Characterization of Ce SUP 3+-tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary
Coordination complexes containing Ce(III) and tri-n-butyl phosphate (TBP) in the 1+, 2+ and 3+ charge states were generated using desorption electrospray ionization (DESI) mass spectrometry, in which the analyte solutions were supplied via a target capillary orthogonally situated with respect to the electrospray. Comparison with direct electrospray (ESI) showed that the same coordination complexes were produced in each experiment, and could be described by the general formula [Ce(NO3)m=0-2(TBP)n](3-m)+. This result indicates that DESI has utility for measuring metal speciation for metal ligand solutions where the gas-phase complexes generated by ESI have been correlated with solution speciation. Such an application would be useful for analyses where it is desirable to limit the total amount of metal being handled, or that have solvent systems that are not readily amenable to ESI. Both the direct ESI and DESI mass spectra showed similar trends with respect to the TBP:Ce ratio, viz. high values tend to favor formation of a larger fraction of the 1+ species, and the 2+ and 3+ species become relatively more important as the ratio is decreased. Within individual charge state ion envelopes, lower TBP:Ce ratios produce coordination complexes with fewer ligands, a trend also seen using both approaches. These trends again point toward strong similarity between the direct ESI and DESI analyses of the metal-ligand solutions. The DESI experiments were less sensitive for measuring the coordination complexes compared to the direct ESI experiments, by a factor of 10 - 100 depending on whether minimum detectable concentration or absolute ion abundances were considered. Nevertheless, mid-picomolar quantities of coordination complexes were measured using the target capillary, indicating that sensitivity would be sufficient for measuring species in many industrial separations processes.
- Research Organization:
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- DE-AC07-05ID14517
- OSTI ID:
- 1035214
- Report Number(s):
- INL/JOU-10-19814; TRN: US201204%%513
- Journal Information:
- Journal of Mass Spectrometry, Vol. 46, Issue 12; ISSN 1076-5174
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHARGE STATES
DESORPTION
IONIZATION
MASS SPECTRA
MASS SPECTROSCOPY
PHOSPHATES
SENSITIVITY
SOLVENTS
TARGETS
coordination complex
DESI
desorption electrospray ionization
electrospray ionization mass spectrometry
lanthanide
mass spectrometry
separations chemistry
TBP