Molecular octopus: octa functionalized calix[4]resorcinarene-hydroxamic acid [C4RAHA] for selective extraction, separation and preconcentration of U(VI)

A solvent extraction separation of uranium, in the presence of thorium, cerium and lanthanides with a new calix[4]resorcinarene bearing eight hydroxamic acid groups (C4RAHA) is described. Quantitative extraction of uranium is possible in ethyl acetate solution of C4RAHA at pH 8.0. The lambda(max) and molar absorptivity (varepsilon) for uranium is 356nm and 8352Lmol(-1)cm(-1). The Binding ratio of uranium with C4RAHA as evaluated by Job's method is 4:1. The system obeys Beer's law over the range 0.075-6.0mugml(-1) of uranium with Sandell sensitivity 0.0284mugcm(-2). A preconcentration factor of 142 was achieved by directly aspirating the extract for GF-AAS measurements. The two-phase stability constant evaluated at 25 degrees C for uranium is 15.91. The complexation is characterized by favorable enthalpy and entropy changes. A liquid membrane transport study of uranium was carried out from source to the receiving phase under controlled conditions and a mechanism of transport is proposed. Uranium has been determined in standard and environmental samples.     

Solid-phase extractive preconcentration and separation of lanthanum(III) and cerium(III) using a polymer-supported chelating calix [4] arene resin

In the present paper, solid-phase extractive preconcentration and separation of lanthanum(III) and cerium(III) using calix[4]arene-o-vanillinsemicarbazone immobilized on a polymeric matrix, a Merrifield peptide resin, is proposed. The diamino derivative of calix[4]arene was first diazotized and coupled with o-vanillinsemicarbazone to obtain a new “upper-rim” functionalized calix[4]arene-o-vanillinsemicarbazone. It was then covalently linked to the Merrifield peptide resin and characterized by FT-IR and elemental analysis. Quantitative studies were carried out by spectrophotometry and ICP-AES with a relative standard deviation of 1.7%. Various physicochemical parameters like pH, concentration of eluting agents, flow rate, total sorption capacity, metal-ligand stoichiometry, exchange kinetics, preconcentration factor, distribution coefficient, breakthrough capacity, resin stability, and effect of electrolytes and associated metal ions have been studied. The uptake and stripping of these metal ions on the resin was fast, indicating a better accessibility of La(III) and Ce(III) towards the chelating sites. Detection limits corresponded to three times the standard deviation of the blank (3σ_B) and amounted to 3.05 and 6.86 μg/L, along with preconcentration factors of 153 and 133 for La(III) and Ce(III), respectively. The robustness of the procedure is demonstrated by the recoveries obtained (>97.5%) for La(III) and Ce(III) in the presence of several cations and anions. The proposed method was satisfactorily applied to the separation of La(III) and Ce(III) from each other and also from U(VI) and Th(IV) by sequential acidic elution and varying pH. The validity of the method was tested by analyzing these metal ions in monazite sand and standard geological materials. The text was submitted by the authors in English.     

Synthesis of natural triisopentenylated flavanone, euchrenone a2

Euchrenone a₂ (7) isolated from the roots ofEuchresta japonica has been synthesised from 3-prenylphloroacetophenone (1) by other workers. We carried out its cyclodehydrogenation with dichloro dicyano quinone (DDQ) to obtain 6-acetyl-5,7-dihydroxy-2,2-dimethylchromene (2) which was ethoxymethylated in the 7-position to give 6-acetyl-7-ethoxymethoxy-5-hydroxychromene (3). Chalcone condensation of3 and 4-ethoxymethoxy-3-C-prenylbenzaldehyde (4) gave 4,6′-bisethoxymethoxy-2′-hydroxy-6″, 6″-dimethyl-3-C-prenylpyrano (2″, 3″–4,3) chalcone (5) which cyclised with methanolic sodium acetate to give protected 5,4′-bisethoxymethoxy-6″, 6″-dimethyl-3′-C-prenylpyrano (2″, 3″–7,8) flavanone (6). Deprotection of6 with 4% methanolic HCl yielded (7) with melting point and spectral data identical to that of the natural compound.     

Extraction of tri- and tetravalent actinides with dihexyl N,N-diethylcarbamoylmethyl phosphonate (DHDECMP) and TBP from nitric acid solutions

Extraction of trivalent (Pu³⁺, Am³⁺, actinides and Eu³⁺, a representative of lanthanides) and tetravalent (Np⁴⁺ and Pu⁴⁺) actinides has been studied with dihexyl N,N-di-ethylcarbamoylmethyl phosphonate (DHDECMP) in combination with TBP in benzene from 2M nitric acid. The stoichiometries of the species extracted were found to be M(NO₃)₃·(3–n) TBP·n DHDECMP (for trivalent ions) and M(NO₃)₄·(2–n) TBP·n DHDECMP (for tetravalent ions) by the slope ratio method. The extraction constants evaluated (from the distribution data) indicate that for tetravalent ions (with solvation number two) the extraction constant increases when TBP (Kh=0.17) molecules are successively replaced by more basic DHDECMP (Kh=0.34) molecules. However, for trivalent ions (with solvation number three) when TBP molecules are totally replaced by DHDECMP molecules stereochemical factors appear and instead of increase, a substantial decrease in extraction constants is observed for Eu³⁺ and Am³⁺, a lesser decrease being observed for Pu³⁺ (larger ion).