Breaching the 10 Second Barrier of Total Analysis Time for Complex Matrices via Automated Coated Blade Spray

Abstract

In the development of modern analytical workflows, parameters such as sample turnaround time, cost of analysis, and ease of use must be prioritized. Automation enables reductions in total analysis time, human intervention, and cost per sample. In this report, a suitable automated coated blade spray (CBS) workflow is proposed for the screening and quantitation of multiple substances (i.e., drugs of abuse and pesticides) in complex matrices. In an attempt to reduce the total sample analysis time, several parameters were investigated, including tandem mass spectrometry (MS) dwell time, CBS spray time, and extraction time. Solid-phase microextraction (SPME) method parameters are explored, such as reduction of extraction time for increased signal-to-noise. Model compounds with a moderately wide range of molecular weights (150–500 Da), polarities, and structural diversity were selected in order to monitor analytical figures of merit during method optimization. The resultant automated CBS method proved capable of analyzing the model compounds in human urine in under 10 s total analysis time with excellent accuracy (95–120%) and precision (RSD < 12%). As an application, an automated method for the screening and quantitation of more than 150 pesticides from apple juice was demonstrated on both triple quadrupole and orbitrap instruments in under 15 s total sample analysis time.

Analysis of food samples made easy by microextraction technologies directly coupled to mass spectrometry

“…For instance, Kasperkiewicz et al proposed for the first time optimization of extraction time based on signal‐to‐noise ratios instead of mere instrumental signal. The work demonstrated that it is important to consider the coextraction of other sample components as this may affect quantitative results 28 . In addition, the same work demonstrated that, because of the power of state‐of‐art instrumentation, spray times can be shortened and instrumental analysis time driven by the total number of analytes that can be monitored.…”

“…Since its inception, the use of CBS has been primarily focused on bioanalysis 31 . Recently, the technology was shown to be also suitable for rapid food screening and quantitation by work that has set important breakthroughs, not only in food analysis but also in microextraction technology interfaces with MS instrumentation 28,29 . For instance, Kasperkiewicz et al proposed for the first time optimization of extraction time based on signal‐to‐noise ratios instead of mere instrumental signal.…”

“…The added advantage was that one of the coated sides of the blade was used for quantitative analysis whereas the opposite side for the untargeted screening approach on the high‐resolution instrument. As a proof of concept, the automated CBS injection method was used for screening and quantitation of more than 150 pesticides from apple juice 28 . The total sample analysis time was within 15 s with LOQs under the 10 ng/mL for most analytes of interest while using fewer than 10 deuterated internal standards for the screening of the entire panel of analytes.…”

“…Voltage is applied to the blade via a metal passthrough the 12‐blade cartridge (circled in D). Reprinted with permission from Kasperkiewicz et al 28 Copyright 2020 American Chemical Society…”

“…It is worth mentioning that in certain cases, matrix effects are also because of the amount of coextracted molecules that can intrinsically affect the ionization efficiency of the targeted analytes, as such matrix‐matched calibration strategies are always recommended. Likewise, the incorporation of deuterated analogs as internal standards remains the preferred option to deliver the most accurate quantitative results as long as these are available and/or not prohibitively expensive 12,28,29 . The optimization of SPME geometry enabled convenient coupling to already existing ion sources such as DART, 13 or the development of innovative technologies such as CBS 30 .…”