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 lanthanidefunctionalized surfactants, ytterbium and erbium bis(2-ethylhexyl)sulfosuccinate ((AOT)3Yb and (AOT)3Er), 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)3Yb and (AOT)3Er 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 intracluster 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 C28H54O7S, from some positively charged aggregates has been rationalized.

Self-assembly and intra-cluster reactions of erbium and ytterbium bis(2-ethylhexyl)sulfosuccinates in the gas phase

MELE, ANDREA;CASTIGLIONE, FRANCA;
2014-01-01

Abstract

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 lanthanidefunctionalized surfactants, ytterbium and erbium bis(2-ethylhexyl)sulfosuccinate ((AOT)3Yb and (AOT)3Er), 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)3Yb and (AOT)3Er 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 intracluster 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 C28H54O7S, from some positively charged aggregates has been rationalized.
2014
File in questo prodotto:
File Dimensione Formato  
143_RapidCommMS2014-28_2523_2530.pdf

Accesso riservato

: Post-Print (DRAFT o Author’s Accepted Manuscript-AAM)
Dimensione 1.17 MB
Formato Adobe PDF
1.17 MB Adobe PDF   Visualizza/Apri
Self-assembly and intra-cluster reactions of erbium and ytterbium_11311-865140_Mele.pdf

accesso aperto

: Post-Print (DRAFT o Author’s Accepted Manuscript-AAM)
Dimensione 1.04 MB
Formato Adobe PDF
1.04 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/865140
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 3
  • ???jsp.display-item.citation.isi??? 3
social impact