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TRANSCRIPT
Corso di
CHIMICA ANALITICA STRUMENTALEII semestre, 6 + 2 crediti (48 + 30 ore)
Prof. Ilario Losito
e-mail: [email protected]
Sito Internet: http://puccini.chimica.uniba.it/~losito/indexChAnStr.htm
Corso di Laurea Magistrale in Scienze Chimiche
Università degli Studi di Bari
Outline
Introduction to mass spectrometry (an historical perspective)
Ionization Methods
Electron Ionization/Impact (EI), Chemical Ionization (CI),Matrix Assited Laser Desorption Ionization (MALDI), DesorptionIonization on Silicon (DIOS), ElectroSpray Ionization (ESI), DesorptionElectrospray Ionization (DESI)
Mass Analyzers
Quadrupoles (Q), Quadrupole 3D Ion Trap (QIT) and Linear Ion Trap(LIT), Fourier Transform-Ion Cyclotron Resonance (FT-ICR), Orbitrap(O), Time of Flight (TOF), hybrid or multiple configurations (QIT-ToF,Q(q)ToF, LIT-FTICR, LIT-O, TOF-TOF)
Tandem Mass Spectrometry
Operating modes, fragmentation strategies alternative to CollisionalInduced Dissociation (CID)
Signal acquisition strategies for hyphenated techniques: GC-MS, GC× GC-MS.
Study of Biological Systems by Mass Spectrometry
Proteomics: peptide and protein analysis by LC-ESI-MS and MALDI-ESI-MS, MS-based bioinformatic approaches, profiling and imagingof proteins by MALDI-MS; diagnostic proteomics by SELDI-TOF-MS.
Lipidomics: analysis of phospholipids by LC-ESI-MS
Secondary Ion Mass Spectrometry (SIMS)
General principles. Dynamic and Static SIMS. Charging andconcentration profiles. Instrumentation. ToF-SIMS instruments. ImagingSIMS: Ion Microscope and Ion Microprobe instruments.
Borman S., Russell H., Siuzdak G. Today's Chemist, 2003, p.47-49
The history of science clearly shows that MS had its roots in physics,branched into chemistry, and in the past two decades has budded intobiology.
Nobel laureates
Mass spectrometry has a dynamic history dotted with Nobel laureatesand a continuously advancing technology that has made significantinroads into drug discovery, protein characterization and even diseasediagnosis.
MS History
J.J. Thomson
(1906)
F.W. Aston
(1922)
W. Paul
(1989)
J.B. Fenn K. Tanaka
(2002)
The Physical RootsThe history of MS begins with Sir Joseph John Thomson at the University ofCambridge. Thomson’s "theoretical and experimental investigations onthe conduction of electricity by gases" led to the discovery of theelectron in 1897, for which Thomson was awarded the 1906 Nobel Prize inPhysics.
In the first decade of the 20th century, Thomson went on to construct thefirst mass spectrometer (then called a parabola spectrograph), in whichions were separated by their different parabolic trajectories inelectromagnetic fields and detection occurred by the ions striking afluorescent screen or photographic plate .
J.J. Thomson and acathode ray tube used toperform some of the firstm/z measurements.
Deflection of the electronwas observed once theelectric field was turnedon.
Distinguished innovators in Mass Spectrometry
Klaus Biemann
Michael Karas
Catherine Fenselau
Fred W. McLafferty
Franz Hillenkamp
R. Graham Cooks
1899 Early Mass Spectrometry
1934 Double focusing analyzer
1946 Time of Flight MS
1949 Ion Cyclotron Resonance (ICR)
1953 Reverse Geometry Double Focusing MS
Quadrupole MS
3D Ion trap
1956 GC/MS
Identifying Organic Compounds with MS
1966 Chemical Ionization
1969 Field Ionization
1974 Fourier Transform ICR
Extraterrestrial Mass Spectrometry
1976 Californium-252 Plasma Desorption MS
1980 Inductively Coupled Argon Plasma MS
1981 Fast Atom Bombardment (FAB) MS
1985 MALDI
1988 Linear Ion Trap
1989 ESI of Biomolecules
1990 Protein Conformational Structure
1991 Noncovalent Interactions with ESI
1992 Low Level Peptide Analysis
1993 Oligonucleotide Sequencing
1993 Protein Mass Mapping/Fingerprinting
1996 MS of a Virus
1999 Desorption/ionization on silicon (DIOS)
1999 Isotope-Coded Affinity Tags (ICAT)
2004 Desorption Electrospray Ionization (DESI)
2005 Orbitrap
A Mass Spectrometry Timeline
Mass Spectrometry during World War II
Magnetic sectors were used for the separation of uranium 235 and 238isotopes, a key step in the research for the first atomic bomb (TheManhattan Project). Tuballoy was the coded term used for naturaluranium.
Examples of extra-terrestrial mass spectrometry
Launch occurred at 4:43 a.m. EDTon October 15, 1997 from LaunchComplex 40 at Cape CanaveralAir Force Station, Florida. Thespace-probe entered the Saturnorbit in July 2004. The missionended in September 2017.
A quadrupole Ion and Neutral MassSpectrometer (INMS) was mounted on theCassini-Huygens probe to collect data usefulto determine the composition and structureof positive ions and neutral particles in theupper atmosphere of Titan and themagnetosphere of Saturn.
It was also used to measure the positive ionand neutral environments of Saturn's ringsand icy moons.
MS search for organic compounds on meteorites
http://trace.smithsdetection.com/products/Default.asp?Product=55§ion=Military
MS detection of explosives and narcotics
• Dual Ion Mobility Spectrometry (IMS) Technology
• Operating Modes: Explosives/Narcotics simultaneously, Explosives only, Narcotics only
•Explosives detected include RDX, PETN, NG, TNT, HMX, TATP and others
•Narcotics detected include Cocaine, Heroin, Amphetamine, Methamphe-tamine, MDA, THC and others
•Sensitivities
Explosives: picogram range
Narcotics: sub-nanogram range
• 8 second analysis time