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  1. Abstract

    Matrix‐assisted laser desorption ionization (MALDI) was introduced 35 years ago and has advanced from a general method for producing intact ions from large biomolecules to wide use in applications ranging from bacteria identification to tissue imaging. MALDI was enabled by the development of high energy pulsed lasers that create ions from solid samples for analysis by mass spectrometry. The original lasers used for MALDI were ultraviolet fixed‐wavelength nitrogen and Nd:YAG lasers, and a number of additional laser sources have been subsequently introduced with wavelengths ranging from the infrared to the ultraviolet and pulse widths from nanosecond to femtosecond. Wavelength tunable sources have been employed both in the IR and UV, and repetition rates have increased from tens of Hz to tens of kHz as MALDI has moved into mass spectrometry imaging. Dual‐pulse configurations have been implemented with two lasers directed at the target or with a second laser creating ions in the plume of desorbed material. This review provides a brief history of the use of lasers for ionization in mass spectrometry and describes the various types of lasers and configurations used for MALDI.

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  2. Rationale

    A two‐component matrix of 2‐nitrophloroglucinol (2‐NPG) and silica nanoparticles was used for matrix‐assisted laser desorption ionization (MALDI) mass spectrometry imaging of high‐charge‐state biomolecules in tissue. Potential advantages include increased effective mass range and efficiency of fragmentation.


    A mixture of 2‐NPG matrix and silica nanoparticles was applied to cyrosectioned 10 μm thick mouse brain tissue. The mixture was pipetted onto the tissue for profiling and sprayed for tissue imaging. MALDI images were obtained under high vacuum in a commercial time‐of‐flight mass spectrometer.


    The combined 2‐NPG and nanoparticle matrix produced highly charged ions from tissue with high‐vacuum MALDI. Nanoparticles of 20, 70, 400, and 1000 nm in diameter were tested, the 20 nm particles producing the highest charge states. Images of mouse brain tissue obtained from highly charged ions show similar spatial localization.


    The combined 2‐NPG and nanoparticle matrix produces highly charged ions from tissue through a mechanism that may rely on the high surface area of the particles which can dry the tissue, and their ability to bind analyte molecules thereby assisting in crystal formation and production of multiply charged ions on laser irradiation.

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