Chain electrospray ionization mass spectrometry for ultra-low volume sample analysis

Area of Science:

• Analytical Chemistry
• Biochemistry
• Mass Spectrometry

Background:

• Traditional mass spectrometry methods require significant sample volumes, limiting analysis of scarce biological materials.
• Electrospray ionization (ESI) is a common technique but can be affected by electro-redox reactions, altering analyte states.

Purpose of the Study:

• To develop a novel ionization technique, chain electrospray ionization (chain-ESI), for efficient trace sample analysis.
• To enable sensitive mass spectrometry analysis with minimal sample consumption and preservation of native analyte states.

Main Methods:

• Development of chain electrospray ionization (chain-ESI) as a primary ion source.
• Utilizing chain-ESI to induce secondary electrospray ionization at picoliter per minute (pLs/min) consumption rates.
• Analysis of metabolites from single biological samples, such as Broussonetia papyrifera trichomes and A549 cancer cells.

Main Results:

• Chain-ESI demonstrated an extraordinarily low sample consumption rate (pLs/min).
• Substantial tandem mass spectrum (MS2) data were generated from low-volume samples, facilitating metabolite annotation.
• Chain-ESI effectively prevented electro-redox reactions, ensuring the native state of analytes was reflected.
• Detection of 1426 metabolites from a single B. papyrifera trichome and 617 metabolites from a single A549 cancer cell.

Conclusions:

• Chain-ESI provides direct, rapid analysis of biological samples with extreme-low volumes and high metabolite coverage.
• This technique enables the measurement of crucial bio-information from limited sample quantities.
• Chain-ESI represents a significant advancement for mass spectrometry-based metabolomics on trace samples.