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Orbitrap Mass Spectrometry
Component in Mass Spectrometer
Mass Analyser
• Ion seperator
• Heart of Mass spectrometry
Characterisation of mass spectrometry
• High resolution
• High rate of transmission of time.
Types of Mass Analyser
• Quadrupole Mass Analyzer.
• Time of Flight Mass Analyzer.
• Magnetic Sector Mass Analyzer.
Single focusing & Double focusing
• Electrostatic Sector Mass Analyzer.
• Quadrupole Ion Trap Mass Analyzers.
• Ion Cyclotron Resonance.
Magnetic Sector Mass Analyzer.
Quadrupole Mass Analyzer
Time of flight mass analyser
Electrostatic Sector Mass Analyzer
Quadrupole Ion Trap Mass Analyzers
Fourier Transform Ion Cyclotron
Resonance Mass Spectrometry
FTMS
FTMS - Fourier transform ion cyclotron
resonance (FTICR) mass spectrometry.
In such instruments, ions are trapped in a strong
magnetic field combined with a weak electric
field.
Excited trapped ions is detected, digitized, and
converted using Fourier transform into the
frequency domain and then mass spectra.
Advantage of FTMS
This technique an ultimate champion in mass
resolving power and mass accuracy.
This ability to detect ions with closely located
mass-to-charge ratios (m/z), e.g., isotopic peaks
of high-mass ions.
Allowed researchers to measure their masses m
with relative accuracies at the level of
<10−7−10−6.
INVENTION
The Orbitrap
a new type of
mass
analyzer
invented by
Alexander
Makarov.
Overview
• Newest addition to the family of
high-resolution mass spectrometry
analyzers.
• It combines high speed with
excellent quantification properties.
• Ranking favorably in many analytical
applications.
Why need for more analyser?
combination of the mass
analyzer with the detector
that ultimately determines
the quality and reliability of
analysis.
Thirst for orbitrap
• Numerous attempts were made over decades
to develop FTMS on the basis of
radiofrequency ion traps, electrostatic traps,
and multireflection systems.
• Such conditions created fertile soil for the
appearance and growth of a new member of
the FTMS family: the Orbitrap analyzer.
Stages of orbitrap analyser
• Appearing first as a cute scientific curiosity in
patent literature .
• Presented first at a conference of the
American Society for Mass Spectrometry in
1999.
• In 2005 as an accurate and compact mass
detector.
• The first commercial implementation was in a
hybrid instrument (LTQ Orbitrap) featuring a
linear ion trap front-end.
• Since then thousands of Orbitrap-based
instruments were produced and became a
common sight in analytical laboratories and
facilities worldwide.
The commercial orbitrap mass spectrometer has
the following performance characteristics:
• Mass resolution up to 150,000
• Mass accuracy of 2–5 ppm
• An ion abundance range of 1:5,000
over which accurate mass
measurements can be made .
• As good as 0.2 ppm mass accuracy for
peaks with signal‐to‐noise (S/N) ratio
>10,000,
• Published upper mass‐to‐charge (m/z)
limit of at least 6,000.
• Larger trapping capacity compared to
FT‐ICR and the 3‐D Paul trap
PRINCIPLE
Traping
• Ions are trapped because their electrostatic
attraction to the inner electrode is balanced
by their inertia.
• Thus, ions cycle around the inner electrode on
elliptical trajectories [route].
• In addition, the ions also move back and forth
along the axis of the central electrode.
• Their route in space resemble helices.
Injection
Proof-of-principle of the technology was
carried out using the direct injection of
ions from an external laser desorption and
ionization ion source.
This method of injection works well with
pulsed sources such as MALDI but cannot
be interfaced to continuous ion sources
like electrospray.
Injection
In order to inject ions from an external ion source,
the field between the electrodes is first reduced.
As ion packets are injected tangentially into the
field, the electric field is increased by ramping the
voltage on the inner electrode.
Ions get squeezed towards the inner electrode until
they reach the desired orbit inside the trap.
At that moment ramping is stopped, the field
becomes static, and detection can start.
Excitation
coherent axial oscillations of ion rings could be
excited by applying RF waveforms .
Detection
Axial oscillations of ion rings are detected by their image
current induced on the outer electrode which is split into
two symmetrical pick-up sensors connected to a
differential amplifier.
Like in FTICR-MS, all the ions are detected simultaneously
over some given period of time and resolution can be
improved by increasing the strength of the field or by
increasing the detection period.
The Orbitrap differs from FTICR-MS by the absence of a
magnetic field and hence has a significantly slower
decrease of resolving power with increasing m/z.
The Orbitrap mass analyzer consists
essentially of three electrodes as shown in
Figure .
Ions are stored and cooled
in a curved RF- only
quadrupole (C- trap)
RF is ramped down, radial
DC is applied
Ions are ejected along
lines converging on the
orbitrap entrance).
As ions enter orbitrap,
they are picked up and
squeezed by its electric
field
All ions start simul-
taneously, but light ions
enter Orbitrap analyzer
earlier that heavy ions
C-TRAP
lenses
Deflector
Scheme showing potential implementation of
ion activation in the orbitrap
C-Trap injection
C-TRAP
• All commercial Orbitrap mass spectrometers
utilize a curved linear trap for ion injection (C-
trap).
• By rapidly ramping down trapping RF voltages
and applying DC gradients across the C-trap.
• ions can be bunched into short packets similar to
those from the laser ion source.
• The C-trap is tightly integrated with the analyzer,
injection optics and differential pumping.
LTQ orbitrap in 2005
LTQ -Orbitrap
References
• https://onlinelibrary.wiley.com/doi/full/10.10
02/mas.20186
• Roman A. Zubarev and Alexander Makarov
Orbitrap Mass Spectrometry Anal. Chem.
2013, 85, 5288−5296.
• http://www.massspecpro.com/mass-
analyzers/orbitrap
• Thank you

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Orbitrap mass spectrometry

  • 2. Component in Mass Spectrometer
  • 3. Mass Analyser • Ion seperator • Heart of Mass spectrometry
  • 4. Characterisation of mass spectrometry • High resolution • High rate of transmission of time.
  • 5. Types of Mass Analyser • Quadrupole Mass Analyzer. • Time of Flight Mass Analyzer. • Magnetic Sector Mass Analyzer. Single focusing & Double focusing • Electrostatic Sector Mass Analyzer. • Quadrupole Ion Trap Mass Analyzers. • Ion Cyclotron Resonance.
  • 8. Time of flight mass analyser
  • 10. Quadrupole Ion Trap Mass Analyzers
  • 11. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
  • 12. FTMS FTMS - Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. In such instruments, ions are trapped in a strong magnetic field combined with a weak electric field. Excited trapped ions is detected, digitized, and converted using Fourier transform into the frequency domain and then mass spectra.
  • 13. Advantage of FTMS This technique an ultimate champion in mass resolving power and mass accuracy. This ability to detect ions with closely located mass-to-charge ratios (m/z), e.g., isotopic peaks of high-mass ions. Allowed researchers to measure their masses m with relative accuracies at the level of <10−7−10−6.
  • 14. INVENTION The Orbitrap a new type of mass analyzer invented by Alexander Makarov.
  • 15. Overview • Newest addition to the family of high-resolution mass spectrometry analyzers. • It combines high speed with excellent quantification properties. • Ranking favorably in many analytical applications.
  • 16. Why need for more analyser? combination of the mass analyzer with the detector that ultimately determines the quality and reliability of analysis.
  • 17. Thirst for orbitrap • Numerous attempts were made over decades to develop FTMS on the basis of radiofrequency ion traps, electrostatic traps, and multireflection systems. • Such conditions created fertile soil for the appearance and growth of a new member of the FTMS family: the Orbitrap analyzer.
  • 18. Stages of orbitrap analyser • Appearing first as a cute scientific curiosity in patent literature . • Presented first at a conference of the American Society for Mass Spectrometry in 1999. • In 2005 as an accurate and compact mass detector.
  • 19. • The first commercial implementation was in a hybrid instrument (LTQ Orbitrap) featuring a linear ion trap front-end. • Since then thousands of Orbitrap-based instruments were produced and became a common sight in analytical laboratories and facilities worldwide.
  • 20. The commercial orbitrap mass spectrometer has the following performance characteristics: • Mass resolution up to 150,000 • Mass accuracy of 2–5 ppm • An ion abundance range of 1:5,000 over which accurate mass measurements can be made .
  • 21. • As good as 0.2 ppm mass accuracy for peaks with signal‐to‐noise (S/N) ratio >10,000, • Published upper mass‐to‐charge (m/z) limit of at least 6,000. • Larger trapping capacity compared to FT‐ICR and the 3‐D Paul trap
  • 23. Traping • Ions are trapped because their electrostatic attraction to the inner electrode is balanced by their inertia. • Thus, ions cycle around the inner electrode on elliptical trajectories [route]. • In addition, the ions also move back and forth along the axis of the central electrode. • Their route in space resemble helices.
  • 24. Injection Proof-of-principle of the technology was carried out using the direct injection of ions from an external laser desorption and ionization ion source. This method of injection works well with pulsed sources such as MALDI but cannot be interfaced to continuous ion sources like electrospray.
  • 25. Injection In order to inject ions from an external ion source, the field between the electrodes is first reduced. As ion packets are injected tangentially into the field, the electric field is increased by ramping the voltage on the inner electrode. Ions get squeezed towards the inner electrode until they reach the desired orbit inside the trap. At that moment ramping is stopped, the field becomes static, and detection can start.
  • 26. Excitation coherent axial oscillations of ion rings could be excited by applying RF waveforms .
  • 27. Detection Axial oscillations of ion rings are detected by their image current induced on the outer electrode which is split into two symmetrical pick-up sensors connected to a differential amplifier. Like in FTICR-MS, all the ions are detected simultaneously over some given period of time and resolution can be improved by increasing the strength of the field or by increasing the detection period. The Orbitrap differs from FTICR-MS by the absence of a magnetic field and hence has a significantly slower decrease of resolving power with increasing m/z.
  • 28. The Orbitrap mass analyzer consists essentially of three electrodes as shown in Figure .
  • 29.
  • 30. Ions are stored and cooled in a curved RF- only quadrupole (C- trap) RF is ramped down, radial DC is applied Ions are ejected along lines converging on the orbitrap entrance). As ions enter orbitrap, they are picked up and squeezed by its electric field All ions start simul- taneously, but light ions enter Orbitrap analyzer earlier that heavy ions C-TRAP lenses Deflector
  • 31.
  • 32. Scheme showing potential implementation of ion activation in the orbitrap
  • 34. C-TRAP • All commercial Orbitrap mass spectrometers utilize a curved linear trap for ion injection (C- trap). • By rapidly ramping down trapping RF voltages and applying DC gradients across the C-trap. • ions can be bunched into short packets similar to those from the laser ion source. • The C-trap is tightly integrated with the analyzer, injection optics and differential pumping.
  • 35.
  • 36.
  • 39.
  • 40.
  • 41. References • https://onlinelibrary.wiley.com/doi/full/10.10 02/mas.20186 • Roman A. Zubarev and Alexander Makarov Orbitrap Mass Spectrometry Anal. Chem. 2013, 85, 5288−5296. • http://www.massspecpro.com/mass- analyzers/orbitrap