1─（2─吡啶偶氮）─2─萘酚─6─磺酸衍生化反相高效液相色谱法测定铁、钴、镍

本文研究了水溶性试剂１－（２－吡啶偶氮）－２－萘酚－６－磺酸（ＰＡＮ－Ｓ）与铁（Ⅱ）、钴（Ⅱ）和镍（Ⅱ）之螯合物的衍生和液相色谱分离条件。在Ｎｏｖａ－ＰａｋＴＭＣ１８柱上，用含１０ｍｍｏｌ／Ｌ的ｐＨ５．０的醋酸－醋酸钠缓冲溶液的甲醇－水溶液（５０：５０，Ｖ／Ｖ）作流动相，溴化四丁基铵（ＴＢＡ·Ｂｒ）作离子对试剂，流动相流速为１．０ｍＬ／ｍｉｎ，在５５０ｎｍ波长处进行光度检测。在Ⅱｍｉｎ内用高效液相色谱分离测定了Ｆｅ（Ⅱ）、Ｃｏ（Ⅱ）和Ｎｉ（Ⅱ）与ＰＡＮ—Ｓ的螯合物，提出了离子对反相高效液相色谱快速分离测定痕量铁、钴、镍的新方法。信噪比（ＳＮＲ）为２时，检测下限分别为０．０４３、０．００７和０．０１２ｍｇ／Ｌ。     

浊点萃取-流动注射电感耦合等离子体原子发射光谱法同时测定水中镉钴铜镍锌

本文提出了浊点萃取-流动注射电感耦合等离子体原子发射光谱（FI—ICP—AES）法同时测定水中镉、钴、铜、镍、锌的新方法。利用5-Br—PADAP将待测金属离子转化为水不溶性的螯合物，并萃取到表面活性剂Triton X-114的浓缩相，以乙醇-硝酸溶液稀释含富集离子的浓缩相，并以FI—ICP-AES法测定。考察了流动注射进样体积、积分时间、萃取体系介质酸度、螯合剂和表面活性剂用量等实验条件的影响。在折衷条件下，镉、钴、铜、镍和锌的浓缩倍率可达18、10、16、10和8，检出限分别为0．7μg／L、1．6μg／L、1．3μg／L、5．7μg／L、3．2μg／L。方法成功应用于自来水、河水和海水中痕量镉、钴、铜、镍和锌的分析。在0．02mg／L和0．10mg／L二个水平进行加入回收试验，回收率在80％与118％之间。     

PVC-PP树脂分离富集/火焰原子吸收光谱法测定海水中痕量铜镍钴

采用自制的聚氯乙烯多乙烯多胺（PVC-PP）树脂，在pH值为5．0的条件下，分离富集海水中的痕量铜、镍、钴，以1．2mol／L盐酸溶液洗脱．火焰原子吸收光潜法测定，富集倍数最大可达100倍（回收率大于90％）。研究了吸附与洗脱的最佳条件，方法检出限分别为铜0．81μg/L、镍0．98μg/L、钴0．57μg/L（富集倍数100，S／N=3），相对标准偏差小于5％（n=7），样品加标回收率在90％-105％之间。     

催化动力学光度法测定痕量镍（Ⅱ）的研究

本文发现痕量镍（Ⅱ）在氨性介质中能催化高碘酸钾与靛红之间的褪色反应，研究了反应的最优化条件和动力学参数，建立了测定痕量镍（Ⅱ）的新方法，方法的最低检测限为２．３３×１０＾－１１ｇ／ｍＬＮｉ（Ⅱ）检测范围为０～１．０μｇ／２５ｍＬＮｉ（Ⅱ）用于测定人发及共它生物样品中的痕量Ｎｉ（Ⅱ）获得了满意结果。     

液—液萃取浮选法分离Ni（Ⅱ）,Co（Ⅱ）,Fe（Ⅲ）的研究

研究了在（ＮＨ４）２ＳＯ４存在下，乙醇与水分相的条件。试验表明，丁二酮肟与镍生成的螯合物沉淀可以被萃取浮选在乙醇与水两相之间，钴与丁二酮肟生成的螯合物被乙醇萃取，Ｆｅ（Ⅲ）留在水相中，实现了同一体系中三相分离Ｎｉ（Ⅱ），Ｃｏ（Ⅱ），Ｆｅ（Ⅲ），结果满意。     

螯合微粒共振散射光谱分析测定痕量钴

研究了螯合微粒共振散射光谱的分析应用。结果表明,在pH为9．5的NH3-NH3Cl缓冲溶液中,Co（Ⅱ）与DDTC形成稳定的螯合物微粒体系,存在共振散射效应。在一定质量浓度范围内,Co（Ⅱ）的质量浓度与共振散射强度（IRS）呈较好的线性关系。其线性范围为0．012～1．44μg／mL,检出限为0．0012μg／mL,用于针剂维生素B12中钴的测定,方法简单、灵敏度高、重现性好,结果满意。     

2-(2-噻唑偶氮)-对-甲酚螯合物反相高效液相色谱同時分离测定镍、钴的研究——合金中微量钴和镍的测定

本文研究了2-(2-噻唑偶氮)-对-甲酚(TAC)与镍(Ⅱ)、钴(Ⅱ)螯合物的柱前衍生条件和液相色谱的分离条件。于KYWG-C_(18)柱上,用含有0.03mol/L KH_2PO_4-Na_2HPO_4(pH7.77)和2.5×10~(-4)mol/L TAC的甲醇-四氢呋喃-水(40∶10∶50 V/V)混合液为流动相,流速为1.0mL/min。于580nm处检测。该法用于四种标准合金中镍和钴的测定,回收率在98%～101.5%之间。Ni(Ⅱ)和Co(Ⅱ)的检出限(信噪比为2∶1)分别为0.2ng和1.5ng。建立了同时测定镍,钴的高灵敏、高选择性,快速的HPLC-光度法。     

纳米二氧化钛分离／富集-石墨原子吸收光谱法测定环境样品中痕量镉

以石墨炉原子吸收（GFAAS）为检测手段，研究了纳米二氧化钛（TiO2，锐钛型）对金属Cd（Ⅱ）的吸附性能，考察了吸附和解吸的主要影响因素。结果表明，在较宽的pH范围内，纳米TiO2对Cd（Ⅱ）具有良好的吸附性能，3．0mol／L HCl能将所吸附的Cd（Ⅱ）完全洗脱。在优化的实验条件下，具有吸附容量大、吸附速度快的特点。本法的检出限（3σ）为10．6ng／L；相对标准偏差（RSD）为1．5％，（n=7，C=2．0μg/L），富集50倍。本法测定标准样品的测定值与参考值吻合。用于土壤类样品中Cd（Ⅱ）的测定，结果令人满意。     

化学发光—流动注射—胶束增敏连续测定钴铬研究

基于钴（Ⅱ）和铬（Ⅲ）对鲁米诺－过氧化氢化学发光反应均有催化作用，加入ＣＴＭＡＢ能明显提高发光的信噪比，可测定亚纳克量的钴和铬，加入ＥＤＴＡ掩蔽钴（Ⅱ）测得铬（Ⅲ）量，再由钴和铬总量求得钴（Ⅱ）量，实现钴和铬的不经分离而流动注射连续测定。此法线性范围宽达４个数量级（１０－１１～１０－７ｇ／ｍＬ），检测下限低（Ｃｏ２＋１．２×１０－１１ｇ／ｍＬ，Ｃｒ３＋１．０×１０－１１ｇ／ｍＬ），再现性好，工效高（１２０个样品／ｈ），用于三种矿泉水中痕量钴（Ⅱ）、铬（Ⅲ）连续测定，结果良好     

1-(2-吡啶偶氮)-2-萘酚-6-磺酸反相高效液相色谱分离测定铜、铁、钴、镍

1 引言近年来利用有机显色剂与金属离子形成稳定的有色螯合物,通过高效液相色谱分离,用光度检测器测定痕量金属离子的高效液相色谱的研究十分活跃.1-(2-吡啶偶氮)-2-萘酚(PAN)是光度法测定金属离子的常用显色剂,并已用于液相色谱中,因PAN及螯合物不溶于水,使操作不便,本文研究了水溶性的1-(2-吡啶偶氮)-2-萘酚-6-磺酸(PAN-S)与铜(Ⅱ)、铁(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)的衍生条件及HPLC分离条件,提出了反相高效液相色谱快速分离测定痕量铜、铁、钴、镍的新方法.方法用于试剂和茶叶中铜、铁、钴、镍的同时测定,结果与原子吸收分光光度法一致。     

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.