Synthesis and Ion-Binding Affinities of Calix[4]arenes Immobilized on Cross-Linked Polystyrene

Abstract

Calix[4]arene and its diphosphorylated derivative have been immobilized onto cross-linked polystyrene beads through an etherification reaction. The supported calixarene complexes 96.7% Cs(I) from a 10-4 N solution in 1 M NaOH. Poly(hydroxystyrene) complexes 35.6% Cs(I) from the same solution. Immobilization of the calixarene onto a polymer support thus does not affect its inherently high affinity for cesium ions. Substituting two of the three remaining hydroxyl groups on the calixarene with diethoxyphosphoryl moieties allows for quantitative complexation of Fe(III) and Pb(II) from 0.01 M nitric acid solutions. The unsubstituted calixarene complexes 6.00% Fe(III) and 7.36% Pb(II) while diethoxyphosphoryl-substituted poly(hydroxystyrene) complexes 10.0% Fe(III) and 3.76% Pb(II). The calixarene therefore acts as a platform on which ligands can be immobilized in close enough proximity to permit cooperative binding of metal ions.

Coordination chemistry of calix[4]arene derivatives with lower rim functionalisation and their applications

“…Alexandratos and Natesan immobilised calix [4]arene and its diphosphorylated derivatives on cross-linked polystyrene and examined their ion-binding affinities [295]. The supported calixarene (R = H, 367) complexed Cs(I) from a 10 −4 M NaOH solution while the diphosphorylated derivatives complexed both Fe(III) and Pb(II) metal ions (Fig.…”

Potentiometric Response Characteristics of Membrane-BasedCs+-Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

“…One concern that is associated with this approach is the impact that immobilization will have on the selectivity of the ionophore. Extraction experiments using a microsphere-immobilized Cs + -selective calix [4]arene have indicated that ionophore selectivity is indeed retained [15]; however, this behavior has not been confirmed for ISE applications.…”

“…One approach for immobilizing ion-selective ligands that is becoming increasingly more popular for chromatographic separations, but has yet to be studied for its applicability in ISEs, is grafting the ionophore onto cross-linked polymeric microspheres [15][16][17]. One concern that is associated with this approach is the impact that immobilization will have on the selectivity of the ionophore.…”

Synthesis and Characterization of Partially Substituted at Lower Rim Phosphorus Containing Calix(4)arenes

“…It is therefore of particular interest to synthesize new phosphorus containing calixarenes, partially substituted at lower rim, aiming at their potential reactivity as co-monomers in polymerization [23,24]. In this article we report the synthesis and characterization of calix (4)arenes partially substituted at the lower rim and bearing mainly a phosphine oxide moiety.…”