Spettrometria di massa

Indice

La spettrometria di massa (MS)

Sviluppo storico della strumentazione in MS
Strumentazione analitica in MS: sorgenti ioniche ed
analizzatori di massa
Database analitici e library
Spettrometria di massa Tandem
Tecniche infenate con MS per l’analisi di miscele
complesse

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 Spettrometria di massa

La spettrometria di massa studia gli ioni in fase gassosa

Particella atomica o molecolare avente una
Cos’e’ uno ione?
carica (IUPAC)
Quali ioni è possibile Inorganici, organici a basso PM fino a 108
studiare? Dalton
Come vengono prodotti gli
Ionizzazione
ioni?
Campo elettrico
Come vengono studiati gli Campo magnetico
ioni? Radiofrequenze
Field-free regions
Quale tipo di informazione
Qualitativa e quantitativa
è possibile ottenere?

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 Spettrometria di massa

Identificazione di composti

Spettro di Massa Massa Molecolare

HR MS Stechiometria

Schema di frammentazione Informazioni strutturali

MSn Informazioni strutturali, an. qualitativa

Ion mobility Conformazione

Imaging Mappa degli Analiti

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 Spettrometria di massa
Mobilità Ionica - Spettrometria di massa (IM-MS)
ioni separati fatti
correre nel campo
elettrico con un
gas inerte in
controcorrente.
Separazione in
base alla sezione
trasversale
collisionale
https://research.fit.edu/chouinard/research/

i o n e
l icaz
ap p Strumenti portatili per la determinazione
d i
Ion Mobility in the Common Life
p i o di esplosivi o sostanze stupefacenti
se m
E

https://youtu.be/f1rhrDzSo9I

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 Spettrometria di massa

MS IMAGING analisi su sezione del

m pio
E s e cervello di un topo

a) Representative protein DESI

mass spectrum of a washed
mouse brain tissue section
w i t h o p t i m i z e d FA I M S
parameters. Mass spectra are
an average of 25 scans.
Different charge states of the
same protein species are
denoted by same colored
labels. (b) DESI-MS ion
images of selected protein
species as well as an optical
image of a serial H&E stained
mouse brain tissue section are
shown.

Desorption electrospray ionization (DESI)

High field asymmetric waveform ion mobility (FAIMS) Anal. Chem. 2018, 90, 13, 7785-7789

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 Spettrometria di massa

La spettrometria di massa è una

tecnica distruttiva. Il campione
analizzato in MS non può essere
riutilizzato.

però ne uso quantità

minime

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 Spettrometria di massa
Componenti di uno spettrometro di massa.

L’analizzatore di massa è mantenuto in condizioni di alto vuoto (10-3–10-8 torr), per evitare che le
molecole vengano deviate dalla loro traiettoria a seguito di collisioni con le molecole gassose
dell’ambiente.

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 Spettrometria di massa
Ionizzazione
Molecola ! Ione
M + e- è M+* +2e-
M + H+ è [MH]+
M + nH+ è [MHn]n+
M - H+ è [M-H]-
M - nH+ è [M-Hn]n- Analizzatore
Settore magnetico Separazione degli

Quadrupolo ioni secondo il
Sistema di introduzione Sorgente Ionica Tempo di volo l o r o r a p p o r t o
(Sistemi di introduzione a (EI, CI, FD, FAB, Trappola ionica, massa/carica
carica o a sonda; GC; HPLC; SIMS, ESI, APCI, FT-ICR (m/z)
CE…) MALDI, DESI..) Orbitrap
Ibridi
Nello spazio:
Settore
Quadrupolo
m/z - rapporto massa/carica:
Tempo di volo
Spettrometria di massa tandem Ibridi

massa di uno ione (espressa in
Dalton oppure u) divisa per il
Nel tempo:
Trappola ionica, FT-ICR,
numero di cariche sullo ione Orbitrap

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 Spettrometria di massa
Simon Maher, Fred P. M. Jjunju, and Stephen Taylor: Colloquium: 100 years of mass spectrometry: … 123

Più di 100 anni di spettrometria di massa

REVIEWS OF MODERN PHYSICS, VOLUME 87, JANUARY–MARCH 2015

FIG. 10 (color online). Summary time line of major advances in MS.

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 through a slit in a grounded metal plug (B). A voltage is applied between aluminum plates (D and E) and a scale situated on the end of
the tube measures the ray deflection. Adapted from Thomson, 1897.
Spettrometria di massa
cathode rays (Goldstein, 1876). In 1886 he discovered what he mean velocity of the particles. Thomson then proceeded to
termed “canal rays” while studying the electrical discharges measure the deflection of the cathode rays due to the electric
In a series of experiments using cathode
observed when the cathode of a cathode-ray tube was ray field alone; knowing the length, separation, and applied
tubes, JJ Thomson
perforated concluded
(Goldstein, 1898). He thatobserved
cathode that rays
canal rays voltage across the metal plates as well as the horizontal speed
traveled in the opposite direction
were particles with a negative charge and much to the (then unidentified) of the rays, the charge-to-mass ratio (e=m ) was calculated
negatively charged particles of cathode rays and therefore using1
smaller in size than an atom. Thomson published
must be positively charged (Fig. 3).
this work Inin1895 1897, for which
the French physicist hePerrin
receivedconfirmedmuch that canal
! "
e Vl
acclaim rays - he was awarded the Nobel Prize
were positively charged and that the charge magnitude for tan θ ¼ . ð1Þ
m dv2x
physics was in approximately
1906 for equal this towork.
that of theHiscathode
negative
rays (Perrin,
1895). This discovery
particles were later renamed 'electrons'.prepared the way for the historic Here V is the voltage applied to the plates, l is the length
experiments of Thomson (1897) leading to the discovery of of the plates, d is the plate separation, vx is the horizontal
116 the electron (originally termed
Simon Maher, “corpuscle”)
Fred P. M. Jjunju, andwhich
StephenledTaylor:
to him velocity
Colloquium: of theof cathode
100 years rays, and…θ is the angle of the beam
mass spectrometry:
receiving the Nobel prize in Physics (1906). deflection.
Thomson confirmed that cathode rays consist of negatively Thomson had discovered the essential nature of the
charged particles and was able to measure the ratio of the cathode rays; however, the nature of the canal rays remained
electric charge of a particle to its mass (e=m ). Using a similar to be identified. The magnetic and electric deflection of
experimental approach to Perrin, Thomson deflected the canal rays was first measured by Wilhelm Wien in 1898. He
cathode rays with a magnet to determine if the charge and found that the velocity of canal rays was much smaller than
rays could be separated. He found that they could not and that of the cathode rays and that the corresponding ratio e=m
concluded that they are the same thing. This was confirmed by was also smaller. In his experiments, Wien identified an
deflecting the cathode rays with a magnet away from the unknown positive particle (which we now know as a proton)
detector for which no appreciable signal was observed. to be equal in mass to the hydrogen atom (Wien, 1898).
However, when the cathode rays were deflected toward the
Wien also received a Nobel prize in physics (1911) but for
detector the signal increased. In his second experiment,
his earlier work regarding heat radiation. Thomson, in
Thomson attempted to deflect the cathode rays by applying
considering the work of Wien with canal rays (positive
an electric field between a pair of metal plates, an experiment
rays), commented:
previously carried out by Hertz (1892). Thomson was able to
FIG. 4 (color online).
observe Thomson’s
the beam cathode-ray
deflection produceddeflection
by theapparatus. Rays from the cathode (C) pass through a slit in the anode (A) and
electrically
through charged
a slit in ametal
grounded
plates (Fig. 4). Hertz had previously observed aluminum
metal plug (B). A voltage is applied between “The composition
plates (D and E) of andthese positive
a scale situatedrays [investi-
on the end of
the tubenomeasures the ray
effect. This wasdeflection.
possibly dueAdapted
to poorfromvacuum
Thomson, 1897.
conditions gated by W. Wien] is much more complex than that
and/or space charge effects on (or near) the sides of the tube ofhttps://edu.rsc.org/feature/mass-spectrometry-the-early-days/2020189.article
the cathode rays, for whereas the particles in the
REVIEWS OF MODERN PHYSICS, VOLUME 87, JANUARY–MARCH 2015
shielding the externally applied field. In the third of cathode rays are all of the same kind, there are in the
positive rays many different kinds of particles. We
cathodeThomson’s historic
rays (Goldstein, experiments
1876). In 1886 hehediscovered
used a combination
what he of
mean velocity of the particles. Thomson then proceeded to
Metodi
termed electric
“canal whileStrumentali
and magnetic
rays” fields andthe
studying was in
able to infer
electrical Chimica
the
discharges ratio e=mmeasureAnalitica,
the deflection of theAA
can, however, by the following 2020-2021
cathode
method sort these
rays due to the electric
!11
 and quantitative
observed when massthespectrometric
cathode of analysis is centered
a cathode-ray on the
tube was firstfield alone; knowing
idea of direct in situ MS analysis on unprocessed samples in introduced by Faradaythe(1834).length,He separation, and applied
used it to describe the
their natural environment. Such
Spettrometria di massa
perforated (Goldstein, 1898). He observed that canal rays charge
samples could be bricks,
voltage acrosswhich
carriers the metal
passedplates as well
between as the horizontal
electrodes immersedspeedin
traveled in the opposite direction to the (then unidentified) anofaqueous the rays, the charge-to-mass
medium. In 1870 the Englishratio (e=m ) was Crookes
physicist calculated
bodily fluid (e.g., blood, urine), clothing, biological tissue, 1
negatively charged particles of cathode rays and therefore invented using the “Crookes tube,” an electrical discharge tube
etc. In the DESI ionization method, a fine nebulized electro-
must be positively charged (Fig. 3).
One year later, in 1898, Wilhem Wien, while working as
spray of high velocity charged liquid microdroplets is directed developed from the earlier “Geissler ! " tube.” The key advance
an assistant
In 1895 the French physicist Perrin confirmed that canal made by Crookes was to use an improvedto Hermann Helmholtz in
e Vl Sprengel vacuum Berlin, was
at a surface. A solvent desorbs sample molecules from inspired the tan θ .
rays were positively charged and that the charge magnitude pumpby(Crookes, Thomson's1875). Thework¼
m
reduced andtube
dv 2 began
pressure his own
meant an
ð1Þ
surface, ionizes them, and carries them to the mass spectrom- x
was approximately equal to that of the cathode rays (Perrin,
eter in secondary microdroplets through a transfer capillary
investigations into free
increased mean cathode
path forand canal rays.
the negatively charged Using very
particles
1895). This discovery prepared the way for the historic powerful makingelectromagnets,
Here Vupis the
the cathode-ray he beams.
voltage applied observed Anplates,
to the thatlobserver
early isthe canal
of
the length
(Fig. 2, upper). In parallel with the development of DESI
experiments of Thomson (1897) leading to the discovery rays of deflected
charged in ad was
of the particles
plates, direction
is thetheplate opposite
German scientist
separation, vto isthe
x Goldstein cathode
who
the horizontal
another ambient ionization source, direct analysis in real time
the electron (originally
Laramée,termed “corpuscle”)
2005) waswhich led to In
him advanced
velocity the understanding
of the cathode of glow
rays, and θadischarge
ispositive
the angletubesof naming
the beam
(DART) (Cody, and Durst, introduced. rays, which implied they carried charge of
receiving the Nobel prize in Physics (1906).
DART an electrical potential is applied to a gas with a high the observable
deflection. light emissions (from the Crookes tube) as
Thomson confirmed electricity, and this led them to be renamed as 'positive
ionization potential (e.g., that cathode
nitrogen rays consist
or helium) to formof anegatively
plasma
rays'.
Thomson had discovered the essential nature of the
charged particles and was able to
of excited-state atoms and ions, and these desorb lowmeasure the ratio of the cathode rays; however, the nature of the canal rays remained
electric charge of a particle to its mass
molecular-weight molecules (Fig. 2, lower). The advance (e=m ). Using a similar to be identified. The magnetic and electric deflection of
experimental
represented
approach to Perrin, Thomson deflected the canal rays was first measured by Wilhelm Wien in 1898. He
Thomsonby ambient ionization methods addresses the
cathode raysinwith
his laboratory
a magnet to determine if the charge and found that the velocity of canal rays was much smaller than
practical aspect of laborious sample preparation prior to
rays could be separated. He found that they could not and that of the cathode rays and that the corresponding ratio e=m
MS analysis.
concluded that they are the same thing. This was confirmed by was also smaller. In his experiments, Wien identified an
deflecting the cathode rays with a magnet away from the unknown positive particle (which we now know as a proton)
II. LAYING THE FOUNDATIONS
detector for which no appreciable signal was observed. to be equal in mass to the hydrogen atom (Wien, 1898).
However, when the cathode rays were
MS in its modern form has been the consequence of deflected toward the
Wien also received a Nobel prize in physics (1911) but for
detector the signal increased. In his
important scientific and technological advances in the past,second experiment,
his earlier work regarding heat radiation. Thomson, in
Thomson attempted to deflect the cathode
in particular, developments in the 19th century which eluci- rays by applying
3. Canal rays
considering
FIG. the formed
work of in front
Wien of the
withperforated
canal rayscathode (C)
(positive
an electric
dated field between
the electrical nature ofa matter
pair of and
metal plates,
later an experiment
the application of in rays),
a discharge tube. A is the anode. Adapted from Wien, 1923.
commented:
previously carried out by Hertz (1892). Thomson was able to
observe the beam deflection produced by the electrically
Rev. Mod. Phys., Vol. 87, No. 1, January–March 2015
charged metal plates (Fig. 4). Hertz had previously observed “The composition of these positive rays [investi-
no effect. This gated by W. Wien] is much more complex than that
Thomson's cathode ray was
tube, possibly
1897 due to poor vacuum conditions
and/or space charge effects on (or near) the sides of the tube of the cathode rays, for whereas the particles in the
shielding the externally applied field. In the third of cathode rays are all of the same kind, there are in the
Thomson’s historic experiments he used a combination of positive rays many different kinds of particles. We
electric and magnetic fields and was able to infer the ratio e=m can, however, by the following method sort these
ofhttps://edu.rsc.org/feature/mass-spectrometry-the-early-days/2020189.article
the corpuscles. particles out…” (Thomson, 1913).
By adjusting the magnetic field strength in the region
REVIEWS OF MODERN PHYSICS, VOLUME 87, JANUARY–MARCH 2015
Thomson began working with positive rays in 1899
between the metal plates Thomson was able to cancel the
following his interest in the experiments of Wien
Metodi
deflection essentiallyStrumentali
balancing the forces due intoChimica
the electric Analitica, AA 2020-2021
(Thomson, 1899). By 1911, using a refined version of
!12
 Thomson could then plot a mass spectrum of ion abundance other about 22” (Thomson, 1913).
against relative mass. Mass spectrometry was born.
Spettrometria di massa
Ion detection methods had shifted from fluorescent tubes
B. Discovery of isotopes
(Thomson, 1907) to photographic plates (Thomson, 1911) and
then ion collectors (Faraday cup). The difference is subtle yet Following the end of World War I, Aston, previously a
Nascita della MS: Photographic plates (and fluorescent tubes) pro-
significant. research assistant to Thomson but now under the direction of
Rutherford, tried to understand the mystery of the m=e 22 line
“Parabola Spectrograph”
vided a visible trace of all the various ions, i.e., simultaneous
detection of all the e=m species present were recorded at any
given time. However, these detection methods were capable
only of providing a qualitative and at best semiquantitative
measurement, the net result being an image spectrum.
Whereas incorporating ion counting detection methods and
Using an oscilloscope-like screen at the end of
causing only a single e=m to be recorded for a given set of
the tube (i.e. a screen coated
conditions, Thomsonwith
was a material
able to measurethat
ion intensity and
fluoresced whenproduce
hit bya mass
the spectrum
rays, thus(Fig. 5). enabling
the deflections induced by the electrical and
magnetic fields to be recorded accurately)
Thomson identified the positive ions from H2 and
He. His mass spectrograph later (in 1913)
showed that neon has a relative atomic mass of
20, but was always accompanied by a much
weaker parabola associated with mass 22.7  He
suggested various possibilities (eg  doubly
ionised CO2 impurity, or the presence of a
hydride NeH2), but soon hit on the notion of a
heavier isotope of neon, thus accounting for the
non-integral measured atomic mass of the gas,
20.2.
Thomson’s mass spectrum of carbon
FIG. 5 (color online). FIG. 6. Parabola spectrograph result showing isotopes of 20 Ne

monoxide (CO). From Thomson, 1913. and 22 Ne.Adapted from Thomson, 1907.

Rev. Mod. Phys., Vol. 87, No. 1, January–March 2015

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 Spettrometria di massa
Nascita della MS: “Parabola Spectrograph”

Thomson was, however, dissatisfied with his photographic method of

recording the parabolas. The problem was that lightweight species
penetrated the film deeply, causing a disproportionate amount of
blackening, compared to heavier ions, and thus quantitative
estimations of beam intensities were impossible.  He eventually solved
this problem by constructing a slit in the tube where the photographic
film would normally sit. Behind this slit was a Faraday cup that
collected any ion charge. The intensity of the charge was estimated by
noting the time it took for a charged electroscope to discharge. By
slowly changing the magnetic field, the ion beams could be
positioned, one at a time, on the slit, and their intensities noted. From
his results he plotted intensity against relative mass: Thomson had
Figure 1 Thomson's mass spectrum CO
invented the world's first scanning mass spectrometer.

In 1913, Thomson published a monograph entitled “Rays of Positive

Electricity and Their Application to Chemical Analysis” (Thomson,
1913). The foresight of Thomson regarding the potential of this
analytical technique was evident in the foreword:
“... one of the main reasons for writing this book was the hope that it
might induce others, and especially chemists, to try this method of
analysis. I feel sure that there are many problems in Chemistry which Figure 2 Modern mass spectrum of CO
could be solved with far greater ease by this than by any other
method.”
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 nesium (Dempster, 1921), four isotopes of zinc (Dempster, providing improved measur
1922), and is credited with the discovery of uranium 235. Furthermore, the resulting
Spettrometria di massa Dempster’s magnetic sector analyzer established the basic
design theory that is still used for sector instruments today
fragmentation pattern which
print” for characterizing a s
(Fig. 7). In Dempster’s instrument ions are accelerated from sources was made by se
the ion source (G) through a narrow slit (S1 ). They are then including Mattauch (Matta
Milestones: Analizzatori a settore magnetico: (Herzog, 1934), Bainbridg
(Nier, 1947). Such advances
of complex molecular str
(Hustrulid, Kusch, and Tate
The resolution of the 1
developed by Dempster wa
conditions of the ions in to
the ion velocity (large ion e
this and proposed a so-called
included velocity as well as
Dempster, 1929). The basis
as a Wien filter) was previou
Around the same time in 1918, Dempster at the his investigations of canal r
Aston’s mass spectrograph
University of Chicago constructed a magnetic magnetic fields perpendicula
sector analyzer. spectrum and permitting onl
to be transmitted.
Further improvement in
the sector instrument led to
focusing sector instrument. T
direction and velocity focusi
magnetic and electric sector
is able to obtain higher resol
https://en.wikipedia.org/wiki/Electron_ionization

focusing instrument with a

refocuses ion beams that are
FIG. 7. Dempster’s 180° magnetic sector instrument. From and direction without loss of
Dempster, 1918. instrument was described b

Rev. Mod. Phys., Vol. 87, No. 1, January–March 2015

Magnetic sector instruments separate ions in a magnetic field according to their charge and momentum.
In Dempster’s instrument ions are accelerated from the ion source (G) through a narrow slit (S1). They are
then deflected through 180° by a homogenous magnetic field in the analyzer region (A) and ions of a
particular m/z are allowed to pass through a second slit (S2) and register a charge on the electrometer (E).

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 Spettrometria di massa

Milestones: Ionizatore ad impatto elettronico

Bleakney (1929) improved on the work of

Dempster through the development of the
electron impact ion source [also known as
electron ionization (EI)]. This is now used as a
standard ionization source in MS.

https://en.wikipedia.org/wiki/Walker_Bleakney

The improvement made by Bleakney was to separate the fields controlling the electron and ion
beams thus providing improved measurements of molecular ionization. Furthermore, the resulting
mass spectrum would include a fragmentation pattern which could be considered as a “fingerprint”
for characterizing a sample.

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 Spettrometria di massa

Up until the early 1950s the majority of mass

spectrometers (or spectrographs) which had
been developed relied on magnetic fields for
mass analysis. These instruments are
commonly referred to as “static.” Static
instruments have electric and/or magnetic
fields that remain constant during the
passage of an ion, exemplified by the mass
spectrograph which records various e/m ion
beams at different locations on a
photographic plate. In contrast a dynamic
instrument uses time varying (dynamic) fields
to focus ions of a given m/z on to a suitable
detector and therefore allowing rapid By the late-1940s mass spectro meters were being
used to identify 
identification of a wide range of constituent
components from a sample.

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 Spettrometria di massa

Milestones: Analizzatore a quadrupolo e a trappola ionica

In 1950-1960, new concepts in mass analysis,

the quadrupole mass spectrometer (QMS), first
described by Paul and Steinwedel (1953) and
the quadrupole ion trap (QIT), which utilizes a
three-dimensional field to trap ions, were
introduced.
The QIT functions as both an ion store and a
mass spectrometer. Paul’s pioneering work
was recognized by the award of the Nobel
prize in physics (1989) which he shared with
Hans Dehmelt and Norman Ramsey.
Photo from the Nobel Foundation archive.
Wolfgang Paul
The first experiments on trapping atoms and ions were made in the laboratory of Wolfgang Paul in Bonn in
the 1950s. Paul showed that it was possible to focus atoms in a beam by using a six-pole magnetic field.
Together with his collaborator H. Steinwedel he showed that ions with different masses could be separated
by a four-pole electrical field with a radio-frequency field superimposed. This was developed into a standard
method for mass separation, now widely used. The “Paul trap” now used in ion-trap spectroscopy is a
further development of this mass filter. Another kind of ion trap, the “Penning trap”, also used for this
purpose, was developed simultaneously in Paul’s laboratory and by Hans Dehmelt and his co-workers in
Seattle, Washington
https://www.nobelprize.org/prizes/physics/1989/press-release/
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 Spettrometria di massa
Introduction
Milestones: Sorgente ionica ESI e MALDI
Nobel Prize Winning Technology
John Fenn and Koichi Tanaka won the Nobel Prize in Chemistry in 2002
John Fenn
for the and KoichiofTanaka
development won
two soft the Nobel
ionization Prize in Chemistry in
technologies:
2002 for the development of two soft ionization technologies:

• Electrospray technology, Dr. Fenn

Electrospray technology, Dr. Fenn

Soft laser
• Soft desorption,
laser Dr.Tanaka
desorption, Dr. Tanaka

Introduzione
Passaggi fondamentali
Procedura di MS standard
• Il campione (solido, liquido, gassoso) viene
ionizzato
Campione
• Durante la ionizzazione le molecole del campione
possono rompersi generando frammenti carichi
• Gli ioni vengono separati in funzione del loro
rapporto massa/carica (m/z) +
Ionizzazione +
• Gli ioni vengono rivelati da un meccanismo in grado + + + +
(positiva o negativa)
di identificare le particelle cariche (per es., un
elettromoltiplicatore)
• I risultati sono visualizzati sotto forma di spettri con + + +
Separazione in base al + +
l'abbondanza relativa in funzione del rapporto m/z rapporto massa/carica +
• L'identificazione viene eseguita correlando masse (o dimensioni/carica)
note alle masse identificate o tramite un pattern di

Intensity
frammentazione caratteristico

Concert Hall, Stockholm Sweden, Dec 2002 Dr. Fenn getting his Nobel Prize from the King of Sweden
Rivelazione
m/z

Sommario
Esclusivamente per la didattica
5 aprile 2016
8

For Teaching Purpose Only

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5. April 2016
4
!19
11. Good luck! Spettrometria di massa
Premi Nobel con studi relativi alla spettrometria di massa

A.14 Nobel Prizes for Mass Spectrometry

Laureate Category Prize motivation

and year
Joseph John Thomson Physics In recognition of the great merits of his theo-
1906 retical and experimental investigations on the
conduction of electricity by gases
Francis William Aston Chemistry For his discovery, by means of his mass spec-
1922 trograph, of isotopes in a large number of non-
radioactive elements, and for his enunciation of
the whole-number rule
Wolfgang Paul Physics For the development of the ion trap technique
1989
John B. Fenn jointly with Chemistry For their development of soft desorption ioniza-
2002 tion methods for mass spectrometric analyses of
Koichi Tanaka biological macromolecules

REVIEWS OF MODERN PHYSICS, VOLUME 87, JANUARY–MARCH 2015

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