Karen Yannell (Presenter)
Purdue University
Bio: Karen received her B.A. in biochemistry from the University of San Diego. After graduating she worked for two years at Millennium Health in San Diego where she helped developed LC-MS/MS assays for urinalysis. Currently, she is a PhD candidate at Purdue University and is advised by Dr. Graham Cooks. Her areas of study include paper spray ionization, biofluid analysis and quantitative analysis.
Authorship: Karen E. Yannell (1), Kristina R. Kesely (2), Philip S. Low (2), and R. Graham Cooks (1)
(1) Department of Chemistry and Center for Analytical Instrumentation Development, Purdue University, West Lafayette, IN 47907 (2) Department of Chemistry, Purdue University, West Lafayette, IN 47907
| Short Abstract Paper spray ionization (PS) is an emerging technique that combines sample collection, preparation and ionization on a paper substrate for rapid analysis of small analytes by mass spectrometry. Currently, there are many commercially available DBS devices that may be integrated with PS. Coupling PS and DBS devices eliminates the need of offline extraction of the analytes from the DBS. Additionally, with this new approach, the PS measurement may utilize specialized DBS devices for improved sample volume precision and accuracy or filtration of the biological matrix. Analytical figures of merit of DBS collection devices coupled with PS are investigated. |
Long Abstract
Paper spray ionization (PS) is an emerging ionization technique that combines sample collection, preparation and ionization on a paper substrate for rapid analysis by mass spectrometry (MS). Conventionally, this technique uses a small amount of dried sample (2 – 20 µl) on a triangularly shaped piece of paper. After the sample is dried, a spray solution and high voltage (3.5 kV) are applied to the paper to create ions off of the paper’s tip with an ionization mechanism similar to electrospray.
To date, several biological matrices have been studied with PS including blood, urine, oral fluid and cerebral spinal fluid for analyzing drugs and endogenous analytes. Blood remains a very common matrix to study because of the quick pharmacokinetic studies that can be carried out with as little as 10 µl of blood. However, many of these studies have focused on analyzing blood spots on Whatman 31 or Whatman 1 chromatography papers which are not commonly used for dried blood spot (DBS) analysis.
Currently, there are many commercially available DBS devices that may be adapted to use with PS. For certain studies, it may be advantageous to use these devices for blood collection and integrate them into PS for rapid analysis. The coupling of the two technologies eliminates the need of offline extraction of the analytes from the DBSs. Additionally, PS has always joined the sample collection and analysis steps which requires precise spotting of whole matrix samples. With this new approach, the PS measurement may utilize specialized DBS devices for improved volume precision and accuracy as well as filtration of the biological sample. In this poster, the analytical performance of DBS and plasma collection devices integrated with PS are investigated. Specifically, Whatman FTA DMPK-C, TomTec PDMS, and Novilytic Noviplex devices have been compared.
For this study, imatinib and its metabolite were used as model compounds in whole blood. Experiments were performed with a Thermo Fisher Quantum Access Max triple quadrupole mass spectrometer. Whole blood spiked with imatinib, N-desmethyl-imatinib, imatinib-D8 and N-desmethyl-imatinib-D8 was spotted onto the blood spot collection device and dried. Whatman FTA-DMPK spots were cut out of the card while the TomTec and Novilytic spots were precut circles that were placed on top of a precut Whatman 31ET triangle. A 100% methanol priming solution was used for the TomTec and Novilytic spots and a spray solution composed of 95% methanol, 5% water and 0.1% formic acid was used to create a spray and form ions. The data was collected for 30 s in positive mode with multiple reaction monitoring.
The limit of detection of imatinib and N-desmethyl-imatinib on the Whatman FTA DMPK-C, TomTec PDMS, and Novilytic Noviplex were 5 ng/mL and 6 ng/mL, 2.5 ng/mL and 6 ng/mL and 60 ng/mL and 100 ng/mL, respectively. Precision, accuracy, and linearity were compared, as well as the MS background of these devices and extraction efficiency. Generally, the performance and background from these devices varied which is likely from paper substrate and manufacturing differences.
Utilizing commercially available DBS devices in the field may be more convenient for sample collection or may work better for the parameters of the study. Additionally, some biofluid collection devices are specialized such as the Noviplex which offers whole blood filtration for plasma collection. These devices are now able to be the mode of collection while maintaining fast and easy analysis by paper spray-mass spectrometry.
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