Corso di

CHIMICA ANALITICA STRUMENTALEII semestre, 6 + 2 crediti (48 + 30 ore)

Prof. Ilario Losito

e-mail: illosdid@hotmail.com

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

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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