title: The Development of Novel Nanodiamond Based MALDI Matrices for the Analysis of Small Organic Pharmaceuticals.
abstract: The utility of novel functionalized nanodiamonds (NDs) as matrices for matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) is described herein. MALDI-MS analysis of small organic compounds (<1000 Da) is typically complex because of interferences from numerous cluster ions formed when using conventional matrices. To expand the use of MALDI for the analysis of small molecules, novel matrices were designed by covalently linking conventional matrices (or a lysine moiety) to detonated NDs. Four new functionalized NDs were evaluated for their ionization capabilities using five pharmaceuticals with varying molecular structures. Two ND matrices were able to ionize all tested pharmaceuticals in the negative ion mode, producing the deprotonated ions [M - H](-). Ion intensity for target analytes was generally strong with enhanced signal-to-noise ratios compared with conventional matrices. The negative ion mode is of great importance for biological samples as interference from endogenous compounds is inherently minimized in the negative ion mode. Since the molecular structures of the tested pharmaceuticals did not suggest that negative ion mode would be preferable, this result magnifies the importance of these findings. On the other hand, conventional matrices primarily facilitated the ionization as expected in the positive ion mode, producing either the protonated molecules [M + H](+) or cationic adducts (typically producing complex spectra with numerous adduct peaks). The data presented in this study suggests that these matrices may offer advantages for the analysis of low molecular weight pharmaceuticals/metabolites. Graphical Abstract ᅟ.
authors.affiliation: University of Saskatchewan, Saskatoon, Canada.
authors.forename: Jackson M
authors.initials: JM
authors.lastname: Chitanda
authors.affiliation: University of Saskatchewan, Saskatoon, Canada.
authors.forename: Haixia
authors.initials: H
authors.lastname: Zhang
authors.affiliation: University of Saskatchewan, Saskatoon, Canada.
authors.forename: Erica
authors.initials: E
authors.lastname: Pahl
authors.affiliation: University of Saskatchewan, Saskatoon, Canada.
authors.forename: Randy W
authors.initials: RW
authors.lastname: Purves
authors.affiliation: University of Saskatchewan, Saskatoon, Canada. anas.el-aneed@usask.ca.
authors.forename: Anas
authors.identifier: 0000-0003-1060-3609
authors.initials: A
authors.lastname: El-Aneed
mesh_terms: D008970:Molecular Weight; D058612:Nanodiamonds; D009930:Organic Chemicals; D004364:Pharmaceutical Preparations / Q000032:analysis / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
chemical_list: D058612:Nanodiamonds; D009930:Organic Chemicals; D004364:Pharmaceutical Preparations
keywords: MALDI; Matrix; Nanodiamond; Small molecule