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Compare the Advantages

and Disadvantages of
GC-MS to LC-MS
Gas Chromatography GC/liquid & gas
Injection
(vaporised)
Oven
Detector, Flame
FID ionisation
detector
Column
- capillary
Cylinder

- packed
(PC)
Integrator
Computer
C
y
l Carrier gas
Printer
i He, N2 plotter
n
d
e
Intensity

time
GC Chromatogram
GC-MS/liquid & gas
GC-MS / liquid & gas
Injection
(vaporised)

Oven
Detector, Flame
FID ionisation
detector
Column
Cylinder - capillary
- packed

Intensity
time
Chromatogram
Carrier gas Detector
He, N2 FID Flame Ionisation Detector
ECD Electron Capture Detector
He 4 GC, GCMS NPD Nitrogen phosphorus Detector
H2 2 GC, GCMS TCD Thermal Conductivity Detector
FPD Filter Photometric Detector
N2 28 GC, GCMS MS Mass Detector
AR/CH4 ECD
FID - general/universal detector
ECD - Ni63 radioisotop - halogenated compounds/Cl, Br
NPD - pesticide compounds
FPD - sulphurous/phosphorus compoundspesticides/ petrochemicals
FID qualitative & quantitative
A Full Range of Detectors

Interchangeable ionization detectors

TRACE GC
What is a Mass Spectrometer?
Ionization Mass Sorting Detector
+
M
Analyser Ion Detection
EI
Source 20eV Electric field Photo- Electron
70eV or multiplier multiplier
Magnetic field
Data Analysis
> Solid
Inlet > Liquid
> Gas
Source Spectrum
Introduction
M+
Intensity
Relative

m/z
Ion Source
Filament

e- EI/CI
To Mass
CI
CH4 Analyzer EI

Removable
Ionization
Volume
Lenses
GC-MS/liquid & gas
1. Mass ionization
Filament sample size
e e M+ Too much sample
e e create secondary ionization
Sample [M-1]+
Trap

2. Quadrupole 3. Detector
photomultiplier

M 1+
+
M 3+ M + M 3+ M 2 M 1+
2

4. Vacuum
10 6 torr
oil + air molecules

oil
GC-MS/liquid & gas
Injection
(vaporised)
O ven
Flam e
D etector,
FID ionisation
detector
C olum n
- capillary

Intensity
Cylinder

- packed

tim e
Chrom atogram

C arrier gas M+ M+ M+
He, N 2

108 150 178


OMe
CH 2 OH CH 2 OAc OMe

C 7 H 8 O = 108 C 9 H 10 O 2 = 150 C 11 H 14 O 2 = 178


Liquid Chromatography

Classical techniques
Quantitative evaluation
1. Select column to provide best separation
2. Sample collection
3. Evaporation
4. Weight
Liquid Chromatography
Introduction
of sample
Normal phase
Reverse phase
Solvent
pump Injector Column

Response A C

Solvent
mobile phase time (t)
Chromatogram
Very elaborate method
HPLC/liquid
Sample Normal phase
Gradient elution
variable polarity Reverse phase
Solvent Injector
Column
pump "Valve"

Detector
A C

Response
B
Two solvent system
mobile phase
Degassing time (t)

A C A C
Response

B Response B

time (t) time (t)


Advanced Techniques
Detectors V ery simple method
A C

Response
B

time (t)
HPLC Chromatogram
Universal
Ref ractive Index RI UV - single wavelength
UV-Visible Diode Array - multiple wavelengths

Selective
Electrochemical (Amperometric)
Conductivity (Ion chromatography)
Fluorescence detector
Light Scattering detector

High Sensitivity
Mass Spectrometry
HPLC versus GC Instrumentation
H P LC M o b ile Pum p In je c to r
p h a se
S ta tio n a ry a n d Liq u id <400 <400µl
m o b ile p h a se
bar
1
m l/m in
D a ta D e te c to r C o lu m n
e v a lu a tio n DAD oven
lig h t < 1 0 0 oC
d e te c to r
Id e n tic a l
S ta tio n a ry Flo w
C a rrie r In je c to r
p h a se c o n tro lle r
gas
GC
G as <5 bar <5 µl
1
m l/m in
D a ta D e te c to r C o lu m n
e v a lu a tio n MS oven
fla m e < 4 0 0 oC
d e te c to r
Ionisation
Forming Charged Particles (Ions):
* Electron impact (EI)
* Chemical Ionization (CI)
* Fast atom bombardment (FAB)
* Field desorption (FD)
* Electrospray ionization (ESI)
* Laser desorption (LD)
MS in LC/GC-MS
Detect and quantify the various species
eluting off the column according to their
m/z value with the help of electrical or
magnetic fields, or combination of both.

Provide definitive information as to


species identity
GC-MS
Combines high-resolution separation of
components with very selective and
sensitive detection.

Its use in all areas of science has


expended to the point of routine analysis.
LC-MS
Is a hyphenated technique, combining:
Separation power of HPLC,
Detection power of mass spectrometry.

Highly sensitive and capable of detecting the


target compounds.

Useful to remove the interferences from the


sample that would impact the ionization.
Natural Synergy between
Chromatography technology with MS
GC-MS LC-MS
Relatively straightforward Not so straightforward
interfacing of a capillary “odd couple relation” as if
GC effluent to MS interfacing fish (HPLC) to
bird (MS)
Sample Types
GCMS LCMS

Relatively low Nonvolatile, polar


molecular weight, non macromolecules,
labile, thermally thermally labile
stable, reasonably compounds especially
volatile and biopolymer with high
derivatizable molecular weight
Sample Preparation
GCMS LCMS

Derivatization reactions Large, polar, and


may be needed to thermally labile analytes
increase the volatility or that are not amenable to
block some polar sites of GC may be studied by
molecules LC/MS without
derivatization or with
minimal derivatization
Mobile phase
GCMS
LCMS
Relatively cheap with
the use of mobile Has a gradient
phase eg N2 system available is
the ability to change
Cannot use more the elution mixture
than one solvent easily
system. Expensive
Injection
GCMS LCMS
The vaporization of There are no inserts, no
sample (solvent, analytes thermal degradation and
and matrix) remains a few surface activity
fundamental limitation issues.
Thus it is a simple and
Might cause losses of precise injection
thermally labile and polar
compound

The injection advantage goes to LC-MS


Separation
GCMS LCMS
High resolution column Restricted to simple
generates high peak isocratic or gradient
capacity mixture of volatile buffers
and organic one
Use of gas mobile phase
Use of temperature
program and electronic
flow control
Relatively simple
maintenance

The separation advantage goes to GC-MS


Ionization
GCMS LCMS
Minimal success on EI
EI has a reproducible interface
foundation for spectral
database and a almost
universal application Most of the successful
ionization interface are
soft ionization process
Has the option for eg: ESI, APCI
switching to softer
ionization techniques of
positive or negative CI

A difficult decision
Sample Recovery
GCMS LCMS

Samples are Samples are


destroyed after reproducible after
analysis. analysis.

The sample recovery advantage goes to LCMS


Mass Spectral Coupling
GCMS LCMS
Stable mass spectral data Does not have nice
can be acquired with very analog peaks coming off
narrow chromatographic
peaks. Neither distortion one after another as MS
nor reduced intensity is simply monitors a series
observed in the mass of m/z values and records
spectrum. the intensity of ion current
at each value

The mass spectral advantage goes to GCMS


GCMS Application

Petroleum

Gasoline
Hydrocarbon gas analysis
Fuel and fuel oil analysis
Oxygenated additives in gasoline

Environmental

Determination of pesticides
Detection of PCBs (polychlorinated biphenyls) Air
pollution consituent analysis
Fast Analysis of Dioxin and related compounds
GCMS Application
Forensics

Blood alcohol analysis


Clandestine lab analysis
Monitoring drug purity
Analysis of commonly abused inhalants

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# " " $
LCMS Application

LC-MS is always the method of choice in


the pharmaceutical industry for
measurement of drugs and their
metabolites in biological matrices, and
proteomics
LCMS Application

Study of Proteomics
identification, isolation and purification of
proteins in a cell or body fluid
involves protease digestion (usually Trypsin)
followed by LC-MS with peptide mass
fingerprinting or LC-MS/MS (tandem MS) to
derive sequence of individual peptides.
LCMS Application

Routine drug analysis and selective


quantitation at trace levels
Separation and analysis of complex compound
mixtures
Structural interpretation and identity confirmation
of a diverse range of organic compounds
Molecular weight determination
Purity check of LC peaks employing 3D u/v and
visible wavelength monitoring with simultaneous
MS detection
LCMS Application

The advantages:

High sensitivity, specificity, small sample


requirements, minimal sample preparation, rapid
throughput and simultaneous measurement.

The disadvantages:

initial capital layout for equipment and availability of


suitably skilled scientific staff.
LCMS Application
MS source
capable of operating in both electrospray ionization
(ESI) and atmospheric pressure chemical ionization
(APCI) modes
compatible with most chromatographic separations
and having the ability to monitor both positive and
negative ion formations.

High flow rates without splitting

Take half the time


One injection accomplishes simultaneous ESI and APCI,
plus positive/negative ion switching
Simultaneous ESI/APCI mode increases throughput.
GC-MS and LC-MS
Both GC and LC-MS have equivalent
importance in chemical analysis depending on the
sample types and applications.
GC-MS -->the first choice of most analysts due
to its simplicity, cheaper cost and better ionization
and separation process.
LC-MS --> as the logical solution to handle the
sample which is not amenable to GC-MS