Direct coupling, mass spectrometry

Frequently industrial hygiene analyses require the identification of unknown sample components. One of the most widely employed methods for this purpose is coupled gas chromatography/ mass spectrometry (GC/MS). With respect to interface with mass spectrometry, HPLC presently suffers a disadvantage in comparison to GC because instrumentation for routine application of HPLC/MS techniques is not available in many analytical chemistry laboratories (3). It is, however, anticipated that HPLC/MS systems will be more readily available in the future ( 5, 6, 1, 8). HPLC will then become an even more powerful analytical tool for use in occupational health chemistry. It is also important to note that conventional HPLC is presently adaptable to effective compound identification procedures other than direct mass spectrometry interface. These include relatively simple procedures for the recovery of sample components from column eluate as well as stop-flow techniques. Following recovery, a separated sample component may be subjected to, for example, direct probe mass spectrometry infra-red (IR), ultraviolet (UV), and visible spectrophotometry and fluorescence spectroscopy. The stopped flow technique may be used to obtain a fluorescence or a UV absorbance spectrum of a particular component as it elutes from the column. Such spectra can frequently be used to determine specific properties of the component for assistance in compound identification (9). 

Coupling mass spectrometry (MS) to capillary electrophoresis provides detection and identihcation of amino acids, peptides, and proteins based on the accurate determination of their molecular masses [15]. The most critical part of coupling MS to CE is the interface technique employed to transfer the sample components from the CE capillary column into the vacuum of the MS. Electrospray ionization (ESI) is the dominant interface which allows a direct coupling under atmospheric pressure conditions. Another distinguishing features of this soft ionization technique when applied to the analysis of peptides and proteins is the generation of a series of multiple charged, intact ions. 

In some instances, microdialysis sampling can be coupled on-line with mass spectrometry without prior separation or cleanup with techniques such as GC or LC. Continuous flow fast atom bombardment (cfFAB) has been used for the ionization of microdialysis samples without prior sample preparation. Coupling micro-dialysis directly to mass spectrometry via FAB was more feasible with cfFAB because it provided for a more robust, efficient ionization and prevented source fouling. 

GC is an ideal separation technique for small thermally stable volatile molecules. Capillary columns provide high-resolution separation of complex mixtures. These columns, owing to their low gas flow requirements, can be coupled directly to mass spectrometry. A variety of interfaces, such as an open-split interface, a jet-separator interface, and a molecular-effusion interface, are used to handle larger carrier gas flows of packed GC columns. 

An alternative, and a more elegant approach to analyzing large polymers is to couple a GPC via an electrospray ionization interface to the FT/MS. Each oligomeric fraction that elutes from the GPC would be measured directly by mass spectrometry with minimal interference from the multiple charge states of adjacent oligomers. 

Supercritical fluid chromatography, uses a supercritical fluid as the mobile phase, can be coupled directly to mass spectrometry by using capillary columns. 

Inductively coupled plasma (icp) emission, direct current plasma (dcp), and inductively coupled plasma mass spectrometry (icp/ms) have taken over as the methods of choice for the simultaneous detection of metallic impurities in hafnium and hafnium compounds (29,30). 

Laser based mass spectrometric methods, such as laser ionization (LIMS) and laser ablation in combination with inductively coupled plasma mass spectrometry (LA-ICP-MS) are powerful analytical techniques for survey analysis of solid substances. To realize the analytical performances methods for the direct trace analysis of synthetic and natural crystals modification of a traditional analytical technique was necessary and suitable standard reference materials (SRM) were required. Recent developments allowed extending the range of analytical applications of LIMS and LA-ICP-MS will be presented and discussed. For example ... 

A ceramic electrochemical microreactor for the methoxylation of methyl-2-furoate with direct mass spectrometry coupling. 

Specifically for triazines in water, multi-residue methods incorporating SPE and LC/MS/MS will soon be available that are capable of measuring numerous parent compounds and all their relevant degradates (including the hydroxytriazines) in one analysis. Continued increases in liquid chromatography/atmospheric pressure ionization tandem mass spectrometry (LC/API-MS/MS) sensitivity will lead to methods requiring no aqueous sample preparation at all, and portions of water samples will be injected directly into the LC column. The use of SPE and GC or LC coupled with MS and MS/MS systems will also be applied routinely to the analysis of more complex sample matrices such as soil and crop and animal tissues. However, the analyte(s) must first be removed from the sample matrix, and additional research is needed to develop more efficient extraction procedures. Increased selectivity during extraction also simplifies the sample purification requirements prior to injection. Certainly, miniaturization of all aspects of the analysis (sample extraction, purification, and instrumentation) will continue, and some of this may involve SEE, subcritical and microwave extraction, sonication, others or even combinations of these techniques for the initial isolation of the analyte(s) from the bulk of the sample matrix. 

Becker JS, Dietze H-J, McClean JA, Montaser A (1999) Ultratrace and isotope analysis of long-hved radionuclides by inductively coupled plasma quadrupole mass spectrometry using a direct injection high efficiency nebulizer. Anal Chem 71 3077-3984... 

Liu, C. L. and Verma, S. S., Direct coupling of ionic high performance liquid chromatography with electrospray ionization mass spectrometry utilizing a microdialysis junction interface, ]. Chromatogr. A, 835, 93, 1999. 

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). 

Gas and liquid chromatography directly coupled with atomic spectrometry have been reviewed [178,179], as well as the determination of trace elements by chromatographic methods employing atomic plasma emission spectrometric detection [180]. Sutton et al. [181] have reviewed the use and applications of ICP-MS as a chromatographic and capillary electrophoretic detector, whereas Niessen [182] has briefly reviewed the applications of mass spectrometry to hyphenated techniques. 

Laser desorption methods (such as LD-ITMS) are indicated as cost-saving real-time techniques for the near future. In a single laser shot, the LDI technique coupled with Fourier-transform mass spectrometry (FTMS) can provide detailed chemical information on the polymeric molecular structure, and is a tool for direct determination of additives and contaminants in polymers. This offers new analytical capabilities to solve problems in research, development, engineering, production, technical support, competitor product analysis, and defect analysis. Laser desorption techniques are limited to surface analysis and do not allow quantitation, but exhibit superior analyte selectivity. 

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