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Fourier
transform mass spectrometry (FTMS) has received considerable attention for
its ability to make mass measurements with a combination of resolution and
accuracy that is higher than any other mass spectrometer, most recently
for biomolecules ionized by electrospray ionization (ESI) and
matrix-assisted laser desorption/ onization (MALDI). It is a versatile
instrument that can be adapted to a variety of analytical and physical
chemistry measurements and to examine ion chemistry and photochemistry.
Its versatility follows from the fact that it is an ion trapping
instrument, as is the rf quadrupole ass spectrometer. The FTMS instrument
mass analyzes and detects ions using methods which are unique among mass
spectrometers.
Fourier transform mass spectrometry derives from ion cyclotron
resonance (ICR) spectrometry. The theory of cyclotron resonance was
developed by Lawrence in the 1930s. Lawrence built the first cyclotron
accelerator and used to study the fundamental properties into a mass
spectrometer called the omegatron, by Sommer et al. Other designs followed
over the next 15 years, producing instruments that were used principally to
study ion-molevule reactions. In 1978, Comisarow and Marshall adapted
Fourier transform methods to ICR spectrometry and built the first FTMS
instrument. Since that time, interest in FTMS has increased exponentially,
as has the number of FTMS instruments.
Several types of FTMS instruments can be found in laboratories
throughout the world. Many have been built by investigators to perform
experiments that demand high performance under a variety of conditions, such
as ultra-precision mass measurements of low molecular mass ions or high
molecular mass ions, while interfacing sources with supersonic jet
expansion, atmospheric ionization or laser microprobe capabilities. All FTMS
instruments have in common four main components. First is a magnet, which
can be either a permanent magnet, an electromagnet or a superconducting
magnet. Permanent magnets have low field strengths that limit the
performance of an FTMS instruments and only a few systems have been built
with these. Electromagnets are limited to field strengths below 2 T,
although 1 T is most common. At these fields, FTMS instruments are capable
of achieving high performance for ions of relatively low mass-to- charge
ratio. The performance of the FTMS instrument improves as the magnetic field
strength increases and so the trend is to design instrument with stronger
fields using superconducting magnets. These are solenoidal magnets with
relatively wide bores compared with those used for NMR spectroscopy. The
NbTi superconducting magnets used for FTMS have field strengths ranging from
3 to 9.4 T. The practical and economical high end FTMS magnetic field at
present time is 7 T to 9.4 T, however.
The second component common to FTMS instruments is the analyzer cell.
The cell is the heart of the FTMS instrument, where ions are stored, mass
analyzed and detected. Several analyzer cell design have been developed. Two
common types of analyzer cells
are cubic cell and open end cylindrical cell.
The cubic cell was the first type of analyzer used for FTMS and is
still widely used today. It is composed of six plates arranged in the shape
of a cube. This cell is oriented in the magnetic field so that one opposing
pair of plates is orthogonal to the direction of the magnetic field lines
and two pair of plates lie parallel to the field. The plates that are
perpendicular to the field are called the trapping plates. It is common for
trapping electrodes of cubic cells to have openings that permit electrons or
ions to enter the cell along the magnetic field lines. The four remaining
plates are used for ion excitation and ion detection.
The open-ended cylindrical cell differs in appearance from the cubic
cell but has six electrodes that perform the same function as those of the
cubic cell. This cell is oriented so that the principal axis of the cylinder
aligns with the magnetic field. The trapping electrodes in this design are
the two cylinders at the ends of the cell. The center cylinder is divided
into four electrodes that function as excitation and detection plates. The
shape and dimensions of this type of cell make it more suitable to fit into
the bore of a superconducting magnet, while the cubic cell is better matched
with the narrow gap between the pole caps of an electromagnet.
The third feature required of FTMS instruments is an ultra-vacuum
system. While all mass spectrometers require vacuum for the analysis and
detection of ions, the performance of the FTMS instrument is more sensitive
to pressure than other instruments. High vacuum is required to achieve high
resolution. A vacuum of 10-9–10-10 Torr (1 Torr =
133.3 Pa) is required. To achieve these low pressures, cryogenic pumps or
turbomolecular pumps are used more frequently then diffusion pumps. Low
pressure is required only when ions are detected. Ion formation and
detection occur at different times in an FTMS experiment, so that ion
formation of these instruments can also operate at elevated pressure
provided that high vacuum is restored during ion detection. Most FTMS vacuum
systems are equipped with pulsed valves so that the pressure can be
increased for a brief duration, for example to introduce a sample for ion
molecule studies or to collisionally activate trapped ions.
The fourth feature that is shared y all FTMS instruments is a
sophisticated data system. Many of the components of the data system are
similar to those used for FT-NMR. They include a frequency synthesizer,
delay pulse generator, broadband r.f. amplifier and preamplifier, a fast
transient digitizer and a computer to coordinate all of the electronic
devices during the acquisition of data, as well as to process and analyze
the data. The tremendous growth and development of the semiconductor
industry have benefited FTMS. Electronics hardware costs for FTMS have
remained level over the last decade, while performance has increased
dramatically.