Upper-rim CMPO-substituted calix[6]- and calix[8]arene extractants for the An³⁺/Ln³⁺separation from radioactive waste

Abstract

Two new ligands (1 and 2) for actinide/lanthanide separation derived from calix[6]- and calix[8]arenes functionalised at the upper rim with six or eight CMPO binding units were synthesised. These ligands, having a methoxy group at the lower rim, are conformationally mobile in solution at room temperature. Extraction data from water to a NPHE/n-octanol (90/10) solution of ligands 1 and 2, in the presence of bromo-cosan as synergist, show that these derivatives are less efficient and selective than the previously reported homologues derived from calix[4]arenes or from the lower rim CMPO calix[6]- and calix[8]arenes, especially at high nitric acid concentrations. However, although compound 1 and 2 do not appear promising for the actinide/lanthanide separation from high acidity radioactive waste, the results obtained in this work disclose some important structural results which can be useful for the design of new efficient and selective polytopic ligands

Radiochemistry

“…Ion-beam cross-sections have been measured 13 for the reactions [ 209 Bi( 50 Ti,n) 258 Db], [ 208 Pb( 51 V,xn) 259Àx Db] and [ 74 Se( 18 O,p + 3n) 88g Nb]. For proton beams crosssections have been determined for reactions with both cadmium 14 and silver, 15 leading to a range of indium isotopes in the first case and cadmium as well as silver in the second; similar data have been collected 16 for deuteron bombardment of lead (isotopes of bismuth and thallium result).…”

“…The possibilities for variation are legion especially when such systems are joined with carboranes and transition metal ions. The separation of trivalent europium, americium and curium cations has been studied using a range of tripodal CMPO ligands 206 and CMPO-calix [4]arenes, 207 CMPO-calix[6 or 8]arenes 208 proposed as extractants in the separation of trivalent lanthanides and actinides from radioactive waste. Ligands derived from p-(1-adamantyl)thiacalix [4]arene and chlorinated cobalt dicarbollide have been successfully used 209 to extract monovalent caesium-137, divalent strontium-85 and trivalent europium-152 from dilute nitric acid solutions.…”

Novel Methodology for the Synthesis of p-tert-Butylcalix[8]arene

“…Calix [8]arenes are the cyclic-oligomers of phenolic array possessing numerous application in recognition 1,2 , catalysis 3 , DNA replications 4 etc. Due to their potential applications in various fields [1][2][3][4][5] , it is a desirable to develop a simple and better approach to synthesize.…”

“…Due to their potential applications in various fields [1][2][3][4][5] , it is a desirable to develop a simple and better approach to synthesize. Gutsche et al, reported p-tert-butylcalix [8]arene synthesized from p-tert-butylphenol and formaldehyde using sodium hydroxide as base in xylene 6 .…”