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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 225, Issue 9-10


Characterization of Rhodamine 6G Release in Electrospray Ionization by Means of Spatially Resolved Fluorescence Spectroscopy

Daniel Riebe / Martin Zühlke / Karl Zenichowski / Toralf Beitz / Carsten Dosche / Hans-Gerd Löhmannsröben
Published Online: 2011-10-06 | DOI: https://doi.org/10.1524/zpch.2011.0149


In the present work, the density distribution of rhodamine 6G ions (R6G) in the gas phase and the droplets of an electrospray plume was studied by spatial and spectral imaging. The intention is to contribute to the fundamental understanding of the release mechanism of gaseous R6G in the electrospray ionization (ESI) process. Furthermore, the influence of ESI-parameters on the release efficiency of R6G, e.g. solvent flow, R6G and salt concentration were examined via direct fluorescence imaging of R6G. A solvent-shift of the fluorescence maximum, λmax = 555 nm in methanolic solution and λmax = 505 nm in gas phase, allows the discrimination between solvated and gaseous R6G. Two experimental setups were used for our measurements. In the first experiment, the R6G fluorescence and the light scattered from the spray plume were imaged in two spatial dimensions using a tunable wavelength fil ter. The second experiment was designed for obtaining 1-dimensional spatially resolved emission spectra of the spray. Here, the intensity distribution of solvated and gaseous R6G as well as scattered light (λ=355 nm) were measured simultaneously.

The results show the distribution of gaseous R6G in the plane, orthogonal to the ESI capillary, decreasing slightly towards the spray center and showing maxima at the cone margins. The distribution of gaseous R6G confirms the preferred release of gaseous ions from nano-droplets, indicating the ion evaporation model (IEM) to be the dominating release mechanism. Up to now, only a few fluorescence spectra of ionic compounds in the gas phase were published because the measurement of emission spectra of mass-selected ions in an ion trap is experimentally challenging. The fluorescence spectrum of gaseous lucigenin at atmospheric pressure is reported for the first time. This spectrum of lucigenin in the gas phase exhibits a blue shift of about Δλ=10 nm in comparison to the corresponding spectrum in methanol.

Keywords: Fluorescence; Electrospray Ionization; Rhodamine 6G; Gaseous ions; Lucigenin

About the article

* Correspondence address: Universität Potsdam, Physikalische Chemie, Karl-Liebknecht-Str. 24-25, Haus 25, 14476 Potsdam-Golm,

Published Online: 2011-10-06

Published in Print: 2011-10-01

Citation Information: Zeitschrift für Physikalische Chemie, Volume 225, Issue 9-10, Pages 1055–1072, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1524/zpch.2011.0149.

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