Fragmentation Resilience Energy Mass Spectrometry (FREMS): Methods Validation and Compound Differentiation

Area of Science:

• Analytical Chemistry
• Physical Chemistry

Background:

• Energy-resolved mass spectrometry methods like Survival Yield are established techniques.
• Existing methods provide foundational understanding for advanced approaches.

Purpose of the Study:

• To introduce Fragmentation Resilience Energy Mass Spectrometry (FREMS) as a novel technique.
• To enhance compound differentiation, contaminant identification, and structural elucidation.
• To establish a reliable and high-resolution method for analyzing ion breakdown energies.

Main Methods:

• Acquiring ion breakdown/formation curves with incrementally increased collision energy.
• Utilizing near "continuous" ramp (0.2% NCE increments) for detailed energy analysis.
• Analyzing breakdown curves to derive the Fragmentation Resilience (FR50) metric.

Main Results:

• FREMS provides experimentally interchangeable metrics with modified-Survival Yield (m-SY50) and Cross-Intersect (C-I).
• Breakdown energies are dependent on ion trap parameters: number of ions, Maximum Inject time, and Activation Time.
• A linear relationship (R2 > 0.95) was observed between FR50, m-SY50, C-I metrics and controllable parameters, enabling reliable calibration.

Conclusions:

• FREMS is applicable to ions from any atmospheric pressure ionization process.
• The technique allows for in vacuo experimental treatment of ions.
• FREMS demonstrates that precursor ion decomposition rate equals fragment formation rate under CAD conditions.