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High‐performance liquid chromatography with electrospray ionisation mass spectrometry and diode array detection in the identification and quantification of the degradation products of calix[4]arene crown‐6 under radiolysis
Author(s) -
Lamouroux C.,
Aychet N.,
Lelièvre A.,
Jankowski C. K.,
Moulin C.
Publication year - 2004
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.1513
Subject(s) - chemistry , radiolysis , mass spectrometry , nitric acid , electrospray , electrospray ionization , degradation (telecommunications) , chromatography , solvent , radical , organic chemistry , telecommunications , computer science
The extraction of 135 Cs from high‐activity liquid waste, arising from reprocessing of spent nuclear fuel, can be achieved by using calix[4]arene crown‐6 compounds. The radiolytic degradation of di(n‐octyloxy)calix[4]arene crown‐6 (octMC6), in aliphatic or aromatic solvent in contact with 3 M nitric acid, was studied by high‐performance liquid chromatography directly coupled to electrospray ionisation mass spectrometry (LC/ESI‐MS). More than 50 distinct degradation products were observed, and about 30 of these were identified. These compounds can be assigned to three categories, namely, products of reactions involving radical cleavage or addition, of oxidation reactions, or of aromatic substitution reactions. The major product, corresponding to substitution by an NO 2 group, was quantified by external standard calibration using a purified synthetic sample. Despite the observation of all these degradation compounds, octMC6 appears to be remarkably stable under these drastic conditions, combining hydrolysis (HNO 3 3 M) and an extreme exposure to radiolysis (10 6 Gy). Less than 35% degradation of octMC6 was observed in aromatic solvent under these conditions. Copyright © 2004 John Wiley & Sons, Ltd.