Quadrupole-FT-ICR

Since 2000, the field has moved increasingly toward hybrid FT-ICR instruments in which the FT-ICR is interfaced with a front-end mass analyzer. The groups of Marshall [46,47] and Smith [48,49] introduced the quadrupole-FT-ICR. That configuration is available commercially. The hybrid linear ion trap FT-ICR [87] was introduced commercially in 2003. Hybrid instruments offer greater versatility in terms of mass-selective external accumulation with the associated increase in sensitivity and dynamic range. 

Williams, D.K. Hawkiidge, A.M. Muddiman, D.C. Sub-ppm mass measurement accuracy of intact proteins and product ions achieved using a dual electrospray ionisation quadrupole FT-ICR mass spectrometer. J. Am. Soc. Mass Spectrom. 2007,18 ), 1-7. Witt, M. Fuchser, J. Baykut, G. FT-ICR mass spectrometry with NanoLC/microelec-trospray ionization and MALDI Analytical performance in peptide mass fingerprint analysis. /. Am. Soc. Mass Spectrom. 2003,14(6), 553-561. 

Myoglobin peptides [146] Marine muscle tissue protein, probably of seal species Alaskan pottery fragment, 1200-1400 A.D. NanoESI operating in positive-ion mode, hybrid quadrupole FT-ICR operating in single and tandem mass spectrometry... 

Triacylglycerols Animal fats [169] Ceramic oil lamps NanoESI in positive-ion mode Hybrid quadrupole-FT-ICR/MS... 

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. 

Various analyzers have been used to analyze phenolic compounds. The choice of the MS analyzer is influenced by the main objective of the study. The triple quadrupole (QqQ) has been used to quantify, applying multiple reaction monitoring experiments, whereas the ion trap has been used for both identification and structure elucidation of phenolic compounds. Moreover, time-of-flight (TOF) and Fourier-transform ion cyclotron resonance (FT-ICR) are mainly recommended for studies focused on obtaining accurate mass measurements with errors below 5 ppm and sub-ppm errors, respectively (Werner and others 2008). Nowadays, hybrid equipment also exists, including different ionization sources with different analyzers, for instance electrospray or atmospheric pressure chemical ionization with triple quadrupole and time-of-flight (Waridel and others 2001). 

Usually, concentration is measured as a pressure and may differ widely according to the type of mass spectrometer used. The triple quadrupole mass spectrometer may operate with pressures up to 1 x 10 1 Pa in the reaction region. At the other extreme, ion cyclotron resonance mass spectrometers operate poorly at pressures >1 X 10 4 Pa. A pressure of 1 x 10 4 Pa may be regarded as fairly high pressure for FT-ICR measurements. Converting the pressure into a more normal value of concentration means that reactions are carried out at concentrations < 10 9M (often several orders of magnitude < 10 0 M). 

Classically, high-resolution work is the domain of double-focusing magnetic sector instruments. More recently, TOP and to a certain degree triple quadrupole instruments are also capable of resolutions up to about 20,000. However, the rapid development of FT-ICR instruments has established those as the systems of choice if ultrahigh-resolution (>100,000) and highest mass accuracy (1 ppm) are required (Chap. 4.6). 

The majority of H/D studies that have been reported employ quadrupole ion trap (QIT) instruments due to their ease of use, excellent sensitivity, ability to perform MS/MS experiments, compact size, and low cost. Other reports discuss the use of instruments with higher mass-resolving power such as the hybrid QqTOF instruments [47]. A few groups have utilized FT-ICR mass spectrometry, which offers ultra-high mass-resolving power and improved mass accuracy [48, 49]. 

In recent years the application of electrospray ionization (ESI) mass spectrometry, quadrupole time-of-flight (QqTOF) mass spectrometry, and Fourier transform ion cyclotron resonance (FT-ICR) are used for further structural characterization of DOM (Kujawinski et al., 2002 Kim et al., 2003 Stenson et al., 2003 Koch et al., 2005 Tremblay et al., 2007 Reemtsma et al., 2008). MS/MS capabilities provide the screening for selected ions, and FT-ICR allows exact molecular formula determination for selected peaks. In addition, SEC can be coupled to ESI and FTICR-MS to study different DOM fractions. Homologous series of structures can be revealed, and many pairs of peaks differ by the exact masses of -H2, -O, or -CH2. Several thousand molecular formulas in the mass range of up to more than 600 Da can be identified and reproduced in element ratio plots (O/C versus H/C plots). Limitations of ESI used by SEC-MS are shown by These and Reemtsma (2003). 

The MALDI-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (MALDI-FT-ICR-MS) and MALDI-Quadrupole-Ion-trap-TOF Mass Spectrometry (MALDI-QIT-TOF-MS) can be used on IMS. The FT-ICR-MS could provide the high resolution, expansive mass range and high sensitivity imaging MS data and good for determining the elemental composition of small molecules [60],... 

The quadrupole ion trap is seen as a compact and less expensive alternative to FT-ICR mass spectrometers employed for gas-phase metal ion chemical and mass analysis [28,29]. Although lacking the high mass resolving powers available in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), the quadrupole ion trap has been investigated by using nonselective and resonance-selective ionization of ablated metal samples. 

There are several types of ionization sources [MALDI, ESI, FAB (fast atom bombardment), PD (Cf-252 plasma desorption), El (electron ionization), Cl (chemical ionization) etc.], different types of mass analyzers [combinations of magnetic and electric sectors, quadrupolar filters (Q) and ion traps (IT), time-of-flight (TOF) and FT-ICR] and different detectors, each with its own advantages and drawbacks. We describe herein only the systems that presently have widespread use for the study of biomolecules ESI coupled to a quadrupole (or triple quadrupole, QqQ) mass analyzer or an ion trap, the MALDI source with the linear or reflectron TOF analyzer, and the FT-ICR system which can be equipped with both ESI and MALDI sources. 

A third type of MS/MS instruments is a hybrid of tandem-in-space and tandem-in-time devices, including the Q-trap (QQ-2D-linear trap) [45] and the ion trap-FT-ICR (2D-linear ion trap-FT-ICR) [46]. The Q-trap takes the configuration of triple quadrupole, with the third quadrupole replaced by a 2D-linear ion trap. The uniqueness of this design is that the 2D-linear ion trap component can be used to perform either (a) a normal quadrupole scan function in the RF/DC mode or (b) a trap scan function by applying the RF potential to the quadrupole. It is well-suited for both qualitative and quantitative studies. In the case of ion Trap-FT-ICR, it combines ion accumulation and MS" features of a 2D-linear ion trap with excellent mass analysis capability (mass resolution, mass accuracy, and sensitivity) of FT-ICR. 

Alternatively, the high resolving power of the FT-ICR-MS in the measurement of fragment ions can be exploited by performed fragmentation of the precursor ion, prior to introduction into the FT-ICR cell, e.g., via in-source CID, or a hybrid instrument consisting of a quadrupole or LIT front-end and a FT-ICR-MS back end. Both types of instruments are commercially available. 

The types of tandem mass spectrometers capable of performing MS/MS experiments fall into two basic categories tandem in space and tandem in time. Tandem-in-space instruments have discrete mass analyzers for each stage of mass spectrometry examples include multisector, triple-quadru-pole, and hybrid instruments (instruments having mixed types of analyzers such as a magnetic sector and a quadrupole). Tandem-in-time instruments have only one mass analyzer where each stage of mass spectrometry takes place in the same analyzer but is separated in time via a sequence of events. Examples of this type of instrument include Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometers and quadrupole ion traps, described in Chapter 3. 

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