Mass spectrometry

Major components in a mass spectrometry

Formation (ionization), Separation (mass analyzer by m/z), Detection of ions

Ion source
Soft method: gives molecular weight information Hard method: Can used for remodeling structure
+
Electron ionization (M ) results in more fragmentation. (Hard method)
Chemical ionization (MH+), the soft technique giving little fragmentation, molecular ion is dominant.

Matrix assisted laser desorption (ionization), a very soft technique, very very few fragment
Matrices are typically small organic compounds (DHB, HABA, can absorb UV light)
The primary propose of matrix relative to the analyses is:
1. Matrix can co-crystallize with the analyses
2. Combination absorb radiation supplied by laser
3. Matrix then to be desorbed and excited into the gas phase upon irradiation, and initiate
proton transfer to the analyses to create the ion of interest for subsequence mass analysis
Electrospray ionization (ESI) can generate multiple charges (MH+, MH22+), used for large molecule

Atmospheric-pressure chemical ionization (APCI)

Similar source as ESI, but instead of putting a voltage on the spray itself, the voltage is placed on a
needle that creates a corona discharge at atmospheric pressures.
Compared to ESI: for less polar analyses is more effective then ESI

Desorption electrospray ionization

Gas Chromatography–Mass spectrometry (GC/MS)

Hyphenated (combined 2 technique together) analytical technique

For volatile and thermally stable substitutes, high temperature
Common interfaces: EI, CI

Liquid chromatography–mass spectrometry (HPLC/MS)

Room temperature, can be operated at normal atmosphere
Common interfaces: ESI, APCI
Analyzer
The main function of a mass analyzer is to separate the ions according to their m/z ratio.
1. Quadrupole mass filter: trajectory stability

2. Quadrupole ion trap filter: resonance frequency. It traps the ions in a two dimensional field,
have higher injection efficiencies and higher ion storage capacities
3. Time of flight (TOF): velocity (flight time)
Without the use of an electric or magnetic field, the separation is based on the kinetic energy
and velocity of the ions. Good for large molecules.

Ions are accelerated through same process and have same constant kinetic energy.
With lots of different m/z, they travel at different velocity and detected at different time.
4. Magnetic sector:
A magnetic field is used to separate the ions. Basically the ions of a certain m/z will have a
 unique path radius which can be determined if both magnetic field magnitude, and voltage
difference for region of acceleration (control of velocity)
Mass detector – MCP (electron multipliers as micro-channel plate)
Resolving power
m m
Higher resolving power means more ability to differentiate two m/z peaks 𝑅= 𝑜𝑟
∆𝑚 𝑚1⁄2 (𝐹𝑊𝐻𝑀)

Tandem mass analyzers–more than one analyzer (selected ion monitoring, SIM)