Three-Dimensional Printed Microdevice to Enhance Headspace Microextraction for Enrichment of Histamine in Milk

In this work, a three-dimensional (3D) printed microdevice was designed to fix a drop of extractant that was applied to the enrichment of the most toxic biogenic amine, histamine, by headspace single-drop microextraction (HS-SDME). Concomitantly, based on the hybridization chain reaction of the histamine aptamer isothermal nucleic acid amplification strategy, a new fluorescence sensing method was developed to realize the highly sensitive detection of histamine. This is the first application of a 3D-printed microdevice to realize the HS-SDME process, which, among other advantages, effectively solves the problem of unstable and variable drop volumes that can plague traditional SDME and ensures the accuracy and repeatability of the extraction process. The calibration linear range of this SDME-fluorescence method was from 10 pM to 5 μM (R2 > 0.98), and the limit of detection was as low as 3 pM. In addition, the method was successfully demonstrated to determine histamine spiked in milk, with recoveries of between 93% and 104%, and relative standard deviations of less than 5%. The method established in this study has important practical significance for food safety monitoring and human health and provides new ideas and solutions for the design and application of biosensors.