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Self‐assembly and intra‐cluster reactions of erbium and ytterbium bis(2‐ethylhexyl)sulfosuccinates in the gas phase
Author(s) -
Indelicato Serena,
Bongiorno David,
Turco Liveri Vincenzo,
Mele Andrea,
Panzeri Walter,
Castiglione Francesca,
Ceraulo Leopoldo
Publication year - 2014
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.7045
Subject(s) - chemistry , lanthanide , mass spectrometry , electrospray ionization , tandem mass spectrometry , collision induced dissociation , fragmentation (computing) , electrospray , pulmonary surfactant , cluster (spacecraft) , ion , molecule , ion mobility spectrometry , organic chemistry , chromatography , computer science , programming language , operating system , biochemistry
RATIONALE The study of surfactant organization in vacuum allows surfactant–surfactant interaction to be unveiled in the absence of surrounding solvent molecules. Knowledge on their chemical‐physical properties may also lead to the definition of more efficient gas‐phase carriers, air‐cleaning agents and nanoreactors. In addition, the presence of lanthanide‐group ions adds unique photochemical properties to surfactants. METHODS The structural features, stability and fragmentation patterns of charged aggregates formed by lanthanide‐functionalized surfactants, ytterbium and erbium bis(2‐ethylhexyl)sulfosuccinate ((AOT) 3 Yb and (AOT) 3 Er), have been investigated by electrospray ionization mass spectrometry (ESI‐MS), tandem mass spectrometry (ESI‐MS/MS) and energy‐resolved mass spectrometry (ER‐MS). RESULTS The experimental data indicate that the self‐assembling of (AOT) 3 Yb and (AOT) 3 Er in the gas phase leads to the formation of a wide range of singly charged aggregates differing in their aggregation number, relative abundance and stability. In addition to specific effects on aggregate organization due to the presence of lanthanide ions, ER‐MS experiments show rearrangements and in‐cage reactions activated by collision, eventually including alkyl chain intra‐cluster migration. CONCLUSIONS Analysis of the experimental findings suggests that the observed chemical transformations occur within an organized supramolecular assembly rather than in a random association of components. The fragmentation pathways leading to the neutral loss of a fragment of nominal mass 534 Da, assigned as C 28 H 54 O 7 S, from some positively charged aggregates has been rationalized. Copyright © 2014 John Wiley & Sons, Ltd.