Laser ablation electrospray ionization

Principle of operation

LAESI produces ions for MS analysis under normal atmospheric conditions for samples containing water. The entire process can be divided into two steps.

Generation of analyte species

When a mid-IR laser beam is applied to a target which contains a hydroxide group, the target will absorb energy from this laser beam leading to evaporation of moisture from the targeted area. A small-scale explosion occurs in the target and a small portion of the sample is ablated into the gas phase by a short (5 ns), mid-IR (2,940 nm) laser pulse. The plume expands until it collapses into the sample due to the pressure exerted by the atmosphere. At this point a jet of material is ejected from the sample surface. As mid-IR has low energy most of the ejected particles from sample remain neutral.

Reacting analyte species with charged solvent species

An electrospray ionization (ESI) source is located above the sample for post-ablation ionization. The jet of ablated material is intersected and ionized by a spray plume from the ESI source located above the sample. The ionized molecules are then swept into the mass spectrometer for analysis. Because an ESI source is used for ionization, the LAESI mass spectra are similar to traditional ESI spectra, which can exhibit multiply charged analyte peaks, and extend the effective mass range of detection to biomolecules 100,000 Da in size.

Applications

LAESI can be used to perform MS imaging experiments of diverse tissue samples, not only in three dimensions but also with respect to time. Similarly, LAESI can also be used for process monitoring applications because each individual analysis requires less than 2 seconds to perform. Because of the speed of a LAESI analysis, the technique is amenable to rapid, sensitive, and direct analysis of aqueous samples in 96- and 384-well microplates. These analyses can also be performed on liquid samples, such as biofluids, containing peptides, proteins, metabolites, and other biomarkers for clinical, diagnostic, and discovery workflows. LAESI technology allows high throughput analysis of these sample types and the use of internal standards and calibration curves permit the absolute quantitation of targeted biomolecules.

Advantages and limitations

Advantages

This technique needs very little or no sample preparation and it has high sensitivity. This ionization technique does not need any external matrix. Therefore, the spatial resolution is not compromised by the presence of matrix crystal resulting in high spatial resolution. This ionization technique can be carried out in natural and uneven biological surface. Finally, as laser ablation and electronspray ionization work independently, they can be independently manipulated to achieve greater resolution.

Limitations

LAESI is a relatively new technique for those samples which contain water and are relatively stable. However, it has limitations for those samples which have a lower water content. For example, this technique does not ionize dry skin, nails, tooth and bone well; this is due to low water content in these samples. Also, it needs a relatively large sampling area, compared to some other common ionization techniques.

References

References

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