Octafunctionalized calix[4]resorcinarene-N-fenil-acetohydroxamic acid for the separation, preconcentration and transport studies of cerium(IV)

Abstract

Um novo método para extração líquido-líquido, separação e pré-concentração de cério(IV) com um derivado ácido do calix [4]resorcinareno [C4RAHA] é descrito. Cério foi extraído em pH 9 com etilacetato, e recuperado de areias monazíticas, na presença de tório, urânio, lantânio e um grande número de cátions e ânions. Cério(IV) forma um complexo colorido, amarelo, λ max 381 nm, absortividade molar de 1,06 × 10 4 L mol -1 cm -1 e obedece a lei de Beer no intervalo entre 0,4 e 15 mg mL -1 . A razão metal-ligante encontrada para cério(IV) foi de 4:1 (M:L). Estudos de transporte foram realizados em um sistema de três fases, através de uma membrana líquida contendo C4RAHA. Para medidas por ICP OES, o extrato pode ser diretamente aspirado, o que aperfeiçoa a sensibilidade em 25 vezes e os limites de estimativa são 5-150 μg L -1 de cério. O método foi aplicado para a determinação de cério em materiais geológicos de referência, areia monazítica e amostras de água de mar.A new method for liquid-liquid extraction, separation and preconcentration of cerium(IV) with a calix[4]resorcinarene acid derivative [C4RAHA] is reported. Cerium was extracted at pH 9 in ethyl acetate and recovered from monazite sands in the presence of thorium, uranium, lanthanum and large number of cations and anions. Cerium(IV) forms yellow coloured complex, λ max 381 nm, molar absorptivity 1.06 × 10 4 L mol -1 cm -1 and obeys Beer's law over the range 0.4-15 mg mL -1 . The metal ligand ratio for cerium (IV) was found to be 4:1 (M:L). Transport studies were carried out in a three phase system across a liquid membrane containing C4RAHA. For ICP OES measurements, the extract can be directly aspirated, which enhances the sensitivity 25-fold and the limits for estimation are 5-150 μg L -1 of cerium. The method was applied for the determination of cerium in standard geological samples, monazite sand and sea water samples.Keywords: cerium(IV), calix [4]resorcinarene-N-fenil-acetohydroxamic acid(C4RAHA), transport studies, spectrophotometry IntroductionThe chemistry of bowl shaped macrocyclic compounds that can complex organic and inorganic guests has been receiving significant attention in the field of supramolecular chemistry. 1 Among the different macrocyclic compounds, calix[4]resorcinarenes and calixarenes 2 have been widely employed as changeable units with a well defined structure and easy accessibility. The calixresorcinarenes are unique three-dimensional cyclic tetramer and hexamer that belong to a class of metacyclophanes in which resorcinol units are linked by methylene bridges. 3 The interest towards this class of compounds which are capable of forming host guest complexes is stimulated by the development of supramolecular chemistry which uses them for the possible creation of synthetic receptors and carriers of cations, anions and neutral molecules. 4 The host properties of calix[4]resorcinarenes continue to draw research interests due to its potential application as macrocyclic receptors, 5 as dendrimers in biological systems, 6 nano-capsule, 7 na...

Liquid - Liquid Extraction of Cerium(iv) From Salicylate Media Using N-7v-Octylaniline in Xylene as an Extractant

“…A number of extractants such as di-(-2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP) [2][3][4], cyanex 923 [5][6][7][8], lueco xylene cyanol FF [9], 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate (KSM-17) [10], N, N'-Dimethyl-N,N'-diphenylpyridine-2, 6-dicarboxyamide (DMDPhPDA) [11], N-phenylbenzo-18-crown-6-hydroxamic acid [12], 1-octyl-3-methylimidazolium hexafluorophosphate [13], high molecular weight carboxylic acids [14], N -phenyl -(1,2-methanofullerene C 60 ) 61-formohydroxamic acid [15], tri-nbutyl phosphate (TBP) [16], tridodecylamine (TDA), 1-[thenoyl- (2)]-3-3-3-trifluoroacetone (HTTA), di (2-ethylhexyl) phosphoric acid (HDEHP) and tricaprylmethylammonium chloride (TCMA) [17], calyx [4] resorcinarene-N-fenil-acetohydroxamic acid [18], have been used for the extraction and separation of Ce(IV). However, these methods have limitations such as interference of different ions, emulsion formation, co-extraction, and use of high reagent concentrations.…”

Synthesis, spectral characterization of azo dyes derived from calix[4]resorcinarene and their application in dyeing of fibers

“…Calix [4]resorcinarenes are synthesized by the acid-catalyzed cyclocondensation of resorcinol with various aliphatic or aromatic aldehydes [2][3][4][5]. They have found application as macrocyclic receptor [6], as dendrimers in biological systems [7][8][9], nano-capsule [10], nanoparticales [11,12], opticalchemosensors [13], supramolecular tectons [14][15][16], host molecules [17,18], as components in liquid crystals [19,20], photo resists [21][22][23], selective membranes [24,25], surface reforming agents [26], HPLC stationary phase [27], as ion channel mimics [28], and metal ion extraction agents [29][30][31].…”

Extraction of cerium (IV) using di-n-butylsulfoxide in chloroform from nitric acid and determination with arsenazo (III) as chromogenic Reagent

“…[3][4][5][6] The extraction chemistry of cerium has been studied and different extractants such as lueco xylene cyanol (FF), N-phenylbenzo-18-crown-6-hydroxamic acid, tri-n-butyl phosphate (TBP), resorcinarene-N-fenil-acetohydroxamic acid, di-(-2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP), cyanex 923, 2-ethylhexyl hydrogen 2-ethylhexyl phosphonate, N,N'-Dimethyl-N,N'-diphenyl-pyridine-2, 6-dicarboxyamide (DMDPhPDA), tridodecylamine (TDA), 1-[thenoyl- (2)]-3-3-3-trifluoroacetone (HTTA), di (2-ethylhexyl) phosphoric acid (HDEHP) and tricaprylmethyl-ammonium chloride (TCMA) have been used. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] In addition to this the extraction chemistry of cerium has also been explored with N-n-octylaniline, acetophenone 2,5 dihydroxy, semicarbazone, Variamine blue, 2,4, dihydroxy benzophenoe benzoic hydrazone, 2,6-dibromo-4-chloro carboxyarsenazo, 4-dimethyl amino-azo benzene-arsenic acid, pyrogallol red, dibromo-p-methyl chloro sulphanzo, propionil promazine phosphate, N-P-chlorophenyl-p-methoxy hydroxamic acid, tributylphosphine oxide (TBPO), tricaprylmethylammonium chloride, calix [IV] resorcinarene acid derivative [C 4 RAHA], butyl phosphate, 3-phenyl-4-benzoyl-5-isoxazolone (HPBI), bifunctional ionic liquids, octacarboxymethyl-C-methylcalix , organophosphorous extractants, malachite green, arsenazo (III). However, there are certain limitations associated with extraction of cerium such as interference of different ions, co-extraction, emulsion formation, use of high reagent concentrations less sensitivity and expensive back-stripping reagents.…”