Many ambient desorption/ionization mass spectrometry (ADI-MS) techniques rely critically on thermal desorption. Meanwhile, the analyte classes that are successfully studied by any particular ADI-MS methods are strongly dependent on the type of ionization source. Generally, spray-based ionization sources favor polar analytes, whereas plasma-based sources can be used for more hydrophobic analytes and are more suitable for molecules with small molar masses. In the present work, classic atmospheric-pressure chemical ionization (APCI) is used. To provide improved desorption performance for APCI, a surface acoustic wave nebulization (SAWN) device was implemented to convert liquid analytes into fine airborne particles. Compared to conventional SAWN that is used solely as an ionization source for liquid samples, the coupling of SAWN and APCI significantly improves ion signal by up to 4 orders of magnitude, reaching comparable ion abundances to those of electrospray ionization (ESI). Additionally, this coupling also extends the applicable mass range of an APCI source, conventionally known for the ionization of small molecules <500 Da. Herein, we discuss cursory evidence of this applicability to a variety of analytes including both polar and nonpolar small molecules and novel peptides that mimic biomolecules upward of 1000 Da. Observed species are similar to ESI-derived ions including doubly charged analyte ions despite presumably different charging mechanisms. SAWN–APCI coupling may thus involve more nuanced ionization pathways in comparison to other ADI approaches.
The concept of direct mass-spectrometric analysis, especially exploited by ambient desorption/ionization (ADI) methods, provides numerous means for convenient sample analysis. While many simple and versatile ionization sources have been developed, challenges lay in achieving efficient sample introduction. In previous work, a sample introduction method employing direct current corona discharge (CD) coupled to a surface acoustic wave nebulization (SAWN) device enhanced sampling performance for both polar and nonpolar analytes by up to 4 orders of magnitude. In fact, the SAWN-CD method generated a multiply charged peptide ion signal comparable to that of conventional ESI. Unfortunately, the high cost of the SAWN devices themselves limits their accessibility. Herein, we report on an analogous implementation of CD with an inexpensive ultrasonic nebulizer (USN) on the basis of a commercial room humidifier demonstrating equivalent exemplary performance. We subsequently compare the two methods of SAWN-CD and USN-CD in a screening application of milk for the detection of two antibiotic drugs, ciprofloxacin and ampicillin. Finally, we further investigate the relative softness of these CD-coupled acoustic nebulization methods in comparison to that of ESI using a survival yield study of the thermometer ion nitrobenzylpyridinium.
Concomitant species that appear at the same or very similar times in a mass-spectral analysis can clutter a spectrum because of the coexistence of many analyte-related ions (e.g., molecular ions, adducts, fragments). One method to extract ions stemming from the same origin is to exploit the chemical information encoded in the time domain, where the individual temporal appearances inside the complex structures of chronograms or chromatograms differ with respect to analytes. By grouping ions with very similar or identical time-domain structures, single-component mass spectra can be reconstructed, which are much easier to interpret and are library-searchable. While many other approaches address similar objectives through the Pearson’s correlation coefficient, we explore an alternative method based on a modified cross-correlation algorithm to compute a metric that describes the degree of similarity between features inside any two ion chronograms. Furthermore, an automatic workflow was devised to be capable of categorizing thousands of mass-spectral peaks into different groups within a few seconds. This approach was tested with direct mass-spectrometric analyses as well as with a simple, fast, and poorly resolved LC–MS analysis. Single-component mass spectra were extracted in both cases and were identified based on accurate mass and a mass-spectral library search.
Mass spectrometry (MS) has played a remarkable role in exploring the chemical make‐up of our solar system. In situ probes were historically developed to analyze inorganic/elemental compositions while leveraging native ions or harsh ionization methods to aid in exploring astrophysics applications (e.g., heliophysics). The part played by MS is demonstrated in a majority of scientific payloads focused on exploration, particularly at the turn of the century with missions including Cassini‐Huygens, Rosetta, and now Mars Science Laboratory. Plasma mass spectrometers have grown more sophisticated to interrogate fundamental inorganic analysis (e.g., solar wind and magnetospheres) including both native ions and neutrals. Cosmic dust floating in‐between and orbiting planetary bodies has been targeted by unique sampling via impact ionization. More complex systems rely on landed planetary instrumentation with lessons learned from pioneering missions in the 1970s and 1980s to near neighbors Mars and Venus. Modern probes have expanded applicable target chemicals by recognizing the needs to provide for molecular analyses, extended mass range, and high resolution to provide unequivocal detection and identification. Notably, as the field surrounding astrobiology has gained momentum, so has the in situ detection of complex molecular chemistry including the chemical evolution of organic molecules. Mission context often includes long term timelines from spacecraft launch to arrival and additionally the diverse target environments across various planets. Therefore, customized experimental designs for space MS have been born of necessity. To this point, the development of MS instrumentation on Earth has now far outpaced development for experiments in space. Therefore, exciting developments lie ahead among various international space agencies conducting current and future mission planning with increasingly enhanced instrumentation. For instance, near‐neighbor Mars has entertained considerable attention with complex MS instrumentation with laser desorption ionization aboard the Mars Organic Molecule Analyzer instrument. To study comets, the Rosetta mission employs a secondary ionization mechanism. Meanwhile, the various moons of Jupiter and Saturn have intriguing surface and subsurface properties that warrant more advanced analyzer systems. Instrumentation design will continue to evolve as requirements develop and this review serves as a reflection of the contribution of in situ MS to space exploration in the past 20 years and the anticipated contribution yet to come. © 2020 John Wiley & Sons Ltd. Mass Spec Rev
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