Orthogonal Acceleration Time of Flight Mass Spectrometer Wrap-Around Correction

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Solution Overview

Problem

Conventional orthogonal acceleration Time of Flight mass spectrometers face issues with time of flight spectral wrap-around, leading to incorrect mass to charge ratio assignments due to the periodicity of the orthogonal acceleration electric field, resulting in suboptimal ion sampling duty cycles, especially for ions with lower mass to charge ratios.

Innovation Solution

The method involves repeatedly energizing the orthogonal acceleration electrode with a periodicity less than the time of flight of ions having the maximum mass to charge ratio, allowing for the combination and comparison of mass spectral data sets to identify and correct for wrap-around effects, thereby enhancing the sampling duty cycle and accuracy across a wide range of mass to charge ratios.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Measurement precision

If the periodicity of the orthogonal acceleration electric field is set to prevent time of flight spectral wrap-around, then measurement precision is improved, but productivity decreases due to reduced ion sampling duty cycle

Engineering Contradiction:
Improvemass to charge ratio assignment accuracyVSAvoidion sampling duty cycle
Core Design Contradiction:
Measurement precisionVSProductivity

Solution Approach 1:

The patent applies periodic action by using multiple orthogonal acceleration frequencies (f1, f2, f3) in sequence. Each frequency operates periodically to accelerate ion packets, and by combining data from multiple periods with different frequencies, the system achieves both high measurement precision (preventing wrap-around at each frequency) and high productivity (increasing overall sampling duty cycle through multi-frequency operation).

Inventive Principle:
Principle #19Periodic action

Solution Approach 2:

The patent segments the ion sampling process into multiple frequency components. Instead of using a single periodic frequency, the system divides the sampling into several orthogonal acceleration events at different frequencies (f1, f2, f3), each contributing a portion of the total sampling duty cycle. This segmentation allows the system to overcome the limitation of single-frequency operation while maintaining precision at each segment.

Inventive Principle:
Principle #1Segmentation

2Measurement precision

If the time period between successive orthogonal acceleration events is increased to accommodate high mass to charge ratio ions, then measurement precision is improved, but loss of time increases

Engineering Contradiction:
Improveprevention of spectral wrap-aroundVSAvoidtime period between acceleration events
Core Design Contradiction:
Measurement precisionVSLoss of time

Solution Approach 1:

The system uses multiple periodic acceleration frequencies to reduce the effective time period between acceleration events. By operating at higher frequencies (f2, f3) in addition to the base frequency (f1), the system achieves more frequent sampling without increasing the maximum time period for any single frequency, thus preventing wrap-around while reducing overall time loss.

Inventive Principle:
Principle #19Periodic action

Solution Approach 2:

The patent maintains continuity of useful action by continuously accelerating ion packets at multiple overlapping frequencies. Instead of having long idle periods between acceleration events, the system ensures continuous ion packet generation and acceleration through multi-frequency operation, eliminating unnecessary time losses while maintaining the precision required to prevent spectral wrap-around.

Inventive Principle:
Principle #20Continuity of useful action

3Productivity

If the orthogonal acceleration frequency is increased to improve sampling duty cycle, then productivity is improved, but measurement precision deteriorates due to spectral wrap-around

Engineering Contradiction:
Improveion sampling duty cycleVSAvoidmass to charge ratio assignment accuracy
Core Design Contradiction:
ProductivityVSMeasurement precision

Solution Approach 1:

The patent segments the high-frequency sampling into multiple discrete frequency components (f1, f2, f3). Each frequency component operates at a level that prevents spectral wrap-around, maintaining measurement precision. The segmented frequencies collectively achieve the high overall sampling duty cycle that would be impossible at any single frequency, thus resolving the contradiction between productivity and precision.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The system uses coordinated periodic actions at multiple frequencies to achieve high productivity without sacrificing precision. Each frequency (f1, f2, f3) performs periodic acceleration at controlled intervals that prevent wrap-around, while the combination of these periodic actions creates an effective high-duty-cycle sampling system that improves productivity.

Inventive Principle:
Principle #19Periodic action

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 increases the ion sampling duty cycle and improves the accuracy of mass spectrometry by reducing wrap-around errors, allowing for more efficient and precise analysis of ions across a broader range of mass to charge ratios.

Implementation Method 1

An orthogonal acceleration electric field is then periodically applied across the orthogonal acceleration region

Methodology Applied
Scientific EffectOrthogonal acceleration electric field: Electric Field

Implementation Method 2

The length of the orthogonal acceleration region, the energy of the ions and the frequency of application of the orthogonal acceleration electric field determine the sampling duty cycle for sampling ions for analysis in the Time of Flight mass analyser

Methodology Applied
Scientific EffectTime of flight: Time of Flight

Implementation Method 3

Ions having approximately the same energy but different mass to charge ratios will have different velocities

Methodology Applied
Scientific EffectElectrical energy to kinetic energy conversion:

Data Source

PatentEP2104947B1Method of mass spectrometry and mass spectrometer
Publication Date: 2013.09.18 MICROMASS UK LTD
  • EP2104947B1 patent drawingFigure 1A~1B
  • EP2104947B1 patent drawingFigure 2A
  • EP2104947B1 patent drawingFigure 2B

AI summary

A Time of Flight mass analyser is disclosed wherein the time period between successive orthogonal acceleration pulses is less than the time of flight of ions having the maximum mass to charge ratio of interest. As a result, some ions are subject to wrap-around and will appear in a subsequent mass spectrum. Mass spectra obtained at two different sampling rates may be compared and mass peaks relating to ions which have and have not been subject to wrap-around may be identified.