Mass Spectros
Mass Spectros
Mass Spectros
The bulk of the ions usually carry a unit positive charge, thus
m/z is equivalent to the MW of the fragment.
Mass analyzer
Detector
Sample
Readout
Ion Source
http://www.chem.uic.edu/web1/ocol/spec/MS1.htm
Sample Introduction
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Sample Ionization
Ionizing Agent
Electron Impact (EI) Energetic electrons
M + e → M.+ + 2e
Radical cation
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Chemical Ionization (CI) (1965)
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Electrospray Ionisation (ESI) (1985)
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In positive ionization mode, a trace of formic acid is often
added to aid protonation of the sample molecules
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Samples (M) with molecular weights greater than ca. 1200 Da give rise to
multiply-charged molecular-related ions such as
(M+nH)n+ in positive ionization mode and
(M-nH)n- in negative ionization mode.
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The number of charges on an ion is usually not known, but can be
calculated if the assumption is made that any two adjacent members in
the series of multiply charged ions differ by one charge.
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MALDI is also a "soft" ionization method
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MALDI is based on the bombardment of sample molecules with
a laser (N2 @ 337nm) light to bring about sample ionization.
The matrix transforms the laser energy into excitation energy for
the sample, which leads to sputtering of analyte and matrix ions.
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Fast Atom Bombardment (FAB)
Quadrupoles analyzer
Fourier transform
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Magnetic Sector Mass Spectrometers
The dependence of
mass-to-charge
ratio on the electric
and magnetic fields
is easily derived.
http://www.ivv.fraunhofer.de
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Trapped-Ion Mass Analyzers
Operates by storing ions in the trap and manipulating the ions by using
DC and RF electric fields in a series of carefully timed events.
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Detection and recording of sample ions
detector - monitors the ion current and amplifies it
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The output of the mass spectrometer (mass spectrum) is a
plot of relative intensity vs the mass-to-charge ratio (m/z).
base peak
(Intensity: 100%)
The most intense peak in the spectrum is termed the base peak
and all others are reported relative to it's intensity.
The most stable cations and radical cations predominate and give
intense signals in the spectrum.
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Generally, small peaks (so-called M+1, M+2, etc) are also
observed beyond M+ due to the natural isotopic abundance of
13C, 2H, etc.
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Many molecules with especially labile protons do not display
molecular ion (M+) peak.
Example:
Alcohol (R-O-H) – hydroxyl H is slightly acidic; highest
MW in the spectrum corresponds to
M-1 fragment.
Benzyl cation
due to loss of H; stable
due to πe delocalization
(i.e. base peak)
It is often more
informative to
identify fragments
by the mass which
has been lost.
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Commonly Lost Fragments m/z value
CH3 M – 15
OH M – 17
H2O M – 18
CN M – 26
CH2=CH2 M – 28
CH2CH3 M – 29
OCH3 M – 31
Cl M – 35
CH3C=O M – 43
OCH2CH3 M – 45
CH2 M - 91
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Common Stable Ions
O+. +.
H3C C O
R C O
+
R H
m/z = 43 m/z = M - 1
+.
+.
CH2
m/z = 91
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The relatively stable benzyl cation is thought to undergo
rearrangement to a very stable tropylium cation.
CH3+. CH2+.
M+ M-1
+.
-C2H2
+.
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Alkanes
Simple alkanes tend to undergo fragmentation by the initial
loss of a methyl group to form a (M-15) species.
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Aromatic Hydrocarbons
The fragmentation of the aromatic nucleus generates a
series of peaks having m/z = 77, 65, 63, etc.
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Carbonyl compounds (and in nitriles, etc.) undergoes expulsion
of neutral ethene via a process known as the McLafferty
rearrangement.
from unsubstituted
from acid amide
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Alcohols
In addition to losing a proton (M-1) and hydroxy radical (M-17),
alcohols tend to lose one of the α-alkyl groups (or hydrogens) to
form the oxonium ions.
Ethers
Following the trend of alcohols, ethers will fragment, often by
loss of an alkyl radical, to form a substituted oxonium ion.
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Halides
Organic halides fragment with simple expulsion of the halogen.
The 35Cl/37Cl ratio is roughly 3:1 and for bromine, the 79Br/81Br
ratio is 1:1.
m/z = 88 M+
m/z = 87 M-1; loss of H
m/z = 73 M-15; loss of CH3
m/z = 70 M-18; loss of H2O , charac. of alcohols
m/z = 45 must be the oxonium ion R’CR”=OH+,
where R’ = CH3 and R” = H
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Structure:
2-pentanol
MS Fragments:
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Example 2
Analysis: C7H12Br MW = 171.04
Tropylium ion;
Benzyl unit is present
- C2H2 M+ = 2 peaks of
equal intensity ;
characteristic of Br-
containing compound
Structure:
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Example 3
Analysis: C9H10O MW = 134.18
tropylium
Acylium ion;
CH3C≡O+)
- C2H2 M+
M-15;
loss of Me
Structure:
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Example 4
Analysis: C11H12O3 MW = 192.21
Structure:
4-nonanone
M+
http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/MassSpec 41
4,4-dimethylcyclohexene
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Thank you for your time
and attention!