茶汤及河水中铁的形态分析

本文采用阳离子交换、活性炭分离－光度法研究了铁的形态分离及测定条件，建立了铁的形态分析方法。应用此法测定了茶汤及河水中铁的总量、悬浮态、溶解态、无机态、有机态、Ｆｅ（Ⅲ）和Ｆｅ（Ⅱ）等形态，结果令人满意。     

不同价态铬离子的毛细管电泳分离与测定

１引言由于元素的不同价态、不同存在形态具有不同的物理、化学性质与生理活性。如Ｃｒ（Ⅲ）是人体必需的元素，而Ｃｒ（Ⅵ）则是有害的。因此，离子的价态分析具有十分重要的意义。由于毛细管电泳可实现阴阳离子的同时分析，与离子色谱相比，具有简单、快速的特点。本文采用样品与ＥＤＴＡ络合的办法，用毛细管电泳在ＣＨ３ＣＯＯＮａ－ＣＨ３ＣＯＯＨ体系中（含电渗流改性剂和络合剂），对ＣｒＯ４２－、Ｃｒ３＋的分离测定进行了研究。用直接紫外法检测在５．５ｍｉｎ内可完成两种价态铬离子的测定，特别适于电镀废液或其它水质的分析。…     

富铬酵母中铬的化学种态及结合形态研究

对富铬酵母中铬的化学种态进行了分析和初步探讨。在铬的化学种态测定中铬的使用离子交换和火焰原子吸收法测定了富铬酵母中的Ｃｒ（Ⅲ）,方法快速简便、定量回收,结果表明,总铬呈为１５８２μｇ／ｇ的富铬酵母中,无机态铬占１６％,其中Ｃｒ（Ⅲ）为２３２μｇ／ｇ,Ｃｒ（Ⅵ）为２４．５μｇ／ｇ。酵各过程中的８４％以上的无机铬化合物转化成有机铬。说明铬参与了酵母细胞的生物合成,促进生物转化,对提高富铬酵母的生物疚极     

流动注射化学发光同时测定废水中的三价铬和六价铬

首次将镀铜锌粒作成优良的还原柱，在线还原Ｃｒ（Ⅵ）成Ｃｒ（Ⅲ），以鲁米诺－Ｈ２Ｏ２（ＫＢｒ）体系流动注射化学发光同时测定废水中两种价态的铬。分析速率为６０试样／ｈ；线性范围为１．０×１０＾－５－１．０×１０＾－９ｍｏｌ／Ｌ；测Ｃｒ（Ⅲ）及Ｃｒ（Ⅵ）的相对标准偏差（ｎ＝６）分别为０．３７％－４．０％及１．２％－４．４％；测定Ｃｒ（Ⅲ）的检出限２．３×１０＾－１１ｍｏｌ／Ｌ。测定结果与标准方法无显差     

流动注射在线富集分离—火焰原子吸收光谱法测定水体中的铬（Ⅲ）和铬（Ⅳ）

内装活性氧化铝（碱式）和阴离子交换树脂的微型柱流动注射在线富集分离水体中的铬（Ⅱ）和铬（Ⅳ），火焰原子吸收法直接检测，微型柱可同时富集两种价态的离子，分别用１ｍｏｌ／Ｌ的ＮＨ４ＮＯ３和ＨＮＯ３洗脱Ｃｒ（Ⅳ）和Ｃｒ（Ⅲ）于喷雾器中，进样时间２５ｓ，铬（Ⅳ）和铬（Ⅲ）的富集倍数分别为１１倍和２０倍，实际水样的加标回收率在９０％～１０６％之间，分析速率为５０个样／ｈ，铬（Ⅳ），铬（Ⅲ）的检出限（３δ）分     

巯基棉分离吸附溶出伏安法测定茶叶及茶汤中痕量砷

本文研究了巯基棉纤维（ＳＣＦ）对Ａｓ（Ⅲ）和Ａｓ（Ⅴ）的吸附性能，建立了ＳＣＦ分离Ａｓ（Ⅲ）和Ａｓ（Ⅴ）吸附溶出伏安法测定生物样品中痕量砷的方法。结果表明：在１ｍｏｌ／Ｌ盐酸介质中，ＳＣＦ可定量吸附Ａｓ（Ⅲ），Ａｓ（Ⅴ）不被吸附；用ＫＩ－（ＮＨ２）２ＣＳ预先还原Ａｓ（Ⅴ），通过ＳＣＦ分离，可消除干扰离子对测定砷的影响。方法用于测定桃叶、煤飞灰及番茄叶标样中的砷，其结果与标准值相符；应用此法还测定了几种茶叶及茶汤中的痕量砷和不同价态的砷，结果令人满意。     

纳米二氧化钛分离富集和ICP-AES测定水样中Cr(Ⅵ)/Cr(Ⅲ)

利用ＩＣＰ－ＡＥＳ研究了纳米ＴｉＯ２材料对Ｃｒ（Ⅵ）／Ｃｒ（Ⅲ）的吸附性能,并将其用于水样中铬的形态分析。结果表明,该法对１０ｍＬ试样测定Ｃｒ（Ⅵ）和Ｃｒ（Ⅲ）的检测限分别为６１ｎｇ／ｍＬ和４５ｎｇ／ｍＬ,其浓度在０．１～１０ｕｇ／ｍＬ范围内线性关系良好,５０倍量的Ｃｒ（Ⅵ）对Ｃｒ（Ⅲ）的检测不产生干扰。本法测定Ｃｒ（Ⅵ）和Ｃｒ（Ⅲ）的相对标准偏差分别为３．６％和４．２％（ｃ＝２．０ｕｇ／ｍＬ,ｎ     

固体表面化学发光分析 Ⅲ.超基性岩和钢中铬的微量测定

本文在不渗透阻挡滤纸上，用过氧化氢将Ｃｒ（Ⅵ）还原为Ｃｒ（Ⅲ），建立了Ｌｕｍｉｎｏｌ－Ｈ２Ｏ２－Ｃｒ（Ⅲ）体系的固体表面化学发光分析法。铬测定的线性范围为１．０～１０００ｎｇ，检测限为０．１３ｎｇ。与微量离子交换柱结合，快速测定了微量超基性岩和钢铁试样中的铬。     

湘江(长沙段)水中铬的形态分布及其迁移

研究了湘江水中铬的存在形态、分离方法和分析流程。用极谱催化法测定了江水中的总铬、总溶解铬、颗粒态铬、有机态铬、溶解无机铬、溶解无机态Cr(Ⅵ)、溶解无机态Cr(Ⅲ)。分析了不同季节里铬的存在形态及其迁移转化。结果表明溶解无机态铬是主要的存在形态,其中溶解无机态Cr(Ⅵ)较易转化成毒性较小的Cr(Ⅲ)。不同季节中铬的各形态的含量不同,其中颗粒态铬和有机态铬在夏季的含量较高,而其余各形态的铬在秋、冬两季的含量高于春、夏两季。江水对铬污染的自净能力较强,铬造成的污染的范围较小。     

流动分析法同时测定铬（Ⅵ）及铬（Ⅲ）过程中铈（Ⅳ）氧化剂的影响

以Ｃｅ（Ⅳ）为氧化剂，采用流动分析在线氧化技术，实现了对Ｃｒ（Ⅵ）和Ｃｒ（Ⅲ）的同时在线分析，发现Ｃｅ（Ⅳ）氧化剂在测定过程中产生负干扰，在而Ｃｒ（Ⅲ）存在时会使Ｃｒ（Ⅵ）的测定结果偏高，本文提出了一个校正模型，通过数学方法消除上述干扰，所建立的分析方法对Ｃｒ（Ⅵ）和Ｃｒ（Ⅲ）分析的平均相对误差不大于６．５％。     

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.