CF-FAB

The mass spectra of mixtures are often too complex to be interpreted unambiguously, thus favouring the separation of the components of mixtures before examination by mass spectrometry. Nevertheless, direct polymer/additive mixture analysis has been reported [22,23], which is greatly aided by tandem MS. Coupling of mass spectrometry and a flowing liquid stream involves vaporisation and solvent stripping before introduction of the solute into an ion source for gas-phase ionisation (Section 1.33.2). Widespread LC-MS interfaces are thermospray (TSP), continuous-flow fast atom bombardment (CF-FAB), electrospray (ESP), etc. Also, supercritical fluids have been linked to mass spectrometry (SFE-MS, SFC-MS). A mass spectrometer may have more than one inlet (total inlet systems). 

Different options are available for LC-MS instruments. The vacuum system of a mass spectrometer typically will accept liquid flows in the range of 10-20 p,L min-1. For higher flow-rates it is necessary to modify the vacuum system (TSP interface), to remove the solvent before entry into the ion source (MB interface) or to split the effluent of the column (DLI interface). In the latter case only a small fraction (10-20 iLrnin ) of the total effluent is introduced into the ion source, where the mobile phase provides for chemical ionisation of the sample. The currently available commercial LC-MS systems (Table 7.48) differ widely in characteristics mass spectrometer (QMS, QQQ, QITMS, ToF-MS, B, B-QITMS, QToF-MS), mass range m/z 25000), resolution (up to 5000), mass accuracy (at best <5ppm), scan speed (up to 13000Das-1), interface (usually ESP/ISP and APCI, nanospray, PB, CF-FAB). There is no single LC-MS interface and ionisation mode that is readily suitable for all compounds... 

The mobile phase in LC-MS may play several roles active carrier (to be removed prior to MS), transfer medium (for nonvolatile and/or thermally labile analytes from the liquid to the gas state), or essential constituent (analyte ionisation). As LC is often selected for the separation of involatile and thermally labile samples, ionisation methods different from those predominantly used in GC-MS are required. Only a few of the ionisation methods originally developed in MS, notably El and Cl, have found application in LC-MS, whereas other methods have been modified (e.g. FAB, PI) or remained incompatible (e.g. FD). Other ionisation methods (TSP, ESI, APCI, SSI) have even emerged in close relationship to LC-MS interfacing. With these methods, ion formation is achieved within the LC-MS interface, i.e. during the liquid- to gas-phase transition process. LC-MS ionisation processes involve either gas-phase ionisation (El), gas-phase chemical reactions (Cl, APCI) or ion evaporation (TSP, ESP, SSI). Van Baar [519] has reviewed ionisation methods (TSP, APCI, ESI and CF-FAB) in LC-MS. 

Many excellent reviews on the development, instrumentation and applications of LC-MS can be found in the literature [560-563]. Niessen [440] has recently reviewed interface technology and application of mass analysers in LC-MS. Column selection and operating conditions for LC-MS have been reviewed [564]. A guide to LC-MS has recently appeared [565]. Voress [535] has described electrospray instrumentation, Niessen [562] reviewed API, and others [566,567] have reviewed LC-PB-MS. For thermospray ionisation in MS, see refs [568,569]. Nielen and Buytenhuys [570] have discussed the potentials of LC-ESI-ToFMS and LC-MALDI-ToFMS. Miniaturisation (reduction of column i.d.) in LC-MS was recently critically evaluated [571]. LC-MS/MS was also reviewed [572]. Various books on LC-MS have appeared [164,433,434,573-575], some dealing specifically with selected ionisation modes, such as CF-FAB-MS [576] or API-MS [577],... 

Capillary HPLC-MS has been reported as a confirmatory tool for the analysis of synthetic dyes [585], but has not been considered as a general means for structural information (degradant identification, structural elucidation or unequivocal confirmation) positive identification of minor components (trace component MW, degradation products and by-products, structural information, thermolabile components) or identification of degradation components (MW even at 0.01 % level, simultaneous mass and retention time data, more specific and much higher resolution than PDA). Successful application of LC-MS for additive verification purposes relies heavily and depends greatly on the quality of a MS library. Meanwhile, MB, DLI, CF-FAB, and TSP interfaces belong to history [440]. 

The combination of CE with continuous-flow fast atom bombardment (CF-FAB-MS) requires the use of an interface, because of the incompatibility of the CF-FAB process and CE for liquid flow [888], The CF-FAB source requires a solvent, usually water/glycerol (95-5 v/v), which is maintained at a steady flow-rate of 2-15mLmin 1. Flow-rate in CE does not exceed 1 nLmin-1. 

CZE-APCI-MS [887] andCZE-CF-FAB-MSn [533] couplings have been described. CEC-MS coupling offers ... 

CF-FAB MS Continuous-flow fast atom bombardment mass spectrometry... 

DGE a AC AMS APCI API AP-MALDI APPI ASAP BIRD c CAD CE CF CF-FAB Cl CID cw CZE Da DAPCI DART DC DE DESI DIOS DTIMS EC ECD El ELDI EM ESI ETD eV f FAB FAIMS FD FI FT FTICR two-dimensional gel electrophoresis atto, 10 18 alternating current accelerator mass spectrometry atmospheric pressure chemical ionization atmospheric pressure ionization atmospheric pressure matrix-assisted laser desorption/ionization atmospheric pressure photoionization atmospheric-pressure solids analysis probe blackbody infrared radiative dissociation centi, 10-2 collision-activated dissociation capillary electrophoresis continuous flow continuous flow fast atom bombardment chemical ionization collision-induced dissociation continuous wave capillary zone electrophoresis dalton desorption atmospheric pressure chemical ionization direct analysis in real time direct current delayed extraction desorption electrospray ionization desorption/ionization on silicon drift tube ion mobility spectrometry electrochromatography electron capture dissociation electron ionization electrospray-assisted laser desorption/ionization electron multiplier electrospray ionization electron transfer dissociation electron volt femto, 1CT15 fast atom bombardment field asymmetric waveform ion mobility spectrometry field desorption field ionization Fourier transform Fourier transform ion cyclotron resonance... 

The compatibility is excellent with continuous ion sources such as ESI, dynamic SIMS, CF-FAB, ICP, El, Cl, etc. Sector instalments are not well-suited for pulsed ionization methods, although there are examples where MALDI sources have been utilized [225-229]. Sector instruments are usually larger and more expensive than other mass analyzers, such as TOFs, quadrupole filters, and traps. 

Several years later, the next step in the application of MS-MS for mixture analysis was developed by Hunt et al. [3-5] who described a master scheme for the direct analysis of organic compounds in environmental samples using soft chemical ionisation (Cl) to perform product, parent and neutral loss MS-MS experiments for identification [6,7]. The breakthrough in LC-MS was the development of soft ionisation techniques, e.g. desorption ionisation (continuous flow-fast atom bombardment (CF-FAB), secondary ion mass spectrometry (SIMS) or laser desorption (LD)), and nebulisation ionisation techniques such as thermospray ionisation (TSI), and atmospheric pressure ionisation (API) techniques such as atmospheric pressure chemical ionisation (APCI), and electrospray ionisation (ESI). 

The determination of alkyltrimethyl ammonium surfactant compounds with the general formula RN (CH3)3 X- were performed using continuous flow (CF) FAB (CF-FAB) and ESI. Dodecyl-, tetradecyl- and... 

The determination of alkyltrimethyl ammonium compounds with the general formula RN (CH3)3X surfactant were performed using CF-FAB and ESI. The compounds examined were dodecyl-, tetradecyl-, and hexadecyl-trimethyl ammonium compounds dissolved in water. The product ion spectra of dodecyltrimethyl ammonium compound and its methyl-deuterated homologue were presented. The product ion at m/z 60 [(CH3)3NH]+of the non-deuterated compound at m/z 228 was the only ion that shifted after deuteration to m/z 69 [38],... 

In standard FAB, the surface of the matrix solution is depleted of analyte and suffers from radiational damage during elongated measurements. Refreshment of the surface proceeds by diffusion (limited by the viscosity of the matrix) or evaporation. Continuous-flow fast atom bombardment (CF-FAB) continuously refreshes the surface exposed to the atom beam. [107,108] The same effect is obtained in slightly different way by the frit-fast atom bombardment (frit-FAB) technique. [109,110] In addition, both CF-FAB and frit-FAB can be used for online-coupling of liquid chromatography (LC, Chap. 12) [111] or capillary electrophoresis (CE) to a FAB ion source. [112]... 

Fig. 9.15. Experimental setups of CF-FAB (a) and frit-FAB (b). Reproduced from Ref. [108] by permission (a). Academic Press, 1986. Reproduced from Ref. [110] by permission (b). Elsevier Science, 1988.

Example The significant increase in sensitivity and the improvements of sig-nal-to-background ratio (Chap. 5.2.4) in CF-FAB spectra are demonstrated by comparison of the standard FAB and CF-FAB mass spectra of peptides. [108,116] In case of 10 pmol of the peptide des(gln)-substance P (Fig. 9.16) solely CF-FAB reveals the low-intensity signals due to some loss of side chain groups and several a-type fragments. 

Nowadays, moving belt, PBI, API, TSP, and CF-FAB have mostly been replaced by ESI [1,25], APCI, [23,71-73] and APPI [74,75] (Chap. 11). ESI, APCI, and APPI intrinsically represent perfect FC-MS interfacing technologies. Even FC-nanoESI operation is feasible. [18]... 

The most commonly used FAB interface in LC/MS is known as continuous-flow fast-atom bombardment (CF-FAB) ionization, in which the fast atoms or ions are directed at a target along which the LC eluent flowsd In a CF-FAB, the LC eluent, mixed with a FAB matrix such as 5% aqueous glycerol, is continuously introduced and deposited on the tip of a FAB probe. The maximum flow rate is in the range of 5 to 15 pL/min. A comprehensive review of the principles and application of CF-FAB for LC/MS has been written by Caprioli. ... 

The first approaches to the coupling of liquid-phase separation techniques with mass spectrometry were designed for HPLC needs, starting in the 1970s with since-forgotten techniques such as direct liquid introduction (DLI) and moving belt. In the 1980s, techniques such as thermospray, continuous-flow-fast atom bombardment (CF-FAB), and particle beam arose. 

During the last decade, research efforts in the field of LC-MS have changed considerably. Technological problems in interfacing appear to be solved, and a number of interfaces have been found suitable for the analysis of flavonoids. These include TSP, continuous-flow fast-atom bombardment (CF-FAB), ESI, and APCI. LC-MS is frequently used to determine the occurrence of previously identified compounds or to target the isolation of new compounds (Table 2.11). LC MS is rarely used for complete structural characterization, but it provides the molecular mass of the different constituents in a sample. Then, further structural characterization can be performed by LC-MS-MS and MS-MS analysis. In recent years, the combination of HPLC coupled simultaneously to a diode-array (UV-Vis) detector and to a mass spectrometer equipped with an ESI or APCI source has been the method of choice for the determination of flavonoid masses. Applications of LC-MS (and LC-MS-MS) in flavonoid... 

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