Internal Energy Deposition in Infrared Matrix-Assisted Laser Desorption Electrospray Ionization With and Without the Use
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J. Am. Soc. Mass Spectrom. (2019) DOI: 10.1007/s13361-019-02323-2
RESEARCH ARTICLE
Internal Energy Deposition in Infrared Matrix-Assisted Laser Desorption Electrospray Ionization With and Without the Use of Ice as a Matrix Anqi Tu,1 David C. Muddiman1,2 1
FTMS Laboratory for Human Health Research, Department of Chemistry, North Carolina State University, Raleigh, NC 27695, USA 2 Molecular Education, Technology and Research Innovation Center (METRIC), North Carolina State University, Raleigh, NC 27695, USA
Abstract. The internal energy deposited into analytes during the ionization process largely influences the extent of fragmentation, thus the appearance of the resulting mass spectrum. The internal energy distributions of a series of para-substituted benzyl pyridinium cations in liquid and solid-state generated by infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) were measured using the survival yield method, of which results were subsequently compared with conventional electrospray ionization (ESI). The comparable mean internal energy values (e.g., 1.8–1.9 eV at a collision energy of 15 eV) and peak widths obtained with IR-MALDESI and ESI support that IR-MALDESI are essentially a soft ionization technique where analytes do not gain considerable internal energy during the laser-induced desorption process and/or lose energy during uptake into charged electrospray droplets. An unusual fragment ion, protonated pyridine, was only found for solid IR-MALDESI at relatively high collision energies, which is presumably resulted from direct ionization of the pre-charged analytes in form of salts. Analysis of tissue with an ice layer consistently yielded ion populations with higher internal energy than its counterpart without an ice layer, likely due to a substantially enhanced number of IR absorbers with ice. Further measurements with holo-myoglobin show that IR-MALDESI-MS retains the noncovalently bound heme-protein complexes under both native-like and denaturing conditions, while complete loss of the heme group occurred in denaturing ESI-MS, showing that the softness of IR-MALDESI is equivalent or superior to ESI for biomolecules. Keywords: Internal energy deposition, IR-MALDESI, Mass spectrometry imaging, Survival yield method, Thermometer ions, Ambient ionization Received: 28 June 2019/Revised: 13 August 2019/Accepted: 14 August 2019
Introduction
M
ass spectrometry imaging (MSI) has rapidly evolved as an invaluable analytical approach in biological science over the years for its
Electronic supplementary material The online version of this article (https:// doi.org/10.1007/s13361-019-02323-2) contains supplementary material, which is available to authorized users. Correspondence to: David Muddiman; e-mail: [email protected]
capability of simultaneously monitoring numerous biomolecules and their spatial locations. Fragmentation is not desired because it confounds the extremely complex mass spectra and places challenges to molecular weight determination and data interpretation. To addre
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