Wide Quadrupole RF Window Scanning With Multi-Energy Fragmentation

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Solution Overview

Problem

Conventional data-independent acquisition (DIA) workflows in tandem mass spectrometry face challenges in de-convolving co-eluting product ions due to the non-specific nature, which limits the provision of sufficient precursor ion information for deconvolution.

Innovation Solution

Fragmenting each precursor ion isolation window multiple times with varying fragmentation parameters, including low and increasingly aggressive collision energies, to produce combined product ion spectra that allow for the correlation of precursor and product ions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Measurement precision

If conventional DIA workflows use a single fragmentation parameter per precursor ion window, then the acquisition speed is maintained, but the ability to de-convolve co-eluting product ions and identify precursor ions is insufficient

Engineering Contradiction:
Improveprecursor ion identification accuracyVSAvoiddata acquisition speed
Core Design Contradiction:
Measurement precisionVSProductivity

Solution Approach 1:

The patent segments the fragmentation process by dividing it into multiple stages with different collision energy values. Instead of using a single fragmentation parameter, the system performs sequential fragmentations at low, medium, and high collision energies, each providing complementary information about precursor ions. This segmentation allows detailed spectral analysis without sacrificing overall acquisition throughput.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The system implements periodic action by cycling through multiple collision energy values in a systematic sequence for each precursor ion window. This periodic variation in fragmentation parameters enables comprehensive product ion spectral acquisition across different energy levels, improving precursor identification while maintaining structured data collection rhythm.

Inventive Principle:
Principle #19Periodic action

2Quantity of substance

If wide precursor ion isolation windows are used in DIA, then the comprehensiveness of data collection is improved, but the complexity of de-convolving co-eluting product ions increases

Engineering Contradiction:
Improvecoverage of precursor ionsVSAvoiddata processing complexity
Core Design Contradiction:
Quantity of substanceVSDevice complexity

Solution Approach 1:

The patent applies local quality by tailoring the fragmentation conditions to specific regions of the precursor ion spectrum. Different collision energy values are applied systematically across the m/z range, with each energy level providing optimized fragmentation patterns for specific mass regions. This localized optimization within the wide window enables better resolution of co-eluting ions without reducing overall coverage.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The system adds another dimension to the data by introducing collision energy as an additional parameter beyond just m/z and intensity. This dimensional expansion creates a multi-dimensional spectral space where co-eluting product ions can be distinguished not only by their mass-to-charge ratio but also by their fragmentation patterns at different energy levels, thereby simplifying the de-convolution process despite wide window coverage.

Inventive Principle:
Principle #17Another dimension (Dimensionality change)

3Loss of information

If multiple fragmentations are performed per precursor ion window with varying collision energies, then precursor ion information is enhanced, but the time required for data collection increases

Engineering Contradiction:
Improveprecursor ion information completenessVSAvoiddata collection time
Core Design Contradiction:
Loss of informationVSLoss of time

Solution Approach 1:

The system performs preliminary action by first acquiring low collision energy spectra that provide intact precursor ion information and minimal fragmentation. This initial low-energy scan establishes a baseline for precursor identification before proceeding to higher energy fragmentations. This preliminary step optimizes information gain while minimizing redundant data collection at higher energies.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent implements dynamics by adaptively adjusting the number and energy levels of fragmentations based on the specific characteristics of each precursor ion window. Rather than applying a fixed multi-energy protocol uniformly, the system dynamically selects collision energy values and repetition counts tailored to the observed ion populations, thereby reducing unnecessary measurement time while preserving essential precursor information.

Inventive Principle:
Principle #15Dynamics

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach enhances the reproducibility and comprehensiveness of data collection by providing additional precursor ion information, enabling effective de-convolution of co-eluting product ions and improving the identification of precursor ions.

Implementation Method 1

an ion source that receives a sample and ionizes the sample, producing an ion beam

Methodology Applied
Scientific EffectIonization: Ionisation

Implementation Method 2

Fragmenting each precursor ion isolation window multiple times with varying fragmentation parameters, including low and increasingly aggressive collision energies

Methodology Applied
Scientific EffectCollision-induced dissociation:

Data Source

PatentEP3254298B1Rapid scanning of wide quadrupole RF windows while toggling fragmentation energy
Publication Date: 2023.10.18 DH TECH DEVMENT PTE
  • EP3254298B1 patent drawingFigure 1
  • EP3254298B1 patent drawingFigure 2
  • EP3254298B1 patent drawingFigure 3

AI summary

A sample is ionized using an ion source and the ion beam is received using a tandem mass spectrometer. An m/z range is divided into two or more precursor ion isolation windows. Two or more values for a fragmentation parameter are selected. A first value of the two or more values for the fragmentation parameter has a level that fragments a minimal amount of ions of the ion beam. The one or more additional values have increasingly aggressive levels that produce increasingly more fragmentation of the ions of the ion beam. For each precursor ion isolation window, the tandem mass spectrometer is instructed to perform a selection and fragmentation of the ion beam using the precursor ion isolation window and the first value and is instructed to perform one or more additional selections and fragmentations of the ion beam using the precursor ion isolation window and using the one or more additional values.