Issue 1, 2015

Evaluation of a membrane desolvator for LC-ICP-MS analysis of selenium and platinum species for application to peptides and proteins

Abstract

Analysis of peptides and proteins and their interactions with endogenous elements and metal-based drugs in biological systems demands highly efficient chromatographic systems with the possibility of performing gradient elution to achieve efficient separations. As the detector of choice in metal analysis, the ICP-MS, does not tolerate a high load of organic solvents, these should be removed from the chromatographic eluent prior to the entrance of the ICP-MS detector. The purpose of this study was to evaluate a membrane desolvation (MD) system (Aridus II) for its capability of removing organic solvents from the eluent prior to the ICP-MS introduction and at the same time study the influence on sensitivity and examine if the desolvator system jeopardized the inherent species independent sensitivity of ICP-MS. Selenium and platinum were used as model elements. The MD system was optimized regarding to sweep gas and nitrogen gas flow rates. Sensitivity was highly dependent on the combination of sweep gas flow and N2 addition, and the desolvator system should be optimized for each element. After optimization, 100% methanol and acetonitrile were tolerated by the ICP-MS with an eluent flow rate of 0.2 mL min−1. This opens the possibility of performing LC-ICP-MS analysis by gradient elution with 0–100% organic solvents. Sensitivities were generally increased by employment of the MD system, but the species independent sensitivity of ICP-MS was lost for selenium compounds (trimethylselenonium ion (TMSe), selenomethionine (SeMet), Se-methylselenocysteine (Se-MeSeCys), Se-methylseleno-N-acetyl-galactosamine (SeGalac), selenite and selenate). Sensitivities of the different Se compounds were highly dependent on the desolvator temperature. Different Pt compounds (inorganic Pt-salt, cisplatin and oxaliplatin) showed no species dependent behavior. Linearity was obtained for flow injection analysis of SeMet, TMSe and a selenopeptide in 50% methanol and of inorganic Pt, cisplatin and oxaliplatin in 50% acetonitrile. The optimized system was applied for gradient elution LC-ICP-MS of a cisplatin-albumin adduct and lysate and media samples from a cell uptake study of a selenopeptide.

Graphical abstract: Evaluation of a membrane desolvator for LC-ICP-MS analysis of selenium and platinum species for application to peptides and proteins

Article information

Article type
Paper
Submitted
11 Aug 2014
Accepted
31 Oct 2014
First published
31 Oct 2014

J. Anal. At. Spectrom., 2015,30, 277-284

Author version available

Evaluation of a membrane desolvator for LC-ICP-MS analysis of selenium and platinum species for application to peptides and proteins

L. H. Møller, C. S. Jensen, T. T. T. N. Nguyen, S. Stürup and B. Gammelgaard, J. Anal. At. Spectrom., 2015, 30, 277 DOI: 10.1039/C4JA00277F

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