λｍａｘ＝５５５ｎｍ,ε＝１．３４×１０５Ｌ·ｍｏｌ－１·ｃｍ－１,铝的含量在０～３．５μｇ／２５ｍＬ内符合比尔定律,方法已用于天然水样中铝的测定。     

新试剂N-间甲苯基-N′-(氨基对苯磺酸钠)硫脲(MMPT)的合成及其在分析化学中的应用

本文合成新试剂Ｎ－间甲苯基－Ｎ′－（氨基对苯磺酸钠）硫脲（ＭＭＰＴ），经红外、紫外、核磁、元素分析等测试，确定其结构。研究测定了试剂与４０多种离子的反应及其配合物的表观摩尔吸光系数，它可作为Ｃｕ２＋（ｍ＝０．０１５μｇ，ｃ＝０．５μｇ／ｍＬ）、Ａｇ＋（ｍ＝０．１μｇ，ｃ＝３．３μｇ／ｍＬ）的新鉴定试剂和光度法测定Ｐｄ２＋（ε３０９．７＝６．３２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）、Ｐｔ（Ⅳ）（ε７５４．４＝８．５８×１０４Ｌ·ｍｏｌ－１·ｃｍ－１）等的显色剂，方法灵敏度高、选择性好，用于阳极泥、人发、矿石及催化剂中上述元素的鉴定或测定，均获满意结果。     

新显色剂5—（4—氯—2—羟基苯偶氮）罗丹宁与银（Ⅰ）显色反应的研究和应用

本报道了新显色剂５－（４＇－氯－２＇－羟基苯偶氮）罗丹宁的合成及其光度法测定银的条件，在ｐＨ＝５．０的缓冲介质中，该显色剂与银形成黄色络合物，其络合比为Ａｇ（Ｉ）：Ｒ＝１：２，摩尔吸光系数为１．１×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１，用拟定的方法测定阳极泥，废定影液中银的含量，结果满意。     

分光光度法同时测定中草药中的钼和铜

本文建立了在混合显色剂（ＰＦ＋ＰＡＮ）的胶束体系中，利用分光光度法同时测定中草药中的钼和铜。实验表明：在混合体系中，钼量在０～１０μｇ／２５ｍＬ，铜量在０～５０μｇ／２５ｍＬ的范围内符合比尔定律，ε′Ｍｏ＝９．２×１０４Ｌ·ｍｏｌ－１·ｃｍ－１；ε′Ｃｎ＝１．５×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。该法用于中草药样品的分析，结果满意，回收率可达９２～１１１％。     

迭代目标转换因子分析光度法同时测定钯,铑

钯，铑二元素于ＨＡｃ－ＮａＡｃ缓冲介质中，在表面活性剂Ｔｒｉｔｏｎ Ｘ－１００存在下与５－Ｂｒ－ＰＡＤＡＰ形成灵敏度较高的紫红色络合物，其摩尔吸光系数分别为ε５６５＾ｐｄ＝１．４４×１０＾５，ε５６２＾Ｒｈ＝１．１７×１０＾５（Ｌ·ｍｏｌ＾－１·ｃｍ＾－１）。二元素络合物吸收光谱发生严重重叠。本文探讨了在上述体系中同时测定Ｐｄ，Ｒｈ的最佳条件，并采用迭代目标转换因子分析法（ＩＴＴＦＡ）对Ｐｄ，Ｒｈ     

Cu（Ⅰ）的高灵敏度显色反应的研究Ⅱ．及其在绿茶测定中的应用

本文研究了在硫酸介质中，Ｃｕ（Ⅰ）－ＳＣＮ￣－罗丹明Ｂ体系当有明胶和聚乙醇辛基苯基醚存在时的显色反应。该反应的λｍａｘ＝５９５ｎｍ，ε＝２．０×１０５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），铜在０～５．００μｇ／２５ｍＬ范围内具有良好的线性关系。据此拟定的分析方法，用于测定绿茶中的痕量铜，选择性好，灵敏度高，结果满意。     

新显色剂2-(5-羧基-1,3,4-三氮唑偶氮)-5-二乙氨基酚的合成及其与铋的显色反应

首次合成了新显色剂２－（５－羧基－１，３，４－三氮唑偶氮）－５－二乙氨基酚（简称ＣＴＺＡＰＮ），研究了它的性质及其与铋显色反应的条件。结果表明：试剂的分子式Ｃ１３Ｈ１６Ｎ６Ｏ３分子量３０４．３２，ｍ．ｐ． ２５２℃，各级酸离解常数为ＰＫａ１＝３．１，ＰＫａ２＝７．５，ＰＫａ＝９．６；在ＰＨ ７的 ＮＨ４Ａｃ介质中，试剂与铋形成紫红色络合物，λｍａｘ为 ５４０ ｎｍ，对比度△λ为 １２０ ｎｍ，络合比Ｂｉ３＋：Ｒ＝１：２，摩尔吸光系数５．１３ ×１０４Ｌ·ｍｏｌ－１·ｃｍ－１，Ｂｉ３＋在０～１．８ ｍｇ／Ｌ范围内遵守比耳定律，在掩蔽剂的作用下，可不经分离直接测定合金样品及合成工业废水中微量铋，结果满意。     

微乳液的增敏作用研究—5－Br－PADAP分光光度测定锰（Ⅱ）

以含水量８０％的Ｏ／Ｗ型ＳＤＳ／正丁醇／正庚烷／水微乳液为介质，以５－Ｂｒ－ＰＡＤＡＰ为显色剂，分光光度测定Ｍｎ（Ⅱ）．表观摩尔吸光系数ε５７０＝１．０８×１０５Ｌ·ｍｏｌ－１·ｃｍ－１，与相同含水量的ＳＤＳ胶束体系相比，测定灵敏度有显著提高，改善了实验条件．方法用于铝合金和茶叶中Ｍｎ（Ⅱ）的测定，结果令人满意     

二安替比林对甲氧基苯基甲烷与锰(Ⅳ)的高选择性显色反应研究及应用

在碱性介质中，空气氧化Ｍｎ（Ⅱ）为Ｍｎ（Ⅳ），然后在酸性介质中，Ｍｎ（Ⅳ）氧化二安替比林对甲氧基苯基甲烷（ＤＡｐＭＭ）生成黄色产物，λｍａｘ＝４５０ｎｍ，ε＝５．４５×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。锰含量在０～２０μｇ／２５ｍＬ内符合比尔定律。方法用于钢样中锰的测定，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.