Università degli Studi di Bari CHIMICA ANALITICA STRUMENTALE

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1 Università degli Studi di Bari Corso di Laurea Magistrale in Scienze Chimiche Corso di CHIMICA ANALITICA STRUMENTALE 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), Matrix Assited Laser Desorption Ionization (MALDI), Desorption Ionization on Silicon (DIOS), ElectroSpray Ionization (ESI), Desorption Electrospray 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 Collisional Induced Dissociation (CID)

3 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 imaging of 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 and concentration profiles. Instrumentation. ToF-SIMS instruments. Imaging SIMS: Ion Microscope and Ion Microprobe instruments.

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 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

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 Examples of extra-terrestrial mass spectrometry

10 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 orbit in July The mission is still active (Cassini Solstice Mission, until September 2017). 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 was also used to measure the positive ion and neutral environments of Saturn's rings and icy moons.

11 MS search for organic compounds on meteorites

12 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