Increasing DESI-MS Ion Signal by Plasma Treatment.

Many studies are focused on using plasma in mass spectrometry as an ionization source or postionization method. In this study, the effect of plasma treatment in the sample preparation step of desorption electrospray ionization (DESI) has been investigated. The plasma treatment of polar samples, including morphine, codeine, captopril, theophylline, fructose, and amphiphilic compounds such as phosphatidylethanolamine (PE) in E. coli bacteria, as well as nonpolar compounds, including thebaine, papaverine, and noscapine, has been followed for ionization efficiency in DESI technique. An atmospheric-pressure glow discharge plasma (GDP) along with the electrospray ionization technique is examined. Plasma treatment before ambient ionization has a dramatic effect on polar and nonpolar sample signals in DESI-TOF mass spectrometry. The intensity of the mass spectrum shows an increase of 1.9-3.4 times for polar compounds, 2.1-2.5 times for nonpolar compounds, and 3.0 times for PE in E. coli bacteria (N = 4). Plasma is a source of reactive atoms, molecules, ions, radicals, and ultraviolet radiation. Plasma surface treatment before DESI analysis by energetic species through momentum/energy transfer yields higher energy surface molecules, leading to more/easier desorption. Under optimal treatment conditions, an improved ion signal intensity is observed without any fragmentation, decomposition, or chemical changes. Ion signals are increased possibly by both increased ionization through protonation of molecules and enhanced subsequent desorption during DESI analysis.

Protein ion yield enhancement in matrix-assisted laser desorption/ionization mass spectrometry after sample and matrix low-pressure glow discharge plasma irradiation.

RATIONALE: Plasma-assisted ionization is widely used in mass spectrometry; in this study, a low-pressure glow discharge is introduced as a new method to improve the detection of large proteins, and bovine serum albumin (BSA) is used as a protein model. The treatment of analyte, matrix, and the matrix/analyte mixture is evaluated under optimal conditions. METHODS: Low-pressure radio-frequency capacitively coupled plasma (RF-CCP) treatment is utilized in the sample preparation step of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to enhance the protein MALDI ion signal. Plasma treatment can be an effective tool for enhancing the non-covalent binding of the analyte with the matrix, incorporation of the analyte into the matrix, production of matrix/analyte crystals, and analyte protonation through plasma activation, resulting in an improved MALDI ion signal. RESULTS: Fourier-transform infrared (FTIR) spectroscopy allows us to distinguish between the functional groups of plasma-treated and control samples. In addition, optical emission spectroscopy (OES) determines the plasma species, and zeta potential analysis characterizes the potential difference between plasma-treated and control samples before MALDI-TOF MS analysis. Plasma-treated BSA can provide a five-times enhancement of ion intensity. The combination of the plasma-treated analyte with the plasma-treated matrix leads to an increase in the ion intensity by a factor of 14. CONCLUSIONS: Low-pressure glow discharge plasma treatment greatly enhances MALDI ion signals, with a noticeable increase in incorporation, co-crystallization, protonation, and the concentration of the sample functional groups.