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UV-Vis and ESI MS/MS Study of Ester and Amide Derivatives of Calix[4]arene and Their Lanthanide Complexes (CROSBI ID 670947)

Prilog sa skupa u zborniku | sažetak izlaganja sa skupa

Tranfić Bakić, Marina ; Espinosa, Mariela Soledad ; Klarić, David ; Frkanec, Leo ; Babay, Paola Alejandra ; Galić, Nives UV-Vis and ESI MS/MS Study of Ester and Amide Derivatives of Calix[4]arene and Their Lanthanide Complexes // II. simpozij supramolekulske kemije : Knjiga sažetaka / Frkanec, Leo ; Namjesnik, Danijel ; Tomišić, Vladislav (ur.). Zagreb: Institut Ruđer Bošković, 2018. str. 17-17

Podaci o odgovornosti

Tranfić Bakić, Marina ; Espinosa, Mariela Soledad ; Klarić, David ; Frkanec, Leo ; Babay, Paola Alejandra ; Galić, Nives

engleski

UV-Vis and ESI MS/MS Study of Ester and Amide Derivatives of Calix[4]arene and Their Lanthanide Complexes

In the management of nuclear waste, the intra- and inter group separation of lanthanide and actinide families of elements plays an important role.1 Actinides, long-lived radionuclides, are among the most hazardous components of high level liquid waste (HLLW). Their recovery should significantly enhance the environmental safety and the efficiency of the nuclear fuel cycle.2 Some decades ago, in the idea of using calixarenes for the selective extraction of radio-nuclides like 99Tc and 135Cs from HLLW was introduced, 1, 3 and some phosphorylated calixarene derivatives were proven to be good extractants for such separation in the frame of nuclear reprocessing research.4, 5 On the other hand, to be incinerated to a gaseous product after utilization and not giving rise to the increase of secondary solid waste, the ideal extractant should only consist of C, H, O, and N atoms.6 Therefore, in this work, we present UV- Vis spectroscopic and mass spectrometric investigations of interesting alternatives in the search of an ideal extractant to be used in nuclear waste partitioning, namely ester (1, 5, 11, 17, 23-tetra-tert-butyl-25, 26, 27, 28- tetrakis-[(eth-oxycarbonyl)methoxy]- calix[4]arene) and secondary amide (2, 5, 11, 17, 23- tetra-tert-butyl-25, 26, 27, 28- tetrakis(N- ethyl-carbamoylmethoxy)- calix[4]arene) and tertiary amide (3, 5, 11, 17, 23-tetra-tert- butyl-25, 26, 27, 28- tetrakis(N-ethyl-N-methyl- carbamoylmethoxy)calix[4]arene) derivatives of calix[4]arenes, as well as their coordination properties towards selected lanthanide cations (La3+, Eu3+, Yb3+). No complexation was observed with ester derivative, while amide derivatives formed 1:1 complexes and bound lanthanide cations very efficiently (lgKLa2 = 5.1 ; lgKEu2 ≥ 6 ; lgKYb2 ≥ 6 ; lgKLa3 ≥ 6 ; lgKEu3 ≥ 6 ; lgKYb3 ≥ 6). The ligands and complexes were also analyzed by ESI MS and MS/MS spectrometry. Both inductive cleavage and proton rearrangement fragmentation reactions were observed. Corresponding fragmentation pathways were proposed. The results obtained by MS analysis were in accordance with those obtained by spectrophotometric titrations.

calixarenes, lanthanides, complexation, spectrophotomery, mass spectrometry

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Podaci o prilogu

17-17.

2018.

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objavljeno

978-953-7941-26-0

Podaci o matičnoj publikaciji

II. simpozij supramolekulske kemije : Knjiga sažetaka

Frkanec, Leo ; Namjesnik, Danijel ; Tomišić, Vladislav

Zagreb: Institut Ruđer Bošković

Podaci o skupu

2. simpozij supramolekulske kemije

poster

12.12.2018-12.12.2018

Zagreb, Hrvatska

Povezanost rada

Kemija