Università degli Studi di Bari SPETTROMETRIA DI MASSA

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1 Università degli Studi di Bari Corso di Laurea Magistrale in Scienze Chimiche Corso di SPETTROMETRIA DI MASSA II semestre, crediti ( ore) Prof. Ilario Losito illosdid@hotmail.com Sito Internet:

2 Outline Introduction to mass spectrometry (an historical perspective) Ionization Methods Electron Ionization/Impact (EI), Chemical Ionization (CI), Field Ionization (FI), Field Desorption (FD), Fast Atom Bombardment (FAB), Matrix Assited Laser Desorption Ionization (MALDI), Desorption Ionization on Silicon (DIOS), ElectroSpray Ionization (ESI), Desorption Electrospray Ionization (DESI) Mass Analysers 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 Collisional Induced Dissociation (CID)

3 Signal acquisition strategies for hyphenated techniques: GC-MS, GC GC-MS. Analysis of Biological Systems by Mass Spectometry Proteomics: peptide and protein analysis by LC-ESI-MS and MALDI- ESI-MS, MS-based bioinformatic approaches, profiling and imaging of proteins by MALDI-MS; diagnostic proteomics by SELDI-TOF-MS. Lipidomics: analysis of cell membrane lipids by LC-ESI-MS

4 MS History Mass spectrometry has a dynamic history dotted with Nobel laureates and a continuously advancing technology that has made significant inroads into drug discovery, protein characterization, and even disease diagnosis. J.J. Thomson (1906) F.W. Aston (1922) W. Paul J.B. Fenn (1989) Nobel laureates (2002) K. Tanaka The history of science clearly shows that MS had its roots in physics, branched into chemistry, and in the past two decades has budded into biology. Borman S., Russell H., Siuzdak G. Today's Chemist, 2003, p.47-49

5 The Physical Roots The history of MS begins with Sir Joseph John Thomson at the University of Cambridge. Thomson s "theoretical and experimental investigations on the conduction of electricity by gases" led to the discovery of the electron in 1897, for which Thomson was awarded the 1906 Nobel Prize in Physics. In the first decade of the 20th century, Thomson went on to construct the first mass spectrometer (then called a parabola spectrograph), in which ions were separated by their different parabolic trajectories in electromagnetic fields and detection occurred by the ions striking a fluorescent screen or photographic plate. J.J. Thomson and a cathode ray tube used to perform some of the first m/z measurements. Deflection of the electron was observed once the electric field was turned on.

6 Distinguished innovators in Mass Spectrometry Catherine Fenselau Fred W. McLafferty Klaus Biemann R. Graham Cooks Franz Hillenkamp Michael Karas

7 A Mass Spectrometry Timeline 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 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 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

8 Mass Spectrometry during World War II Magnetic sectors were used for the separation of uranium 235 and 238 isotopes, a key step in the research for the first atomic bomb (The Manhattan Project). Tuballoy was the term used for natural uranium.

9 The Calutron (California university cyclotron) Alpha 1 Calutron Detail of the two ion source guns of the initial alpha calutron. Ion beams exit upwards into the funnel-shaped electrode boxes.

10 Y-12 alpha 1 racetrack In the critical production period, in the first months of 1945, the calutrons, particularly the six beta calutrons of 36 tanks each, produced weaponsgrade U-235 using feed from the modified alpha calutrons and other sources. Virtually all the U-235 sent by courier on the train to Chicago and on to Los Alamos had passed through the beta calutrons. From these shipments Oppenheimer's physicists assembled the bomb that was to destroy Hiroshima.

11 Examples of extra-terrestrial mass spectrometry

12 Launch occurred at 4:43 a.m. EDT on October 15, 1997 from Launch Complex 40 at Cape Canaveral Air Force Station, Florida. The space-probe entered the Saturn in July The mission is still active. A quadrupole Ion and Neutral Mass Spectrometer (INMS) was mounted on the Cassini-Huygens probe to collect data useful to determine the composition and structure of positive ions and neutral particles in the upper atmosphere of Titan and the magnetosphere of Saturn. It is also used to measure the positive ion and neutral environments of Saturn's rings and icy moons.

13 MS search for organic compounds on meteorites

14 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, Methamphetamine, MDA, THC and others Sensitivities Explosives: picogram range Narcotics: sub-nanogram range 8 second analysis time

15 GID-3 - Chemical Warfare Agent Detection System GID-3 detects the most common nerve and blister agents and can be programmed to detect other agents such as blood, choking and chlorine gas. IMS (Ion Mobility Spectrometry) technology

16 Portable mass spectrometers for military protection Mass spectrometers act as sensitive chemical warfare detectors to protect troops in war on Iraq. A portable GC-mass spectrometer can detect the faintest trace of chemical agents used as weapons in the environment and are being used ahead of troop movements to provide protection. Low Detection Limits to Parts Per Trillion A microtrap concentrator enables detection and identification of volatile organic compounds in the low parts per billion/parts per trillion range, providing unprecedented sensitivity for on-scene analysis.