Nanospray desorption electrospray ionization

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Typical setup of a nanospray desorption electrospray ionization probe. Nano-DESI.jpg
Typical setup of a nanospray desorption electrospray ionization probe.

Nanospray desorption electrospray ionization (nano-DESI) is an ambient pressure ionization technique used in mass spectrometry (MS) for chemical analysis of organic molecules. [1] In this technique, analytes are desorbed into a liquid bridge formed between two capillaries and the sampling surface. [2] Unlike desorption electrospray ionization (DESI), from which nano-DESI is derived, nano-DESI makes use of a secondary capillary, which improves the sampling efficiency. [1]

Contents

Principle of operation

The typical nano-DESI probe setup consists of two fused silica capillaries – primary capillary, which supplies solvent and maintains a liquid bridge, and secondary capillary, which transports the dissolved analyte to the mass spectrometer. [1] High voltage (several kV) is applied between the inlet of the mass spectrometer and the primary capillary, creating a self-aspirating nanospray. The liquid bridge is maintained by continuous flow of the solvent and the contact area between the solvent bridge and sample surface can be controlled by changing the solvent flow rate, varying the diameter of the utilized capillaries and regulating the distance between the sample and the nano-DESI probe. [3] In this way, the spatial resolution in mass spectrometry imaging applications can be improved, with typical resolution ranging between 100–150 μm. [4]

Pneumatically-assisted nano-DESI

To enhance sensitivity, the secondary capillary of the nano-DESI probe can be equipped with a nebulizer, which takes benefit of the Venturi effect, facilitating the aspiration of the liquid. [5] This enables the secondary probe to be longer, while still maintaining stable electrospray. The probe can be incorporated into a 3D printed cassette, creating a plug and play device. [6]

Applications

Mass spectrometry imaging

By continuously scanning a surface, such as tissue section, nano-DESI can be used for imaging. By carefully choosing the experimental conditions, such as the nano-DESI solvent, additives, and the ionization mode (positive or negative) we can map the distribution of a wide variety of complex molecules on different surfaces. A few examples to mention are proteins, [7] lipids, [8] small metabolites, [9] drugs [10] or even the distribution of endogenous alkali metals. [11] Nano-DESI has been applied for localized analysis of complex molecules and imaging of tissue sections, microbial communities and environmental samples. [12]

Single-cell analysis

By decreasing the inner diameter of the primary and secondary capillaries, spatial resolution can be decreased to 20x20 µm or even smaller facilitating the analysis of individual cells. This way even various proteoforms can be measured in single cells [13] as well as global and spatial metabolomics. [14]

References

  1. 1 2 3 Roach PJ, Laskin J, Laskin A (September 2010). "Nanospray desorption electrospray ionization: an ambient method for liquid-extraction surface sampling in mass spectrometry". The Analyst. 135 (9): 2233–2236. Bibcode:2010Ana...135.2233R. doi:10.1039/C0AN00312C. PMID   20593081.
  2. ↑ Hotta K, Takeda K, Iinoya K (1974-10-01). "The capillary binding force of a liquid bridge". Powder Technology. 10 (4): 231–242. doi:10.1016/0032-5910(74)85047-3. ISSN   0032-5910.
  3. ↑ Laskin J, Lanekoff I (January 2016). "Ambient Mass Spectrometry Imaging Using Direct Liquid Extraction Techniques". Analytical Chemistry. 88 (1): 52–73. doi:10.1021/acs.analchem.5b04188. PMC   5767520 . PMID   26566087.
  4. ↑ Lanekoff I, Laskin J (2015). "Imaging of lipids and metabolites using nanospray desorption electrospray ionization mass spectrometry". In He L (ed.). Mass Spectrometry Imaging of Small Molecules. Methods in Molecular Biology. Vol. 1203. New York, NY: Springer New York. pp. 99–106. doi:10.1007/978-1-4939-1357-2_10. ISBN   978-1-4939-1356-5. PMID   25361670.
  5. ↑ Duncan, Kyle D.; Bergman, Hilde-Marléne; Lanekoff, Ingela (2017). "A pneumatically assisted nanospray desorption electrospray ionization source for increased solvent versatility and enhanced metabolite detection from tissue" . The Analyst. 142 (18): 3424–3431. doi:10.1039/C7AN00901A. ISSN   0003-2654.
  6. ↑ Mavroudakis, Leonidas; Golubova, Anastasia; Lanekoff, Ingela (May 2025). "Spatial metabolomics platform combining mass spectrometry imaging and in-depth chemical characterization with capillary electrophoresis". Talanta. 286: 127460. doi:10.1016/j.talanta.2024.127460.
  7. ↑ Hale, Oliver J.; Cooper, Helen J. (2021-03-16). "Native Mass Spectrometry Imaging of Proteins and Protein Complexes by Nano-DESI". Analytical Chemistry. 93 (10): 4619–4627. doi:10.1021/acs.analchem.0c05277. ISSN   0003-2700. PMC   8034770 . PMID   33661614.
  8. ↑ Sharma, Varun V.; Lanekoff, Ingela (2023-12-05). "Revealing Structure and Localization of Steroid Regioisomers through Predictive Fragmentation Patterns in Mass Spectrometry Imaging". Analytical Chemistry. 95 (48): 17843–17850. doi:10.1021/acs.analchem.3c03931. ISSN   0003-2700. PMC   10701710 . PMID   37974413.
  9. ↑ Davidová, Lucie; Lanekoff, Ingela (2025-05-27). "Standard Addition as a Method for Quantitative Mass Spectrometry Imaging". Analytical Chemistry. doi: 10.1021/acs.analchem.5c00549 . ISSN   0003-2700. PMC   12163875 .
  10. ↑ Lanekoff, Ingela; Thomas, Mathew; Carson, James P.; Smith, Jordan N.; Timchalk, Charles; Laskin, Julia (2013-01-15). "Imaging Nicotine in Rat Brain Tissue by Use of Nanospray Desorption Electrospray Ionization Mass Spectrometry" . Analytical Chemistry. 85 (2): 882–889. doi:10.1021/ac302308p. ISSN   0003-2700.
  11. ↑ Mavroudakis, Leonidas; Duncan, Kyle D.; Lanekoff, Ingela (2022-02-08). "Host–Guest Chemistry for Simultaneous Imaging of Endogenous Alkali Metals and Metabolites with Mass Spectrometry". Analytical Chemistry. 94 (5): 2391–2398. doi:10.1021/acs.analchem.1c03913. ISSN   0003-2700. PMC   8829828 . PMID   35077136.
  12. ↑ Lanekoff I, Heath BS, Liyu A, Thomas M, Carson JP, Laskin J (October 2012). "Automated platform for high-resolution tissue imaging using nanospray desorption electrospray ionization mass spectrometry". Analytical Chemistry. 84 (19): 8351–8356. doi:10.1021/ac301909a. PMID   22954319.
  13. ↑ Su, Pei; Hollas, Michael A. R.; Butun, Fatma Ayaloglu; Kanchustambham, Vijaya Lakshmi; Rubakhin, Stanislav; Ramani, Namrata; Greer, Joseph B.; Early, Bryan P.; Fellers, Ryan T.; Caldwell, Michael A.; Sweedler, Jonathan V.; Kafader, Jared O.; Kelleher, Neil L. (2024-06-07). "Single Cell Analysis of Proteoforms". Journal of Proteome Research. 23 (6): 1883–1893. doi:10.1021/acs.jproteome.4c00075. ISSN   1535-3893. PMC   11406863 . PMID   38497708.
  14. ↑ Marques, Cátia; Friedrich, Felix; Liu, Liangwen; Castoldi, Francesca; Pietrocola, Federico; Lanekoff, Ingela (2023-11-01). "Global and Spatial Metabolomics of Individual Cells Using a Tapered Pneumatically Assisted nano-DESI Probe". Journal of the American Society for Mass Spectrometry. 34 (11): 2518–2524. doi:10.1021/jasms.3c00239. ISSN   1879-1123. PMC   10623638 . PMID   37830184.
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