同时测定三辛妥和三辛胺盐酸盐的双波长分光光度法

提出了利用双波长分光光度法测定三辛胺及三胺盐酸盐的一种新方法,即ＴＯＡ和ＴＯＡ．ＨＣｌ在ＣＣｌ４溶液中与Ｉ２生成电荷转移化合物,其最大吸收波长分别为２９３ｎｍ和２６３ｎｍ,两组分同时存在时可利用吸光度和加和性得联立方程分别求出两组分的含量。     

利用碘—三辛胺盐酸盐反应分光光度测定TOA,HCl

研究了测定三辛胺盐酸盐的一种新方法－碘光谱法。ＴＯＡ，ＨＣｌ在四氯化碳溶液中与生成电荷转移化合物，该物质的最大吸收波长为３７０ｎｍ，ＴＯＡ，ＨＣｌ在０－４×１０＾－４ｍｏｌ．Ｌ范围内符合比耳定律。该方法准确，简便，快速，其它溶剂的干扰较小，回收率在９４．５％－１０１．９％，能够满足分析的需要。     

用三辛胺萃取法处理高浓度含Cr（Ⅵ）废水

用三辛胺萃取法处理高浓度含Ｃｒ（Ⅵ）废水褚莹，刘沛妍，阎淑荣，吴子生，严忠（东北师范大学化学系长春１３００２４）关键词三辛胺，Ｃｒ（Ⅵ），萃取处理含Ｃｒ（Ⅵ）废水的萃取剂有三烷基胺（Ｎ２３５）、三辛胺（ＴＯＡ）、季胺盐及磷酸三丁脂（ＴＢＰ），稀释剂为...     

以三正辛胺为流动载体的乳状液膜迁移,分离钒（Ⅴ）

１引言钒的分离方法很多，但利用三正辛胺（ＴＯＡ）作为乳状液膜分离Ｖ（Ⅴ）的研究还未见报道。本文研究了以ＴＯＡ为载体的乳状液膜迁移Ｖ（Ⅴ）行为及机理。试验表明：ＴＯＡ－Ｓｐａｎ　８０二甲苯乳状液膜体系能使Ｖ（Ⅴ）得到高效、快速、完全迁移，并能与常见离子得到完全分离。２实验部分２．１仪器与试剂７２１型分光光度计；ｐＨＳ－２酸度计；高速搅拌制乳器（自制）。Ｖ（Ⅴ）标准溶液１．０ｇ／Ｌ，ＴＯＡ和Ｓｐａｎ８０分别配成０．１０ｍｏｌ／Ｌ和１０％（Ｗ／Ｖ）二甲苯溶液，所用其他试剂均为分析纯。２．２乳状液膜的制…     

铁（Ⅲ）—过氧化氢—水杨基荧光酮—溴化十六烷基三甲铵荧光猝灭反应？…

在ｐＨ３．１～５．２的ＨＣｌ－ＮａＡｃ缓冲介质中,溶液中的铁（Ⅲ）与过氧化氢（Ｈ２Ｏ２）,水杨基荧光酮（ＳＡＦ）和溴化十六烷基三发（ＣＴＭＡＢ）反应产生一多元混合络合物,使水杨基荧光酮溶液的荧光明显猝灭,据此建立了测定痕量铁的荧光猝灭分析法,该体系的激发波长λｅｘ＝４３５．８ｎｍ,发射波长λｅｍ＝５４０ｎｍ。铁的浓度在２～１００ｕｇ／Ｌ范围内有良好的线性关系;方法的检出限为０．４１ｕｇ／Ｌ。该方法     

三卤代锡钨（钼）双核化合物的制备和晶体结构

ＣｐＭ（ＣＯ）３ＳｎＰｈ３和ＣｐＭ（ｃｏ）３ｓＮｐＨ２ｘ（Ｃｐ＝Ｃ５Ｈ４ＣＨ３，Ｃ５Ｈ４ＣＯＣＨ３；Ｍ＝Ｍｏ，Ｗ；Ｘ＝Ｃｌ，Ｂｒ）与ＨＣｌ或ＨＢｒ发生取代反应，得到三氯、三溴以及混合三卤代锡钨（钼）双核化合物，并经元素分析、＾１Ｈ ＮＭＲ、ＩＲ表征。化合物Ｃｌ３ＳｎＷ（ＣＯ）３Ｃ５Ｈ４ＣＯＣＨ３的晶体属单斜晶系，空间群为Ｐ２１／ｃ，ａ＝０．７６８６（３）ｎｍ，ｂ＝１．２６２２（２）ｎｍ，ｃ＝１．６     

偏最小二乘催化极谱法同时测定铂,钯,铑

应用Ｍ２７３Ａ电化学系统中的线性扫描技术，确定了０．７５ｍｏｌ／ＬＨ２ＳＯ４－１．５％ＮＨ４Ｃｌ－２．８ｍｍｏｌ／Ｌ（ＣＨ２）６Ｎ４－０．００２５％Ｎ２Ｈ４．Ｈ２ＳＯ４为偏最小二乘极谱法同时测定Ｐｔ、Ｐｄ、Ｒｈ的最佳极谱体系。Ｐｔ、Ｐｄ、Ｒｈ的线性范围为３．２ｍｇ／Ｌ、０－１５．０ｍｇ／Ｌ和０－１．０ｍｇ／Ｌ。模拟样品及实际样品的回收率在９０．３－１０７．７％之间。     

桑色素荧光光度法测定二氯化双(丁氧羰乙基)锡

在ｐＨ３．０的ＨＡｃ－ＮａＡｃ缓冲溶液中和有Ｔｒｉｔｏｎ Ｘ－１００存在下,二氯化双（丁氧羰乙基）锡（简写为Ｒ２ＳｎＣｌ２）与桑色素形成１：１的荧光络合物。络合物的激发波长和发射波长分别为４４３．２ｎｍ和５１４。４ｎｍ。Ｒ２ＳｎＣｌ２中的Ｓｎ浓度在０￣３．０ｍｇ／Ｌ范围内,与络合物荧光强度呈线性关系。方法检出限为７．８１μｇ／Ｌ Ｓｎ,用于ＰＶＣ中间产品和污水中Ｒ２ＳｎＣｌ２的测定,结果满意,相对     

基于四氧杂四烯衍生物荧光增强的苯酚传感器

苯酚对固定在增塑的聚氯乙烯（ＰＶＣ）敏感膜中的２，２，７，７，１２，１２，１７，１７－八甲基－２１，２２，２３，２４－四氧杂四烯（ＴＯＥ）有可逆荧光增强作用，据此研制了测定水溶液中苯酚含量的荧光化学传感器。该敏感膜最佳组成为：５０ｍｇ ＰＶＣ、１００ｍｇ癸二酸二异辛脂（ＤＯＳ）、１．５ ｍｇ ＴＯＥ。该传感器在ｐＨ７．４的 Ｔｒｉｓ／ＨＣｌ缓冲溶液中，对苯酚的线性响应范围为４．４７×ｌ０~（－６）～４．１７×１０~（－３）ｍｏｌ／Ｌ；检出限为６．３０×ｌ０~（－７）ｍｏｌ／Ｌ；其响应时间小于３０ｓ。该传感器具有良好的重现性、可逆性和选择性，常见阴离子和阳离子不干扰测定。该传感器应用于工业废水中苯酚含量的测定，结果满意。     

含三正辛胺微胶囊对六价铬的富集

本文将对六价铬有效的萃取剂ＴＯＡ（三正辛胺）微胶囊化，制成填充柱型的酸性体系六价铬的富集分离装置。实验结果表明，微胶囊填充柱中每毫升ＴＯＡ对六价铬的最大萃取容量为１５８．０ｇ／ｍＬ，为纯ＴＯＡ液相萃取的４．９倍。微胶囊经碱／水洗涤后，可再生使用。     

三异辛胺-硅胶柱高效液相色谱分离与测定矿石中微量金

研究用三异辛胺（ＴＩＯＡ）－硅胶柱反相萃取色谱分离、孔雀绿萃取光度法测定金（Ⅲ）、金回收率在９６％以上。应用于矿石中微量金匠测定,结果满意,测定的最大相对误差（ｎ＝５）为６．３％。     

三正辛胺-二甲苯液膜迁移Cd(Ⅱ)的研究

研究了三正辛胺-二甲苯支撑液膜体系中搅拌速率、反萃剂、三正辛胺浓度、料液中H+浓度等因素对Cd(Ⅱ)离子迁移的影响.用大块液膜测定了不同温度时Cd(Ⅱ)离子跨膜迁移的萃取及反萃取的表观速率常数k₁和k_2.实验表明,温度升高,k₁和k₂均增大(k₁>k₂),且达到膜相最大镉离子浓度时所需的时间逐渐减少.膜相积累的镉离子浓度达最大时,Cd(Ⅱ)离子跨膜传输为稳态传输.根据Arrhenious关系得到膜相萃取反应和反萃取反应的活化能分别为23.8和19.3kJ/mol.     

萃取色层分离同位素稀释ICP-MS测定空气中费克 量钚

ICP-MS测定环境样品中超痕量^2^3^9Pu时,^2^3^8UH^+会对m/z239的测量带来干扰。测得UH^+的产生几率为4.6×10^-^5,通过三正辛胺色层分离后,对铀的去除率为10^4,可以有效地去除^2^3^8UH^+离子峰对^2^3^9Pu测定的干扰。钚的回收率为75%。同位素稀释法对^2^3^9Pu的检出限为4.5×10^-^1^5g/mL,方法的定量测定限为16×10^-^1^5g/mL。用所建立的方法测得我国某地区空气中^2^3^9Pu的浓度为4.8×10^-^1^7g/m^3。     

Post‐functionalization of perfluorophenyl ester‐functional acyclic diene metathesis polymer

The acyclic diene metathesis (ADMET) polymerization was utilized for the design of the ADMET polymer (M_n = 21,200 g/mol, M_w/M_n = 1.74) with pendant perfluorophenyl ester functionality using Grubbs first generation catalysis overnight in bulk at 80 °C. Next, a wide variety of functional groups, like benzyl, octyl, propargyl, allyl, and furfuryl was quantitatively incorporated to the ADMET polymer backbone through various amines using activated ester substitution reaction. The ADMET polymers studied in this work were characterized using ¹H, ¹³C, and ¹⁹F NMR, GPC and DSC and displayed a monomodal distribution and a rather broad polydispersity index in the range of ?1.33 to 1.90. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2593–2598     

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.