Fourier-transform mass spectrometer, FTMS

Time-of-flight (TOF) MS detectors (Fig. 15.7) are commonly used in pro-teomics studies of proteins and protein fragments because this type of detector can handle and analyze very large molecular and fragmentation ions. Fourier transform mass spectrometers (FTMS) are being incorporated into commercial LC/MS systems and offer the advantage of being nondestructive detectors that can trap and repeatedly analyze the same sample in order... 

Other Mass Analyzers. Other analyzers, such as quadrupole ion trap (QIP) and Fourier transform mass spectrometer (FTMS), are of some interest for proteomics. The quadrupole ion trap mass analyzer was devised by Wolfgang Paul it works on the principle of trapping ions with a particular RF in the quadrupole mass analyzer. This device provides a way to eject ions of certain radio frequency and retain the others, only the latter are allowed to reach the detector by scanning ions of a particular radio frequency. In this method, the selected ions can be subjected to fragmentation by collision-induced dissociation (CID), which is useful for the analysis of peptides. 

The most widely used type of trap for the study of ion-molecule reactivity is the ion-cyclotron-resonance (ICR) [99] mass spectrometer and its successor, the Fourier-transform mass spectrometer (FTMS) [100. 101]. Figure A3.5.8 shows the cubic trapping cell used in many FTMS instruments [101]. Ions are created in or injected into a cubic cell in a vacuum of 10 Pa or lower. A magnetic field, B, confines the motion in the x-y... 

Fourier Transform Mass Spectrometer (FTMS) Fourier transformation (FT) of time-dependent image from the detector to m/z intensity is utilized for two types of mass spectrometers ion cyclotron resonance (ICR) and Orbitrap. FTICR mass spectrometers operate based on the ion cyclotron resonance principle ions in a magnetic field (B) move in circular orbits at frequencies (ft>c) characteristic of their m/z values as shown below (Marshall et al., 1998,2002) ... 

Figure 2.17 Quadrupole Fourier transform mass spectrometer (FTMS). Reprinted with permission from Ref [8]. 2003 American Chemical Society.

Because of the low collision rate in the high vacuum environment of a Fourier transform mass spectrometer (FTMS), vibrationally excited molecular ions cool predominantly by IR fluorescence. For typical IR transition dipole moments and frequencies in the mid-IR, spontaneous emission is expected to occur at a rate in the range of 1-100 s To energize an ion efficiently using IR multiple-photon excitation (MPE), the rate of photon absorption - the product of absorption cross section and photon flux - should exceed the emission rate. From such a back-of-an-envelope estimate, one finds that radiation sources producing several Watts/cm are required to induce efficient dissociation [141], Note that the demands on laser power may further increase because of the limited residence time of the ions in the laser field, collisional deactivation in traps at higher pressures, limited spectral overlap between molecular absorption and laser emission profiles, etc. 

The detector in capillary electrophoresis is the main component in nanoanalyses. Many detectors can be used for this purpose but the mass spectrometer is the best one due to its wide ranges and low concentration detection capabilities. In the last few years, time-of-flight-mass spectrometry (TOF-MS) instruments have come onto the market and are available in many sizes, but small instruments are preferred in NCE. Bruker (Billerica, MA) has provided a micro-TOF-MS-LC (2x2x4 feet) system for nanoanalyses. Bruker also introduced a Q-q-FTMS (Fourier transform mass spectrometer) for proteomics called the APEX-QE. It offers fast, dual quadrupoles, which provides the first stages followed by FTMS for the highest mass accuracy. It can be coupled to NCE and controlled by Bmker s ProteinScape work flow and warehousing... 

Although there are many attractive features of Fourier transform mass spectrometry (FTMS), there are problems with current implementations. The FT mass spectrometer is still a relatively young instrument when compared to the double-focussing mass spectrometer, and comparisons of the spectrometers and their... 

All experiments were performed using a Nicolet Analytical Instruments FTMS-2000 dual-cell Fourier transform mass spectrometer with optional GC and laser desorption interfaces. The FTMS-2000 dual cell is specially constructed of stainless steel with low magnetic susceptibility. This permits very efficient ion transfer between the source and analyzer cells, if the cells are properly aligned in the magnetic field. 

The theory and instrumentation of Fourier transform mass spectrometry (FTMS) have been discussed extensively in this book and elsewhere [21-23]. All experiments were performed on a Nicolet prototype FTMS-1000 Fourier transform mass spectrometer previously described in detail [24] and equipped with a 5.2 cm cubic trapping cell situated between the poles of a Varian 15 in. electromagnet maintained at 0.85 T. The cell was constructed in our laboratory and utilizes two 80 transmittance stainless steel screens as the transmitter plates. This permits irradiation with a 2.5 kW Hg-Xe arc lamp, used in conjunction with a Schoeffel 0.25 m monochromator set for 10 nm resolution. Metal ions are generated by focusing the beam of a Quanta Ray Nd YAG laser (either the fundamental line at 1064 nm or the frequency doubled line at 532 nm) into the center-drilled hole (1 mm) of a high-purity rod of the appropriate metal supported on the transmitter screen nearest to the laser. The laser ionization technique for generating metal ions has been outlined elsewhere [25]-... 

Fig. 1 Schematic representation of a mass spectrometer depicting its main components and the different modes used. Abbreviations DIP direct insertion probe DEP direct exposure probe GC gas chromatography LC liquid chromatography CE capillary chromatography TEC thin-layer chromatography FEE field-flow fractionation APCI atmospheric pressure ionization El electron impact Cl chemical ionization FAB fast-atom bombardment PD plasma desorption MALDI matrix-assisted laser desorption ionization ED laser desorption TSP thermospray ESI electron spray ionization HSI hypherthermal surface ionization Q quadropole QQQ triple quadropole TOE time-of-fiight FTMS Fourier transform mass spectrometer IT ion trap EM electrom multiplier PM photomultiplier ICR ion cyclotron resonance.

The first step is the priming of the NRPS active site and a subsequent limited tryptic digest of the protein. The digested sample is loaded on a reverse-phase liquid chromatography (RPLC) C18 column, which is directly connected to the inlet of an FT mass spectrometer. During online LC separation, the eluent is analyzed by MS and MS2 on an LC timescale. In the mass spectrometer the eluent is first analyzed by broadband Fourier transform mass spectrometry (FTMS). Then, peaks in the resulting broadband FT mass spectrum are... 

Electrospray Fourier Transform Mass Spectrometer (ESI-FTMS)... 

Once the polymer molecules have been transferred to the gas phase as ions, they are separated on the basis of their mass-to-charge ratio. Mass spectrometers nsed for MALDI analysis may differ, but for those that are commercially available, separation is effected by TOE Other methods such as quadrupole filter and Fourier transform mass spectrometry (FTMS) may also be used. 

Fourier analysis permits any continuous curve, such as a complex spectrum of intensity peaks and valleys as a function of wavelength or frequency, to be expressed as a sum of sine or cosine waves varying with time. Conversely, if the data can be acquired as the equivalent sum of these sine and cosine waves, it can be Fourier transformed into the spectrum curve. This requires data acquisition in digital form, substantial computing power, and efficient software algorithms, all now readily available at the level of current generation personal computers, laptops, and handheld devices. The computerized instruments employing this approach are called FT spectrometers—FTIR, FTNMR, and Fourier transform mass spectrometry (FTMS) instruments, for example. 

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