Synthesis and solvent extraction studies of novel calixarene-based uranophiles bearing hydroxamic groups

Takeshi Nagasaki, Seiji Shinkai

Research output: Contribution to journalArticle

70 Citations (Scopus)

Abstract

Calix[n]arene-based uranophiles bearing hydroxamic groups on the lower rim (2n; n = 4 and 6) have been synthesized and the extractability (Ex%) and the selectivity towards uranyl ion (UO22+) estimated in a two-phase (water-chloroform) solvent-extraction system. Ex% for 2 4 and 26 increases from pH 2 and saturation is reached at around pH 5 where 100% extractability occurs. Since the pKa values for hydroxamic acids are 8-9, the apparent pKa shift caused by the UO22+-complexation amounts to 6-7 pK units. Extraction of UO22+ from aqueous carbonate solution established that 26 in the organic phase can compete efficiently with CO 32- ions in the aqueous phase for UO2 2+ whereas in 24 and a calix[6]arene-based uranophile bearing six carboxy groups (16) UO22+ is reextracted to the aqueous phase. The difference indicates that 26, which has the hexacoordination geometry preorganized for the binding of UO 22+, is superior to 24 as a uranophile. We also found that the selectivity of 26 is superior to 16: the Ex% values for 26 is scarcely affected by the addition of competing metal cations (except Fe3+). These results show that 26 serves as an excellent UO22+-selective extraction reagent.

Original languageEnglish
Pages (from-to)1063-1066
Number of pages4
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number7
Publication statusPublished - 1991

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Bearings (structural)
Calixarenes
Solvent extraction
Ions
Hydroxamic Acids
Carbonates
Carbon Monoxide
Chloroform
Complexation
Cations
Metals
Geometry
Water

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Synthesis and solvent extraction studies of novel calixarene-based uranophiles bearing hydroxamic groups. / Nagasaki, Takeshi; Shinkai, Seiji.

In: Journal of the Chemical Society, Perkin Transactions 2, No. 7, 1991, p. 1063-1066.

Research output: Contribution to journalArticle

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AB - Calix[n]arene-based uranophiles bearing hydroxamic groups on the lower rim (2n; n = 4 and 6) have been synthesized and the extractability (Ex%) and the selectivity towards uranyl ion (UO22+) estimated in a two-phase (water-chloroform) solvent-extraction system. Ex% for 2 4 and 26 increases from pH 2 and saturation is reached at around pH 5 where 100% extractability occurs. Since the pKa values for hydroxamic acids are 8-9, the apparent pKa shift caused by the UO22+-complexation amounts to 6-7 pK units. Extraction of UO22+ from aqueous carbonate solution established that 26 in the organic phase can compete efficiently with CO 32- ions in the aqueous phase for UO2 2+ whereas in 24 and a calix[6]arene-based uranophile bearing six carboxy groups (16) UO22+ is reextracted to the aqueous phase. The difference indicates that 26, which has the hexacoordination geometry preorganized for the binding of UO 22+, is superior to 24 as a uranophile. We also found that the selectivity of 26 is superior to 16: the Ex% values for 26 is scarcely affected by the addition of competing metal cations (except Fe3+). These results show that 26 serves as an excellent UO22+-selective extraction reagent.

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