Nanospray desorption electrospray ionization

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Short description: Technique used in mass spectrometry
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]

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

Schematic illustration of the pneumatically-assisted nano-DESI secondary capillary. The nebuliser device consists of a high-pressure tee connecting to the nitrogen supply, and a secondary capillary fitted with a Teflon sleeve at both ends.

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, thereby simplifying the setup process. Moreover, it offers greater versatility in nano-DESI solvent selection, allowing water to be used as an extraction solvent.[5] This expands the technique’s chemical coverage and enhances the customization of solvent components for selective extraction of polar compounds. Additionally, the capillaries can be integrated into a custom 3D-printed cassette, creating a convenient 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. ↑ 1.0 1.1 1.2 "Nanospray desorption electrospray ionization: an ambient method for liquid-extraction surface sampling in mass spectrometry". The Analyst 135 (9): 2233–2236. September 2010. doi:10.1039/C0AN00312C. PMID 20593081. Bibcode: 2010Ana...135.2233R. 
  2. ↑ "The capillary binding force of a liquid bridge" (in en). Powder Technology 10 (4): 231–242. 1974-10-01. doi:10.1016/0032-5910(74)85047-3. ISSN 0032-5910. 
  3. ↑ "Ambient Mass Spectrometry Imaging Using Direct Liquid Extraction Techniques". Analytical Chemistry 88 (1): 52–73. January 2016. doi:10.1021/acs.analchem.5b04188. PMID 26566087. 
  4. ↑ "Imaging of lipids and metabolites using nanospray desorption electrospray ionization mass spectrometry". Mass Spectrometry Imaging of Small Molecules. Methods in Molecular Biology. 1203. New York, NY: Springer New York. 2015. pp. 99–106. doi:10.1007/978-1-4939-1357-2_10. ISBN 978-1-4939-1356-5. 
  5. ↑ 5.0 5.1 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" (in en). The Analyst 142 (18): 3424–3431. doi:10.1039/C7AN00901A. ISSN 0003-2654. PMID 28828451. Bibcode: 2017Ana...142.3424D. https://xlink.rsc.org/?DOI=C7AN00901A. 
  6. ↑ Mavroudakis, Leonidas; Golubova, Anastasia; Lanekoff, Ingela (May 2025). "Spatial metabolomics platform combining mass spectrometry imaging and in-depth chemical characterization with capillary electrophoresis" (in en). Talanta 286. doi:10.1016/j.talanta.2024.127460. PMID 39805200. https://linkinghub.elsevier.com/retrieve/pii/S0039914024018423. 
  7. ↑ Hale, Oliver J.; Cooper, Helen J. (2021-03-16). "Native Mass Spectrometry Imaging of Proteins and Protein Complexes by Nano-DESI" (in en). Analytical Chemistry 93 (10): 4619–4627. doi:10.1021/acs.analchem.0c05277. ISSN 0003-2700. 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" (in en). Analytical Chemistry 95 (48): 17843–17850. doi:10.1021/acs.analchem.3c03931. ISSN 0003-2700. PMID 37974413. 
  9. ↑ Davidová, Lucie; Lanekoff, Ingela (2025-05-27). "Standard Addition as a Method for Quantitative Mass Spectrometry Imaging" (in en). Analytical Chemistry 97 (22): 11572–11580. doi:10.1021/acs.analchem.5c00549. ISSN 0003-2700. PMID 40421780. Bibcode: 2025AnaCh..9711572D. 
  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" (in en). Analytical Chemistry 85 (2): 882–889. doi:10.1021/ac302308p. ISSN 0003-2700. PMID 23256596. https://pubs.acs.org/doi/10.1021/ac302308p. 
  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" (in en). Analytical Chemistry 94 (5): 2391–2398. doi:10.1021/acs.analchem.1c03913. ISSN 0003-2700. PMID 35077136. 
  12. ↑ "Automated platform for high-resolution tissue imaging using nanospray desorption electrospray ionization mass spectrometry". Analytical Chemistry 84 (19): 8351–8356. October 2012. 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. et al. (2024-06-07). "Single Cell Analysis of Proteoforms" (in en). Journal of Proteome Research 23 (6): 1883–1893. doi:10.1021/acs.jproteome.4c00075. ISSN 1535-3893. 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. PMID 37830184. Bibcode: 2023JASMS..34.2518M. 



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