GC-MS检测萃取剂中内分泌干扰物

烷基酚作为内分泌干扰物的代表物成为环境毒理学研究的热点,多支链取代也最难生物降解.在湿法冶金工业中壬基酚作为基质改善剂在大量使用[1],而且萃取剂主要品种多含壬基酚结构单元,它们通过降解将释放出壬基酚,为此建立对壬基酚的分析检测十分有必要,尤其是西部开发更应注意新工艺后边有许多新的化学药品还未进行的环境评价,应防止类似农药666的错误再次出现.萃取剂中壬基酚的GC-MS检测方法以国内外3种主产品为对象,其分析样品编号分别为12102,12103,12104,壬基酚对照编号为12101.样品直接溶于甲醇中进样.     

Cyanex272-P507浸渍树脂协同萃取色层分离铥镱镥的研究

以Cyanex272-P507浸渍树脂采用萃取色层法对铥镱镥富集物进行了吸附和淋洗分离研究,考察了淋洗剂浓度、稀土负载量、淋洗液流速等因素对分离铥镱镥富集物的影响。结果表明,在充填的树脂粒度为0.3~0.6 mm的色层柱中,以0.2 ml.cm-2.min-1进料流速时能得到较大的吸附率;在稀土负载量为树脂重量的0.6%,淋洗液流速为1.0 ml.cm-2.min-1,温度为30℃,装柱树脂高度为400 mm(高径比为25∶1)的条件下,用1.0,1.5,2.0 mol.L-1盐酸梯度淋洗Tm,Yb,Lu,可实现铥镱镥富集物三者的完全分离。     

Cyanex272萃取分离稀土Nd(Ⅲ)-Y(Ⅲ)体系的性能研究

研究了Cyanex272从盐酸介质中萃取Nd(Ⅲ)和Y(Ⅲ)的性能,考察了平衡相酸度、振荡时间和平衡相温度对萃取的影响。结果表明,分配比在一定时间内随振荡时间、平衡相温度的增加而增加。在pH 1.54、振荡时间为20 m in时,Nd(Ⅲ)的分配比最小;而在pH 2.62、振荡时间为25 min时,Y(Ⅲ)能很好地被萃取。Nd(Ⅲ)-Y(Ⅲ)能很好地分离。     

Cyanex923对稀土元素硝酸盐的萃取

研究了Ｃｙａｎｅｘ９２３在正庚烷溶液中对１５种稀土元素硝酸盐的萃取，计算了分离系数，得出了反应机理，考察了温度对萃取平衡的影响以及萃合物的红外光谱，发现ｙａｗｎｅｘ９２３遥可能应用于从在土中分离镧以及从重稀土中分离钇。     

Cyanex 923对稀土元素硝酸盐的萃取

研究了Ｃｙａｎｅｘ９２３在正庚烷溶液中对１５种稀土元素硝酸盐的卒取，计算了分离系数，得出了反应机理，考察了温度对萃取平衡的影响以及萃合物的红外光谱，发现Ｃｙａｎｅｘ９２３有可能应用于从轻稀土中分离镧以及从重稀土中分离钇。     

以Cyanex272为载体的乳状液膜迁移和分离铅的研究

用Ｃｙａｎｅｘ２７２－Ｓｐａｎ８０－甲苯乳状液膜体系研究了铅的迁移行为，确定了铅迁移的适宜条件。在此条件下，许多常见离子如Ｃｕ＾２＋、Ｃｏ＾２＋、Ｎｉ＾２＋、Ｃｄ＾２＋等均不迁移，Ｈｇ＾２＋迁移率很低。因此Ｐｂ＾２＋能与这些离子得到快速且完全的分离。这对分析测定及三废处理等工作具有实际意义。     

Extraction of Polonium from Aqueous α-Hydroxyisobutyric Acid Solutions Using Dioctyl Sulphide, Cyanex 272, Cyanex 301 or Cyanex 302 in Toluene

A study of the extraction of polonium from aqueous solutions containing -hydroxyisobutyric acid (-HIBA) was performed with four different extractants, di-n-octyl sulphide (DOS), Cyanex 272, Cyanex 301 and Cyanex 302, dissolved in toluene. The extracted complex for DOS at low -HIBA concentrations is most likely PoO(-HIB)₂·2DOS, while at higher -HIBA concentrations there seems to be a solvating effect implicating an extracted complex of the type PoO(-HIB)₂(-HIBA)₂·2DOS. For the extraction of polonium with Cyanex 272 the results are inconclusive. The extracted complex is either PoOA₂ or PoO(-HIB)₂·2HA. For extraction with Cyanex 301 or Cyanex 302 the major extracted species does not contain any -HIBA molecules. The neutral species in both cases is PoOA₂, extracted at low extractant concentrations, while at higher extractant concentrations a complex of the type PoOA₂·xHA is extracted. The extraction of polonium increases in the order Cyanex 272 < DOS < Cyanex 302 < Cyanex 301.     

中性萃取剂协同萃取研究

前言自从发现协同萃取以来,许多作者对协同萃取进行了广泛的研究。Reddy等人应用亚砜等中性萃取剂研究了两种中性萃取剂的协同萃取(以下简称B-B类协萃),认为在第一萃取剂(S~Ⅰ)浓度([S~Ⅰ])固定时,萃取分配比D的对数值对第二萃取剂(S~Ⅱ)的浓度([S~Ⅱ])的对数值作图是直线,其斜率为S~Ⅱ的溶剂化数n,随[S~Ⅰ]的增加直线斜率逐渐下降。似乎难以用斜率分析法来确定溶剂化数目。本文研究了二-正-辛基亚砜(以下简称DOSO),TBP和TOPO从NH_4SCN溶液中萃取Ce(Ⅲ)。分析了实验数据,提出了B-B类协萃分配比D的计算公式。     

HBTMPTP与Cyanex925协同萃取Sc（Ⅲ）的研究

研究了二（２，４，４－三甲基戊基）单硫代膦酸（ＨＢＴＭＰＴＰ，ＨＬ）和支链三烷基氧化膦（Ｃｙａｎｅｘ９２５，Ｂ）的正己烷溶液在Ｈ２ＳＯ４介质中对Ｓｃ（Ⅲ）的萃取性能，结果表明，在较低酸度（ＣＨ２ＳＯ４〈０．２５ｍｏｌ／Ｌ）时存在协同效应，用斜率法确定了Ｓｃ（Ⅲ）的协萃配合物的组成为Ｓｃ（ＨＬ２）２Ｂ３（ＳＯ４）１／２，计算了协萃反应的平衡常数，讨论了协萃配合物的ＩＲ谱和ＦＡＢ－ＭＳ。     

Extraction of rare earth metals from nitrate solutions with a binary extractant based on Cyanex 272

Mechanisms for the extraction of rare earth metals with a binary extracting agent based on bis(2,4,4-trimethylpentyl)phosphinic acid with the formation of various complexes in the organic phase were proposed. The compositions of the extracted compounds were determined, and the distribution of these compounds was adequately described by calculated curves.     

景洪哥纳香生物碱的MS-MS 及GC-MS研究

蕃荔枝科哥纳香属植物常作为药用植物使用,可以治疗水肿、风湿病等.哥纳香属植物中生物碱部分包括了阿卟菲类生物碱,1-aza-anthrquinone类生物碱等.本文在利用质谱的不同方法对单体化合物进行裂解特征的研究基础上,采用GC-MS研究了生物总碱中的化学成分.     

油页岩裂解色谱质谱分析

油页岩是一种含油有机质的沉积岩,从油页岩提炼可得到页岩油,是石油的部分替代能源.随着原油储量的日趋减少,油页岩的研究及利用将会受到更多的重视.油页岩热加工得到的页岩油类似天然石油,但与石油相比,其不饱和烃和杂原子化合物含量较高,定性极差,但这些非烃化合物是宝贵的化工原料.对页岩油的烃类、非烃类杂原子化合物进行深入的研究,对页岩油的进一步加工以及非烃化合物的综合利用,都是非常必要的.     

Photodegradation and by-products identification of commercial extractant Cyanex 302

The photodegradation of the organothiophosphorous extractant Cyanex 302 and purified bis(2,4,4-trimethylpentyl)monothiophosphinic acid dissolved in toluene was carried out in photoreactor using UV–Vis light irradiation. Possible degradation products were identified with the assistance of FT-IR, LC/MS/MS and GC/MS. The catalytic influence of zinc(II), copper(II) and cobalt(II) ions and the presence of trace values of water and aqueous solutions of sulphuric acids on the photodecomposition of Cyanex 302 were studied. The results demonstrated that the presence of trace amounts of water causes mainly the degradation of bis(2,4,4-trimethylpentyl)monothiophosphinic acid with the simultaneously fourfold increase in bis(2,4,4-trimethylpentyl)phosphinic acid concentration. The shaking with aqueous solution of sulphuric acids results in the decrease in the photodegradation probably by blocking of OH radical. Metal ions also affect the degradation causing the increase in bis(2,4,4-trimethylpentyl)phosphinic acid concentration. The photodegradation was also carried out in open atmosphere under sunlight and the obtained results were compared with those obtained in a Heraeus photoreactor.     

Separation of americium from europium by biopolymer microcapsules enclosing Cyanex 301 extractant

Microcapsules enclosing an extractant with strong affinity for Am were prepared by employing a biopolymer gel as an immobilization matrix. A relatively large separation factor between Am and Eu was exhibited by the microcapsule containing of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301, HA) and alginic acid (HALG). The chromatographic separation of these metal ions was accomplished by gradient elution through the column packed with HA-HALG.     

气相色谱-质谱联用仪对二苯氰胂的分析

<禁止化学武器公约>生效后,我国就面临着处理日军在华遗留化学武器的重大任务.据公约规定,日本将负责销毁遗弃在我国的全部化学武器.我们要配合遗弃化武销毁期间的安全保卫工作,防止因泄漏和销毁不彻底,影响当地人民群众的正常生活秩序,危及人民群众的生命和财产安全.销毁场工作区是化学检测的重点部位.因此建立销毁化学武器废气监测标准分析方法是势在必行的.     

气相色谱-质谱联用法检定食品中毒中的氟乙酰胺

氟乙酰胺分子式为FCH2CONH2,是合成很早的化合物.50年代以后,被用于灭鼠与杀虫,毒力甚强,并容易引起二次中毒[1].虽然,早在1982年我国政府已严禁使用氟乙酰胺和毒鼠强为灭鼠药,但不法分子至今仍在生产和销售,引起误食和投毒.对毒鼠强的GC-MS分析已有一些报道[2,3],但是由于氟乙酰胺对热不稳定(170℃分解),在一般的非极性柱子中的保留时间很短,易与溶剂混合,一般方法很难检定.我们选用GC-MS,通过选择进样方式,色谱条件,溶剂,对氟乙酰胺进行了检定.本法比较简便,定性准确,有较高的灵敏度.     

Component analysis of the commercial metal extractant, Cyanex 302, by GC-MS.

The composition of the commercial reagent Cyanex 302 was investigated by GC-MS. Mass spectrometric studies allowed us to confirm that bis(2,4,4-trimethylpentyl)monothiophosphinic acid is the major compound and that a considerable amount of tris(2,4,4-trimethylpentyl)phosphine oxide is also present. The study also revealed that the extractant has three minor components. These were identified as bis(2,4,4-trimethylpentyl)phosphinic acid, bis(2,4,4-trimethylpentyl)phosphine oxide and bis(2,4,4-trimethylpentyl)dithiophosphinic acid. The mass spectra of these compounds are discussed and some fragmentation processes are postulated.     

应用色质联机对淫羊藿多糖结构的研究

淫羊藿多糖(Epimedium polysaccharide,EPS)能够刺激机体免疫系统,增强免疫应答功能,同时,淫羊霍多糖还有刺激骨髓DNA合成的作用.近年来对淫羊藿甙及淫羊藿总黄酮的研究较多,而对淫羊藿多糖的研究较少.用化学实验方法研究淫羊藿多糖的结构,存在时间长、实验步骤多等问题.寻找快速、准确的测试手段,对研究淫羊藿多糖的结构有着重要的意义.本文从淫羊藿茎叶中提取水溶性多糖,经甲基化后,再经色质联机(GC-MS)分析,初步确定了糖苷的键型,并用化学实验方法进行了验证.     

残留有机氯农药用GC-MS鉴定

国外对有机氯农药残留限量要求很严格.目前对残留有机氯农药的常规检验,仍多采用气相色谱-电子俘获检测器(GC-ECD)[1],被认为是检出限最低,定量准确度较高的方法.但GC-ECD定性功能不强,对基底复杂样品常给出假阳性结果.随着近年GC-MS技术的不断发展、完善,仪器的检测灵敏度也随之提高.发达国家已将GC-MS法广泛应用到日常检验中.本实验参照国外限量要求,采用GC-MS的EI-SIR和NCI技术,对应用较多机氯农药进行鉴定,有效地解决了痕量有机氯农药定性问题.