现代有机质谱概论
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Modern Organic Mass Spectrometry ( OMS )
Molecular Mass Spectrometry
OMS is a basic and high-technical science,
In which,physics,electronics and computer
science were applied to study physical and
chemical character of organic molecules
? Mass Spectrometry had its origin in early last century
? Application of organic mass spectrometry for chemical
analysis occurred in early 1940s
Quantitative analysis of hydrocarbon mixtures ( 9 )
produced in catalytic crackers
Methods require time
Fractional distillation,refractive index > 200 hours
Organic mass spectrometry one hour or more
Beginning in the 1950s,chemists have used
commercial organic mass spectrometer for
identification and structural elucidation of a wide
variety of organic compounds
The use of the MS combined with the NMR
IR and UV revolutionized the way organic
chemists went about identifying and determining
the structure of organic molecules
Mass Spectrometry
? Determine molecular weight
? Elucidate structure of organic molecule
? Identify unknown compounds
? Quantify known materials
? Accuracy,sensitive and rapid
OMS has been a powerful
analytical tool in modern structure
chemistry and analytical chemistry
Before the middle of the 1970s
OMS could only analyze organic
molecules with molecular weight
below 1000 Da
1974 Plasma Desorption Mass Spectrometry PD-MS
1981 Fast Atom Bombardment Mass Spectrometry FAB-MS
1988 Electrospray Ionization Mass Spectrometry ESI-MS
1988 Matrix-assisted Laser Desorption Ionization
Time of Flight Mass Spectrometry MALDI-TOF-MS
Nobel Prizes have been awarded to a number of scientists associated with the
birth and development of mass spectrometry,or in which mass spectrometry has
aided an important discovery,
Sir Joseph John Thomson - Nobel Prize for Physics 1906
"in recognition of the great merits of his theoretical and experimental investigations on
the conduction of electricity by gases"
Frederick Soddy - Nobel Prize for Chemistry 1921
"for his contributions to our knowledge of the chemistry of radioactive substances,and
his investigations into the origin and nature of isotopes"
Francis William Aston - Nobel Prize for Chemistry 1922
"for his discovery,by means of his mass spectrograph,of isotopes,in a large number of
non-radioactive elements,and for his enunciation of the whole-number rule"
Hans G,Dehmelt and Wolfgang Paul - shared Nobel Prize for Physics 1989
"for the development of the ion trap technique"
Robert F,Curl Jr,& Sir Harold W,Kroto & Richard E,Smalley - shared Nobel Prize
for Chemistry 1996
"for their discovery of fullerenes" - using mass spectrometry
John Fenn and Koichi Tanaka with Kurt Wuthrich - share the Nobel Prize in
Chemistry 2002
"for their development of soft desorption ionisation methods for mass spectrometric
analyses of biological macromolecules"
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Organic Mass Spectrometry is a
name for a collection of techniques
used to measure the masses of organic
ions and their abundance in the gas phase
Main components of OMS
? Ion Sources
? Mass Analyzer
? Main Specification of OMS
Ion sources for organic mass spectrometry
Basic type Name and acronym Ionizing agent
Gas phase Electron impact ( EI ) Energetic electrons
Chemical ionization ( CI ) Reagent gaseous ions
Field ionization ( FI ) High-potential electrode
Desorption Field desorption ( FD ) High-potential electrode
Electrospray ionization ( ESI ) High electrical field
Matrix-assisted laser desorption ionization (MALDI ) Laser beam
Plasma desorption ( PD ) Fission fragments from 252Cf
Fast atom bombardment ( FAB ) Energetic atomic beam
Secondary ion mass spectrometry ( SIMS ) Energetic beam of ion
Thermospray ionization ( TS ) High temperature
Gas phase sources, the sample is first
vaporized and then ionized
Desorption sources, the sample in a solid
or liquid state is converted directly
into gaseous ions
MALDI-TOF-MS of rhEGF
Main components of OMS
? Ion Sources
? Mass Analyzer
? Main Specification of OMS
Mass Analyzer
? Magnetic Sector Analyzer
? Quadrupole Mass Analyzer
? Ion Trap Mass Analyzer
? Time of Flight Mass Analyzer
? FT-ICR Mass analyzer
Reverse Geometry Double Focusing Mass Spectrometer
V Kinetic energy of the ion
E Potential field applied across the plate
Ion Trap Mass Analyzer
Time of Flight Mass Analyzer
Fourier Transform Ion Cyclotron Resonance
Mass Analyzer
A diagram of an ion cycling in the magnetic
field between two electrode plates
Character of FTICR-MS
? Ultra-high resolution
? Ultimate mass accurate
? Enhances dynamic range
? The power of M S n
Main components of OMS
? Ion Sources
? Mass Analyzer
? Main Specification of OMS
Main Specification of OMS
? Mass Range
? Resolution
? Mass Accuracy
? Sensitivity
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Qualitative Analysis
? Pure substance identification
? Mixture Separation identification
Mass spectrometry is a powerful
analytical tool for identification
of pure organic molecules
Tandem Technology
? Gas Chromatography-Mass Spectrometry GC-MS
? Liquid Chromatography-Mass Spectrometry LC-MS
? Capillary Electrophoreses-Mass Spectrometry CE-MS
? Tandem Mass Spectrometry MS/MS
Liquid Chromatography-Mass Spectrometry
? LC-MS interface has been studied for more
than 1/4 century
? About 25 kinds of LC-MS interface has been
reported
? Before API,attempts were made to
couple HPLC analysis with a variety
of mass spectrometry techniques,But
these attempts were some success,
? The great advantages of API – MS is
its ready compatibility with separation
techniques such as HPLC and CE,
Atmosphere Pressure Ionization ( API )
? Atmosphere pressure chemical ionization ( APCI ) is
mainly used for HPLC-MS,
? Electrospray ionization ( ESI ) is used for HPLC-MS
and CE-MS
HPLC – APCI - MS
LC-MS is now a mature technique
Innovation in chromatographic part
? Short HPLC column ( 10 – 50 mm )
? Micro packing materials ( 5,3.5,1.7 um )
? 1 D HPLC - MS
? 2 D HPLC - MS
Capillary Electrophoresis – Mass Spectrometry
Tandem Mass Spectrometry
1978 Mclafferty Cornell University
1978 Cook Purdue University
Reversed geometry double-focusing mass spectrometer
MIKES ( Mass analyzed ion kinetic energy spectrometry )
1979 Yost
Triple Stage Quadrupole Mass Spectrometer
( TSQ-MS )
Tandem Mass Spectrometry ( MS/MS )
C I D of Peptide
Mass Spectrometry used in Biomedicine
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Identification of Pure Organic Compounds
? Molecular weight from mass spectrometry
? Molecular formulas from exact molecular weight
? Molecular formulas from isotopic ratios
? Structure information from fragmentation patters
? Compound identification from comparison spectra
? Computerized library search systems
Analysis of mixtures by tandem methods
? Gas Chromatography-Mass Spectrometry GC-MS
? Liquid Chromatography-Mass Spectrometry LC-MS
? Capillary Electrophoreses-Mass Spectrometry CE-MS
? Tandem Mass Spectrometry MS/MS
Mass spectrometry is now applied to
all the disciplines associated with
organic molecules
Main application of mass spectrometry in biomedicine
? Elucidation of the structure of organic and biological molecules
? Determination of the molecular weight of peptides,proteins and
oligonucleotides
? Determination of amiono acid sequences of peptides and proteins
? Identification of proteins
? Determination of protein mutation
? Determination of -SH and disulfide bond in proteins
? Determination of post-translational modification of proteins
? Study on high structure of proteins
? Study on non-covalent bond interaction between biomolecules
? Mass Spectrometry-based proteomics
? Oligonucleotides sequencing
? SNP determination
? Study on drug metabolism
? New drug discovery by proteomics approach
? study on drug mechanisms by proteomics approach
? Mass spectrometry-based metabonomics
? Diagnosis of metabolism disease
? Forensic application
? Determination of pesticides residues in food
? Testing for the presence of drugs in blood and urine in thoroughbred
racing horses and in Olympic athletes
? Analysis of aerosol particles
? Detection and identification of microorganism
? Modernization research of Chinese traditional herbs
谢 谢 ！
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Modern Organic Mass Spectrometry ( OMS )
Molecular Mass Spectrometry
OMS is a basic and high-technical science,
In which,physics,electronics and computer
science were applied to study physical and
chemical character of organic molecules
? Mass Spectrometry had its origin in early last century
? Application of organic mass spectrometry for chemical
analysis occurred in early 1940s
Quantitative analysis of hydrocarbon mixtures ( 9 )
produced in catalytic crackers
Methods require time
Fractional distillation,refractive index > 200 hours
Organic mass spectrometry one hour or more
Beginning in the 1950s,chemists have used
commercial organic mass spectrometer for
identification and structural elucidation of a wide
variety of organic compounds
The use of the MS combined with the NMR
IR and UV revolutionized the way organic
chemists went about identifying and determining
the structure of organic molecules
Mass Spectrometry
? Determine molecular weight
? Elucidate structure of organic molecule
? Identify unknown compounds
? Quantify known materials
? Accuracy,sensitive and rapid
OMS has been a powerful
analytical tool in modern structure
chemistry and analytical chemistry
Before the middle of the 1970s
OMS could only analyze organic
molecules with molecular weight
below 1000 Da
1974 Plasma Desorption Mass Spectrometry PD-MS
1981 Fast Atom Bombardment Mass Spectrometry FAB-MS
1988 Electrospray Ionization Mass Spectrometry ESI-MS
1988 Matrix-assisted Laser Desorption Ionization
Time of Flight Mass Spectrometry MALDI-TOF-MS
Nobel Prizes have been awarded to a number of scientists associated with the
birth and development of mass spectrometry,or in which mass spectrometry has
aided an important discovery,
Sir Joseph John Thomson - Nobel Prize for Physics 1906
"in recognition of the great merits of his theoretical and experimental investigations on
the conduction of electricity by gases"
Frederick Soddy - Nobel Prize for Chemistry 1921
"for his contributions to our knowledge of the chemistry of radioactive substances,and
his investigations into the origin and nature of isotopes"
Francis William Aston - Nobel Prize for Chemistry 1922
"for his discovery,by means of his mass spectrograph,of isotopes,in a large number of
non-radioactive elements,and for his enunciation of the whole-number rule"
Hans G,Dehmelt and Wolfgang Paul - shared Nobel Prize for Physics 1989
"for the development of the ion trap technique"
Robert F,Curl Jr,& Sir Harold W,Kroto & Richard E,Smalley - shared Nobel Prize
for Chemistry 1996
"for their discovery of fullerenes" - using mass spectrometry
John Fenn and Koichi Tanaka with Kurt Wuthrich - share the Nobel Prize in
Chemistry 2002
"for their development of soft desorption ionisation methods for mass spectrometric
analyses of biological macromolecules"
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Organic Mass Spectrometry is a
name for a collection of techniques
used to measure the masses of organic
ions and their abundance in the gas phase
Main components of OMS
? Ion Sources
? Mass Analyzer
? Main Specification of OMS
Ion sources for organic mass spectrometry
Basic type Name and acronym Ionizing agent
Gas phase Electron impact ( EI ) Energetic electrons
Chemical ionization ( CI ) Reagent gaseous ions
Field ionization ( FI ) High-potential electrode
Desorption Field desorption ( FD ) High-potential electrode
Electrospray ionization ( ESI ) High electrical field
Matrix-assisted laser desorption ionization (MALDI ) Laser beam
Plasma desorption ( PD ) Fission fragments from 252Cf
Fast atom bombardment ( FAB ) Energetic atomic beam
Secondary ion mass spectrometry ( SIMS ) Energetic beam of ion
Thermospray ionization ( TS ) High temperature
Gas phase sources, the sample is first
vaporized and then ionized
Desorption sources, the sample in a solid
or liquid state is converted directly
into gaseous ions
MALDI-TOF-MS of rhEGF
Main components of OMS
? Ion Sources
? Mass Analyzer
? Main Specification of OMS
Mass Analyzer
? Magnetic Sector Analyzer
? Quadrupole Mass Analyzer
? Ion Trap Mass Analyzer
? Time of Flight Mass Analyzer
? FT-ICR Mass analyzer
Reverse Geometry Double Focusing Mass Spectrometer
V Kinetic energy of the ion
E Potential field applied across the plate
Ion Trap Mass Analyzer
Time of Flight Mass Analyzer
Fourier Transform Ion Cyclotron Resonance
Mass Analyzer
A diagram of an ion cycling in the magnetic
field between two electrode plates
Character of FTICR-MS
? Ultra-high resolution
? Ultimate mass accurate
? Enhances dynamic range
? The power of M S n
Main components of OMS
? Ion Sources
? Mass Analyzer
? Main Specification of OMS
Main Specification of OMS
? Mass Range
? Resolution
? Mass Accuracy
? Sensitivity
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Qualitative Analysis
? Pure substance identification
? Mixture Separation identification
Mass spectrometry is a powerful
analytical tool for identification
of pure organic molecules
Tandem Technology
? Gas Chromatography-Mass Spectrometry GC-MS
? Liquid Chromatography-Mass Spectrometry LC-MS
? Capillary Electrophoreses-Mass Spectrometry CE-MS
? Tandem Mass Spectrometry MS/MS
Liquid Chromatography-Mass Spectrometry
? LC-MS interface has been studied for more
than 1/4 century
? About 25 kinds of LC-MS interface has been
reported
? Before API,attempts were made to
couple HPLC analysis with a variety
of mass spectrometry techniques,But
these attempts were some success,
? The great advantages of API – MS is
its ready compatibility with separation
techniques such as HPLC and CE,
Atmosphere Pressure Ionization ( API )
? Atmosphere pressure chemical ionization ( APCI ) is
mainly used for HPLC-MS,
? Electrospray ionization ( ESI ) is used for HPLC-MS
and CE-MS
HPLC – APCI - MS
LC-MS is now a mature technique
Innovation in chromatographic part
? Short HPLC column ( 10 – 50 mm )
? Micro packing materials ( 5,3.5,1.7 um )
? 1 D HPLC - MS
? 2 D HPLC - MS
Capillary Electrophoresis – Mass Spectrometry
Tandem Mass Spectrometry
1978 Mclafferty Cornell University
1978 Cook Purdue University
Reversed geometry double-focusing mass spectrometer
MIKES ( Mass analyzed ion kinetic energy spectrometry )
1979 Yost
Triple Stage Quadrupole Mass Spectrometer
( TSQ-MS )
Tandem Mass Spectrometry ( MS/MS )
C I D of Peptide
Mass Spectrometry used in Biomedicine
Outline
? Introduction
? Instrument of OMS
? Tandem Technology
? Main Application
Identification of Pure Organic Compounds
? Molecular weight from mass spectrometry
? Molecular formulas from exact molecular weight
? Molecular formulas from isotopic ratios
? Structure information from fragmentation patters
? Compound identification from comparison spectra
? Computerized library search systems
Analysis of mixtures by tandem methods
? Gas Chromatography-Mass Spectrometry GC-MS
? Liquid Chromatography-Mass Spectrometry LC-MS
? Capillary Electrophoreses-Mass Spectrometry CE-MS
? Tandem Mass Spectrometry MS/MS
Mass spectrometry is now applied to
all the disciplines associated with
organic molecules
Main application of mass spectrometry in biomedicine
? Elucidation of the structure of organic and biological molecules
? Determination of the molecular weight of peptides,proteins and
oligonucleotides
? Determination of amiono acid sequences of peptides and proteins
? Identification of proteins
? Determination of protein mutation
? Determination of -SH and disulfide bond in proteins
? Determination of post-translational modification of proteins
? Study on high structure of proteins
? Study on non-covalent bond interaction between biomolecules
? Mass Spectrometry-based proteomics
? Oligonucleotides sequencing
? SNP determination
? Study on drug metabolism
? New drug discovery by proteomics approach
? study on drug mechanisms by proteomics approach
? Mass spectrometry-based metabonomics
? Diagnosis of metabolism disease
? Forensic application
? Determination of pesticides residues in food
? Testing for the presence of drugs in blood and urine in thoroughbred
racing horses and in Olympic athletes
? Analysis of aerosol particles
? Detection and identification of microorganism
? Modernization research of Chinese traditional herbs
谢 谢 ！
