Matrix-assisted laser desorption/ionization mass spectrometry with re-engineered 2,5-dihydroxybenzoic acid derivative.
Dihydroxybenzoic acid was modified to three analogues (M2, M4 and M6). The analogues exhibited specific properties that resulted in enhancement of analyte signal intensity with or without addition of iodine compared to the underivatized parent. Addition of iodine to M2, an ester of dihydroxybenzoic acid that had a terminal double bond in the alkyl chain, resulted in peak intensities comparable to the parent, indicating that iodine interaction across the double bond resulted in enhancement although the exact mechanism is not fully understood. No enhancement on addition of iodine was observed for M4, which had a long alkyl chain that contained no double bonds. The alkyl chain allowed micelle formation in solution, which in turn allowed more uniform analyte-to-matrix mixing. The final analogue combined the long alkyl chain of M4 with the double bond of M2 and exhibited either similar peak intensities to that of dihydroxybenzoic acid or better. Micelle formation in solution was examined using spectroscopy and in the solid by reflective microscopy. The standard deviation from spot to spot was considerably lower relative to dihydroxybenzoic acid (RSD 3.4%vs. 14.2%). Unlike dihydroxybenzoic acid, the novel matrix M6 was able to yield characteristic peaks for analytes such as ubiquitin.
Bashir
Sajid
S
Institute of Mass Spectrometry and Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL. br9@hotmail.com
Mutter
Roger
R
Derrick
Peter J
PJ