Quadrupole Ion Trap - Vibrational Action Spectroscopy (QIT-VAS) for Identification of Biomolecules

Mass spectrometers (MS) are a proven and mature instrument class that have been deployed with great success for the in-situ analysis of planetary environments. Increasingly sophisticated MS technologies are desired in order to meet the analysis demands associated with challenging sample environments anticipated in search for life missions to ocean/icy worlds or investigations of organic molecule rich planetary atmospheres such as Titan. Time-of-flight instrumentation with folded ion paths can offer the state of the art in terms of mass resolution, however, come at the cost of high operational complexity and diminished implementation flexibility. In contrast, moderate resolution quadrupole ion trap (QIT) systems are attractive in that they provide a robust platform that is also flexible by allowing for multiple mass selection events with a single hardware stage. This unique capability opens the door to the development of potent new analysis routines that can be used to parse complex sample mixtures even for cases of compounds with identical (or near identical) mass.

The proposed effort will demonstrate a novel in-situ sensor that combines the operating principles and high sensitivity associated with QIT-MS hardware with the molecular specificity associated with vibrational spectroscopic techniques. This hybrid analysis approach is not without precedent with related schemes having been deployed by the academic community for decades in studies of molecular structure and ion kinetics. Only recently has this dual approach been made viable for in-situ sensing applications through the advent of high TRL QIT-MS hardware and advances in small, low power consumption mid-infrared quantum cascade laser sources.

A basic description of the operational procedure is as follows. A molecular ion cloud of the desired mass-to-charge ratio is selected and contained in a cryogen-free ion trap. The ion cloud is then irradiated with the coherent output of a tunable mid-infrared laser source. If the wavelength of light is resonant with a vibrational mode of the trapped ion, a photon induced dissociation event will take place breaking the trapped species into new fragments. The initial confined mass-to-charge ratio, known vibrational spectra, and the new fragmentation pattern that is observed after irradiation combine to serve as a unique fingerprint verifying the molecular identity of the initial trapped sample. The resulting instrument thus has the favorable sensitivity associated with moderate resolution mass analysis systems yet can also provide specific insight into molecular composition without invoking complex chromatography-based front-end systems.

Demonstration of this hybrid MS/laser system falls in direct alignment with the program scope by significantly improving the measurement capabilities of the existing hardware with the system platform also addressing initiatives in NASA’s technology roadmap for system sensors to distinguish between organic compounds with nearly identical molecular weight. The flight heritage quadrupole ion trap hardware adopted for proposed instrument demonstrations show system size, weight, and power are commensurate with requirements for planetary science applications. Experimental trials will employ direct sampling of liquids containing a dilute mixture of amino acids to demonstrate relevance to Discovery and New Frontiers planetary science missions with priorities in alignment with those outlined in the Planetary Science Decadal Survey.

Developing Instrument technology to improve measurements for future planetary science missions

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