Tandem quadrupole instruments

These are not the only types of tandem mass spectrometers. There are numerous configurations of instruments that are based on the type of ion separation and many new terms associated with these instrument types. For example, there are instruments known as ion traps. The ion trap is a device that can measure mass, fragment a selected mass (as could be done in a collision cell) and then measure the mass of the fragment. The product ion produced by this all in one device is the same product ion that would be produced in a tandem quadrupole instrument. However, there is only one mass analyzer that functions as both the collision cell and mass measuring device. These types of instruments are sometimes referred to as tandem mass spectrometers, but are not abbreviated as MS/MS. The MS/MS analysis is done by separating the analysis in time (tandem in time) rather than two devices separated in space. A more generic term is best suited. This term is MS , where the n represents... 

There are three MS/MS experiments that are of use in carbohydrate analysis. These can be depicted schematically (Fig. 11) and are described using a tandem quadrupole instrument as an example. Quadrupole-based tandem-in-space instruments operate at low CID energies (up to 100-200 eV). 

The latter two experiments can be best performed on a tandem quadrupole instrument, although software data manipulation can allow this type of data to be extracted from experiments on other instruments. 

Figure 2.4 MDMS of a chloroform extract of mouse retina prepared by a modified Bligh and Dyer method [25]. Direct-infusion ESI spectra were acquired directly from the diluted lipid extract (total Upid 50 pmol/pL) using a TSQ Quantum Ultra tandem quadrupole instrument. The first (x) dimension is represented in the top panel (negative-ion ESI-MS). The second dimension (y) is represented by successive neutral-loss (NL) and precmsor-ion (PI) scans. All traces were displayed after normalization to the base peak in each spectrum. Internal standard (IS) m n, acyl chain containing m carbons and n double bonds. (Modified with permission from Han, X. et al., 2005, Shotgun Lipidomics of Phosphoethanolamine-Containing Lipids in Biological Samples after One-Step in Situ Derivatization, /. Upid Res. 46 1548-60.)...

Fragment ions observed in MS/MS spectra recorded on Q-TOF and tandem quadrupole instruments, and in [Mp, [M-59F and [M], [M-79j MS spectra recorded on ion traps from GT and GP hydrazones, respectively. 

Fig. 4.3 Schematic diagram and photo of tandem quadrupole mass spectrometer. The photo is taken from a Waters tandem-quadrupole instrument, featuring a travelling wave stacked ring RF-only collision cell. ( 2013, hyphen MassSpec)...

Tandem quadrupole and magnetic-sector mass spectrometers as well as FT-ICR and ion trap instruments have been employed in MS/MS experiments involving precursor/product/neutral relationships. Fragmentation can be the result of a metastable decomposition or collision-induced dissociation (CID). The purpose of this type of instrumentation is to identify, qualitatively or quantitatively, specific compounds contained in complex mixtures. This method provides high sensitivity and high specificity. The instrumentation commonly applied in GC/MS is discussed under the MS/MS Instrumentation heading, which appears earlier in this chapter. 

Chemical ionization can be used at ambient pressures. Chemical ionization was used in tandem MS, using a triple quadrupole instrument, to characterize the antipsychotic agent 2-amino-N(4-(4-(l,2-benzisothiazol-3-yl)-l-piperazinyl)butyl)benzamide from human plasma.5... 

Various tandem MS instrument configurations have been developed, e.g. sector instruments, such as CBCE, CBCECB or CECBCE, and hybrid instruments, e.g. BCECQQ (B = magnetic sector analyser, E = electrostatic analyser, C = collision cell, Q = quadrupole mass spectrometer), all with specific performance. Sector mass spectrometers have been reviewed [168],... 

It should be pointed out that FAB, MALDI, and ESI can be used to provide ions for peptide mass maps or for microsequencing and that any kind of ion analyzer can support searches based only on molecular masses. Fragment or sequence ions are provided by instruments that can both select precursor ions and record their fragmentation. Such mass spectrometers include ion traps, Fourier transform ion cyclotron resonance, tandem quadrupole, tandem magnetic sector, several configurations of time-of-flight (TOF) analyzers, and hybrid systems such as quadrupole-TOF and ion trap-TOF analyzers. 

Fig. 11.16. Representation of three tandem mass spectrometry (MS/MS) scan modes illustrated for a triple quadrupole instrument configuration. The top panel shows the attributes of the popular and prevalent product ion CID experiment. The first mass filter is held at a constant m/z value transmitting only ions of a single mlz value into the collision region. Conversion of a portion of translational energy into internal energy in the collision event results in excitation of the mass-selected ions, followed by unimolecular dissociation. The spectrum of product ions is recorded by scanning the second mass filter (commonly referred to as Q3 ). The center panel illustrates the precursor ion CID experiment. Ions of all mlz values are transmitted sequentially into the collision region as the first analyzer (Ql) is scanned. Only dissociation processes that generate product ions of a specific mlz ratio are transmitted by Q3 to the detector. The lower panel shows the constant neutral loss CID experiment. Both mass analyzers are scanned simultaneously, at the same rate, and at a constant mlz offset. The mlz offset is selected on the basis of known neutral elimination products (e.g., H20, NH3, CH3COOH, etc.) that may be particularly diagnostic of one or more compound classes that may be present in a sample mixture. The utility of the two compound class-specific scans (precursor ion and neutral loss) is illustrated in Fig. 11.17.

This basically means that two instruments have been linked together. The first analyser can replace the traditional chromatographic separation step and is used to produce ions of chosen m/z values. Each of the selected ions is then fragmented by collision with a gas, and mass analysis of these product ions effected in the second analyser. The resulting mass spectrum is used for their identification. The potential combinations of the various magnetic sector and quadrupole instruments to form such coupled systems is considerable. Ion traps may also be operated in a tandem MS mode. 

Scan Modes for Tandem MS with Triple Quadrupole Instruments... 

Fig. 1.6 (A) Electron impact spectrum obtained on a single quadrupole mass spectrometer of a compound with Mr = 355. (B) Product ion spectrum after atmospheric pressure ionization obtained on a triple quadrupole instrument. Chemical ionization and atmospheric pressure ionization give in both cases protonated precursor ions, which is ideal for tandem mass spectrometry.

A triple quadrupole instrument (QqQ) is a combination of two mass quadrupole mass filters (tandem mass spectrometry) separated by a collision cell which is also a quadrupole operating in RE-only mode (Pig. 1.18). A common nomencla-... 

In the absence of tandem mass spectrometry equipment, almost equally reliable estimations of the PA concentrations can be made using gas chromatography-mass spectrometry (GC-MS). A standard quadrupole instrument, such as the one used for organic acid analysis, will be sufficient. Depending on the derivative, a choice between positive and negative ionization will have to be made. In general, a more extensive prepurification of the biological samples, will have to be realized. 

Fig. 8.1.1 Simple illustrations of a various mass spectrometers, a The triple-quadrupole tandem mass spectrometer (top panel). The middle set of quadrupoles are part of the collision cell (CC) and do not perform mass separation. MSI and MS2 indicate the first and second quadrupole mass separation devices, respectively. The bold arrow shows the path of ions, b Ion-trap mass spectrometer (middle left). The charged sections of the ion trap are not elliptical as drawn, but rather hyperbolic. The diagram is also two-dimensional, whereas the ion trap is three-dimensional. The ion path is such that ions enter the device and are trapped until a specific voltage ejects these ions, c Time of Flight mass spectrometer with a Reflectron (middle left). Ions are separated by the time it takes to pass through the instrument. The Reflectron improves/focuses the ions, d Hybrid Tandem mass spectrometer (bottom). The diagram shows that a quadrupole instrument can be combined with a different type of mass spectrometer, forming a tandem hybrid instrument...

Common tandem-in-space instruments employ a quadrupole as the first mass analyzer, a multipole collision cell (usually hexapole) operated in RF-only mode, and then either a second quadrupole or a TOF tube as the second mass analyzer. These instruments are termed triple or tandem quadrupole and quadrupole-time-of-flight mass spectrometers. 

Hopfgartner, G. Chernushevich, I. Covey, T. Bonner, R. 1998. Exact mass measurements on product ions for structural elucidation of drug metabolites with a tandem quadrupole TOF instrument. Proc. 46th ASMS Conf. Mass Spectrom. and Allied Topics (Orlando, Florida), 713. 

In contrast to triple quadrupole instruments, where MS-MS experiments can be conducted in space in separate regions of the instrument, ion traps enable MS-MS sequentially in the same physical space, and thus, occur tandem in time. After the ions have been formed an trapped, a parent ion is selected by resonance ejection of all ions except those of the selected m/z ratio. This is done by applying a resonance ejection radiofrequency voltage to the end-cap electrodes which stimulates motion of the ions in the axial direction. The next step in the MS-MS sequence is to effect collisionally... 

Figure 4. Effects of ion kinetic energy on the MS/MS of 5-indanol (a) MS/MS obtained on MIKES instrument with 7000 eV translational energy (b) spectrum obtained on hybrid BQ (magnet followed by quadrupole) mass spectrometer 95 eV (c) spectrum obtained with QQ (tandem quadrupole) mass spectrometer at 35 eV...

---