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J.C.S. CHEM. COMM., 1981 325

Published on 01 January 1981 on http://pubs.rsc.org | doi:10.1039/C39810000325
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Fast Atom Bombardment of Solids (F.A.B.) : A New Ion Source for

Mass Spectrometry
By MICHAELBARBER, ROBERTS. BORDOLI, R. DONALD SEDGIYICK,* and ANDREWN. TYLER
(Chemistry Department, The University of Munchester Institute of Science and Technology, Manclaester M60 1QD)

Summary A new method for obtaining high-quality mass with varying degrees of both success and experimental
spectra of molecules which previously were difficult or difficulty. In these laboratories we have developed an ion
impossible t o study by ionisation methods is described. source which accommodates solid materials and uses the
phenomenon of ion sputtering, but employs a beam of fast
THElast decade has seen a number of attempts to overcome neutral atoms, typically of Ar of 2-43 keV, as the primary
one of the problems associated with structural mass spectro- particles. The source of fast atoms in our prototype
metry, namely, the requirement that the sample must be apparatus consists of a cold cathode discharge ion source
presented t o the instrument in the gas phase before it is and a collision chamber. The discharge ion source produces
ionised. This has proved especially troublesome in the a beam of Art- of controlled energy in the range 2-10 keV,
case of compounds of biological and biomedical importance, which is focused into the collision chamber which contains
where their thermal instability and general polar nature a high pressure, 10-3-10-4 Torr, of Ar gas. Resonant
precludes volatilisation, except for a few low molecular charge exchange occurs with little or no loss of forward
weight examples. momentum. This results in a particle beam emanating
Field desorption,l secondary ion mass spectrometry using from the collision chamber which consists of a mixture of
ion beams2 and 252Cf radiation3, and laser-induced desorption Ar atoms and Ar+, the latter having escaped without being
of ions from surfaces4 have all been applied to this problem charge exchanged and both components having the kinetic
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326 J.C.S. CHEM. COMM.,1981

energy of the original ion beam. The ionic component is positive ion fast atom bombardment (F.A.B.) mass spectrum
cleansed from the beam by a set of electrostatic deflector of the unprotected undecapeptide, methionyl-lysyl-brady-
plates. kinin, obtained from 1 p g of material. It will be noted that
We have modified the ion source region of an A.E.I. high sensitivity (ca. 107 ions s-l) is obtained in the molecular
MS902 double focusing mass spectrometer to accept our ion region and this is maintained for more than 10 min.
prototype atom gun. Materials can be introduced into the The spectrum is rich in fragmentation which contains all
system by first depositing them from solution onto a metal the information necessary to sequence this peptide. The
stage which is fixed t o the shaft of a solid sample insertion kinins are by no means the largest peptides which can be
probe. This can then be introduced to the ion source studied by this technique. We have to date, successfully
through an axially mounted vacuum lock, in order to ionised the gastrins ( M 2096) and mellitin ( M 2845), a
intercept the fast atom beam. The ions produced from the peptide amide containing 26 amino-acid units.
sample by the sputtering mechanism are then accelerated As part of our studies of this type of molecule we have
to the normal spectrometer potential and pass into the carried out detailed work on tracing the fragmentation
Published on 01 January 1981 on http://pubs.rsc.org | doi:10.1039/C39810000325

analyser region of the instrument. We have carried out pathways of the pseudo-molecular ions in peptides using
similar modifications to a Vacuum Generators ZAB- 1 F first and second field-free region ‘metastable’ ion decom-
mass spectrometer which is an instrument of reversed positions using the MS9025 or alternatively the MIKES
geometry. facility6 on the ZAB-1F machine. We believe that this is
The mass spectra obtained by this method are character- the first time that such phenomena have been demonstrated
ised by high pseudo-molecular ion sensitivity, giving for a ‘sputter’ type ion source.
+
( M H)+ in positive ion spectra and ( M - H)- in the Our prototype apparatus has been operating successfully
negative ion case. The spectra of either polarity contain for 2 years and in this period we have investigated a very
structurally sensitive fragment ions and both first and large number of molecules of both natural and synthetic
second field-free ‘metastables’ are observable. The ion origin (e.g. see Table) which includes molecules which would
source has the facility of producing both positive and be classified as organic, organo-metallic, or metal com-
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negative ion mass spectra with equal ease and similar plexes, or the salts of these. This list gives some idea of the
efficiency and also has a very large potential mass range. versatility of our ion source, especially since it includes such
An example of the quality of the mass spectra produced ‘milestones’ as vitamin B,,, and for the first time by any
by our ion source is shown in the Figure. This is the mass spectrometric method, the co-enzyme of vitamin B12.

-
Met -iys Brady kin i n 13191

1045 1117

I
1100 1200 1300

700 800 900 1000

417 I 419

191
I 1638

FIGURE
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J.C.S. CHEM. COMM.,1981 327

TABLE. Classes of compounds which have been successfully niques we can show that F.A.B. has superiority in producing
investigated by F.A.B. mass spectrometry in their underivatised non-thermally-induced structurally-related fragmentation
form.
and a ready access to metastable information.
Oligo-saccharides, up t o tri-saccharides In conclusion, it is our opinion t h a t the F.A.B. method
Peptide antibiotics, e.g. vancomycin of ionisation has the following advantages which will ensure
Glyco-peptides, e.g. bleomycin
Penicillins, e.g. phenethicillin its widespread use in solving problems in structural chem-
Glycoside antibiotics, e.g. neomycin sulphate istry and analysis. (i) Ionisation occurs from the solid
Oligo-peptides, containing up t o 26 amino-acids which may be a t room temperature. Sample volatilisation
Vitamins, e.g. B,, B,, B,,, Bl,br B,, co-enzyme, C, P is not necessary and thermal effects are avoided. (ii) Sam-
Glycolipids, e.g. the gangliosides
Oligo-nucleotides, e.g. FAD ple preparation is easy in comparison with derivatisation
Neurotoxins, e.g. tetrodotoxin or field desorption techniques. (iii) The method works in
Polynuclear aromatic sulphonic acids and their salts either polarity and gives good pseudo-molecular ion
Platinum amine complexes sensitivity together with structurally significant fragmenta-
Published on 01 January 1981 on http://pubs.rsc.org | doi:10.1039/C39810000325

Triphenylphosphine complexes of gold, both covalent and ionic

Manganese Schiff’s base complexes. tion. (iv) Mass spectra may be obtained from molecules of
relatively high molecular weight. These advantages must
So far we have been successful in obtaining mass spectra be tempered by the problems associated with the inadequacy
from any molecule t o which field desorption has been of most mass spectrometers in terms of their energy focusing
shown t o be applicable. Furthermore, if attention is paid and ion source extraction efficiencies a t the high masses
t o the solvent and support system in our sample handling, which this new ion source now makes possible.
then we can obtain mass spectra which are stable for hours The authors thank their colleagues and collaborators who
compared with the transience of field desorption spectra. provided samples, the S.R.C. and the N.R.D.C. for the
By comparison with the 252Cfsystem, taking into account funding of the research, and V.G. Analytical Ltd., for the
our present mass spectrometer’s limited resolved mass use of their ZAB-1F mass spectrometer.
range, we can show a superiority in spectral quality and
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molecular weight sensitivity for such materials as vitamin

BIZ. Additionally, in comparison with both these tech- (Received, 19th J a n u a ~ y1981; Corn. 063.)

H. D. Beckey, ‘Principles of Field Ionisation and Field Desorption Mass Spectrometry,’ Pergamon, Oxford, 1977.
M. Barber and J. C. Vickerman, Surf. Defect Prop. Solids, 1976, 5 , 162.
R. D. Macfarlane and R. D. Torgerson, Science, 1976, 191, 920.
* M. A. Posthumus, P. G. Kistemaker, and H. L. C. Muezelaar, A n a l . Chem., 1978, 50, 985.
M. Barber and R. M. Elliott, A.S.T.M. Comm. E14; Proc. 12th Ann. Conf. on Mass Spectrom. and Allied Topics, Montreal, Canada,
May 1964.
J. H. Beynon, R. G. Cooks, J. W. Amy, W. E. Baitinger, and T. Y . Ridley, A n a l . Chem., 1973, 45, 1023a.