Flow Injection Spectrofluorimetric Determination of Terbium (III) Based on Solubilizing its Ternary Complex in Micellar Solution

Abstract

A flow injection spectrofluorimetric method has been developed for the determination of terbium (III) based on solubilizing its ternary complex with pi valoyitrifluoroacetone (PTA) and trioctylphosphine oxide(TOPO) in micellar solution of nona (oxyethylene) dodecyl ether (BL-9EX). Accuracy and reproducibility are good up to 16 ng/ml of terbium (III) and 80 samples per hour can be analyzed. The relative standard deviation was less than 1.0 %. No interferences from 20-fold excesses of 11 rare earth ions were observed.     

Simultaneous determination of some rare-earth elements by derivative fluorimetry and use of the Kalman filter

A procedure for the simultaneous determination of dysprosium, europium, samarium and terbium by laser-induced derivative fluorimetry is described. The method is based on the use of 1 x 10(-4)M hexafluoroacetylacetone (HFA) and 2 x 10(-4)M tri-n-octylphosphine oxide (TOPO) as ligands in aqueous solution at pH 3. The first-derivative and Kalman-filter techniques were used for background correction and reduction of interference. The effects of foreign ions were investigated. The procedure is satisfactory for the simultaneous determination of these four lanthanides.     

Fluorimetric estimation of DNA content using sensitized lanthanide fluorescence

Lanthanide fluorescence enhancement on complexation with calf thymus DNA was studied in aqueous solution. The DNA sensitized and enhanced fluorescence of terbium and europium by nearly two orders of magnitude. By applying this ligand sensitized lanthanide fluorescence enhancement, DNA could be estimated at 10 ppb level. Further, effect of addition of TOPO in Triton X-100 micellar medium to Tb-DNA complex in solution was also studied. On addition of TOPO, no synergistic terbium fluorescence enhancement was observed.     

Simultaneous determination of samarium, europium and terbium with quinaldic acid and phenanthroline by synchronous derivative fluorimetry

Synchronous derivative fluorescence of samarium, europium and terbium complexes with quinaldic acid and phenanthroline was examined in aqueous solution. The composition of these complexes was determined. The maximum emission wavelengths are 645 nm, 617 nm and 545 nm for samarium, europium and terbium, respectively. Under the optimal experimental conditions, the fluorescence intensity was a linear function of concentration in the range of 10-250 ppm for samarium, 0.5-50 ppm for europium and 0.5-300 ppm for terbium. Simultaneous determination of samarium, europium and terbium was successfully carried out for samarium oxide and middle rare earth mixture. The precision of the method, expressed as relative standard deviation, is within 1.1-2.5%.     

稀土配合物的时间分辨光谱分析法研究(Ⅰ)TFA-TOPO-农乳-100体系用于测定铕和钐

本文采用自己组装的时间分辨荧光光谱测定装置,研究了铕(钐)-三氟乙酰丙酮-三正辛基膦化氧(Eu(Sm)-TFA-TOPO)在非离子表面活性剂农乳-100存在下的光谱特性、荧光衰减动力学特性和发光机理。提出了能量传递机制和第二配体TOPO在荧光发射过程中的作用,制定出TFA-TOPO-农乳-100体系测定痕量铕和钐的时间分辨荧光光谱分析方法,用于测定高纯氧化钇中的痕量铕和钐,结果令人满意。     

Selective accumulation of light or heavy rare earth elements using gram-positive bacteria

The accumulation of samarium from a solution only containing samarium by Arthrobacter nicotianae was examined. The amount of accumulated samarium was strongly affected by the concentration of samarium and pH of the solution. The accumulation of samarium by the strain was very rapid and reached equilibrium within 3 h. The accumulation of samarium-europium or europium-gadolinium from the solution containing the two metals using various actinomycetes and gram-positive bacteria was also examined. Most of the tested strains could accumulate similar amounts of samarium and europium; however, most of the tested strains could accumulate a greater amount of europium than gadolinium. Especially, the amounts of accumulated europium using gram-positive bacteria were higher than those using actinomycetes. The selective accumulations of light or heavy rare earth elements (REEs) using A. nicotianae and Streptomyces albus were also examined. The amounts of accumulated samarium and europium were higher than those of the other light REEs using both microorganisms. S. albus can accumulate greater lutetium than other REEs from a solution containing yttrium and eight heavy REEs. On the other hand, A. nicotianae can accumulate higher amounts of terbium and ytterbium than that of the other heavy REEs from the same solution. A. nicotianae can also accumulated higher amounts of Sm than other REEs from a solution containing six light REEs.     

Studies on ion transport of some rare earth elements through solvating extractants immobilised on supported liquid membrane

The studies on ion transport of terbium and dysprosium through a porous supported liquid membrane (SLM) containing TOPO (trioctyl phosphine oxide) and TBP (tributyl phosphate) as immobilised carriers have been carried out. The effect of stirring of bulk solutions on permeability coefficient has been investigated. The permeability coefficient increases with increase in pH of source phase from 0–6, and hydrogen ion concentration from 0.01 to 0.1 M of receiving solution. The dependency of permeability coefficient on the carrier concentration has been explored. The effect of ammonium thiocyanate concentration on permeability coefficient has been studied. In order to develop a method for enrichment of rare earth elements, further investigations were carried out by using a hollow fibre membrane extractor. The mechanism of ion transport of terbium and dysprosium in SLM systems has been explained.     

Spectrophotometric determination of samarium(III) with chrome azurol S in the presence of cetylpyridinium chloride

A sensitive, simple method for the determination of trace amounts of samarium by spectrophotometry is described based on the formation of the samarium-chrome azurol S (CAS) complex in micellar medium. The molar absorptivities of the complexes at pH 7.5 at 505 nm were 3.6x10(4) and 1.4x10(5) l mol(-1) cm(-1) for water media and cetylpyridinium chloride (CPC), respectively. Beer's law is obeyed from 0.05-2 mg l(-1) of samarium at 505 nm as Sm-CAS-CPC complex. Optimal conditions such as reagent amounts, and pH for the samarium determination were reported. The effects of foreign ions were also investigated. The proposed method was successfully applied to the determination of samarium contents in synthetic samples.     

Atomic absorption studies on rare earth and refractory metals

The use of atomic absorption spectroscopy for the analysis of rare-earth and refractory metals was studied. Various types of burners and fuel-oxidant mixtures were examined. The effects of organic solvents, sample solution flow rates and the use of continuous light sources on sensitivity are noted. The metals neodymium, samarium, europium, gadolinium, terbium, erbium, dysprosium, yttrium, vanadium, chromium, aluminum, and zirconium were included in this investigation.     

Synergism in the solvent extraction of samarium by thenoyltrifluoroacetone and triphenyl or trioctyl phosphine oxide mixture

Synergistic extraction of samarium with TTA(HA) and TPPO or TOPO (B) mixtures were investigated. The extracted complex was proved to have the general formula SmA₃ · 2B. A graphical determination for the formation constants of these complexes gave the values 3.9 × 10¹³ and 8.2 × 10¹⁰ for SmA₃ · 2TOPO and SmA₃ · 2TPPO in benzene, respectively.     

铽—钆—均苯四甲酸体系的共发光效应及其分析应用

本提出了以均苯四甲酸为配体的铽的荧光测定法，试验表明：在ｐＨ＝６．０－９．０的缓冲溶液中，钆离子能明显增强Ｔｂ＾３＋－均苯四甲酸二元体系的荧光强度。该体系已用于痕量铽的测定，其检出限为４×１０＾－９ｍｏｌ／Ｌ。     

激光诱导荧光光谱分析法研究 Ⅳ.钐-三氟乙酰丙酮-三正辛基膦化氧-浓乳-100的荧光特性研究及应用

采用激光诱导荧光光谱测定装置研究了Sm-三氟乙酰丙酮(TFA)-三正辛基膦化氧(TOPO)体系的激光诱导发光特性和发光机理。根据配合物体系中各组份的光谱特性和光谱能级,提出Sm-TFA-TOPO体系的能量传递机制。拟定了在农乳-100存在下,TFA-TOPO体系测定痕量钐的激光诱导荧光光谱分析新方法。不经分离,用于氧化钇和合成水样中痕量钐的测定,操作简便、快速,结果令人满意     

稀土配合物的发光机理和荧光分析特性研究(Ⅰ)——钐、铕、铽和镝配合物的发光机理

本文采用激光诱导荧光法研究了钐、铕、铽和镝配合物的化学性质、光谱特性与光谱能级间的关系,提出了稀土配合物荧光发射的能量传递模型,并导出速率方程和定态解,根据Dexter固体敏化发光理论讨论了影响荧光产率的各种因素,推导出配体三重态向稀土离子激发态进行有效能量传递的3个条件。     

Synergistic fluorescence enhancement of Tb with aromatic monocarboxylic acids and TOPO-Triton X-100: role of Triton X-100 in synergism

Fluorescence enhancement of Tb3+ has been studied, using substituted benzoic acids as ligands. These ligands enhance the fluorescence of Tb3+ by about three orders of magnitude. The enhancement is observed due to ligand sensitized fluorescence. The fluorescence of Tb3+ in these complexes is synergistically enhanced by the addition of trioctylphosphine oxide (TOPO) in Triton X-100. The synergism displayed by TOPO was observed only when Triton X-100 micellar medium was used. TOPO dissolved in SDS/DTAB micellar medium did not result in synergistic fluorescence enhancement of Tb3+. These observations are discussed in detail and the synergism displayed by TOPO is rationalized on the basis of the structure of the surfactants.     

Luminescence Determination of Europium in High-Purity Yttrium and Gadolinium Oxides

ABSTRACT

A luminescence spectrometric method was developed for the determination of ultratrace amounts of europium (down to 1×10^?10 M) in high-purity yttrium and gadolinium oxides. This is based on the enhanced luminescence of europium thenoyltrifluoroacetone (TTA)-Tri-n-octyl phosphine oxide (TOPO)-Triton X-100 in the presence of terbium. The luminescence intensity is linear with europium concentration in the range 1×10^?9 to 1×10^?6 M under the recommended conditions. The optimized procedure is successfully utilized for the determination of ultratrace amounts of europium in yttrium and gadolinum oxides.     

微波消解-电感耦合等离子体质谱(ICP-MS)法测定板栗中的矿物元素及稀土元素

为了准确测定板栗中矿物元素和稀土元素的含量水平,采用冷冻干燥方式预处理样品,选用硝酸和过氧化氢体系微波消解样品,结合电感耦合等离子体质谱技术,建立了板栗中钠(Na)、钾(K)、镁(Mg)、锰(Mn)、铁(Fe)、钒(V)、钴(Co)等19种矿物元素及镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)等15种稀土元素的同时分析测定方法。方法检出限为0.0027~0.78μg/L,相对标准偏差为1.4%~6.3%。通过国家标准物质GBW10019苹果的准确度实验验证,测定结果均在标准证书值范围内。实验结果表明,方法适用于板栗中矿物元素及稀土元素的同时测定。     

Spectrofluorometric determination of trace amounts of terbium with 4-chlorosalicylic acid, EDTA, and cetyltrimethylammonium bromide.

The quadruple complex formed by terbium with 4-chlorosalicylic acid (CSA), EDTA and cetyltrimethylammonium bromide (CTMAB) has been used for the sensitive spectrofluorometric determination of terbium in mixed rare earths. The effect of the experimental conditions on the fluorescence intensity was defined. Under the optimum conditions selected, the fluorescence intensity was linear with the terbium concentration in the range of 3.0 x 10(-8)-1.0 x 10(-5) mol/L with a detection limit of 8.0 x 10(-9) mol/L (S/N = 3). It has been satisfactory for the determination of terbium in mixed rare earths with good recovery.     

Lanthanide-centered covalently bonded hybrids through sulfide linkage: molecular assembly, physical characterization, and photoluminescence

A series of novel photoactive lanthanide (europium, terbium, dysprosium, samarium) hybrid materials with organic parts covalently bonded to inorganic parts via sulfide linkage have been assembled by the sol-gel process. The organic parts as molecular bridge are obtained from the functionalized thiosalicylic acids by five silane crosslinking reagents, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(triethoxysilyl)propylisocyanate. The intramolecular energy transfer process between lanthanide ions and the molecular bridges took place within these molecular-based hybrids and especially the quantum efficiency of europium hybrids were determined, suggesting that the hybrid material systems derived from different molecular bridges present different luminescence efficiencies.     

Simultaneous determination of benzoic acid and saccharin in soft drinks by using lanthanide-sensitized luminescence

A simple and fast approach is used for the first time to develop a time resolved lanthanide-sensitized luminescence method for the simultaneous determination of a preservative and a sweetener, namely benzoic acid (BZ) and saccharin (SC), respectively, in food samples. The method involves the formation of the corresponding ternary chelates with terbium(III) and trioctylphosphine oxide (TOPO) in the presence of Triton X-100, and the measurement of the initial rate and equilibrium signal of this system, which were obtained in 0.1 and 5 s, respectively. The dynamic ranges of the calibration graphs, obtained by using kinetic and equilibrium measurements, were 0.2-36 micrograms ml-1 and 0.15-30 micrograms ml-1, respectively, for BZ, and 3.3-24 micrograms ml-1 and 4-36 micrograms ml-1 for SC and the detection limits were 0.07 and 0.04 microgram ml-1, respectively, for BZ, and 1.1 and 1.2 micrograms ml-1, respectively, for sodium SC. The relative standard deviation ranged between 2.3 and 3.0%. Both compounds were determined simultaneously by using a system of two equations which were resolved by using the calibration data obtained individually for each analyte and by multiple linear regression. Mixtures of BZ and SC in ratios between 3:1 and 1:9 were satisfactorily resolved by using both approaches. The method was applied to the direct analysis of several soft drinks. Analytical recoveries ranged between 89.3 and 108.5%.