用二安替比林对二乙氨基苯基甲烷和高碘酸钾催化光度法测定痕量钌

在磷酸介质和９０℃水浴条件下,Ｒｕ（Ⅲ）对高碘酸钾氧化二安替比林对二乙氨基苯基甲烷（ＤＡＥＡＭ）的显色反应强催化作用,建立了动力学光度法测定痕量钌的新方法。方法的线性范围为０－１．６μｇ／Ｌ＾－１和１．６－４．４μｇ．Ｌ＾－１;检出限为８．３４＊１０＾－８ｇ．Ｌ＾－１;对３μｇ．Ｌ＾－１Ｒｕ（Ⅲ）测定的ＲＳＤ为１．７９％（ｎ＝１１）本催化反应表观活化能为９１．６７ｋＪ．ｍｏｌ＾－１,表观速率常数为３．５３＊１０＾－３ｓ＾－１。考察了４０多种共存离子的影响,大多数常见离子干扰测定。方法用于矿样中痕量钌的测定,结果满意。     

高碘酸钾-酸性品红-NTA-DDMAA体系催化光度法测定良量锰

报道了以氨三乙酸为活化剂，以Ｎ－十二烷基二甲基铵基乙酸（ＤＤＭＡＡ）为增敏剂，高碘酸钾氧化酸性品红催化光度法测定痕量锰的新方法，在ＤＤＭＡＡ存在下，灵敏度提高了７倍（Ｍｎ２＋量为１．２～２．４μｇ／Ｌ）和１４倍（Ｍｎ２＋量为２．４～５．２μｇ／Ｌ），相对标准偏差为２．０％，检出限为１．４×１０－７ｇ／Ｌ，可用于茶叶中锰的测定。     

钌(Ⅲ)-二安替比林对氯苯甲烷-高碘酸钾体系催化分光光度法测定痕量钉

在磷酸介质中及加热条件下,钌（Ⅲ）对高锰酸钾氧化二安替比林对氯苯基甲烷（ＤＡｐＣＭ）显色反应有强烈的催化作用,由此建立了测定痕量钉的方法。体系的最大吸收波长为 ５００ ｎｍ,钌的含量在 ０．０～４．０μｇ／Ｌ范围内具有线性关系,检测限为 １．９４×１０－１０ｇ／ｍＬ,反应的表观活化能为 ８８．２０ ｋＪ／ｍｏｌ,反应表现速率常数为 ７．７ ０×１０－４／ｓ。本方法用于矿样中痕量钌的测定得到了满意的结果     

高碘酸钾-二安替比林对碘苯基甲烷体系催化光度法测定痕量钌(Ⅲ)

合成了新试剂二安替比林对碘苯基甲烷（ＤＡｐＩＭ）,研究了在磷酸介质中钌（Ⅲ）催化高 碘酸钾氧化ＤＡｐＩＭ的显色反应,建立了一种测定痕量钉的催化光度分析法。方法的线性范 围为 ０～６ μｇ／Ｌ;检测限为１．６ × １０－７ｇ／Ｌ。该体系灵敏度高,稳定性好,用于矿样中痕量钉的 测定,其相对标准偏差为３．０％～４．１％,标准加入回收率为９７％１０５％。     

金钨杂多酸-丁基罗丹明B光度法测定痕量金

研究了金钨杂多酸（ＡｕＷ）－丁基罗丹明Ｂ（ＢＲＢ）－聚乙烯醇（ＰＶＡ）体系的显色反应．离子缔合物的最大吸收位于５６５ｎｍ，表现摩尔吸光系数ε值为２．９６×１０７ｄｍ３·ｍｏｌ－１·ｃｍ－１，金量在０～２．８μｇ／Ｌ范围内服从比耳定律，检出限为０．１２μｇ／Ｌ（ｎ＝１２），对２．４μｇＡｕ（Ⅲ）／Ｌ测定的相对标准偏差为１．９％（ｎ＝１１）．离子缔合物至少稳定２４０ｈ．研究了离子缔合物的红外光谱，考察了４０多种共存离子的影响，大多数常见离子不干扰，允许２００倍量Ｐｔ（ＩＶ）、４００倍量Ｐｄ（Ⅱ）存在．本法用于某些矿物和炭粉中金的测定，结果与ＡＡＳ法吻合     

锡钨杂多酸—耐尔蓝光度法测定纳克量易

本文报道一个光度法测定纳克量锡的新方法,在聚乙烯醇（ＰＶＡ）存在下锡与钨酸盐和耐尔蓝（ＮＢ）反应形成离子缔合物,离子缔合物的最大吸收位于５８０ｎｍ,表现摩尔吸光系数ε值２．９５×１０＾７Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。服从比耳定律范围０－２．０μｇ／Ｌ,检出限（３σ）０．０８３μｇ／Ｌ,对２．０μｇ／Ｌ锡测定的ＲＳＤ为２１．４２％,离子缔合物至少稳定７２ｈ。考察了４０多种共存离子的影响,大多数常见元     

二安替比林对二甲氨基苯基甲烷-高碘酸钾催化光度法测定痕量铑

在磷酸介质和加热条件下,痕量铑（Ⅲ）能灵敏地催化高碘酸钾氧化二安替比林对二甲氨基苯基 甲烷（ＤＡＭＡＭ）的显色反应。研究了该催化反应的最佳实验条件及动力学参数,建立了一种动力学光度 法测定痕量铑的新方法。方法的线性范围为０～８４μｇ／Ｌ;检出限为６．２０×１０－７ｇ／Ｌ。催化反应的表观活 化能为８９．０３ｋＪ／ｍｏｌ,表观速率常数为２．５１×１０－４／ｓ,反应终止后至少稳定６ｈ。本法已用于某些催化剂中 铑的测定,其相对标准偏差为２．７％～３．２％;标准加入回收率为９８．２％～１０３．２％。     

锡钨杂多酸-耐尔蓝光度法测定纳克量锡

本文报道一个光度法测定纳克量锡的新方法。在聚乙烯醇（ＰＶＡ）存在下锡（Ⅳ）与钨酸盐和耐尔蓝（ＮＢ）反应形成离子缔合物,离子缔合物的最大吸收位于５８０ｎｍ,表观摩尔吸光系数ε值２．９５×１０７Ｌ·ｍｏ１－１·ｃｍ－１,服从比耳定律范围０～２．０μｇ／Ｌ,检出限（３σ）０．０８３μｇ／Ｌ（ｎ＝１０）,对２．０μｇ／Ｌ锡测定的ＲＳＤ为１．４２％（ｎ＝１１）,离子缔合物至少稳定７２ｈ。考察了４０多种共存离子的影响,大多数常见元素不干扰。测定锡的适宜条件［Ｈ２ＳＯ４］＝１．２０ｍｏ１／Ｌ,［ＷＯ２－４］＝６．０５×１０－５ｍｏ１／Ｌ,［ＮＢ］＝５．５×１０－５ｍｏ１／Ｌ和ＰＶＡ０．０８％。本法已用于某些合金钢和锌合金中纳克量锡的测定,结果与推荐值吻合,回收率满意。     

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。     

钌催化高碘酸盐氧化亚甲蓝的反应特性及应用

报道在９０±０．５℃和硫酸介质中,Ｒｕ（Ⅲ）催化高碘酸盐氧化亚甲蓝（ＭＢ）的反应,实现了钉的动力学光度法测定,研究了反应的适宜条件及动力学参数,并探讨了反应机理。方法的线性范围为０．０－１．２和１．２－５．６μｇ／Ｌ,检出限为０．００５μｇ／Ｌ。共存离子浓度高于Ｒｕ（Ⅲ）浓度５０倍不干扰测定。本法灵敏度高、选择性好、稳定,已满意地用于岩矿及冶金产品中钉的测定,其ＲＳＤ为１．３％－２．２％,标准加入回收率为 ９９％－１０５％。     

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.