钪—水杨醛苯甲酰腙高灵敏度荧光反应及其应用

研究了水杨醛苯甲酰腙（ＳＡＢＨ）与钪荧光反应新体系的最佳条件。在ｐＨ＝６．４乙醇／水（６．２：３．８）溶液介质中，形成络合物的组成比１：３（钪、试剂），λｅｘ／λｅｍ＝３８５ｎｍ／４５５ｎｍ，建立钪荧光分析法的线性范围为０￣１００μｇ／Ｌ；相对标准偏差１．５％；检出下限为０．０２５μｇ／Ｌ。考察了３０种共存离子的干扰情况，方法成功用于地质中样中痕量钪的测定。     

新试剂7—（2,4—二羟基—5—羧基苯偶氮）—8—羟基喹啉—5—磺酸与铝的荧？…

研究了新试剂７－（２,４－二羟基－５－羧基苯偶氮）－８－羟基喹啉－５－磺酸形成的络合物的荧光性能。在ｐＨ４．６２的ＮａＡｃ－ＨＡｃ体系中形成１：１型强荧光配合物,其λｅｘ＝５１０ｎｍ,λｅｍ＝５７２ｎｍ,铝含量在０－０．０８ｍｇ／Ｌ范围内与荧光强度呈线性关系,方法检出限为１．０４×１０＾－１０ｍｏｌ／Ｌ。     

N—羟基琥珀酰亚胺—3—吲哚乙酸酯柱前衍生高效液相色谱分离…

本文首次报道了一种新的羧酸活性酯试剂，Ｎ－羟基琥珀酰亚胺－３－吲哚乙酸酯作为柱前荧光衍生试剂，流动相为１０ｍｍｏｌ／Ｌ柠檬酸－ＮａＨＰＯ４－ｐＨ３．６的甲醇／水溶液，Ｃ１８柱，于λｅｘ／λｅｍ＝２７８ｎｍ／３５５ｎｍ处进行荧光检测高效液相色谱分离测定了谷胱甘肽，二甘肽，谷氨酸，胱氨酸，甘氨酸，当Ｓ／Ｎ＝３时，检出限为０．２至２．５ｐｍｏｌ。     

水杨醛缩—5—碘—5—氨基喹啉的合成及荧光光度法测定煤渣中痕量镓的研究

报道了新息夫碱试剂水杨醛缩－５－碘－５－氨基喹啉（ＳＡＩＡＱ）的合成。用元素分析、红外光谱法确定了其结构。测定了ＳＡＩＡＱ的酸度常数Ｋａ１＝２．４０×１０＾－４，Ｋａ２＝２．９８×１０＾－９。在ｐＨ３．５０￣５．００范围内ＳＡＩＡＱ与Ｇａ＾３＋形成稳定的荧光螯合物，且在λｅｘ／λｅｍ＝４２８ｎｍ／５４０ｎｍ产生强烈荧光。其荧光强度与Ｇａ＾３＋的浓度在１．５μｇ／Ｌ￣２６０μｇ／Ｌ范围内呈线性关系，     

吡哆醛异烟酰胺与铝荧光反应的研究

合成了新荧光试剂吡哆醛异烟酰腙，研究了该试剂与铝的荧光反应体系，反应在ｐＨ４．８５水溶液介质中进行，络合物的荧光激发波长λｅｘ＝４１０ｎｍ；发射波长λｅｍ＝４５３ｎｍ。铝量在０－０．８μｇ／１０ｍｌ范围内，荧光强度与铝量成正比，方法灵敏度为０．２ｎｇ／ｍｌ。络合物组成比１：１。实验了２８种离子存在下的干扰情况。方法直接应用于化学试剂中痕量铝的测定，精密度好，结果令人满意。     

新试剂5－氟偶氮胂Ⅰ荧光法测定铝的研究

本文报道了新试剂５－氟偶氮胂Ⅰ（５－ＦＡｓＡ－Ⅰ）的合成方法，研究了荧光光度法测定铝的反应条件。Ａｌ（Ⅲ）与试剂在ｐＨ５．６０ＨＡｃ－ＮａＡｃ缓冲介质中形成１＋１红色配合物并呈现荧光，λｅｘ／λｅｍ＝３４８．６／３９１．４ｎｍ，线性范围为０～０．２μｇ／ｍＬ，检测限为３．０ｎｇ／ｍＬ。用于分析茶叶样品中的铝，结果满意。     

新荧光试剂3—对甲苯基—5—（2‘—羧基苯偶氮）绕丹宁的合成及荧光光度…

本文报道了新荧光试剂３－对甲苯基－５－（２＇－羧基苯偶氮）绕丹宁的合成。用元素分析、红外光谱、核磁共振氢谱和质谱确证了其结构，研究了其荧光性质。在ＰＨ５．６时，该试剂与Ｃｕ＾２＋形成稳定的荧光螯合物，且在λｅｘ／λｅｍ＝３０５ｎｍ／４０５ｎｍ产生强烈荧光。     

荧光试剂3—苯基—5—苯甲酰基—2—硫代—4—噻唑啉酮的合成及应用

本文报道了荧光试剂３－苯基－５－苯甲酰基－２－硫代－４－噻唑啉酮（ＰＢＴＴ）的合成。产品经柱层析提纯，用元素分析、ＩＲ、＾１ＨＮＭＲ和ＭＳ确证了其结构；研究了它的荧光性质。在ＰＨ５．６时，与痕量铥（Ⅲ）形成络合物，且在λｅｘ／λｅｍ＝３０５ｎｍ／４０５ｎｍ产生强荧光，测定了人工合成样品的铥，结果比较满意。     

新荧光试剂—3—邻甲苯基—5—（2‘—羧基苯偶氮）绕丹宁的荧光性质研究

本文报道新荧光试剂－３－邻甲苯基－５－（２’－羧基苯偶氮）绕丹宁（３ＯＭＲＡＣＰ）的荧光特性，建立了荧光分析测定铜的方法，在ｐＨ５．６时，３ＯＭＲＡＣＰ与铜（Ⅱ）形成螯合物，并在λｅｘ／λｅｍ＝３０８ｎｍ／４０５ｎｍ产生强烈荧光，其荧光强度与铜（Ⅱ）的浓度在０．１～４．０×１０＾－２μｇ／ｇ范围内呈线性关系，检测限达５×１０＾－４μｇ／ｇ。测定了人发中的痕量铜，结果满意。     

水杨醛缩-5-碘-8-氨基喹啉的合成及荧光光度法测定煤渣中痕量镓的研究

报道了新息夫碱试剂水杨醛缩－５－碘－８－氨基喹啉（ＳＡＩＡＱ）的合成。用元素分析、红外光谱法确定了其结构。测定了ＳＡＩＡＱ的酸度常数Ｋａ１＝２．４０×１０－４，Ｋａ２＝２．９８×１０－９。在ｐＨ３．５０～５．００范围内ＳＡＩＡＱ与Ｇａ３＋形成稳定的荧光螯合物，且在λｅｘ／λｅｍ＝４２８ｎｍ／５４０ｎｍ产生强烈荧光。其荧光强度与Ｇａ３＋的浓度在１．５μｇ／Ｌ～２６０μｇ／Ｌ范围内呈线性关系，检出限１．５μｇ／Ｌ，考察了共存离子的影响，选择性高。已应用于煤渣中痕量镓的分析。     

Elemental analysis of geological samples by cyclic activation using a 14 MeV neutron generator and applying flux corrections

The solvent extraction of the rare earth elements, yttrium and scandium with trioctylphosphine oxide in the presence of strong complexing and various salting-out agents has been studied. As a result, a technique was developed for the extractionchromatography recovery of the rare earth elements and yttrium with simultaneous purification practically from all the elements, including scandium, usually present in the mineral samples.     

铈(Ⅲ)-三乙四胺六乙酸的配合物及其应用于铈的导数分光光度测定

多氨基多羧酸可与稀土离子生成稳定的配合物,EDTA、二乙三胺五乙酸(DTPA)和四乙五胺七乙酸(TPHA)曾用于测定某些单一稀土,但铈(Ⅲ)的测定尚未见报道.本文研究了三乙四胺六乙酸(TTHA)与铈(Ⅲ)的配合物在紫外区的吸收光谱,用导数分光光度法选择测定了混合稀土氧化物中铈的含量。     

Determination of trace scandium by ion-exchanger phase spectrophotometry withp-nitrochlorophosphonazo

Ion-exchanger phase Spectrophotometry withp-nitrochlorophosphonazo (CPApN) has been developed for the determination of scandium. The linear range is 1–8 g of scandium in 50 ml of solution, using 0.8 g of resin, with an apparent molar absorptivity of 2.76 × 10⁵ 1 mol^–1 cm^–1. Aluminum and rare earth elements in reasonable amounts do not interfere. The method has been applied successfully to the determination of scandium in alloys, with relative standard deviations of 2–4%.     

钪-铬天青S-阳离子表面活性剂的显色反应及有机溶剂化效应的研究

本文系统地研究了八种有机溶剂对钪(Ⅲ)-铬天青S-长链季铵盐多元络合物显色反应的溶剂化效应。结果表明不加有机溶剂时,Sc-CAS-OtTAB络合物的摩尔吸光系数为1.4×10⁵升/摩尔·厘米,当适量有机溶剂如甲醇或二甲基甲酰胺存在时,该体系的摩尔吸光系数可提高到3.2×10⁵升/摩尔·厘米。拟定了可以用于直接测定烯土氧化物和镧钪铁氧体中微量钪的分光光度法。测定了钪多元络合物的组成及溶剂化数,探讨了溶剂化效应的机理。     

稀土离子特性与稀土功能材料研究进展

稀土元素是一个包含了由钪、钇与镧系共17种元素的系列统称,它们既具有本质上的物理化学相似性,也具有各自独特和多样的电子结构。 从化学水平上讲,稀土离子的特性决定了稀土永磁、磁致冷、超导、热释电、光学制冷、非线性光学、催化等高新技术应用的本质;从材料水平上讲,稀土功能材料是实现这些技术应用的基础。 从科技发展要求来讲,稀土功能材料的研发是实现稀土资源高质量发展的最重要途径。 本文从稀土离子特性出发,利用轨道杂化模型构建稀土离子与稀土功能材料之间的基本关系,总结了近年来不同应用领域中稀土离子在稀土功能材料的组成设计与性能优化方面的研究进展。     

The thermal decomposition of the 2-methyl-8-quinolinol (8-hydroxyquinaldine) chelates of scandium,thorium, uranium (VI) and the rare earth elements

The thermal decomposition of the 2-methyl-8-quinolinol (8-hydroxyquinaldine) chelates of scandium, thorium, uranium(VI), yttrium and the rare earth elements was studied on the thermobalance. It was found that the scandium and uraniurn(VI) chelates can lose the extra molecule of solvation by thermal decomposition. The thorium chelate was found to be the most stable of all the chelates studied. The temperature limits for the chelates and the minimum oxide level temperatures are given.     

Determination of yttrium, scandium and other rare earth elements in uranium-rich geological materials by ICP-AES

A rapid method is described for the determination of yttrium, scandium, and other rare earth elements (REEs) in uranium-rich geological samples (containing more than 0.1% U) and in pitch blende type of samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) after separation of uranium by selective precipitation of the analytes as hydroxides using H(2)O(2)/NaOH in the presence of iron as carrier. Uranium goes into solution as soluble peruranate complex. The precipitated rare earth hydroxides (including Y and Sc) are filtered and dissolved in hydrochloric acid prior to their aspiration into plasma for their individual estimation after selecting interference free REE emission lines. The method has also been applied to some international reference standards like SY-2 and SY-3 (by doping a known amount of uranium) along with one in-house pitch blende sample and the REE values were found to be in agreement with the most usable values, offering an R.S.D. of 1-8.8% for all the REEs', Y and Sc. The method compared well, with the well- established cation exchange separation procedure.     

Simultaneous spectrophotometric determination of thorium and rare earth metals with pyrimidine azo dyes and cetylpyridinium chloride

Thorium and rare earth elements (REE) react with 5-(2',4'-dimethylphenylazo)6-hydroxypyrimidine-2,4-dione (I) and 5-(4'-nitro-2',6'-dichlorophenylazo)6-hydroxypyrimidine-2,4-dione (II) in the absence of cetylpyridinium chloride (CPC) to form red complexes. The molar absorptivity and Sandell sensitivity were calculated in absence of CPC. In its presence, REE - complexes are not formed due to miceller masking, whereas Th(4+) has a sensitive reaction with the studied reagents I and II, with enhancement of the color intensity of the complex. Most of the foreign ions are tolerated in considerable amounts; 150-2400-fold amounts of rare earth do not interfere with the determination of thorium. The optimum experimental conditions of the complex formation reactions and the compositions of thorium complexes are described. A simple method is proposed for simultaneous determination of thorium and rare earth element without previous separation.     

Extraction of rare earth elements with 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene with the use of 1,1,7-trihydrododecafluoroheptanol as a solvent

Extraction of rare earth elements from nitric acid solutions in a 1,1,7-trihydrododecafluoroheptanol-water system with the use of phosphoryl-containing podand 1-(diphenylphosphorylmethoxy)-2-diphenylphosphoryl-4-ethylbenzene (L) was studied. The content of metals in organic phase was shown to be negligible at nitric acid concentration lower 1 mol/L. Distribution ratio sharply increases with nitric acid concentration from 1 mol/L and reaches 5.5 for the yttrium subgroup elements at HNO₃ concentration of 6 mol/L. The rare earth elements of the yttrium subgroup were found to be extracted much better than the rare earth elements of the cerium subgroup under the same conditions, the distribution ratios in both subgroups smoothly rise with atomic number of element. It was shown using the shift of extraction equilibrium that the M: L ratio in extracted complexes is 1: 2 irrespective of the nature of rare earth element. The structure of complex {Yb[η²-(O,O′)-L]₂(η²-O₂NO)₂}(O₂NOHNO₃), whose single crystals were isolated from extraction solution, was established by X-ray diffraction study. The system can be used for the isolation and separation of rare earth elements.     

稀土环己烷酸配合物合成及振动光谱研究

The solid state complexes of trivalent lanthanid, yttrium and scandium with cyclohexane carboxylic acid have been isolated and characterized by IR and Raman spectroscopy. It was found that there are only chelated carboxylate groups in the scandium complex and that there are the chelated, bridged and chelate-bridged carboxylate groups in other rare earth complexes. The former is a mononuclear complex and the latter is a polynuclear polymer. The RE—O coordinate bonds possess the characters of convalent ionic bond.