Exploring the Importance of the Relative Solubility of Matrix and Analyte in MALDI Sample Preparation Using HPLC

• Published in: Analytical chemistry (Washington) Vol. 76; no. 17; pp. 5157 - 5164
• Main Authors: Hoteling, Andrew J., Erb, William J., Tyson, Robert J., Owens, Kevin G.
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01-09-2004
• Subjects: Analytical chemistry; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, High Pressure Liquid; Exact sciences and technology; Mass spectrometry; Matrix; Other chromatographic methods; Peptides - chemistry; Polymers - chemistry; Samples; Solubility; Solvents - chemistry; Spectrometric and optical methods; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Reversed phase chromatography; Sample preparation; Peptides; Solubility; HPLC chromatography; Polarity; Polymer; Matrix assisted laser desorption ionization; Retention time; Mass spectrometry; Signal to noise ratio
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac049566m

New insight into the role of solubility in the sample preparation process for MALDI MS is reported. Reversed-phase gradient HPLC conditions were developed that enable the analysis of a broad range of analyte polarities with a single method. This HPLC method was used to establish a relative polarity scale for a series of 15 MALDI matrix materials, a set of example peptides, and a series of model polymer materials with a broad range of polarity. Examples of each polymer type within the range of 6000−10 000 were analyzed with six matrixes that cover a broad range of polarity using MALDI TOFMS. With regard to polymer signal-to-noise ratio, the matrix and polymer combinations that had a close match of HPLC retention time produced the best MALDI spectra. Conversely, the matrix and polymer combinations that have a large difference in HPLC retention time produced poor MALDI spectra. The results suggest that there is a relationship between polarity (solubility) and effective MALDI sample preparation. The relative HPLC retention time of an unknown polymer can serve as a starting point for predicting the matrix (or range of matrixes) that would be most effective.