Orbitrap mass spectrometry

gopinathannsriramachandraeduin 2,609 views 42 slides Nov 19, 2020
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About This Presentation

it belongs to advanced instrument analysis. it discuss about the hypenated mass spectrometry orbitrap mass spectrometry


Slide Content

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 & D ouble 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. E xcited 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. A llowed 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 N ewest addition to the family of high-resolution mass spectrometry analyzers. It combines high speed with excellent quantification properties. R anking 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 . P resented first at a conference of the American Society for Mass Spectrometry in 1999. I n 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 I ons 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. T heir r oute 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 D eflector

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 - O rbitrap

References https://onlinelibrary.wiley.com/doi/full/10.1002/mas.20186 Roman A. Zubarev and Alexander Makarov Orbitrap Mass Spectrometry Anal. Chem. 2013, 85, 5288− 5296. http://www.massspecpro.com/mass-analyzers/orbitrap

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