Assessing the properties of internal standards for quantitative matrix-assisted laser desorption/ionization mass spectrometry of small molecules

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DOIResolve DOI: http://doi.org/10.1002/rcm.2498
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TypeArticle
Journal titleRapid Communications in Mass Spectrometry
Volume20
Issue10
Pages15171524; # of pages: 8
Subjectstandards; mass spectrometry; quinolones; carnitine; chemistry
AbstractGrowing interest in the ability to conduct quantitative assays for small molecules by matrix-assisted laser desorption/ionization (MALDI) has been the driving force for several recent studies. This present work includes the investigation of internal standards for these analyses using a high-repetition rate MALDI triple quadrupole instrument. Certain physicochemical properties are assessed for predicting possible matches for internal standards for different small molecules. The importance of similar molecular weight of an internal standard to its analyte is seen through experiments with a series of acylcarnitines, having a fixed charge site and growing alkyl chain length. Both acetyl- and hexanoyl-carnitine were systematically assessed with several other acylcarnitine compounds as internal standards. The results clearly demonstrate that closely matched molecular weights between analyte and internal standard are essential for acceptable quantitation results. Using -cyano-4-hydroxycinnamic acid as the organic matrix, the similarities between analyte and internal standard remain the most important parameter and not necessarily their even distribution within the solid sample spot. Several 4-quinolone antibiotics as well as a diverse group of pharmaceutical drugs were tested as internal standards for the 4-quinolone, ciprofloxacin. Quantitative results were shown using the solution-phase properties, log D and pKa, of these molecules. Their distribution coefficients, log D, are demonstrated as a fundamental parameter for similar crystallization patterns of analyte and internal standard. In the end, it was also possible to quantify ciprofloxacin using a drug from a different compound class, namely quinidine, having a similar log D value as the analyte.
Publication date
PublisherWiley
Copyright noticeCopyright 2006 John Wiley & Sons, Ltd.
LanguageEnglish
AffiliationNRC Institute for Marine Biosciences; National Research Council Canada
Peer reviewedYes
NRC number1622
NPARC number3538413
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Record identifier6ed95de3-5acc-4553-b13f-e0d70df70241
Record created2009-03-01
Record modified2016-05-09
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