3D Printed Coated Blade Spray-Mass Spectrometry Devices.

Coated blade spray-mass spectrometry (CBS-MS) has emerged as a powerful tool for the rapid screening of target compounds at trace levels in complex biological matrices. Despite its potential, the broader adoption of CBS-MS technology has been hindered by the lack of commercially available, user-friendly MS interfaces and extraction devices. In this work, we present comprehensive CBS-MS solutions developed using 3D printing, including a versatile MS interface and two extraction devices tailored to different analytical needs: one is compatible with LC vials for large-volume samples, while the other is optimized for single-drop blood analysis. The MS interface features a novel design that separates the immobilization station from the blade holder, significantly simplifying the operational workflow and minimizing the contamination risks and hazards associated with manual blade handling. The first extraction cartridge can process 48 samples simultaneously with an average sample preparation time of less than 20 s, while the second extraction device enables extraction from 8 single-drop blood samples via on-blade extraction. The developed devices were successfully tested for the rapid screening of seven drugs in both urine and single-drop blood samples, demonstrating a promising analytical performance. Additionally, potential contamination issues related to the use of 3D-printed materials as extraction phases were examined, emphasizing the importance of ensuring that 3D-printed materials do not leach contaminants into samples or solvents and contaminate the MS.

Metabolite profiling of Piper longum L. fruit volatiles by two-dimensional gas chromatography and time-of-flight mass spectrometry: Insights into the chemical complexity.

Piper longum L. (long pepper) is an economically and industrially important medicinal plant. However, the characterization of its volatiles has only been analyzed by gas chromatography-mass spectrometry (GC-MS). In the present study, precise characterization of P. longum fruit volatiles has been performed for the first time through advanced two-dimensional gas chromatography-time-of-flight spectrometry (GC×GC-TOFMS). A total of 146 constituents accounting for 93.79% were identified, of which 30 were reported for the first time. All these constituents were classified into alcohols (4.5%), alkanes (8.9%), alkenes (6.71%), esters (6.15%), ketones (0.58%), monoterpene hydrocarbons (1.64%), oxygenated monoterpenes (2.24%), sesquiterpene hydrocarbons (49.61%), oxygenated sesquiterpenes (13.03%), phenylpropanoid (0.23%), and diterpenes (0.2%). Among all the classes, sesquiterpene hydrocarbons were abundant, with germacrene-D (2.87% ± 0.01%) as the major one, followed by 8-heptadecene (2.69% ± 0.03%), ß-caryophyllene (2.43% ± 0.03%), n-heptadecane (2.4% ± 0.04%), n-pentadecane (2.11% ± 0.05%), and so forth. Further, 20 constituents were observed to be coeluted and separated precisely in the two-dimensional column. The investigation provides an extensive metabolite profiling of P. longum fruit volatiles, which could be helpful to improve its therapeutic potential.

Exploring Negative Chemical Ionization of Per- and Polyfluoroalkyl Substances via a Liquid Electron Ionization LC-MS Interface.

Per- and polyfluoroalkyl substances (PFASs) are a class of aliphatic manufactured compounds comprising fluoro-chemicals with varied functional groups and stable carbon-fluorine bonds. They are defined as "forever chemicals" due to their persistent and bioaccumulative character. These substances have been detected in various environmental samples, including water, air, soil, and human blood, posing significant health hazards. High-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) is typically employed for the analysis of PFASs. Negative chemical ionization (NCI) is generally coupled to gas chromatography (GC) and offers high selectivity and sensitivity for compounds containing electronegative atoms, such as PFASs. The liquid electron ionization (LEI) interface is an efficient mechanism developed to robustly couple a liquid flow rate from an LC system to an EI or a CI source. This interface has been successfully utilized for pesticide determination in UHPLC-LEI-CI in negative ion mode (NCI). This work aims to evaluate different parameters involved in the ionization of PFASs analyzed in LC-LEI-NCI and subsequently develop a method for their detection in real samples. The parameters considered for this study include (i) a comparison of different CI reagent gases (methane, isobutane, and argon); (ii) the use of acetonitrile as both the chromatographic solvent and CI reagent gas; (iii) the presence of water and formic acid as chromatographic mobile phase components; and (iv) the mobile phase flow rate. The optimal combination of these parameters led to promising results. Tentative fragmentation pathways of PFASs in NCI mode are proposed based on the dissociative electron capture mechanism.